HK1126479B - 4-heteroaryl-substituted 1-aminocyclohexane-1- and cyclohexene-1-derivatives having effects on the opiod receptor system - Google Patents
4-heteroaryl-substituted 1-aminocyclohexane-1- and cyclohexene-1-derivatives having effects on the opiod receptor system Download PDFInfo
- Publication number
- HK1126479B HK1126479B HK09105048.2A HK09105048A HK1126479B HK 1126479 B HK1126479 B HK 1126479B HK 09105048 A HK09105048 A HK 09105048A HK 1126479 B HK1126479 B HK 1126479B
- Authority
- HK
- Hong Kong
- Prior art keywords
- indol
- citrate
- methyl
- ethyl
- dimethylamino
- Prior art date
Links
Description
The present invention relates to substituted heteroaryl derivatives, methods of their manufacture, medicinal products containing these compounds and the use of substituted heteroaryl derivatives for the manufacture of medicinal products.
The treatment of chronic and non-chronic pain conditions is of great importance in medicine. There is a worldwide need for effective pain therapies. The urgent need for patient-centred and targeted treatment of chronic and non-chronic pain conditions, including successful and satisfactory pain management for the patient, is documented in the large number of scientific papers published recently in the field of applied analgesics and basic research on nociception.
Classic μ-opioids such as morphine are effective in the treatment of severe to very severe pain and are of major importance for pain management. However, it may be beneficial to influence other opioid receptors, especially the ORL-1 receptor, in addition to the μ-opioid receptor, as the pure μ-opioids also have undesirable side effects such as constipation and atresia, but can also lead to dependence.
The ORL1 receptor is also involved in the regulation of other physiological and pathophysiological processes, including memory and memory formation (Manabe et al., Nature, 394, 1997, p. 577-581), hearing (Nishi et al., EMBO J., 16, 1997, p. 1858-1864) and many others.A review article by Calo et al. (Br.J. Pharmacol., 129, 2000, 1261-1283) provides an overview of the indications or biological processes in which the ORL1 receptor may play a role or be likely to play a role.Examples include analgesia, stimulation and regulation of dopamine uptake, the influence of μ-A-aminobes on the administration of hormones, such as the treatment of blood disorders, the excretion of neurotransmitters, the use of anti-inflammatory drugs (especially anti-oxidants), the use of anti-oxidants (anti-oxidants), the reduction of blood pressure, and the use of anti-oxidants (especially anti-oxidants), the use of anti-oxidants, such as anti-oxidants, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs, anti-inflammatory drugs,
Structurally related compounds with affinity for the ORL-1 receptor are known from the state of the art (WO 02090317) but no affinity for the μ-opioid receptor has been described, but the heteroaryl ring is linked to the cyclohexane ring via nitrogen.
N-aryloxyethylamine derivatives are known from WO 99/51576 and spirocyclic cyclohexane derivatives are known from WO 2004/043967.
The purpose of the present invention was to make available further medicinal products which act on the opioid receptor system and are therefore suitable for use in medicinal products, in particular for the treatment of the various diseases associated with this system and for use in the indications related thereto.
In which
A stands for N or CR7-10 where A stands for N no more than twiceW stands for O, S or NR4 provided that where W stands for O or S, A stands for CR7-10;
one of the residues B or C for H; C1-8 alkyl, whether or not saturated or unsaturated, branched or unbranched, simply or in multiple substitutions or unsubstituted,COR12; SO2R12; C1-3-alkyl-bound aryl, C3-8-cycloalkyl or heteroaryl, whether or not simply substituted or multiple substituted; aryl or heteroaryl, whether or not simply substituted or multiple substituted or unsubstituted; C3-4-cycloalkyl, whether or not simply substituted or multiple substituted or unsubstituted; and the other residue B or C for each of the following:
Other
It stands
Other
wherein
Other
a length of not more than 30 mm,
R1 and R2, independently of each other, for H; C1-5 alkyl, whether or not saturated or unsaturated, branched or unbranched, simply or in multiple substitutions or unsubstituted; C3-8 cycloalkyl, whether or not simply or in multiple substitutions or unsubstituted; aryl or heteroaryl, whether or not simply or in multiple substitutions or unsubstituted; or C1-3 alkyl-bound aryl, C3-8 cycloalkyl or heteroaryl, whether or not simply or in multiple substitutions or unsubstituted,standing up;
Other
or the residues R1 and R2 together give CH2CH2OCH2CH2, CH2CH2NR11CH2CH2 or (CH2) 3-6,
R11H; C1-5 alkyl, whether saturated or unsaturated, branched or unbranched, simply or with multiple substitutions or unsubstituted; C3-8 cycloalkyl, whether simply or with multiple substitutions or unsubstituted; aryl or heteroaryl, whether simply or with multiple substitutions or unsubstituted; or aryl, C3-8 cycloalkyl or heteroaryl, whether simply or with multiple substitutions or unsubstituted, bound by C1-3 alkyl; C ((O) phenyl, C ((O) heteroaryl, C ((O) C1-5 alkyl, where substituted or unsubstituted means:
andR3 for C1-8 alkyl, whether or not saturated or unsaturated, branched or unbranched, simply or with multiple substitutions or unsubstituted; C3-8 cycloalkyl, whether or not simply or with multiple substitutions or unsubstituted; aryl or heteroaryl, whether or not unsubstituted or with simple or multiple substitutions; aryl bound by a C1-3 alkyl group;Heteroaryl or C3-8 cycloalkyl, either unsubstituted or simply or repeatedly substituted;R4 stands for H;C1-5 alkyl, whether saturated or unsaturated, branched or unbranched, unsubstituted or simply or repeatedly substituted;Aryl, or Heteroaryl, either substituted or repeatedly substituted;Aryl, or Heteroaryl, either simply or repeatedly substituted or repeatedly substituted, bound to an alkyl group C1-3;COR12 stands for SO2R12;
Other
R12H; C1-5 alkyl, whether or not saturated or unsaturated, branched or unbranched, simply or in multiple substitutions or unsubstituted; C3-8 cycloalkyl, whether or not saturated or unsaturated, simply or in multiple substitutions or unsubstituted; aryl, or heteroaryl, whether or not simply or in multiple substitutions or unsubstituted; or aryl, C3-8 cycloalkyl or heteroaryl, whether or not simply or in multiple substitutions or unsubstituted, bound by C1-3 alkyl; OR13; NR14R15 means R7,R8, R9 and R10 independently for H, F, Cl, Br, I, NO2, CF3, OR13, SR13, SO2R13, SO2OR13, CN, COOR13, NR14R15, NHC(O)NHR13, NHC(O)R13, NH(CNR13)NHR13, SO2NHR13, C1-5 alkyl, C3-8 cycloalkyl, unsubstituted or simply or repeatedly substituted; aryl or heteroaryl, unsubstituted or simply or repeatedly substituted; or C1-3-alkyl, C3-8 cycloalkyl or heteroaryl, unsubstituted or simply or repeatedly substituted;
Other
R13H; C1-5 alkyl, whether or not saturated or unsaturated, branched or unbranched, unsubstituted or simply or repeatedly substituted; C3-8 cycloalkyl, whether or not saturated or unsaturated, unsubstituted or simply or repeatedly substituted; aryl or heteroaryl, unsubstituted or simply or repeatedly substituted; or C1-3 alkyl-bound aryl, C3-8 cycloalkyl or heteroaryl,'unsubstituted' or 'simply or repeatedly substituted' means:
Other
or R7, R8 and R9 have the meanings given above and R10 together with B stands for - CH2CH2CH2 and R10 and B thus form a six-membered ring,R14 and R15 independently H; C1-5 alkyl, whether or not saturated or unsaturated, branched or unbranched, unsubstituted or simply or repeatedly substituted; or C3-8 cycloalkyl, whether or not saturated or unsaturated, unsubstituted or simply or repeatedly substituted; aryl or heteroaryl, either substituted or simply or repeatedly substituted; or aryl, C3-8 cycloalkyl or heteroaryl, bound to C1-3 alkyl, unsubstituted or simply or repeatedly substituted;
Other
or R14 and R15 together form CH2CH2OCH2CH2, CH2CH2NR16CH2CH2 or (CH2) 3-6,
Other
where R16H; C1-5-alkyl is either saturated or unsaturated,Err1:Expecting ',' delimiter: line 1 column 166 (char 165)Err1:Expecting ',' delimiter: line 1 column 370 (char 369)Other
Other
C1-5 alkyl, C1-3 alkyl or C1-3 alkyl and C3-8 cycloalkyl residues, whether or not with F, Cl, Br, I, -CN, NH2, NH-C1-6 alkyl, NH-C1-6 alkyl-OH, N(C1-6 alkyl) 2, N(C1-6 alkyl-OH) 2, NO2, SH, S-C1-6 alkyl, S-benzyl, OCF3, O-C1-6 alkyl, OH, O-C1-6 alkyl-OH, =O, C1-6 alkyl, O-benzyl, O-phenyl, C(O) C1-6 alkyl, O-C1-6 alkyl, HHC2=, N=O, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO2-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO2-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO2-6 alkyl, CO2-6 alkyl, CO2=, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2=O, CO2
Other
where the aryl or heteroaryl residues referred to above may be replaced either simply or in multiple forms by F, Cl, Br, I, CN, NH2, NH-C1-6-alkyl, NH-C1-6-alkyl-OH, N(C1-6-alkyl) 2, N(C1-6-alkyl-OH) 2, NO2, SH, S-C1-6-alkyl, OH, O-C1-6-alkyl, O-C1-6-alkyl-OH, C(=O) C1-6-alkyl, CO2H, CO2-C1-6-alkyl, CF3, OCF3, C1-6-alkyl or phenoxy,
Other
in the form of racemate; the enantiomers, diastereomers; mixtures of the enantiomers or diastereomers or a single enantiomer or diastereomer; the bases and/or salts of physiologically compatible acids.
If a residue, such as R13, occurs more than once within a compound, such as in NH (CNR13) NHR13, the residue within the same molecule may have different meanings.
Other
I mean.
Err1:Expecting ',' delimiter: line 1 column 57 (char 56)
Err1:Expecting ',' delimiter: line 1 column 56 (char 55)
Err1:Expecting ',' delimiter: line 1 column 56 (char 55)
Err1:Expecting ',' delimiter: line 1 column 56 (char 55)
Err1:Expecting ',' delimiter: line 1 column 56 (char 55)
Err1:Expecting ',' delimiter: line 1 column 63 (char 62)
Err1:Expecting ',' delimiter: line 1 column 56 (char 55)
Compounds of the invention, where R10 together with B represents -CH2CH2CH2 and R10 and B thus form a six-membered ring, have the following general formula:
Other
whereas the remaining residues have the same meaning as above.
For the purposes of this invention, the term salt formed with a physiologically compatible acid is understood to mean salts of the respective work substance with inorganic or organic acids that are physiologically compatible, especially when used in humans and/or mammals. The preferred are hydrochloride, citrate, hemicitrate and methanosulfonate. Particularly preferred is methanosulfonate. Examples of physiologically compatible acids are: hydrochloric acid, hydrobromic acid, sulfuric acid, methanosulfonic acid, formic acid. Essential acids include oxalic acid, bernoxylic acid, citric acid, aspartic acid, hydrochloric acid, benzoic acid, butyl sulfuric acid, maleic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxylic acid, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy, 2-hydroxy
The term (CH2) 3-6 or (CH2) 4-5 shall mean -CH2CH2-CH2, -CH2-CH2-CH2, -CH2-CH2-CH2-CH2, and -CH2-CH2-CH2-CH2-CH2, or -CH2-CH2-CH2-CH2 and -CH2-CH2-CH2-CH2.
It is preferable that R1 and R2 do not mean H at the same time.
Compounds where C is the
Other
and BH; C1-8 alkyl, whether or not saturated or unsaturated, branched or unbranched, simply or with multiple substitutions or unsubstituted, COR12 ; SO2R12; aryl, C3-8 cycloalkyl or heteroaryl, whether or not simply or with multiple substitutions or unsubstituted, C3-8 cycloalkyl, whether or not simply or with multiple substitutions or unsubstituted, means us.
Furthermore, compounds which are single bond are preferred.
A preferred embodiment of the compounds of the invention shall be:
Other
The C1-8 alkyl, C1-5 alkyl, C1-3 alkyl or C1-3 alkylene or C3-8 cycloalkyl residues referred to above may be replaced by F, Cl, Br, I, -CN, NH2, NH-C1-6 alkyl, NH-C1-6 alkyl-OH, N(C1-6 alkyl) 2, N(C1-6 alkyl-OH) 2, NO2, SH, S-C1-6 alkyl, S-benzyl, OCF3, O-C1-6 alkyl, OH, O-C1-6 alkyl, OH, O-C1-6 alkyl, =O, C1-6 alkyl, benzyl, O-benzyl, O-phenyl, C=(O) C1-6 alkyl, OC2HHC, N=(C1-6 alkyl, OC=(C1-6 alkyl, CO2 alkyl, CO1-6 alkyl, CO1-6 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2 alkyl, CO2
Other
the aryl or heteroaryl residues referred to above may be replaced either alone or in combination with F, Cl. Br, I, CN, NH2, NH-C1-6-alkyl, NH-C1-6-alkyl-OH, N(C1-6-alkyl) 2, N(C1-6-alkyl-OH) 2, NO2, SH, S-C1-6-alkyl, OH, O-C1-6-alkyl, O-C1-6-alkyl-OH, C=O) C1-6-alkyl, CO2H, CO2-C1-6-alkyl, CF3, OCF3, C1-6-alkyl or phenoxy,
Other
in the form of racemate; the enantiomers, diastereomers, mixtures of the enantiomers or diastereomers or a single enantiomer or diastereomer; the bases and/or salts of physiologically compatible acids.
The residues and groups or substitutes described below as preferred may be combined in the compounds of the invention with the broadest meaning of the remaining residues, but also with preferred meanings of other residues and groups or substitutes.
The preferred is substituted heteroaryl derivatives, where W stands for NR4.
Furthermore, preference is given to heteroaryl derivatives, where A stands for CR7-10 or the general formula I takes the meanings of the general formula Ia and Ib:
The preferred products are still substituted heteroaryl derivatives, wherein
Other
R1 and R2 are independently of each other for H; C1-5 alkyl, saturated or unsaturated, branched or unbranched, simply or repeatedly substituted or unsubstituted;
Other
or the residues R1 and R2 together form a ring and mean CH2CH2OCH2CH2, CH2CH2NR11H2CH2 or (CH2) 3-6,
In particular, substitution heteroaryl derivatives are preferred, where R1 and R2 stand independently for CH3 or H, where R1 and R2 do not mean H at the same time, or R1 and R2 form a ring and mean CH2CH2OCH2CH2, CH2CH2N(CH3) CH2CH2, CH2CH2CH2, CH2CH2CH2CH2 or CH2CH2CH2CH2CH2.
Especially preferred are substituted heteroaryl derivatives, where R1 and R2 stand for CH3 or H, where R1 and R2 do not mean H at the same time.
Substituted heteroaryl derivatives, wherein
Other
R3 for C1-6-alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, thiazolyl, thiophenyl, triazolyl, benzimidazolyl, benzothiophenyl, furyl, benzofuranyl, benzodioxolanyl, indoyl, indanyl, benzodioxanyl, pyrrolyl, pyridyl, pyrimidyl or pyrazinyl, whether or not substituted or simply substituted or repeatedly substituted; cyclopentyl, cyclohexyl, phenyl, benzyl, naphthyl, benzinyl, benzodioxanyl, pyridyl, pyridyl, thiopentyl, furyl, benzodioxanyl, indoxyl, pyrimidyl, pyrimidyl or repeatedly substituted or simply substituted or repeatedly substituted;
Other
In particular:
Other
R3 Butyl, phenyl, thiophenyl, thiazolyl, cyclopentyl, cyclohexyl, naphthyl, benzyl, benzofuranyl, 1,2,4-triazolyl, benzimidazolyl, benzodioxanyl, benzodioxolanyl, pyridyl or benzothiophenyl, whether or not substituted or simply or more than once; means a phenyl, furyl or thiophenyl bound by a saturated, unbranched C1-3 alkyl group, whether or not substituted or simply or more than once.
In particular, substitution heteroaryl derivatives are preferred, where R3 stands for phenyl, 4-fluorophenyl, benzyl, butyl or benzothiophenyl.
Substituted heteroaryl derivatives, wherein B or C are preferred
Other
For C1-8 alkyl, either saturated or unsaturated, branched or unbranched, simply or multiplely substituted or unsubstituted; preferably for C1-4 alkyl, simply or multiplely substituted or unsubstituted.
Substituted heteroaryl derivatives, wherein B or C is preferred for
Other
with a standing position
X is O, NR20, S or CH2;R5 is =O;H; COOR13, CONR13, OR13, C1-5 alkyl, unsaturated or unsaturated, branched or unbranched, unsubstituted or simply or repeatedly substituted; C3-8 cycloalkyl, unsaturated or simply or repeatedly substituted; C3-8 cycloalkyl, unsaturated or simply or repeatedly substituted; C14 or C14 or C14 or C14 or C14 or C15 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 or C18 C18 or C18 or C18 C18 or C18 C18 or C18 C18 C18 or C18 C18 C18 C18 C18 C18 C18 or C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C18 C
Other
or R5 and R6 together (CH2) n with n = 2, 3, 4, 5 or 6, wherein individual hydrogen atoms may also be replaced by F, Cl. Br, I, NO2, CF3, OR13, CN or C1-5 alkyl;R19 H; aryl; benzyl; C(=O) C1-5 alkyl; C1-5 alkyl means andR20 H or C1-5 alkyl means.
It is preferable that R5 stands for H, CH3, CH2OH, COOH or COOCH3, preferably for H.
Alternatively, substituted heteroaryl derivatives, where R6 stands for H, C1-5 alkyl, aryl or aryl linked via a C1-3 alkyl group, preferably H, are preferred.
In addition, preference is given to substituted heteroaryl derivatives where B or C stands for (CH2)1-4-R21 where R21 stands for H, OH, SH, COOC1-6-alkyl, COOH, OC ((=O) C1-6-alkyl, NH2, NHC ((=O) C1-6-alkyl; or C3-8-Cycloalkyl, aryl or heteroaryl, either unsubstituted or simply or repeatedly substituted, preferably for phenyl, benzimidazole, pyridyl, triazolyl, pyrazole, pyrazole, tetrazol or imidazolyl, phenylhydroxyl, pyridoxyl, tetrahydroxyl, tetrahydroxyl, thiazolid, isohydroxyl, piperyl, piperyl, cycloxyl, cycloxy, pyridoxyl or repeatedly substituted.
In particular, preference shall be given to substituted heteroaryl derivatives where R21 is for OH, SH, COOCH3, COOH, OC ((=O) CH3, NH2, NHC ((=O) CH3, NHC ((=O) CH2C ((CH3) 3); or phenyl, benzimidazole, pyridyl, triazolyl, phenyl, pyrazolyl, tetrazolyl or imidazolyl, each unsubstituted or substituted with COOCH3.CH3; or cyclopropyl, cyclohexyl, pyrrolidinyl, tetrahydroquinoline, pyrrolidinyl, piperazidyl, tetrahydroisoquinoline, isohindinyl, piprahydrin, morphine, or tetrahydroquinoline, each unsubstituted or substituted with CHO3.
Substituted heteroaryl derivatives, where B stands for C3-8 cycloalkyl, in particular cyclopropyl, are also preferred.
In addition, preference is given to substituted heteroaryl derivatives where R7, R8, R9 and R10 stand for H; methyl; ethyl; propyl; butyl; pyridyl, O-benzyl, F, Cl. Br, I, CN, CF3, OCF3, OH, OCH3, NH2, COOH, COOCH3, NHCH3 or N(CH3) 2) or NO2.
Especially preferred are substituted heteroaryl derivatives, where R7, R8, R9 and R10 stand for H.
Preferably substituted heteroaryl derivatives, wherein R4H; C1-3-alkyl-C3-8-cycloalkyl. C1-6-alkyl, unsubstituted or simply or repeatedly substituted; or SO2-phenyl or CO-phenyl, either unsubstituted or simply or repeatedly substituted, in particular R4 means methyloxirane, CH2CH(OH)CH2NCH(3)2, SO2-phenyl, CH2CH2OH, CH2CH(OH)CH2NHCH3 or CH3
In particular, substitution heteroaryl derivatives, where R4 stands for H, continue to be preferred.
The most preferred are substituted heteroaryl derivatives from the group
(1) Dimethyl dimethyl dimethyl (dimethyl) dimethyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methylIt consists of a mixture of hydrocarbons having carbon numbers predominantly in the range of C1 through C1 and boiling in the range of approximately -15 oC to -15 oC (- 40oF to -15oF).] This mixture is then reduced to approximately -15 oC (- 40oF).] This mixture is then reduced to -15 oC (- 40oF).] This mixture is then reduced to -15 oC (- 40oF).] This mixture is then reduced to -15 oC (- 40oF).] This mixture is then reduced to -15 oC (- 40oF).] This mixture is then reduced to -15 oC (- 40oF).The following entries are added in column 1A.10.A.10.B.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.10.A.11.A.10.A.11.A.11.A.11.A.11.A.11.A.11.A.11.A.11.A.11.A.A.11.A.11.A.12.A.A.12.A.A.12.A.A.12.A.A.12.A.A.12.A.A.A.12.A.A.12.A.A.A.12.A.A.A.12.A.A.A.12.A.A.A.A.A.A.12.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.A.AIt consists of a mixture of hydrocarbons having carbon numbers predominantly in the range of C1 through C1 and boiling in the range of approximately -15oC to -15oC and boiling in the range of approximately -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15oC to -15o -15oC to -15o -15oC to -15oC to -15o -15oC to -15o -15oC to -15o -15oC to -15o -15oC to -15o -15oC to -15o -15o -15oC to -15o -15oC to -15o -15o -15o -15oC to -15o -15o -15o -16 -16 -16 -20 -16 -17o -17o -17o -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -18 -It consists of a mixture of hydrocarbons having carbon numbers predominantly in the range of C1 through C1 and boiling in the range of approximately -15 oC to -15 oC (- 40oF to -15oF).] This mixture is then reduced to approximately -15 oC (- 40oF).] It then reacts with oxygen in the presence of oxygen and the remaining oxygen is absorbed by the reaction catalysts.The following entries are added in column 1A.10.A.10.B. to the row concerning the entry concerning the product concerned: 'Diphenyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methN-dimethyl-4- ((1-methyl-1H-indol-2-yl) cyclohex-3-enamine; hydrochloride ((303) N,N-dimethyl-4-(3-(2-(pyridine-4-yl) ethyl) - 1H-dimethyl-2-yl) - 1- (thiophen-2-yl) cyclohexanamine hydrochloride ((303) N,N-dimethyl-4- ((3-(2- ((pyridine-4-yl) ethyl) cyclohexanamine hydrochloride ((306) N-methyl-4-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-meth
The substances of the invention, for example, act on the μ-opioid receptor relevant for various diseases, making them suitable as pharmaceutical active substances in a medicinal product.
The medicinal products of the invention contain, in addition to at least one heteroaryl derivative substituted in accordance with the invention, suitable additives and/or excipients, as appropriate, as well as carriers, fillers, solvents, diluents, dyes and/or binders, and may be administered as liquid forms in the form of solutions for injection, drops or juices, as semi-solids in the form of granules, tablets, pellets, patches, capsules, flakes/spray substitutes or aerosols. The balance of the excipients, as well as the main set of agents to be used, depend on whether the drug is intended for injection, oral or parenteral administration, or for intra-uterine application. The medicinal products may be administered in a perinatal or perinatal form, or in a subcutaneous form, such as a tablet, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a syringe, a, a syringe, a syringe, a, a syringe, a syringe, a, a syringe, a, a syringe, a, a, a syringe, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a, a
The dose to be administered to the patient will vary according to the patient's weight, type of application, indication and severity of the disease, usually 0.00005 to 50 mg/kg, preferably 0.01 to 5 mg/kg, of at least one heteroaryl derivative substituted according to the invention.
The ORL-1 receptor and the μ-opioid receptor have been identified in pain in particular, and therefore substituted heteroaryl derivatives of the invention can be used to manufacture a medicinal product for the treatment of pain, in particular acute, neuropathic, chronic or inflammatory pain.
Therefore, another subject matter of the invention is the use of a heteroaryl derivative substituted according to the invention to produce a medicinal product for the treatment of pain, in particular acute, visceral, neuropathic, chronic or inflammatory pain.
Another subject matter of the invention is the use of a heteroaryl derivative substituted in accordance with the invention to manufacture a medicinal product for the treatment of anxiety, stress and stress-related syndromes, depression, epilepsy, Alzheimer's disease, senile dementia, catalepsy, general cognitive dysfunction, learning and memory disorders (as a nootropic), dysfunction, alcohol and/ or drug abuse and/ or drug dependence, sexual dysfunction, cardiovascular disease, hypotension, hypertension, titrush, pruritus, migraine, difficulty hearing, intestinal insufficiency, nausea, vomiting, nausea, diarrhoea, diarrhoea, and/ or narcolepsy. The drug is used as a local anesthetic to treat mood disorders, neurological disorders, and/or to reduce the effects of narcolepsy, and/or to treat narcolepsy with a narcotic, an opioid, or a drug to reduce the sensitivity to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to narcotic drugs, or to reduce the sensitivity to narcotic drugs, or to narcotic drugs.
It may be preferred in one of the above uses if a substituted heteroaryl derivative used is present as a pure diastereomer and/or enantiomer, as a racemate or as a non-equimolar or equimolar mixture of the diastereomers and/or enantiomers.
The invention also relates to a procedure for the treatment, in particular in one of the above indications, of a non-human mammal or human being requiring the treatment of pain, in particular chronic pain, by the administration of a therapeutically effective dose of a heteroaryl derivative substituted according to the invention or of a medicinal product according to the invention.
The invention also relates to the manufacture of the heteroaryl derivatives substituted in accordance with the invention as described and illustrated below.
Other
For the production of amines of general formula Ic, ketones B are mixed with heteroaromates A in organic solvents or solvent mixtures, such as ethyl acetate, chloroform, dichloromethane (DCM), dichlorethane (DCE), diethyl ether (Et2O), acetonitrile (MeCN) or nitromethane, with the addition of an organic or inorganic acid, such as HCl, HBr, trifluoromethane sulphonic acid, methanosulphonic acid, acetic acid, trifluoroacetic acid or solvent-free in an organic or inorganic acid or acidic mixture at temperatures between 0°C and 150°C, using microwave irradiation if appropriate, and then an organic or trifluoroacetic agent is added to the mixture.
Other
The conversion of heteroaromats of general formula A or A' with cyclohexanones of general formula B to cyclohexane-substituted heteroaromats of general formula Id or Ie may be carried out in organic solvents or solvent mixtures, such as chloroform, dichloromethane (DCM), dichlorethane (DCE), diethyl ether (Et2O), acetonitrile (MeCN) or nitromethane, with the addition of an organic or inorganic acid, such as HCl, HBr, trifluoromethane sulphonic acid, methanosulphonic acid, acetic acid, trifluoromethane acetic acid, at temperatures between 0°C and 150°C, where appropriate using micro-irradiation. The conversion may also be carried out with the addition of an organic or inorganic acid, such as trifluoromethane sulphonic acid, methanosulphonic acid, acetic acid, trifluoromethane sulphonic acid, or trifluoromethylene sulphonic acid, where necessary using micro-irradiation.
Alternatively, compounds of the general formula Id or Ie can be obtained under basic conditions by dissolving a base, e.g. KOH or NaOH, in an organic solvent, e.g. methanol, in which the heteroaromatic of the general formula A/A' and the ketone of the general formula B are converted at temperatures between 20 and 100 °C. The product is cleaned, if necessary, by column chromatography.
The double bond can be reduced by hydrogen in the form of HBr/iron vinegar//Sn or HCl/Sn (nascent hydrogen) or H2 in the presence of a metal catalyst such as palladium on coal, platinum on coal, platinum oxide, Raney nickel, rhodium or ruthenium complexes in a suitable solvent or solvent mixture such as methanol (MeOH), ethanol (EtOH), acetone, acetic acid ethyl ester (AcOEt), HBr or acetic acid (AcOH) at temperatures between 0°C and 150°C. The compounds of the general formulae and If are formed. Hydrogen can also be generated from hydrogen transporters such as cyclohexane.
Other
The conversion of A/A' + B to E/E' can be carried out by using appropriate basic reagents, e.g. organolithium compounds, where appropriate with the addition of secondary amines or hexaalkyldisylazans, in aprotic solvents, e.g. butyllithium in hexans/THF, LDA in hexan/THF or heptane/THF/ethylbenzene or LiHMDS in hexans/THF at temperatures between -100 °C and 50 °C, preferably between -78 °C and 0 °C. In the case of indoles, the indole nitrogen is provided with suitable protective groups previously unknown to the subject, e.g. the benzene sulphate group, or benzyl carbonyl sub-groups or alkyl or substitute oxymethyl groups.
The conversion of E to Id or Ie may be carried out under acidic or dehydrating conditions or after transfer of the hydroxy group to a starting group, e.g. by the use of mineral acids such as HCl or H2SO4 or dehydrating P4O10 or by transferring the hydroxy group to the chloride by SOCl2/pyridine in situ.
Other
The conversion of F + B to G can be carried out by using appropriate basic reagents, e.g. organolithium compounds, with the addition of secondary amines or hexaalkyld silylazanes, if necessary, in aprotic solvents, e.g. butyllithium in hexanes/THF, LDA in hexanes/THF or heptan/THF/ethylbenzene or LiHMDS in hexanes/THF at temperatures between -100 °C and 50 °C, preferably between -78 °C and 0 °C. Other suitable conditions are KO. e.g. Grignard reagents in aprotic solvents, e.g. ethylmagnesium bromide in THF or pulsed alkali hydroxide, preferably in EHCO, without ethanol, or in EHCO, at 0 °C, in a dry medium, at THB; KO.
In step 1, compounds of the general formula H, where X stands for a halogen residue or a sulphonic acid ester, preferably iodine, bromine or trifluoromethane sulfonate, shall be selected for the purpose of a Larock-type indole synthesis with alkynes of general formula G in a reaction medium, preferably from the group consisting of methanol, ethyl acetate, ethanol, isopropanol, n-butanol, dioxane, chloroform, dichloromethane, pyridine, dimethylfoxide, sulphol, tetrahydrofuran, dimethylformamide, acetonitrile, tetrahydride, water and mixtures thereof, preferably from the group consisting of dimethylformamide, tetrahydride, dimethyldiphosphorphorphorphorphorphorphine, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenic acid, dihydrophenicPalladium ((II) acetate [Pd(OAc) 2; Ac = acetate], Bis (acetonitrile) -Palladium ((II) chloride [CH3CN) 2) PdCl2], Bis (benzonitrile) -Palladium ((II) chloride [PhCN) 2PdCl2] and Tetracis (triphenylphosphine) -Palladium [PPh3) 4Pd, preferably selected from the group consisting of PdPPh3) 2OAc) 2, (PPh3) 4Pd and PdCl2 (PPh3) 2, if appropriate in the presence of at least one phosphorus, or at least one tetraphosphorus selected from the group consisting of triphenylphosphate, triphosphylphosphate, triphosphonyl-carbonyl, triphosphonyl-carbonyl-carbonyl, triphosphonyl-carbonyl-carbonyl, or, if appropriate, a diethylphosphoric acid, and preferably selected from the group consisting of triphosphoric acid, triphosphenylamine, triphosphenylamine, triphosphenylamine, triphosphenylamine, tricarbonyl-carbonyl-carbonyl-carbonyl, triphosphate, triphosphenylamine, triphosphenylamine, diethylamine, sodium, sodium, sodium, dihydramine, sodium, and sodium, and sodium, and sodium, prefera, and, if necessary, in the presence of at least one additive, and if necessary, a phosphorbin, and a phosphorib,4]-Diazabicyclo[2.2.2]octane converted into compounds of general formula E and/or their regioisomers at temperatures between -70 °C and 300 °C, and especially between -70 °C and 150 °C.
Compounds of general formula H are commercially available or known from the literature, and syntheses of compounds of general formula A are described in the example section.
In step 2, where residue B in bond G corresponds to a silyl protective group, the compounds of generic formula E in a reaction medium shall be preferably selected from the group consisting of methanol, ethyl acetate, ethanol, isopropanol, n-butanol, dioxane, chloroform, dichloromethane, pyridine, dimethyl sulfoxide, toluene, tetrahydrofuran, dimethyl formamide, acetonitrile, diethyl ether, water and related mixtures, particularly preferably selected from the group consisting of acetonitrile, tetrahydrofuran, methanol, ethanol, ethyl sulfoxide, tetrahydridine, water and related mixtures, in the presence of a misfluoride, preferably selected from the group consisting of potassium-fluoride, especially potassium-fluoride, and/or potassium-fluoride, preferably at a temperature of 300 °C to 150 °C (70 °C, preferably at a temperature of -70 °C, or -70 °C, preferably at a temperature of -300 °C, with a concentration of -70 °C, with a specifically, hydrogen or -70 °C, in the presence of a hydrofluoric acid, especially hydrogen or -70 °C, or -70 °C, with a concentration of -70 °C, with a concentration of -70 °C, with a concentration of -70 °C, preferably with a concentration of -70 °C, with a concentration of -70 °C.
The transition from E to Id or Ic may be carried out under the conditions set out above.
Syntheses of cyclohexane derivatives with the general formula B are known in the literature (WO04043967, WO0290317, US 4065573, Lednicer et al., J.Med.Chem., 23, 1980, 424-430).
The following examples are intended to explain the invention in more detail but do not limit the general idea of the invention.
The yields of the compounds produced are not optimized.
Err1:Expecting ',' delimiter: line 1 column 108 (char 107)
All temperatures are uncorrected.
The following substances are to be classified in the Annex to Regulation (EC) No 396/2005 as 'methanol' and 'methyl' and 'methyl' respectively:
A mixture of 4 N hydrochloric acid (50 ml) and methanol (30 ml) was added to a mixture under freezing conditions containing 40% aqueous dimethylamine solution (116 ml, 0.92 mol), cyclohexane-1,4-dione-monoethylene ketal (30.0 g, 0.192 mol) and potassium cyanide (30.0 g, 0.46 mol). The mixture was stirred at room temperature for 72 h and then extracted after addition of water (80 ml) with ether (4 x 100 ml). After the solution was compressed, the residue was absorbed in dichloromethane (200 ml) and dried overnight with magnesium ketone sulphate. The organic phase was closed and the white solid was obtained.
Other
The yield is 38.9 g (96 %); the melting point is 86-88 °C.
Other
The mean value of the dose of the active substance is calculated as the following:
Other
The maximum residue levels for the active substance are:
8-Methylamino-1,4-dioxa-spiro[4.5]decan-8-carbonitrile A mixture of 4N hydrochloric acid (12.5 ml) and methanol (7.5 ml) was added to a 40% aqueous solution of methylamine (29.0 ml, 0.23 mol), cyclohexane-1,4-dione monoethylene acetate (7.50 g, 0.048 mol) and potassium cyanide (7.50 g) under freezing. The mixture was stirred at room temperature 7 d. After addition of water (20 ml) was extracted with ether (4 x 25 ml). After the solution was chained, the residue was absorbed in dichloromethane (50 ml) and dried with MgSO4.
Other
The yield is 7.05 g (80%)
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.54 (2 H, m); 1.71 (4 H, m); 1.95 (2 H, m); 2.30 (3 H, d); 2.72 (1 H, q); 3.86 (4 H, s).
1-Methyl-4-(8-[1,2,3]triazol-1-yl-1,4-dioxaspiro[4.5]dec-8-yl)piperazine A solution of N-methylpiperazine (2.60 g, 2.88 ml, 26 mmol), 1,4-dioxaspiro[4.5]decan-8-on (3.90 g, 25 mmol) and 1,2,3-triazol (1.87 g, 27 mmol) was heated in a heated flask in toluene (25 ml) 6 at the water separator by backflow.
Other
The reaction solution was then transferred to a locking measuring cylinder and the raw product was further processed.
1-(Benzyl-1,4-dioxaspiro[4.5]dec-8-yl) -methylpiperazine To a solution of 1-methyl-4-(8-[1,2,3]triazol-1-yl-1,4-dioxaspiro[4.5]dec-8-yl)piperazine (12.5 mmol) in toluene (12 ml), a 2 M benzylmagnesium chloride solution in tetrahydrofuran (15 ml, 30 mmol) was dripped with argon to maintain the internal temperature below 24 °C. After completion of the addition, the reaction compound 2 was stirred at room temperature and then cooled to 0 °C and dripped to a 20% ammonium chloride solution (50 ml), the dry phase was extracted with diethylene oxide (3 × 40 ml) and the organic product was mixed with 2 ml (4.70 ml) of Nitrogen (Nitrogen) and water. The product was then washed with water and water.
4-Benzyl-4- ((4-methylpiperazine-1-yl) cyclohexanone (Ket-2) A solution of 1- ((8-benzyl-1,4-dioxaspiro[4.5]dec-8-yl) -methylpiperazine (4.28 g, 13.0 mmol) in acetone (15 ml) was first mixed with water (2.5 ml) and then with concentrated hydrochloric acid (2.5 ml) and stirred overnight at room temperature. The reaction mixture was then alkaline (pH 10) with 2 M potassium carbonate solution, extracted with diethyl ether (3 × 40 ml), the combined organic phases were dried with sodium sulphate and vacuumed. The product was cleaned by flash chromatography (200 g, 20 × 5.7 cm) with methanol.
Other
The yield is 2.63 g (71%) of yellowish solid (Ket-2); melting point is 113 °C to 132 °C.
Other
The mean of the measurements is calculated as follows: 1.36 (dt, 2H, J = 13.8, 4.6 Hz); 1.92 (dd, 2H, J = 14.9, 4.1 Hz), 2.05-2.14 (m. 2H); 2.17 (s, 3H); 2.34-2.47 (m, 6H); 2.61-2.69 (m, 4H); 2.72 (s, 2H); 7.12-7.28 (m, 5H).
Other
The following substances are considered to be toxic if they are administered to the patient:
The reaction mixture was reconstituted by adding saturated ammonium chloride solution (200 ml) and saturated dimethyl ether (100 ml) and extracting them with diethyl ether (3 100 ml). The organic phase was dissolved in water (50 ml) and saturated NaOH solution (50 ml) and then heated. A white solid, called hydrochloric acid, was dissolved in a white solution of ethyl ether (238 ml) and dissolved in a white solution of 23 ml (280 ml) of diethyl ether (234 ml).
The hydrochloride (40.33 g, 130 mmol) was dissolved in water (55 ml), mixed with concentrated hydrochloric acid (100 ml, 1.21 mol) and stirred for 4 days at room temperature. After completion of the hydrolysis, the reaction mixture was extracted with diethyl ether (2 × 100 ml) and the aqueous phase was made alkaline by ice-cooling with 5N sodium salts, with the product being eliminated. The solid was sucked, washed with H2O (3 × 20 ml) and dried.
(8-Butyl-1,4-dioxa-spiro[4.5]dec-8-yl) -dimethyl-amine hydrochloride 8-Dimethylamino-1,4-dioxa-spiro[4.5]decan-8-carbonitrile (10.5 g, 50 mmol) was presented in THF (150 ml) under ice cooling and argon. Within 15 min, 2M butyl magnesium chloride was added to THF (62.5 ml, 125 mmol) and stirred for 16 h at RT.
Other
The solution was reconstituted with a 20% ammonium chloride solution (37 ml) and water (50 ml) and extracted with ether (3 x 50 ml) under ice-cooling; the org phase was washed with water (1 x 50 ml) and saturated sodium chloride solution (1 x 50 ml), the organic phase was dried with Na2SO4 and pressed into a vacuum.
Other
The raw product (2.05 g) was dissolved in ethylmethylketone (75 ml), put under ice-cooling with CISiMe3 (9.5 ml, 75 mmol) and stirred at RT for 6 h. The white precipitate was vacuumed and vacuum dried.
Other
The mean value of the 1H-NMR (DMSO-d6) is 0.91 (3 H, t); 1.31 (4 H, m); 1.56 (2 H, m); 1.75 (8 H, m); 2.64 (6 H, s); 3.87 (4 H, s); 9.87 (1 H, s).
8-Butyl-1,4-dioxa-spiro[4.5]dec-8-yl) dimethyl-amine hydrochloride (3.10 g, 11.1 mmol) was presented in H2O (4.7 ml) and concentrated HCl (7 ml) and stirred at RT for 24 h. The solution was extracted with ether (1 x 15 ml), the aqueous phase was alkalized with 5N NaOH under ice cooling and extracted with dichloromethane (3 x 20 ml). The org phase was dried with Na2SO4 and pressed in a vacuum.
Other
The mean value of the 1H-NMR (DMSO-d6) is 0.88 (3 H, t); 1.23 (4 H, m); 1.40 (2 H, m); 1.68 (2 H, m); 1.91 (2 H, m); 2.31 (2 H, m); 2.22 (6 H, s); 2.42 (2 H, m).
Other
The following information is provided in the summary of the information provided by the Authority:
In a 500 ml tri-half-polyester, 1.6M butyllithium was introduced into hexane (112.5 ml, 180 mmol) and abs. ether (70 ml) under argon atmosphere and cooled to 0 °C in an ice bath. Then benzothiophen (20.1 g, 150 mmol) was dissolved in abs. ether (40 ml) and dripped under ice cooling for 30 minutes and stirred in the ice bath for 2.5 h. The reaction solution was kept overnight in the refrigerator. In a 500 ml tri-half-polyester, iodine (75.0 g) and abs. ether (50 ml) were introduced into argon atmosphere and the liquid of the lithium compound was introduced under ice cooling. The solution was heated at room temperature for a long time, hydrolyzed with water, purified with cyclohexane sodium solution (62%) and dried with a medium-to-medium vacuum solution of sodium chloride. The solution was purified with a liquid crystalline solution (62%) and dried with a liquid crystalline sodium chloride solution (62%).
Other
The mean value of the dose of the active substance is 1.
The reaction solution was cooled in an ice bath and the 8-dimethylamino-1,4-dioxa-spiro[4.5]decan-8-carbonitrile (1.03 g, 4.9 mmol) was added at 10 ml at 10 °C by drip drops. The approach was carried out at room temperature overnight, the reaction was mixed under ice cooling with NH4Cl solution (5 ml) and water (7 ml) and dried with 30 ml (32 ml) of extra virgin iodine (30 ml) and water (66 ml) with extra virgin iodine (20 ml) and water. The reaction was carried out with a vacuum drying phase.
The raw product was dissolved in ethyl methyl ketone (19 ml), put under ice with trimethyl chlorosilane (1.63 ml, 12.8 mmol) and stirred at room temperature for 5 h. The precipitate was vacuumed and dried.
Other
The following information is provided for the purpose of the calculation:
Other
The mean value of the dose of the active substance is 1.46 (2 H, m); 1.79 (2 H, m); 2.37 (2 H, m); 2.63 (6 H, s); 2.75 (2 H, m); 7.47 (2 H, m); 7.91 (1 H, s); 7.95 (1 H, m); 8.06 (1 H, m); 11.40 (1 H, s).
Other
The following information is provided in the summary of the presentation:
After completion of hydrolysis, the reaction mixture was extracted with diethyl ether (2 x 25 ml) and the aqueous phase was alkalinized with 5N sodium salt, ketogenic with dichloromethane (3 x 25 ml), dried with sodium sulphate and i.v. concentrated.
Other
The following information is provided in the summary of the presentation:
A mixture of 4N hydrochloric acid (17 ml) and methanol (10 ml) was added under ice-cooling to contain pyrrolidine (22.5 ml, 0.306 mol), cyclohexane-1,4-dione-monoethylene ketal (10.0 g, 0.064 mol) and potassium cyanide (10.0 g, 0.15 mol). The mixture was stirred at room temperature for 74 h and then extracted after adding water (80 ml) with diethyl ether (4 × 70 ml). The residue was then absorbed in dichloromethane (70 ml) and obtained with magnesium sulphate overnight. The organic phase was dried and the 8-pyrrolidine-1-yl-1,4-dioxycanone[4.5]dehydroxyde-8-carbonylethyl was obtained as a white solid with a melting point of 65-67 °C in a solution of 68% (10.2 g) white.
To prepare the reaction mixture, saturated ammonium chloride (100 ml) was added under ice cooling and then extracted with diethyl ether (3 × 100 ml). The organic phase was re-shaken with water (70 ml) and saturated naphtha (70 ml) and e-swept. A molten crystal (11.8 g) was obtained, except for the gaseous gaseous product, which was dissolved in a white solid of 4-methyl ether (83-milligrams) and was dissolved in a 6 ml (83.3 ml) white liquid.
4- ((8-phenyl-1,4-dioxaspiro[4.5]dec-8-yl) pyrrolidine hydrochloride (5.8 g, 17.9 mmol) was dissolved in 7.5 N hydrochloric acid (16 ml) and stirred at room temperature for 24 h. After completion of hydrolysis, the reaction mixture was extracted with diethyl ether (2 × 50 ml), the aqueous phase was iced with 5 N sodium salt, extracted with dichloromethane (3 × 50 ml) and narrowed. The ketone-8 was isolated as a yellow solid with a melting point of 75-79 °C and a yield of 96 % (4.1 g).
After 30 min, the solution was heated to 50 °C, with the Grignard reaction starting under boiling. Within 20 min, another bromobenzene (15.7 g, 0.1 mol), dissolved in THF (50 ml), was added and boiled for 1.5 h. Under freeze-cooling, 8-pyrrolidine-1-yl-1,4-dioxaspiro[4.5]decan-8-carbonitrile (10.0 g, 0.0396 mol), dissolved in THF (60 ml), was given to the solution within 20 min. The reaction time was then further heated to 70 °C. The reaction time was further reduced by 16 ml of NHL (60 ml) at room temperature by dissolving the solution at E-Cl.The aqueous phase was extracted with diethyl ether (2 × 70 ml), the organic phase was shaken and compressed with water (50 ml) and saturated NaCl solution (50 ml), leaving a yellow crystalline broth (11 g) containing, in addition to the desired phenyl compound, the untransformed aminonitrile educt. The resulting raw product was dissolved in methyl ethyl ketone (140 ml) and put under ice cooling with trimethyl chlorosilan (7.5 ml, 0.059 mol). After 15 min, a white precipitate began to precipitate, which was removed after 6 h. It was possible to obtain 6.5 (49%) % of hydrochloric acid 5 with a melting point of 250-252 °C.
The resulting hydrochloride (6.5 g, 19.1 mmol) was dissolved in 7.5 N hydrochloric acid (22 ml) and stirred at room temperature for 24 h. After completion of hydrolysis, the reaction mixture was agitated with Et2O (2 × 50 ml). The aqueous phase was made alkaline by ice-cooling with 5 N sodium salt, extracted and compressed with dichloromethane (3 × 50 ml). The ketone-9 was thus isolated as a coloured solid with a melting point of 116-119 °C and a yield of 84 % (4.1 g).
To prepare the reaction mixture, saturated ammonium chloride solution (150 ml) was added under ice-cooling and extracted with diethyl ether (3 × 100 ml). The organic phase was dissolved and pressed with water (100 ml) and saturated NaCl (100 ml) solution. Oil (25.2 g) was dissolved. The product was dissolved in ethyl ether (20.8 ml) dissolved in E-methyl ether (14.8 ml) and dissolved in white ether (18.8 ml) as a white solution after a reaction with dimethyl ether (10.8 ml).
Dimethyl- ((8-phenyl-1,4-dioxaspiro[4.5]dec-8-yl) amine hydrochloride (10.5 g, 35.2 mmol) was dissolved in 7.5 N hydrochloric acid (36 ml) and stirred for 96 h at room temperature. After completion of hydrolysis, the reaction mixture was extracted with diethyl ether (2 × 50 ml). The aqueous phase was iced with 5 N sodium salt, alkalized with dichloromethane (3 × 50 ml) and narrowed. 4-dimethylamino-4-phenylcyclohexanone (Ket-10) was thus isolated as a yellow solid with a melting point of 104-108 °C at a yield of 97 % (7.4 g).
After saturation with acetylene, the reaction solution was irradiated under strong stirring at 25°C for 6 hours. The reaction was interrupted by turning off the lamps and air supply and the reaction solution was concentrated. The resulting raw product (5,47 g) was mixed in a dry phase of water (8,7 g) and concentrated saline (15 g) and concentrated overnight. The reaction was treated with RT-32 × 32 ml (32 ml) of diethylammonium nitrate (3 × 32 ml) separated by 32 ml (32 ml) of diethylammonium nitrate (3 × 32 ml) and extracted with a solution of ethylene oxide (NaOH) extracted from the water.
2-lodthiophen (22.9 g, 109 mmol) was dissolved in THF (80 ml) under argon and transferred to THF within 30 min at 0 °C with 2M isopropylmagnesium chloride (35.7 ml, 72 mmol). After a reaction time of 1 h at 3-5 °C, 8-dimethylamino-1,4-dioxa-spiro[4.5]decan-8-carbonitrile (10 g, 47.6 mmol), dissolved in tetrahydrofuran (20 ml), was added and stirred at room temperature for 20 h. The treatment was carried out by adding saturated NH4Cl solution (85 ml) and extraction with diethylketone (3x100 ml). The organic phase was subsequently dissolved with water (50 ml) and saturated NaCl-decanoate (50 ml). The product was dissolved in a white crystalline solution of isopropylmethyl ethanol (CIS-14.1-methylketone) and obtained as a white crystalline solution in 7 ml (18.4-methylketone) of 74-methylketone (11,74 ml).
Dimethyl- ((8-thiophen-2-yl-1,4-dioxaspiro[4.5]dec-8-yl) amine hydrochloride (8.68 g, 28.6 h completed hydrolysis) The reaction mixture was extracted with diethyl ether (2 × 50 ml). The aqueous phase was made alkaline by ice-cooling with 5N sodium salts, extracted and condensed with dichloromethane (3 × 50 ml). Ket-12 was obtained as a yellow solid with a melting point of 108 °C to 110 °C at a yield of 89% (5.66 g).
To prepare the reaction mixture, saturated ammonium chloride solution (150 ml) and water (60 ml) were added under ice cooling and extracted with diethyl (3 × 100 ml). The organic phase was reconstituted with water (50 ml) and dissolved NaCl (50 ml) and allowed to cool for 15 min. A phenyl oil (26.5 g) was obtained, which was dissolved in a white solution of ethyl chloride (15.5 g) with a dissolved white solution of ethyl chloride (16.5 g) and a white solution of ethyl chloride (16.5 g) with a dissolved white solution of ethyl chloride (16.5 g) and a dissolved white solution of ethyl chloride (16.6 g) was obtained.
A solution of 1-bromo-3-fluorbenzole (5.00 g, 28.6 mmol) in abs ether (15 ml) was dripped into a suspension of magnesium (694 mg, 28.6 mmol) in abs ether (10 ml) to sedate the ether. After completion of the addition, the ether was stirred for 10 min at RT, and the magnesium was then completely dissolved. The reaction solution was cooled in an ice bath and dripped at 10 °C at 8-dimethylamino-1,4-dioxa-spiro[4.5]decan-8-carbonitrile (3.00 g, 14.3 mmol) in an abs THF (30 ml) phase. The solution was stirred at room temperature overnight, the reaction table was ice-dried with 20 % solution of chlorine (50 L) and submerged in water and dissolved in water (50 ml) with extract of ether (50 ml) and 50 ml (50 ml) of water (50 ml) and added to the vacuum (50 ml) with a vacuum (50 ml) of water (50 ml) and a vacuum (50 ml) of water (50 ml) and added to the vacuum (50 ml) with a vacuum (50 ml) of water (50 ml) and a vacuum (50 ml) of water (50 ml) with a vacuum (50 ml) of water (50 ml) and a vacuum (50 ml) of water (50 ml) with a vacuum (50 ml) of water (50 ml) and a vacuum (50 ml) of water (50 ml) with a vacuum (50 ml) of water (50 ml) with a vacuum (50 ml) of water (50 ml) and a vacuum (50 ml) of water.
Other
The raw product was dissolved in ethyl methyl ketone (25 ml), put under ice-cooling with CISiMe3 (3.2 ml, 25 mmol) and stirred at room temperature for 5 h. The precipitation was filtered and vacuum dried.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.91 (8 H, m); 2.54 (6 H, s); 3.91 (4 H, d); 7.37 (1 H, m); 7.61 (3 H, m).
[8-(3-fluorophenyl)-1,4-dioxa-spiro[4.5]dec-8-yl]-dimethyl-amine hydrochloride (7,2 g, 22,75 mmol) was dissolved in water (9,6 ml), mixed with concentrated hydrochloric acid (14 ml, 455 mmol) and stirred 4 days at room temperature. After completion of hydrolysis, the reaction mixture was extracted with diethyl ether (2 × 50 ml), the aqueous phase was made alkaline by ice-cooling with 5N sodium chloride, with the product being dissolved. Ketone-13 was isolated as a yellow solid with a melting point of 83-88 °C and a yield of 50 % (6,05 g).
4-Dimethylamino-4- ((3-fluorophenyl) cyclohexanone (Ket-13) [8- ((3-fluorophenyl) --1,4-dioxa-spiro[4.5]dec-8-yl]-dimethyl-amine hydrochloride (2.80 g, 8.86 mmol) was dissolved in water (3.7 ml), added to concentrated hydrochloric acid (5.5 ml) and stirred at RT 4 d. After completion of hydrolysis, the reaction mixture was extracted with ether (2 x 10 ml), the aqueous solution was ice-based with 5N alkaline sodium chloride, the reaction mixture was extracted with dichloromethane (3 x 50 ml), the organic phase was dried over trifluorine and i.e. vacuum. The product was purified by flash chromatography with CH20/OHCl.
Other
The following table shows the results of the analysis of the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as follows:
1-(8-Pyrrolidine-1-yl-1,4-dioxaspiro[4.5]dec-8-yl)-1H-[1,2,3]triazole To a solution of 1,4 dioxaspiro[4.5]decan-8 on (3.9 g, 25 mmol) in toluene (40 ml), pyrrolidine (1.95 g, 2.29 ml, 27.5 mmol), 1,2,3-triazole (2.07 g, 30 mmol) and mibe 4 Å (7.14 g) were administered, the mixture was stirred at 90 °C for 7 h, then decanted and immediately re-used.
1-(8-Butyl-1,4-dioxaspiro[4.5]dec-8-yl) pyrrolidine To a 2 M solution of n-butylmagnesium chloride (25 ml, 50 mmol) in tetrahydrofuran, the reaction solution of 1-(8-Pyrrolidine-1-yl-1,4-dioxaspiro[4.5]dec-8-yl) -1-H-[1,2,3]triazole (approximately 6.9 g, 25 mmol) was dripped into toluene (38 ml) under ice cooling and argon. The reaction gas was stirred overnight at room temperature and then poured into saturated ammonium chloride solution (60 ml). The phases were separated and the aqueous was combined with extracted dietary rock (3 × 70 ml). The organic triatoms were compressed with gaseous sodium, i.e. methanol (9 × 7.00 cm) and methanol, and the residues were purified by flash methylation (12 × 70 ml) and methylation.
Other
Yield: 2.70 g (40% over two stages)
Other
The mean value of the dose for each dose is calculated by dividing the dose by the mean value of the dose for each dose.
A solution of 1-(8-Butyl-1,4-dioxaspiro[4.5]dec-8-yl) pyrrolidine (2.70 g, 10.1 mmol) in acetone (100 ml) was mixed with water (10.0 ml) and 37% hydrochloric acid (14.0 ml) and stirred overnight at room temperature. The mixture was then slowly dripped into 4 ml of natron until pH 10 was reached. The mixture was extracted with diethyl ether (4 × 40 ml), the combined organic phases were dried with sodium sulphate and i.i. compressed. The raw product (2.6 g) was cleaned by flash vacuum chromatography (260 g, 30 × 5.6 cm) with ethyl acetate / methanol (9: 1).
Other
The following is the list of the active substances in the active substance:
The solution was boiled for 4 h under return flow. The reaction mixture was cooled overnight to room temperature. - The solution was cooled to boil with toluene (100 ml) and water (70 mL) of 235 mbar. The organic phase was separated and dissolved with water (170 ml) and dissolved in sodium chloride (110 ml × 50 ml) at a temperature of 7.2 °C. The solution was purified by dissolving the sodium chloride in a liquid solution of 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5- 5-
The reaction mixture was then boiled for 5 h under reflux, during which a beige-colored, brittle suspension was formed. The reaction mixture was cooled overnight to room temperature. Acidic acid (170 N) was added to the solution by a red-hot refrigeration. The solution was then diluted with Toluene (100 ml). The organic phase was extracted from the solution and dissolved in sodium methanol (370 × 70 × 803 ml) at a temperature of 70 °C. The product was then dissolved in sodium chloride (50 × 70 × 70 ml) and dissolved in water as a solvent.
The reaction mixture was stirred at 100°C for 24 hours. The reaction was followed by DC. For preparation, the solution was diluted under ice-cooling with water (400 ml) and extracted with ethyl acetate (3 × 100 ml). The organic phase was then thoroughly washed with water (6 × 100 ml), saturated sodium hydrocarbonate (10 × 100 ml) and dissolved sodium chloride (1 × 100 ml). After drying with NaSO24, the solution was dissolved in the evaporation medium. The product could be distilled in a melting point of 106 °C (92 × 106 °C) with an oil of 5.46% by weight.
After 20 h, no starting product was detectable in the DC. After cooling, the toluene solution was dissolved with water (5 x 30 ml) and saturated aqueous ketone NaCl solution (3 x 20 ml) and agitated above Na2SO4. After removal of the solution from the rotation, the vapour valve falls into a white solid of 6.8% (94%) yellowish-green with a melting point of 108-110 °C.
8-Cyanophenyl-1,4-dioxaspiro[4.5]decan-8-carbonic acid (Schneider, Woldemar; Krombholz, Gottfried; ARPMAS; Arch.Pharm. ((Weinheim Ger.); 313; 6; 1980; 487-498) 8-Cyanophenyl-1,4-dioxaspiro[4.5]decan (4.86 g, 20 mmol) was dissolved in ethylene glycol (40 ml), replaced with NaOH (4 g, 100 mmol) and then heated back to boil. The reaction was followed by DC.
The resulting suspension was cooled to 0 °C in an ice-based salt bath and then heated with triethylamine (2,25 ml, 16 mmol) to produce a clear solution, which was stirred for another 15 min at 0 °C. The mixture was then stirred within 5 min with phosphoric acid diphenylesterazide (2,5 ml, 11,5 mmol). The reaction product was stirred for 20 min at 0 °C, allowed to come to RT for another 20 min, and then heated for 2 h in an oil bath at 100 °C (Bad) to heat the oil. The product was processed by a vacuum distillation of the kiesel oil. The product was obtained by melting the liquid in a crystalline solution of T-chromol (9-11% to 38 °C) in a liquid crystalline solution with a crystalline solution of T-41.
LiAlH4 (535 mg, 14.08 mmol) was suspended in dry THF (4 ml) without moisture, the 8-isocyanate-8-phenyl-1,4-dioxaspiro[4.5]decan (2,29 g, 8.8 mmol, dissolved in 40 ml of dry THF) was dripped within 20 min. After complete addition, the reaction mixture was heated in the return flow for 4 h to boil. After discharge, the reaction viscose was ice-cooled, first with water THF (1 ml H2O in 3 ml), then with 1.7 ml 15% natronla and finally with 5 ml H2O. The solution was stirred for 20 min and then filtered over. The resulting viscose was obtained after washing with a filter oil (91%) in a red-coloured liquid with a thickness of 2.7 g/cm2.
4-Methylamino-4-phenylcyclohexanone (Ket-15) (Upjohn_Lednicer, US4065573A1, 1977) Methyl- (((8-phenyl-1,4-dioxaspiro[4.5]dec-8-yl) amine (2,1 g, 8.4 mmol) was poured with a mixture of concentrated HCl (15 ml) and water (8 ml) and stirred at RT for 5 days. For processing, the reaction mixture was diluted with water (20 ml) and extracted with ether (3 x 30 ml). The etheric phase was discarded. The aqueous phase was then extracted with 2N NaOH ketogenic and with dichloromethane (3 × 30 ml). The resulting phase was dried with Na2SO4 and then agitated at the organic vaporization point. The ketone was obtained by dissolving it in a solid of ethylene glycol (4-38 °C) at a temperature of 32 °C (1-38 °C) in a solution of ethylene glycol (1-38 °C).
A mixture of 4 N hydrochloric acid (8.1 ml), methanol (4.9 ml) and azetidine (8.5 g, 10 ml. 149 mmol) was first given under ice-cooling, 1,4-dioxaspirone[4.5]decan-8-on (4.84 g, 31 mmol) and then potassium cyanide (4.85 g, 74.4 mmol) in water (15 ml). The mixture was stirred at room temperature for 5 days, then added to water (50 ml) and extracted with diethyl ether (3 × 50 ml). The combined organic phases were dried with sodium sulphate and i.e. vacuum-sealed; yield: 6.77 g (98 %), oil
Other
The mean value of the measurements of the 1H-NMR (DMSO-d6) is 1.45-1.63 (m, 4H); 1.67-1.82 (m, 4H); 1.99 (q, 2H, J = 7.1 Hz); 3.21 (t, 4H, J = 7.1 Hz); 3.86 (s, 4H).
After adding saturated ammonium chloride solution (5 ml) and water (5 ml), the phases were separated and the aqueous phases were extracted with diethyl ether (3 × 50 ml). The combined organic P was dried with sodium sulphate and i.e. vacuum cooled. The raw product was purified by flash chromatography (100 g, 20 × 4.0 cm) with ethyl ethanol (1 g/mL); 1.70-1.70 mg/mL; 1.70-1.7 mg/mL; 1.70-1.7 mg/mL; 1.40-1.8 mmHg; 2.40-2.8 mmHg (H, 2.86-88 Ht; 2.75-88 Ht; 2.75-88 Ht; 2.75-78 Ht; 2.75-78 Ht; 2.8-88 Ht (H, 2.8-88 Ht); 2.8 Ht (H, 2.8-8 Ht); 2.8 Ht (H, 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 Ht; 2.8 H; 2.8 Ht; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.8 H; 2.
A solution of the acetal (370 mg, 1.3 mmol) in acetone (30 ml) was added with 6 N hydrochloric acid (2 ml) and stirred overnight at room temperature.
Other
The yields of the test chemical were as follows: 274 mg (92%) white solid (Ket-16) 1H-NMR (DMSO-d6): 1.67 (td, 2H, J = 13.8, 6.9 Hz); 1.95-2.13 (m, 4H); 2.20-2.33 (m, 2H); 2.40-2.47 (m, 1H); 2.52-2.57 (m, 1H); 2.94 (t, 4H; J = 6.9 Hz); 7.28-7.47 (m, 5H).
To make a solution of 1.4 dioxaspiro[4.5]decan-8 on (3.9 g, 25 mmol) in toluene (40 ml), pyrrolidine (1.95 g, 2.29 ml, 27.5 mmol), 1,2,3-triazole (2.07 g, 30 mmol) and molysium 4 A (7.14 g) were added, stirred at 90°C for 7 h, then decanted and immediately recycled.
A 2 M solution of n-butylmagnesium chloride (25 ml, 50 mmol) in tetrahydrofuran was obtained by ice-cooling and argon the reaction solution of the just prepared triazole.
Other
The reaction mixture was stirred overnight at room temperature and then poured into saturated ammonium chloride solution (60 ml). The phases were separated and the aqueous phases were extracted with diethyl ether (3 × 70 ml). The combined organic phases were dried, compressed and the residue (12 g) was cleaned by flash chromatography (400 g, 20 × 7.6 cm) with ethyl acetate/methanol (9:1).
Other
yield: 2.70 g (40% over two stages), brown oil
Other
The mean value of the dose for each dose is calculated by dividing the dose by the mean value of the dose for each dose.
A solution of the acetal (2.70 g, 10.1 mmol) in acetone (100 ml) was added to the mixture with water (10.0 ml) and 37% hydrochloric acid (14.0 ml) and stirred overnight at room temperature. The mixture was then slowly dripped with 4 M sodium salts until pH 10 was reached. The mixture was extracted with diethyl ether (4 x 40 ml), the combined organic phases were dried with sodium sulphate and vacuumed. The raw product (2.6 g) was cleaned by flash chromatography (260 g, 30 × 5.6 cm) with ethyl acetate / methanol (9:1).
Other
Production: 1.06 g (47%) of brown oil (Ket-17)
Other
The mean value of the measurements performed was 1.14 to 1.50 (m, 2H); 1.62 to 1.88 (m, 8H); 2.04 (dt, 2H, J = 15.0, 3.9 Hz); 2.42 (ddd, 2H, J = 6.3, 11.8, 15.5 Hz); 2.63 (t, 4H, J = 6.0 Hz).
Methyl-[8-(4-methyl-thiazol.2-yl)-1,4-dioxa-spiro[4.5]dec-8-yl]-amin Butyllithium (2.5 M in hexane, 9.2 ml, 23.0 mmol) was presented in argon atmosphere and cooled to -78°C in a cold bath. 4-methyl-thiazol (2.09 ml, 23 mmol) was dissolved in tetrahydrofuran (60.0 ml) and added by dripping under ice cooling at -78°C and stirred for 10 min.
Other
For this solution, 8-Methylamino-1,4-dioxa-spiro[4.5]decan-8-carbonitrile (2.12 g, 10.8 mmol) was rapidly dripped into abs. tetrahydrofuran (15 ml) at -78 °C. After addition, the reaction solution was stirred for 1 h in a cold bath and then heated slowly to 0 °C. The reaction mixture was stirred at room temperature overnight. Then hydrolysed with water (10 ml) at 0 °C, the aqueous phase was extracted with chloroform (3 x 50 ml), the organic phase was washed with water (1 x 50 ml) and a concentrated NaCl solution (50 ml), dried with Na2SO4 and i.e. vacuumed.
Other
The product has been purified by flash chromatography with cyclohexane/acetic acid (1:4) and acetic acid yield: 2.71 g (94%).
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.54 (2 H, m); 1.82 (4 H, m); 2.02 (2 H, m); 2.08 (3 H, d); 2.32 (3 H, s); 2.38 (1 H, q); 3.86 (4 H, s); 7.09 (1 H, s).
Other
The following information is provided in the summary of the product characteristics and the manufacturer's specifications:
4-Methylamino) -4-methylthiazol-2-yl) cyclohexanone (Ket-18) Methyl-[8-(4-methylthiazol-2-yl) --1,4-dioxa-spiro[4.5]dec-8-yl]-amine (100 mg, 0.37 mmol) was mixed with 5% sulphuric acid (6 ml) and stirred overnight at RT. After completion of hydrolysis, the reaction mixture was extracted with ether (1 x 5 ml), the aqueous solution was ice cooled with 5N NaOH, the reaction mixture was extracted with dichloromethane (3 x 10 ml), the organic phase was dried over Na2SO4 and i.e. vacuum tight.
Other
The following information is provided in the summary of the product characteristics and the manufacturer's specifications:
Ethyl 5-cyano- ((4-methylthiazol-2-yl)-2-oxocyclohexanecarboxylate A solution of (4-methylthiazol-2-yl) acetonitrile (24.2 g, 0.175 mol) and bromo-propionic acid ethyl ester (51.6 ml, 0.4 mol) in abs. Toluol (700 ml) was added at 0-5°C with sodium amide (58.0 g, 1.48 mol) in portions and then boiled for 3 days under return flow. The reaction solution was cooled to 0 °C and slowly hydrolysed with acetic acid/ ml (2/1, 240 ml) water. The organic was separated, with a separate NaCO3 solution (2 x 400 ml) and water (2 x 400 ml) of sodium, washed and eaten by vacuum.
Other
Production: 45.0 g (88%) of brown oil
Other
The mean value of the dose of the active substance is 1.26 (3 H, t); 2.30-2.62 (4 H, m); 2.38 (3 H, s); 2.84 (1 H, d); 2.93 (1 H, d); 4.22 (2 H, q); 7.39 (1 H, s); 12.21 (1 H, s).
1- ((Methyl-thiazol-2-yl) -4-oxo-cyclohexanecarbonitrile Ethyl 5-cyano-5- ((Methyl-thiazol-2-yl) -2-oxocyclohexanecarboxylate (45.0 g, 0.153 mol) was dissolved in acetic acid (1.23 L) and 10% sulphuric acid (540 ml) and boiled for 4 days in a feed-back.
Other
For preparation, the solution was put under ice-cooling with water (850 ml) and extracted with acetic acid ethyl ester (300 ml three times) (for better phase separation, NaCl solution was added). The organic phase was washed with water (6 x 100 ml), stirred with NaHCO3 solution (1 L) for 20 min, then the organic phase was washed again with NaHCO3 solution and NaCl solution, dried with sodium sulphate and vacuum-sealed.
Other
The yield is 13.3 g (39%) of light brown solid
Other
The mean value of the test chemical is calculated as the sum of the mean values of the test chemical and the mean values of the test chemical.
Other
The maximum residue levels for the active substance are:
8- ((4-Methyl-thiazol-2-yl)-1,4-dioxa-spiro[4.5]decan-8-carbonitril1- ((4-Methyl-thiazol-2-yl)-4-oxo-cyclohexancarbonitril (13.3 g, 61 mmol) and ethylene glycol (6.8 ml, 122 mmol) were dissolved in toluene (250 ml), added to a catalytic amount of p-toluene sulphonic acid and boiled for 3 h at the water separator.
Other
For processing, the organic solution was washed with water (125 ml), namely NaHCO3, water and NaCl, dried with sodium sulphate and pressed in a vacuum.
Other
The mean value of the dose of the active substance is 1.80 (4 H, m); 2.11-2.42 (7 H, m); 4.22 (4 H, s); 7.35 (1 H, s).
8- ((4-Methyl-thiazol-2-yl)-1,4-dioxa-spiro[4.5]decan-8-carbonic acidmid8- ((4-Methyl-thiazol-2-yl)-1,4-dioxa-spiro[4.5]decan-8-carbonitrile (15.2 g, 58 mmol), dissolved in ethanol (200 ml), was added to water (200 ml) with a solution of KOH (12.9 g, 230 mmol) and stirred at RT 48.
Other
The ethanol was removed, a solid was removed from the aqueous solution, separated and briefly boiled with semi-concentrated acetic acid, cooled and sucked.
Other
The product obtained from the extraction of the raw materials is to be classified in the same heading as the product.
Other
The mean value of the dose of the active substance is 1.61 (4 H, m); 2.10 (2 H, m); 2.38 (5 H, m); 3.91 (4 H, s); 7.12 (3 H, m).
Other
The following information is provided in the summary of the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary:
Methyl 8- ((4-methylthiazol-2-yl) -1,4-dioxaspiro[4.5]decan-8-ylcarbamate 8- ((4-methylthiazol-2-yl) -1,4-dioxa-spiro[4.5]decan-8-carbon sulphur amide (2.82 g, 10 mmol) and mercury-II acetate (4.58 g, 12 mmol) were dissolved in absolute DMF (50 ml) In RT methanol (12 ml, 300 mmol) and a solution of N-bromo-succimide (1.96 g, 11 mmol) were added to DMF (15 ml) and mixed for 18 h.
Other
For processing, the solvent was removed in one go and the solid residue was extracted with ether (4 x 50 ml). The organic phase was narrowed and the product mixture separated by flash chromatography with EE/cyclohexane (1:2) yield: 541 mg (19 %).
Other
The mean value of the dose of the active substance is 1.66 (2 H, m); 1.72 (2 H, m); 2.03 (2 H, m); 2.25 (5 H, m); 3.57 (3 H, s); 3.87 (4 H, s); 7.09 (1 H, s).
Other
The following information is provided in the summary of the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary of product characteristics and the information provided in the summary:
Methyl[8-(4-methyl-thiazol-2-yl)-1,4-dioxa-spiro[4.5]dec-8-yl]-amin A solution of methyl 8-(4-methylthiazol-2-yl)-1,4-dioxaspiro[4.5]decan-8-ylcarbamate (520 mg, 1.7 mmol) in absolute THF (20 ml) was added to portions with LiAlH4 (125 mg, 3.3 mmol) and boiled for 5 h under reflux. The reaction mixture was hydrolysed at 0 °C with a Na2SO4 solution, filtered through cellite, washed with THF and i.i. vacuumed. The residue was taken into EE, washed with water and dried with sodium sulphate. Cleaning was achieved by flash chromatography with EE/Cycloxan oil (24 mg:1:1: 106 %),
Other
The mean value of the dose of the active substance is 1.55 (2 H, m); 1.82 (4 H, m); 1.98 (2 H, m); 2.05 (3 H, s); 2.32 (3 H, s); 3.86 (4 H, s); 7.10 (1 H, s).
2- ((fluor-1H-indol-3-yl) ethanol (20.0 g, 112 mmol) was dissolved in CH2Cl2 (250 ml) and replaced with tetrabromethane (56.0 g, 170 mmol) in RT. Then, when water cooled in RT, triphenylphosphine (44.0 g, 165 mmol) was added as a portion. The solution was stirred for 2.5 h in RT and then pressed in i.v. The residue was raised on a silica gel and divided into two equal parts. The raw product was purified by flash chromatography over 2 columns of 500 g silica and cyclohexane/silicon (9:1→14:1) each. Output: 25.4 g (93 s), red 1 H-H-D (MRD-O): 3.18 m (2,11 t; 11.3 t; 3.18 m (2,11 t; 11.3 t; 11.3 t; 11.3 t; 11.6 t; 11.6 t; 11.6 t; 11.6 t).
Other
The following information is provided in the summary of the product characteristics and the data to be collected:
Tryptamine (3.04 g, 19.0 mmol) and phthalate hydrate (3.00 g, 20.2 mmol) were boiled in a water separator for 12 h. The solvent was distilled i.a. and the residue dissolved in methyl chloride.
Other
The mean value of the dose of the active substance is calculated as the following:
Tryptamine (192 mg/ 1.2 mmol) was presented in a THF bottle (5 ml) and topped with triethylamine (179 μ L/ 1.3 mmol). Acetic acid hydride (132 mg/ 1.3 mmol) was added and stirred for 4 h at RT. The solution was pressed dry in i. v. The residue was collected in acetic acid and washed with saturated NaHCO3 solution (twice 20 ml) and NaCl solution (twice 20 ml). The organic phase was dried with Na2SO4 and pressed in i. v.
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.81 (3 H, s); 2.83 (2 H, m); 3.33 (2 H, m); 6.96 (1 H, m); 7.05 (1 H, m); 7.14 (1 H, s); 7.35 (1 H, m); 7.53 (1 H, d); 7.92 (1 H, t, NH); 10.79 (1 H, s).
Other
The following information is provided in the summary of the presentation:
Tryptamine (192 mg/ 1.2 mmol) was presented in a THF bottle (5 ml) and topped with triethylamine (179 μ L/ 1.3 mmol). Acetic acid hydride (132 mg/ 1.3 mmol) was added and stirred for 4 h at RT. The solution was pressed dry in i. v. The residue was collected in acetic acid and washed with saturated NaHCO3 solution (twice 20 ml) and NaCl solution (twice 20 ml). The organic phase was dried with Na2SO4 and pressed in i. v.
Other
The following information is provided for the purpose of the analysis:
Other
The mean value of the dose of the active substance is 1.81 (3 H, s); 2.83 (2 H, m); 3.33 (2 H, m); 6.96 (1 H, m); 7.05 (1 H, m); 7.14 (1 H, s); 7.35 (1 H, m); 7.53 (1 H, d); 7.92 (1 H, t, NH); 10.79 (1 H, s).
Other
The following information is provided in the summary of the presentation:
The reaction was controlled by DC (elue: ethylacetate/hexane 1): 1) for processing. The solvent was distilled in a vacuum. The residue was incorporated into ethylacetate (50) and dried with water (50). After phenol separation, the second phase was combined with ethyl potassium malonate (1.87 g, 11 mmol) and heated for 14 h. The extra solid was added to the solution by means of a vacuum drying process, with the addition of 10 ml of ethyl ether (50°C) and 8 ml of water (50°C) and the remaining water was dried in a crystalline solution (50°C).
Other
The following is added to the list of active substances:
The solution was dissolved in absolute THF (20 ml) under argon atmosphere, the solution was then placed in a water bath with BH3×THF (40 ml, 1 M solution, 40 mmol) and stirred at room temperature for 14 h. The reaction was monitored by DC. After completion of the reaction, the reaction solution was given to a mixture of ethyl acetate (50 ml) and H2O (50 ml). The water phase was separated twice with additional ethyl acetate (30 ml each). The combined organic phases were dried and cooled over Na2SO4 and pressed. The vacuum distillation was detected by filtering the residual oil and leaving it in the solution as a crystalline solution.
Other
The maximum content of the active substance is the maximum content of the active substance in the feed additive.
1-trimethylsilyl) propane (2.23 ml, 1.68 g, 15.0 mmol), 4-amino-3-iodobenzonitryl (3.33 g, 13.65 mmol), lithium chloride (606 mg, 14.3 mmol) and sodium carbonate (4.35 g, 40.95 mmol) were administered successively in dimethylformamide (60 ml) in argon. To this mixture Pd ((dppf) Cl2 (1.116 g, 1.365 mmol) was added, the reaction mixture was heated to 100 °C for 6 h under moisture extraction and then stirred at room temperature for 16 h. To process the solution, water (150 ml) and ethyl sulphate (300 ml) were added and minitril was added. After the separation phase, the phenylalanine was removed from the mixture with 100 ml (35 ml) of ethyl sulphate (35 ml) of ethyl sulphate and extracted from the 3-methyl sulphate (DM-3-methyl-3-hydroxyethyl) sodium.
The trimetylsilyl group was separated in two steps. The nitrile mixture from the previous step (5.15 g, raw product) was dissolved in tetrahydrofuran (60 ml), replaced with tetrabutylammonium fluoride × 3 H2O (5.58 g, 17.7 mmol) and stirred at room temperature for 4 h. The reaction mixture was mixed with water (150 ml) and stirred for 10 min. After the addition of diethyl ether (50 ml), the phases were separated. The aqueous phase was extracted with diethyl ether (3 × 150 ml). The combined organic phases were dried and pressed.A product mixture of indole 3-methyl-1H-indol-5-carbonitrile and 2-methyl-1H-indol-5-carbonitrile (264 mg) was further isolated, which were present in a ratio of approximately 1:1. The silyl compound 3-methyl-2-trimethylsilanyl-1H-indol-5-carbonitrile (1.9 g, 8.32 mmol) was dissolved in tetrahydrofuran (60 g) and heated to 60 °C. The product was then dissolved in water, dissolved in water (150 ml) and separated by diethyl diethyl diethyl extract (1600 ml) for 50 min.The organic phases were dried and compressed to obtain 3-Methyl-1H-indol-5-carbonitrile (Ind-6) as a beige solid at a yield of 99% (1.33 g) and a melting point of 110-112 °C.
3-Methyl-5-trifluorethyl-2-trimethylsilanyl-1H-indol2-iod-4-trifluorethylaniline (1.15 g, 4 mmol), trimethylsilylpropene (494 mg, 0.656 ml, 4.4 mmol), lithium chloride (178 mg, 4.2 mmol) and sodium carbonate (1.27 g, 12 mmol) were combined in an argon atmosphere in a dimethylformamide (20 ml) solution. The 35 phase was added (Pd(dppf) Cl2 × CH2Cl2); the 327 mg, 0.4 mmol phase. The mixture was then stirred for 6 h at 100 °C (oil temperature) and 18 h at room temperature. The mixture was then dissolved in water, filtered with ethylacetate (50 ml) × 30 ml. The mixture was then separated by a filter of ethyl ethylacetate (50 ml) and filtered with water.
Other
The combined organic phases were washed with saturated sodium chloride solution (3 × 35 ml), then dried with sodium sulphate, filtered and vacuum pressed.The resulting dark brown oil ((1,8 g), which contained traces of DMF in addition to 3-methyl-5-trifluoromethyl-2-trimethylsilanyl-1H-indol and the isomer 2-methyl-5-trifluoromethyl-3-trimethylsilanyl-1H-indol, was used as the raw material for the next step.
The trimethylsilyl group was separated in two steps: the raw product from the previous step (1.8 g, 4 mmol, relative to the preliminary step) was stirred with THF (20 ml) and tetrabutylammonium fluoride (1.64 g, 5.5 mmol) for 5 h at RT, and the method was then refined.
Other
The aqueous phase was extracted with diethyl ether (3 × 30 ml). The combined organic phases were dried, filtered and vacuum-sealed with sodium sulphate. 1.8 g of a tough dark brown oil was obtained, which was separated by chromatography [silica gel 60 (60 g); cyclohexane/ethylacetate (15: 1; 500 ml, 10: 1; 500 ml) ] into its constituent parts. 763 mg (2.8 mmol, 70% relative to the previous stage) of 3-methyl-5-trifluoromethyl-2-trimethylfluoryl-1H-indolerance was obtained. This point was again obtained with THF (20) and tetrabutylammoniumfluoride (1.15 g, 3.6 mmol) and was described as a 63-65% aftertreatment with 3-methylfluoride (6-55-69 mg) at 550 °C.
Hydrochloride (3.5 g, 20 mmol) was dissolved in H2O (100 ml) and added to sodium carbonate (2.1 g, 20 mmol). The solution was stirred, resulting in a clear solution within a few minutes after a temporary failure of the free base. The solution was supplemented with propionaldehyde (0.98 g, 16.8 mmol) and ethanol (5 ml as solvent). The mixture was stirred for 14 h at RT, resulting in an oily precipitation. The solution was extracted with ethyl acetate (3 x 20 ml) for processing. The combined organic phases were dried over MgSO4 and then evaporated at the rotary solvent until dry. The resulting residual brunette (3,To complete the reaction, the solution was stirred at 110 °C for another 3 hours and then left to stand overnight in RT - The reaction solution was put on ice (100 g) for processing. The resulting aqueous mixture was extracted with ethyl ether (4 x 20 ml), the combined organic phases were dried with MgSO4. The residue (3.3 g) obtained after evaporation of the solvent was chromatographically purified [silicon gel (100 g); cyclohexan/O 4 (300 ml) ].5-Methoxy-3-methyl-1H-indol (Ind-9) was thus obtained as a sticky solid at a yield of 2.3 g (85%)
3-Cyclopropyl-2-trimethylsilanyl-1H-indolCyclopropylethinyl) trimethylsilane (1.38 g, 10.0 mmol), 2-lodaniline (1.94 g, 9.1 mmol), lithium chloride (404 mg, 9.54 mmol) and sodium carbonate (2.9 g, 27.3 mmol) were added to this mixture in order to form dimethylformamide (40 ml) under argon. To this mixture Pdddppf) Cl2 (744 mg, 0.91 mmol) was added. The reaction mixture was heated at 100 °C for 6 h under moisture extraction and then stirred at room temperature for 16 h. The product was then reduced to dry water (100 ml) and ethyl sulphate (200 ml) for the processing of the approach. The mixture was then extracted to a temperature of 10 min.
3-Cyclopropyl-1H-indol (Ind-11) 3-Cyclopropyl-2-trimethylsilanyl-1H-indol (1.56 g, 6.8 mmol) was dissolved in tetrahydrofuran (40 ml), mixed with tetrabutylammonium fluoride × 3 H2O (2.79 g, 8.84 mmol) and stirred at 70 °C for 2 h. The reaction mixture was compressed, mixed with water (90 ml) and diethyl ether (70 ml) and stirred for 10 min. The phases were separated. The aqueous phase was extracted with diethyl (2 × 50 ml). The combined organic phases were dried and pressed with sodium sulphate. Ind-11 was isolated as a brine oil in a 99 g of oil of 1.04%.
The reaction mixture was maintained at -15 to -20°C (approximately 5 minutes), then the mixture was stirred at 0 to -5°C for 30 min. Then the mixture was stirred at 0 to -5°C, then the mixture was stirred at 0 to -5°C with triethyl chloride (6,6 g, 43,8 mmol) and then stirred overnight at room temperature. The mixture was obtained in a vacuum and the back is heated with water. The mixture was mixed with cyclohexane (39,0 × 30 ml) and the organic components were completely removed in the vacuum (39,99 × 30 ml) as extracted sodium cyclohexane (39,61 × 99 ml).
3-cyclohexylmethyl-2-triethylsilanyl-1H-indol2-iodaniline (5.48 g, 25.02 mmol), (3-cyclohexylmethylprop-1-inyl) trimethylsilan (6.50 g, 27.45 mmol), lithium chloride (1.11 g, 26.19 mmol) and sodium carbonate (7.95 g, 75.01 mmol) were combined in dimethylformamide (absolute, 70 ml) in an argon atmosphere. The catalyst ([Pd-2-dppf) Cl2 x CH2Cl2)), 2.05 g, 2.5 mmol) was then added to the extraction phase. The solution was stirred for 6 h at 100-106°C. The black fluid was brought to the room at room temperature to be cooled: 60 g of cyclohexanol (300 ml) was once separated from the water: 60 g of cyclohexan (350 g) and the remaining 50 g of cyclohexan (350 g) were separated with a vacuum filter containing 1 g of ethanol (150 g/ ml) and 1 g of ethanol (150 g/ ml) was once removed from the vacuum. The remaining residue was then removed with ethanol (150 g/ ml) and the remaining residue was removed in the filter.
3-Cyclohexylmethyl-1H-indol (Ind-12) 5N hydrochloric acid (20 ml, 100 mmol) was added to a solution of 3-Cyclohexylmethyl-2-triethylsilanyl-1H-indol (5.70 g, 17.40 mmol) in MeOH (106 ml). The reaction mixture was stirred overnight at room temperature. Methanol was distilled, the aqueous residue was extracted with dichloromethane (3 × 20 ml). The combined organic phases were dried with sodium sulphate. After filtration, the volatile components were completely removed in a vacuum. The solid residue (unbranded solid, 4.50 g) was decrypted (15 ml) Hexane. 2.70 g (3.3 g) (7 g) (7 g) 3-Cyclohexyl-indol-methyl (Chlorohexyl-1H) (H) (73-7-12) was obtained from 71 °C.
2-Lodaniline (4,65 g, 21,2 mmol), Ttrimethyl ((pent-1-inyl) silane (3.27 g, 23,3 mmol). Lithium chloride (0,96 g, 22,6 mmol) and sodium carbonate (6,75 g, 63,7 mmol) were combined in dimethylformamide (absolute, 64 ml) in an argon atmosphere. The catalyst ([Pd ((dppf) Cl2 x CH2Cl2], 1,78 g, 2,2 mmol) was then added. The solution was stirred for 7 h at 105 °C to 112 °C (oil bath temperature). The black reaction mixture cooled to room temperature was given in succession to water (200 ml) and ethyl acetate (200 ml). Once the mixture was dissolved, the solution was separated by filtration. The solution was diluted with sodium chloride (100 ml) and dissolved in organic water (100 ml) with sodium sulphuric acid.After filtration, the volatile components were completely removed in vacuum, and the residue (7.03 g of brown oil) was chromatographically separated [silica gel 60 (150 g); cyclohexane/trichloromethane 10:1]
Other
The test chemical is a mixture of cyclohexane and trichloromethane (550 ml); cyclohexane/trichloromethane 5:1 (1650 ml).
Other
3-Propyl-1H-indol (Ind-13) 3-Propyl-2-trimethylsilanyl-1H-indol (3.76 g, 16.25 mmol) was dissolved in MeOH (70 ml) and dosed with 2N hydrochloric acid (45 ml, 90 mmol). The reaction mixture was stirred overnight at room temperature. Methanol was distilled, the aqueous residue was extracted with dichloromethane (3 × 20 ml). The combined organic phases were dried with sodium sulphate. After filtration, the volatile components were completely removed in a vacuum.2,66 g (140%) of 3-propyl-1H-indol (Ind-13) was obtained as brown oil.
Indol (5.85 g, 50 mmol) was dissolved in ice vinegar (25 ml) together with 4-vinylpyridine (5.80 g, 55 mmol). The reaction mixture was boiled for 6 h under reflux. The ice vinegar was distilled for processing. The solution was then mixed with saturated NaHCO3 solution (75 ml) and water (15 ml). The mixture was mixed with ethyl acetate (1 ×
Other
The organic phase was dried over Na2SO4 and then evaporated. The residue was decrystallized twice from ethyl acetate (each 30 ml). The product Ind-14 was obtained as a bright yellow solid at a yield of 7.06 g (31.8 mmol, 63 %, SmP: 154-158 °C).
The 3- (((1 H-indol-3-yl) propanoic acid (5 g, 26 mmol) was dissolved in acetone (50 ml) and successively added to caesium carbonate (4.2 g, 13.0 mmol), chloracetonyl (1,8 ml, 28.6 mmol) and potassium iodide (20 mg). After a reaction time of 3 days at room temperature with no humidity, the solid residues were separated by filtration and the filtrate narrowed. The ester product was obtained only in a raw product of 3.6 g. The ester product was re-absorbed in acetonyl (25 ml) and further combined with the intermediate caesium nitrile (25 ml, 28.6 mmol) and potassium iodide (20 mg). This solution was further heated to remove the calcium nitrile, which was removed from the chloracetonyl (18,6 ml, 91 ml) and the remaining residues were obtained by filtration at room temperature with a purified ether product at a temperature of 72 °C. The two products were removed from the ether product at a temperature of 18.6 °C. The raw product was obtained by filtering and re-absorbed at room temperature with a purified ether (15,6 ml, 32.6 mmol) and the remaining residues were obtained by filtration at room temperature at a temperature of 16 °C.
The newly produced cyanmethyl ester (5.1 g, 22.3 mmol) in tetrahydrofuran (100 ml) was agitated to a 25% ammonia solution (125 ml) and stirred at room temperature for 20 h. After this reaction time, the implementation was complete. The process was completed by phase separation and extraction of the aqueous phase with tetrahydrofuran (2 × 30 ml). The organic phases were combined, dried and compressed. The residue was blown and dried with water (3 × 10 ml) and diethyl ether (3 × 10 ml). The desired amide was returned as a white solid at a yield of 76 per cent (3.2 g) with a melting point of 140 °C.
Lithium aluminium hydride (1.42 g, 34 mmol) was administered with argon in portions stirred in ab ab THF (70 ml). A solution of the newly prepared amide (3.2 g, 17 mmol) in ab THF (60 ml) was added to the LiAlH4 suspension stirred for 30 min at 60 °C. After a reaction time of 12 h at 60 °C under argon, the solution was mixed with THF (30 ml) and added slowly under ice cooling (35 ml). The aluminium compounds obtained were separated by filtration and washed with THF (3 × 10 ml) phase. The filter was closed until an oil paint was added. One drop of water (30 ml) was extracted with the amino acetylate (3 × 40 ml) extracted from the water and the remaining water was combined with a solid ethyl alcohol (3 × 94 ml) extracted from the water and obtained as a dry solvent (2 × 377 × 15 ml) and a colouring agent.
LiAlH4 (1.21 mg, 31.71 mmol) was presented in dry THF (50 ml). A solution of 3-indol propionic acid (2.5 g, 13.21 mmol) was dripped into dry THF (80 ml) for 30 min. The reaction mixture was then heated for 3 h under reflux, then stirred at RT 18. Then H2O (60 ml) was added, then a mixture of concentrates H2SO4 (10 ml) and H2O (30 ml) was added. The mixture was stirred for 20 min and finally viscosity was added to the ether (50 ml). The organic phase was separated and the aqueous phase was extracted with ether (3 × 40 ml). The combined ether extracts were pressurised by means of a close filtration of the ether and obtained as 3-indol (228-31%) 3-H2O-propane, 99% (228-34%) e-sulphur.
3-(1H-Indol-3-yl) propanol (1.75 g, 10 mmol) was presented in dry THF (30 ml) and in RT first mixed with hexamethyldisilazan (10 ml, 47 mmol) followed by trimethylchlorsilan (2 ml, 15.7 mmol). It was stirred for 20 h in RT, then the solvent was removed from the rotary evaporator and the residue was base with saturated NaHCO3 solution. The aqueous solution was extracted with ether (3 × 30 ml). The combined organic phases were washed with H2O (2 × 20 ml) and dried over Na2SO4.
Removal of the solvent at the rotary evaporator produced 3-trimethylsilanyloxypropyl) - 1H indole (2,46 g, 100 %, Smp: 34-38 °C) as a crystalline solid.
A solution of tryptamine (3.04 g, 19.0 mmol) and phthalase anhydride (3.0 g, 20.2 mmol) in toluene (300 ml) was boiled for 12 h at the back flow at the water separator.
A solution of 3-(2-bromoethyl) -5-fluoro-1H-indol (7.26 g, 30 mmol), benzimidazole (3.54 g, 30 mmol) and ethyl diisopropylamine (5.1 ml, 30 mmol) in abs. chloroform (80 ml) was boiled for 20 h under reflux, then the reaction solution was washed twice with water, dried over Na2SO4, vacuumed and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (50:1)
Other
The water was deposited with an insoluble solid, which was sucked out and cleaned with a pebble gel column, which was also the product of choice.
Other
The yield is 2.95 g (35%).
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 3.21 (2 H, t); 4.51 (2 H, t); 6.90 (1 H, m); 7.21 (5 H, m); 7.62 (1 H, d); 8.09 (1 H, s); 10.95 (1 H, s).
Piperidin (3.52 g, 4.08 ml, 41.3 mmol) was dissolved in dioxane (100 ml), in RT 3-(2-bromoethyl) -5-fluor-1H-indol (5.00 g, 20.7 mmol) and stirred at 70 °C for 16 h. The solution was compressed, absorbed in CHCl3 (150 ml) and washed with water (2 x 50 ml). The organic phase was dried over Na2SO4, filtered and compressed i.v. The resulting residue was cleaned by flash chromatography with 200 g of silica gel and acetic acid/ethanol (9:1→1:2).
Other
The yield is 3.80 g (75%) of colourless solids
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.43 (2 H, m); 1.59 (4 H, m); 2.67 (6 H, m); 2.92 (2 H, t); 6.89 (1 H, m); 7.24 (1 H, s); 7.31 (2 H, m); 11.05 (1 H, s).
Add piperidine (11.2 ml, 113 mmol) to a solution of 3- ((2-bromoethyl) indole (5.00 g, 22.31 mmol) in dry chloroform (25 ml) at room temperature and then boil the solution for 5 h. After cooling, the organic phase was extracted with dilute sulphuric acid (2 x 50 ml).
Other
The aqueous phase was alkalized with 5N NaOH under ice-cooling and extracted with ether (3 x 50 ml). The organic phase was dried with Na2SO4 and compressed in vacuum. The toluene residue (100 ml) was decrystallized for further purification.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.38 (2 H, m); 1.52 (4 H, m); 2.42 (4 H, m); 2.55 (2 H; t); 3.31 (2 H, t); 7.03 (3 H, m); 7.31 (1 H, d); 7.50 (1 H, d); 10.73 (1 H, s).
A solution of 3-(2-bromoethyl) -5-fluoro-1H-indol (7.26 g, 30 mmol), 1,2,3-triazole (2.07 g, 30 mmol) and ethyl diisopropylamine (5.1 ml, 30 mmol) in abs. chloroform (70 ml) was boiled for 24 h under reflux, then the reaction solution was washed twice with water, dried over Na2SO4, compressed i.e. vacuumed and the remaining residue was cleaned by flash chromatography with EE/cyclohexane (1:1→4:1).
Other
Production: 2.35 g (34%)
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 3.24 (2 H, t); 4.64 (2 H, t); 6.89 (1 H, m); 7.12 (1 H, s); 7.30 (2 H, m); 7.67 (1 H, s); 8.07 (1 H, s); 10.96 (1 H, s).
(4-fluor-3-methoxyphenyl) hydrochloride All steps were performed at 0 °C. 4-fluor-3-methoxy-aniline (4.92 g. 34.8 mmol) was administered by stirring into concentrated hydrochloric acid (30 ml). After 10 min, an aqueous sodium nitrite solution (10 ml, 2.41 g, 34.8 mmol) was dripped to form a suspension. After another 10 min, a tin (II) chloride solution (10 ml, 13.6 g, 73 mmol) was added to concentrated hydrochloric acid. After a yellow precipitation, further concentrated hydrochloric acid (30 ml) was added. The precipitation was concentrated, washed with a vacuum cleaner and repeated by adding a small amount of saline.
Other
The yield is 9.81 g (146%) of colourless solids, melting point 123-127 °C.
Other
The test chemical is used to determine the concentration of the active substance in the test chemical.The time interval between the first and second measurements is defined as the time interval between the first and second measurements.
Other
The following substances are considered to be toxic if they are administered to the human body:
Other
2-5- ((Fluor-6-methoxy-1H-indol-3-yl) ethanol (Ind-26) A solution of (4-fluor-3-methoxyphenyl) hydrazine hydrochloride [1.00 g, 3.46 mmol (referring to a purity of the eductant of 68%) ] in acetonitrile (30 ml) and 4% aqueous sulphuric acid (30 ml) was dripped at room temperature into acetonitrile (10 ml) with a solution of dihydrofuran (242 mg, 3.46 mmol). The temperature was then raised to 80°C and the reaction apparatus was stirred for 2 h at this temperature.The residue was added to a 5% sodium hydrocarbonate solution and extracted with ethyl acetate (3 × 50 ml). The combined organic phases were dried with sodium sulphate and compacted in the i.v.
| Produkt | Reaktionszeit | Ausbeute Schmelzpunkt | |
| R1 = H, R2 = Br, R3 = H. | 15 h | 80 % | |
| (5-Brom-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl)essigsäure-ethylester | 168-170 °C | ||
| R1 = H, R2 = F, R3 = H, | 14 h | 89% | |
| (5-Fluor-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl)essigsäure-ethylester | 133-135 °C | ||
| R1 = Me, R2 = H, R3 = H, | 36 h | 73 % | |
| (3-Hydroxy-1-methyl-2-oxo-2,3-dihydro-1H-indol-3-yl)essigsäure-ethylester | 97-98 °C | ||
| R1 = H, R2 = N02, R3 = H, | 26 h | 86% | |
| (3-Hydroxy-5-nitro-2-oxo-2,3-dihydro-1H-indol-3-yl)essigsäure-ethylester | 194-197 °C |
The corresponding isatin 1a-1d (10 mmol) was dissolved in a mixture of ethanol/pyridine/acetic acid (50 ml, 15: 5: 2) and replaced with ethyl potassium malonate (1.87 g, 11 mmol) and heated at the time of return, as shown in the table. The reaction was controlled by DC (elutant: ethyl acetate/hexane 1:1) and the solvent mixture was distilled in a vacuum for processing. The residue was absorbed in ethyl acetate (50 ml) and dispersed with water (50 ml). After phase separation, the water phase was double crystallised with ethyl potassium malonate (30 ml). The combined organic phases were dried with 2 N HCl (50 ml) of water, which was added to the remaining 20 ml. The corresponding solid was distilled in a vacuum and e-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-hydroxy-
Other Tabelle 2:
Tabelle 2:
| Produkt | Reaktionszeit | Ausbeute Schmelzpunkt | |
| R1 = H, R2 = Br, R3 = H, | 12 h | 75% | |
| 2-(5-Brom-1H-indol-3-yl)ethanol | 78-79 °C | ||
| R1 = H, R2 = F, R3 = H, | 14 h | 95% | |
| 2-(5-Fluor-1 H-indol-3-yl)ethanol | 47-50 °C | ||
| R1 = Me, R2 = H, R3 = H, | 20 h | 98% | |
| 2-(1-Methyl-1H-indol-3-yl)ethanol | Öl | ||
| R1 = H, R2 = N02, R3 = H, | 24 h | 70 % ** | |
| 2-(5-Nitro-1H-indol-3-yl)ethanol | 78-81 °C |
| ** Säulenchromatographische Reinigung: Kieselgel; Eluent: Ethylacetat/Cyclohexan (1 : 4) |
The aldol product 2a-2d (10 mmol) was dissolved in absolute THF (20 ml) under atmosphere of Ar. The solution was then cooled in a water bath with BH3×THF (40 ml, 1 M solution, 40 mmol) and stirred at room temperature according to the times shown in the table. The reaction was monitored by DC. After the reaction was completed, the reaction solution was given to a mixture of ethyl acetate (50 ml) and H2O (50 ml). The acid phase was extracted twice with ethyl acetate (30 ml each). The combined organic phases were instantly dried over Na2SO4 and vacuum-dried. The residue was filtered over ethyl acetate. The solution was removed after the reaction, usually by a crystalline solution of the product, usually in the form of a liquid and, if necessary, in the form of a crystalline solution of ethyl diesel.
5-bromo-tryptopholic acid (1.05 g, 4.39 mmol; see Tables 1 and 2) and pyridine-4 boric acid (10 mg, 6.59 mmol) were suspended in tetrahydrofuran (65 ml) and transferred to Na2CO3 solution (4.65 g, 43.9 mmol in 44 ml H2O). Bistriphenylphosphaladium dichloride (456.2 mg, 0.65 mmol) was then added. The heat-clear reaction table was boiled under stirring at 65°C for 14 h. The reaction was monitored by DC. The reaction solution was filtered for processing. The treatment phase was two-phase. The dilution phase was separated. The solution was dissolved in the red evaporator. The residue was purified by flash ethanol ethanol (400 Oac); [60 ml]
Other
The test chemical is a mixture of two or more of the following:
A solution of chloral hydrate (11 g, 0,066 mol) and sodium sulphate (70 g) in water (240 ml) was given a suspension of 3,5-dichloroaniline (10 g, 0,0617 mol) in water (40 ml) and 37% hydrochloric acid (5,3 ml, 0,066 mol). To this mixture a solution of hydroxylamine hydrochloride (13,5 g, 0,195 mol) in water (60 ml) was added. The reaction mixture was boiled for 1 h under reflux, producing a clear reaction solution from which a reaction product was produced already in the heat. The solution was agitated at room temperature for 16 h and obtained after oximeter filtration and washing with water (3 × 50 ml) in a solution of 84 g (12,1 g) of a yellow solid at 179 °C.
The newly produced N- ((3,5-dichlorophenyl) 2-hydroxy-aminoacetamide (12.1 g, 0.052 mol) was administered in 96% sulphuric acid (56 ml) for 15 min at 50-75 °C. The reaction mixture was then heated to 90 °C by stirring for 15 min. After cooling, the solution was slowly poured on ice (500 g). The resulting solid was removed after 30 min. The desired isatin was isolated as an orange solid at a yield of 81 % (9.12 g). A melting point could not be determined.
(4,6-dichlor-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl)acetic acid ester A solution of 4,6-dichlor-1H-indol-2,3-dions (4.5 g, 20.8 mmol) in a mixture of ethanol/pyridine/acetic acid [15:5:2], 100 ml] was added to malonic acid monoethyl ester potassium salt (3.9 g, 22.88 mmol) and boiled 7 hrs. The reaction mixture was pressurised, incorporated into ethyl acetate (50 ml) and washed with water (50 ml). The aqueous phase was extracted with ethyl acetate (2 × 30 ml). The organic phase was combined and dried with 2N (50 ml) malonic acid, washed and diluted with olive oil (Hydroxy ester) and obtained as a saline extract (82.19%).
The solution of the newly prepared (4,6-dichloro-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl) acetic acid ethyl ester (5.19 g, 17.0 mmol) in tetrahydrofuran (50 ml) was placed in an ice bath with a 1 M boron/THF solution (68 ml, 68 mmol) for 20 min. The reaction mixture was stirred at room temperature for 48 h and agitated for processing in a mixture of ethyl acetate (100 ml) and ethyl acetate (100 ml). The P-acids were separated and the aqueous phase (2 ml) was extracted with ethyl acetate. The organic phases were combined, dried and eaten. The residue was pressed in a mixture of ethyl acetate (50 ml) (3.5 × 2 g) and ethyl acetate (50 ml) (3.5 × 2 ml) and then obtained in water with a solution of ethyl acetate (1 × 2 ml) and a dilute solution of ethyl acetate (1 × 2 ml) (1 × 2 ml) (1 × 2 ml) (1 × 2 ml) (1 × 2 ml) (1 × 2 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 4 × 5 × 5 × 5 × 5 × 5 × 5 × 5 × 5 × 5 × 5 × 5 × 6 × 6 × 6 × 6 × 6 × 6 × 6 × 6 × 6 × 6 × 6 × 6 × 6 × 7 × 7 × 7 × 7 × 7 × 7 × 7 × 7 × 7 × 7
The organic phase was dried, filtered and i.i. vacuumed. The resulting residue was flash chromatographed with 500 g of silica gel and chloroform/methanol (20:1 → 9:1:1 → methanol) and obtained by combining a salt of the compound first with methanol, which could then be separated by an acidic filtration with 2N NaOHCl3 and CHCl3 separated from the Phasyl chloride. The second phase was obtained by combining the organic salt with the extracted PCl2 and HCl3 and using a vacuum.
Other
The yield is 3.27 g (Ind-36.68%) of colourless solids
Other
The mean value of the dose of the active substance is 1.72 (4 H, m); 2.62 (4 H, m); 2.83 (4 H, m); 6.89 (1 H, m); 7.25 (3 H, m); 10.93 (1 H, s).
Other
The following information is provided in the summary of the product characteristics and the manufacturer's specifications:
A solution of 3-(2-bromoethyl) -5-fluoro-1H-indol (7.26 g, 30 mmol), pyrazol (2.04 g, 30 mmol) and ethyl diisopropylamine (5.1 ml, 30 mmol) in chloroform (80 ml) was stirred for 12 hours at 90 °C. The reaction solution was then washed twice with water, dried over Na2SO4, compressed in a vacuum and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (20:1).
Other
Production: 1.91 g (Ind-38.28%)
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 3.16 (2 H, t); 4.35 (2 H, t); 6.17 (1 H, s); 6.86 (1 H, m), 7.24 (3 H, d); 7.44 (1 H, s); 7.64 (1 H, s); 10.93 (1 H, s).
A solution of 3-(2-bromoethyl) -5-fluor-1H-indol (4.84 g, 20 mmol), imidazole (1.36 g, 20 mmol) and ethyl diisopropylamine (3.4 ml, 20 mmol) in abs. dioxane (50 ml) was stirred for 8 hours at 90 °C until no educts were present.
Other
Production: 1.29 g (Ind-39; 28%), which is the same as the average for the Community as a whole.
Other
The mean value of the dose of the active substance is 1.
A solution of 3-(2-bromoethyl) -5-fluoro-1H-indol (7.26 g, 30 mmol), benzimidazole (3.54 g, 30 mmol) and ethyl diisopropylamine (5.1 ml, 30 mmol) in abs. chloroform (80 ml) was boiled for 20 h under reflux, then the reaction solution was washed twice with water, dried over Na2SO4, vacuumed and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (50:1)
Other
The water was deposited with an insoluble solid which was sucked out and cleaned with a pebble gel column, which was also the product of choice.
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 3.21 (2 H, t); 4.51 (2 H, t); 6.90 (1 H, m); 7.21 (5 H, m); 7.62 (1 H, d); 8.09 (1 H, s); 10.95 (1 H, s).
2-lod-4-trifluoromethoxyaniline (1.2.42 g, 8 mmol), trimethylsilylpropine (2.98 mg, 1.31 ml, 8.8 mmol), lithium chloride (356 mg, 8.4 mmol) and sodium carbonate (2.54 g, 24 mmol) were combined in a dimethylformamide (20 ml) flask in an argon atmosphere. The catalyst ([Pddppf) Cl2 × CH2Cl2]; 654 mg, 0.8 mmol) was then added. The reaction mixture was stirred at 100 °C (2.98 mg, 1.31 ml, 8.8 mmol) and 18 h at room temperature. The mixture was then cooled with ice water, filtered with water (100 ml) and ethyl methylated (200 ml) and removed from the vacuum chamber. The product was then separated into three separate sections (3-3 ml) of the liquid filtered with 3-methylmethylated (3-5 ml) ether-3-methylmethylated (3-5 ml) and separated into a 3-methylmethylated (3-5 ml) ether-3-methylmethylated (3-5 ml) and a 3-methylmethylated (1-5 ml) ether-3-methylated with the liquid filter.
The trimethylsilyl group was separated in two steps, the raw product of the silyl compounds (3-methyl-5-trifluormethoxy-2-trimethylsilanyl-1H-indol and 2-methyl-5- ((trimethylmethoxy) -3- ((trimethylsilanyl) -1-H-indol) 2) (2,95 g, 8 mmol, relative to the preliminary step) was stirred with THF (40 ml) and tetrabutylammonium fluoride (3.28 g, 11 mmol) at 4 h. The method was then worked up. After addition of water (40 ml), the mixture was stirred again for 15 min. The resulting liquid was separated by 6,5 ml. The aqueous phase was extracted with difluorethyl sulphate (3 60 ml); the organic phase was extracted with 1,44 × 1,44 g (1: 1,4-Ftributylammonium sulphate) g. The resulting g was obtained by the extraction of 1,0% (5-5 mmol) of ethyl methylammonium methylammonium in a vacuum containing 60 mg of ethyl methylammonium (1,3-5 mmol) and its components were obtained by dissolving the 3-methyl methylammonium (1,5-1,3 g) in a 3-methyl methylammonium (1,5-methyl methylammonium (1,5-5) g) and its components were obtained by the extraction of 1 ml of ethyl methylammonium (1,5-methyl methylammonium (1,5-5) g) in a vacuum (1,5-methyl methylammonium (1,5-methyl methylammonium (1,5-methyl methylammonium) and its components were obtained by the extraction of 1 ml of ethyl methylammonium (1,5-methyl methylammonium (1,5-methyl methylammonium) and its components were obtained by the extraction of 1 ml (1,5-methyl methylammonium (1,5-methyl methylammonium) and its components were obtained by the extraction of ethyl methylammonium (1,5-methyl methylammonium (1,5-methyl methylammonium (1,5-methyl methylammonium) and
3-hydroxy-3-pyridine-2-ylmethyl-1,3-dihydroindol-2-one A mixture of isatin (12.0 g, 82 mmol) and 2-picoline (25.1 g, 24 ml, 0.27 mol) was heated for 5 h under reflux. The reaction mixture was then compressed i.v., the residue repeatedly infused with toluene and then infused again i.v. The remaining 2-picoline was distilled by ball-tube distillation at 60 °C. The residue was dissolved with chloroform (100 ml) and 1 M saline (80) phase, the water separated and the chloroform phase was infused with 1 M saline (40 ml) and the water separated. The product was dissolved in 25% ammonium saline solution and placed in water at an extra pH of 100 °C and the product was dissolved in 25 ml of ammonium saline.
Other
The following is the list of active substances and their active substances:
Other
The mean value of the measurements performed was 1.17 (d, 1H, J = 13.0 Hz); 3.30 (d, 1H, J = 13.1 Hz); 6.29 (s, 1H); 6.64 (d, 1H, J = 7.6 Hz); 6.82 (t, 1H, J = 7.3 Hz); 6.91 (d, 1H, J = 6.9 Hz); 7.04 to 7.17 (m, 3H); 7.57 (dt, 1H, J = 6.9 and 1.4 Hz); 8.29 (d, 1H, J = 4.3 Hz); 10.13 (s, 1H).
3-Pyridine-2-ylmethyl-1H-indol (Ind-49) A solution of 3-hydroxy-3-pyridine-2-ylmethyl-1,3-dihydroindol-2-one (4.80 g, 20 mmol) in anhydrous tetrahydrofuran (250 ml) was mixed with a 2 M solution of the boron dimethyl sulphide complex (20 ml, 40 mmol) and stirred overnight at room temperature. The reaction mixture was carefully mixed with methanol (10 ml) and i. v. narrowed. The residue was repeatedly mixed with methanol, each time again i. v. narrowed and absorbed in 1 N of hydrochloric acid (40 ml). The aqueous suspension was extracted with ethyl acetate (2 × 40 ml). The aqueous phase was mixed with potassium L-carbonyl acetate solution at pH 10 × 30 ml and i. v. narrowed with ethyl nitrate and i. v. extracted with sodium nitrate.The raw product (4.0 g) was cleaned by flash chromatography (400 g, 20 x 7.6 cm) first with ethyl acetate/cyclohexane (2:1) and then chloroform.
Other
The following is the list of substances that are to be used in the preparation of the product:
Other
The mean value of the 1H-NMR (DMSO-d6) is 4.18 (s, 2H); 6.92 (ddd, 1H, J = 8.0 .7.0 and 1.1 Hz); 7.05 (ddd, 1H, J = 8.2, 7.1 and 1.2 Hz); 7.15 (m, 1H); 7.18-7.24 (m, 2H); 7.34 (dt, 1H, J = 8.1 and 0.9 Hz); 7.45 (br d, 1H, J = 7.8 Hz); 7.64 (dt, 1H, J = 7.7 and 1.9 Hz); 8.47 (ddd, 1H, J = 4.9, 1.8 and 0.9 Hz); 10.The maximum value of the product concerned shall be:
CAS No: 830-96-6, commercially available e.g. from Fluka
A mixture of 3-Indolpropionic acid (2.85 g, 15 mmol) and N-Methyl-1,2-phenylenediamine (611 mg, 5.0 mmol) was stirred at 130 °C for 5 h to produce a dark brown solid mass dissolved in chloroform (100 ml), then washed with organic solution containing 10% Na2CO3 solution (2 × 30 ml) and water, dried over Na2SO4, i.e. vacuum compressed and flash chromatography with cyclohexane/EE (1:1) cleaned the residue. Yield: 863 mg (Ind-54.63%) of colourless solid
Other
The mean value of the 1H-NMR (DMSO-d6) is 3.22 (4 H, t); 3.65 (3 H, s); 6.95-7.56 (5 H, m); 7.35 (1 H, d); 7.45 (1 H, d); 7.59 (2 H, m); 10.81 (1 H, s).
CAS No: 16571-51-0 , commercially available e.g. from Sigma-Aldrich
CAS No: 133-32-4, commercially available e.g. from ACROS
LiAlH4 (1.14 g, 30 mmol) was presented in dry THF (100 ml) without oxygen. 4- (((1H-Indol-3-yl) butanoic acid (2.03 g, 10 mmol, dissolved in 80 ml of dry THF) was added to the suspension for 30 min. The solution was then heated for 3 h under return flow to boil. The reaction mixture was stirred overnight at room temperature. The solution was then gently stirred with water (30 ml). The mixture was stirred for 20 min and dissolved with 2N NaOH (10 ml). The organic phase was separated and the remaining aqueous solution was extracted with diethyl alcohol (3 x 40 ml) extracted. The etheric solution was pressurised over a period of approximately 2 hours at the evaporation and evaporated to obtain a net of oil (9-57%) in a dry form.
The solution was heated for 3 h, stirred overnight at RT, filtered the precipitation and washed with acetic acid and EtOH. yield: 3.00 g (Ind-61.60 %)
Other
The mean value of the 1H-NMR (DMSO-d6) is 2.61 (4 H, s); 2.88 (2 H, t); 3.61 (2 H, t); 7.01 (2 H, m); 7.20 (1 H, s); 7.36 (1 H, d); 7.53 (1 H, t); 10.86 (1 H, bs).
Other
The following information is provided in the summary of the product characteristics and the manufacturer's specifications:
The organic phase was extracted with dilute sulphuric acid (2x50 ml). The aqueous phase was cooled with 5N NaOH under ice and extracted with ether (3 x 50 ml). The organic phase was dried over Na2SO4 and compressed i.e. vacuum. Output: 5.35 g (Ind-62.88 %).
Other
The mean value of the dose of the active substance is 1.83 (2 H, m); 2.67 (2 H, m); 2.92 (2 H, m); 3.50 (2 H; m); 6.47 (1 H, m); 6.66 (1 H, m); 6.87 (1 H, m); 7.08 (3 H, m); 7.20 (1 H, m); 7.36 (1 H, m); 7.55 (1 H, m); 10.82 (1 H, s).
The resin was filtered, washed and dried with methanol. The resin was resuspended in DMA (100 ml), 3-bromethyl) indol (0.60 g, 2.67 mmol) and stirred 5 days in RT. It was then resuspended with N,N-dimethyl acetamide (DMA) (30 ml), stirred with sodium acetate (1.78 g, 27.5 mmol, 5 equ.) and stirred at RT for 48 h. The resin was filtered, washed with methanol and dried. The resin was resuspended in DMA (100 ml), 3-bromethyl) indol (0.60 g, 2.67 mmol) and stirred 5 days in RT. It was then resuspended with propyl acetate (0.24 mg, 2.67 mmol), stirred at 20 °C and i. i. 80 mg. The solvent was removed. The product was separated by flash chromatography (93 mg/ ml) with CH3 CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93 mg/ ml) CH3 (93) CH3 (93) CH3 (93) CH3 mg/ ml) CH3 (93) CH3 (93) CH3 (93) CH3 mg/ ml) CH3 (93) CH3 (93) CH3 (93) CH3 mg/ ml) CH3 (93) CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH
Other
The mean value of the dose of the active substance is calculated as the following:
Other
The following information is provided in the summary of the information provided by the Authority and the Authority in the Annex to this Regulation:
A solution of 3-(2-bromoethyl) - 1H-indol (4.48 g, 20 mmol) and isoinol (4.76 g, 40 mmol) in a dioxane solution (50 ml) was stirred at 80 °C for 6 h. The solvent was then removed in a vacuum, the residue added with CHCl3 (100 ml) and washed twice with water. The organic phase was dried over Na2SO4, compressed in a vacuum and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (20:1).
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.95 (4 H, m); 3.93 (4 H, m); 7.18 (2 H, m); 7.20 (5 H, m); 7.35 (1 H, d); 7.57 (1 H, d); 10.79 (1 H, s).
A solution of 3-(2-bromoethyl) -1-H-indol (4.48 g, 20 mmol) and isokinoline (5.33 g, 40 mmol) in a dioxane solution (50 ml) was stirred at 80 °C for 6 h. The solvent was then removed in a vacuum, the residue added with CHCl3 (100 ml) and washed twice with water. The organic phase was dried over Na2SO4, compressed in a vacuum and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (50:1).
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.76 (6 H, m); 2.95 (2 H, m); 3.66 (2 H, s); 7.06 (6 H, m); 7.18 (1 H, s); 7.34 (1 H, d); 7.56 (1 H, d); 10.77 (1 H, s).
Pyrrolidine (3.17 g, 3.7 ml, 44.6 mmol) was dissolved in dioxane (100 ml), in RT with 3- ((2-bromoethyl) -H-indol (5 g, 22.3 mmol) and stirred at 70 °C for 8 h. The solution was compressed, absorbed in CHCl3 (150 ml) and washed with water (2 x 50 ml). The organic phase was dried using Na2SO4, filtered and compressed i. v.
Other
The yield is 3.00 g (Ind-66, 63 %)
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.73 (4 H, m); 2.54 (4 H, m); 2.74 (2 H, t); 2.61 (2 H, t); 6.99 (2 H, m); 7.15 (1 H, s); 7.35 (1 H, d); 7.52 (1 H, d); 10.79 (1 H, s).
3-(2-bromoethyl) indole (3.00 g, 13.39 mmol) was presented in a CHCl3 (25 ml) container and mixed with 1-methylpiperazine (2.68 g, 26.8 mmol). The solution was stirred at 75 °C for 5 h and overnight in RT. The solution was extracted with diluted sulphuric acid (2 x 30 ml), the acidic aqueous phase with 5N NaOH was alkalized under ice cooling and extracted with ether (3 x 30 ml). The organic phase was dried over Na2SO4 and vacuum-sealed. Yield: 1.45 (Ind-68, 45 %).
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.18 (3 H, s); 2.38 (4 H, m); 2.58 (4 H, m); 2.83 (2 H, t); 3.43 (2 H, t); 6.98 (2 H, m); 7.13 (1 H, s); 7.34 (1 H, m); 7.49 (1 H, m); 10.77 (1 H, s).
Morpholine (2.33 g, 2.33 ml, 26.8 mmol) was dissolved in dioxane (50 ml) and replaced in RT with 3- ((2-bromoethyl) -H-indol (3.00 g, 13.4 mmol). The solution was stirred at 70 °C for 14 h, vacuum-pressed, absorbed in CHCl3 (100 ml) and washed with water (2 x 30 ml). The organic phase was dried over Na2SO4, filtered and vacuum-pressed. The boiled residue was crystallized from aqueous methanol.
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.45 (4 H, m); 2.58 (2 H, t); 2.83 (2 H, t); 3.59 (4 H, m); 7.04 (2 H, m); 7.15 (1 H, s); 7.32 (1 H, d); 7.50 (1 H, d); 10.77 (1 H, s).
A solution of 3-(2-bromoethyl) - 1H-indol (4.48 g, 20 mmol) and benzimidazole (4.72 g, 40 mmol) was stirred in a dioxane flask (50 ml) for 13 hours at 90 °C. The solvent was then removed in a vacuum, the residue added to CHCl3 (200 ml) and washed twice with water. The organic phase was dried over Na2SO4, compressed in a vacuum and the remaining residue was cleaned by flash chromatography with CHCl3/OH (40:1) yield: 1.32 g (25%) light brown solid
Other
The mean value of the dose of the active substance is 1.
A solution of 3-(2-bromoethyl) - 1H-indol (1.12 g, 5 mmol) and imidazole (0.68 g, 10 mmol) in abs. dioxane (10 ml) was stirred at 80 °C for 4 h until no educts were present in lt. DC. The solvent was then removed in a vacuum, the residue added with CHCl3 (100 ml) and washed twice with water. The organic phase was dried over Na2SO4, the vacuum compressed and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (20:1) yield: 507 mg (Ind-71, 48 %), colourless solid
Other
The mean value of the dose of the active substance is calculated as the following:
A solution of 3-(2-bromoethyl) --1-indol (4.92 g, 22 mmol) and 1.2.4-triazole (3.03 g, 44 mmol) in a mixture of dioxane (50 ml) was stirred at 80 °C for 24 h. The solvent was then removed in a vacuum, the residue added to CHCl3 (100 ml) and washed twice with water. The organic phase was dried over Na2SO4, compressed in a vacuum and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (50:1).
Other
The mean value of the dose of the active substance is calculated as the following:
3-(2-bromoethyl) indole (3.00 g, 13.4 mmol) and thiazolidine (2.38 g, 26.8 mmol) were stirred in CHCl3 (25 ml) for 5 h at 75 °C. The solution was cooled at RT and extracted with diluted sulphuric acid (2 x 30 ml). The acidic aqueous phase was ice-cooled with 5N NaOH and extracted with ether (3 x 30 ml). The organic phase was dried over Na2SO4, i.e. vacuumed and the residue was cleaned by flash chromatography with CHCl3/OH → 4:1 → MeOH (20:1:1).
Other
The mean value of the dose of the active substance is 1.
A solution of 3-(2-bromoethyl) - 1H-indol (2.24 g, 10 mmol), 5-methyl-1,2,3,4-tetrazol (0.84 g, 10 mmol) and ethyl-diisopropylamine (1.7 ml, 10 mmol) was stirred in abs. dioxane (25 ml) for 8 hours at 90 °C until no conduit was left in the lt. DC. The solvent was then removed in the vacuum, the residue was added with CHCl3 (100 ml) and the organic phase was washed twice with water. The organic phase was dried over Na2SO4, the vacuum was compressed and the remaining residue was cleaned by flash chromatography with EE/Cycloxan (1:41→MeOH)
Other
The following information is provided for the purpose of the analysis:
Other
The total number of active substances in the active substance shall be calculated as follows:
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.44 (3 H, s); 3.36 (2 H, t); 4.87 (2 H, t); 7.05 (3 H, m); 7.35 (1 H, m); 7.49 (1 H, m); 10.85 (1 H, s).
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.16 (3 H, s); 3.25 (2 H, t); 4.58 (2 H, t); 7.07 (3 H, m); 7.36 (1 H, m); 7.43 (1 H, m); 10.87 (1 H, s).
A solution of 3-(2-bromoethyl) - 1H-indol (2.24 g, 10 mmol) and pyrazol (1.36 g, 20 mmol) in a dioxane solution (20 ml) was stirred at 80 °C for 16 h. The solvent was then removed in a vacuum, the residue added with CHCl3 (100 ml) and washed twice with water. The organic phase was dried over Na2SO4, compressed in a vacuum and the remaining residue was cleaned by flash chromatography with CHCl3/MeOH (50:1).
Other
The mean value of the dose of the active substance is calculated as the following:
A solution of 3-(2-bromoethyl) - 1H-indol (4.92 g, 22 mmol) and 1.2.3-triazole (3.03 g, 44 mmol) in a dioxane flask (50 ml) was stirred at 80 °C for 22 h. The solvent was then removed in a vacuum, the residue added to CHCl3 (100 ml) and washed twice with water. The organic phase was dried over Na2SO4, compressed in a vacuum and the remaining residue was cleaned by flash chromatography with CHCl3/meOH (50:1) yield: 0.50 g (Ind-76.11 %), brown oil
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 3.31 (2 H, t); 4.67 (2 H, t); 6.97 (1 H, m); 7.08 (2 H, m); 7.34 (1 H, d); 7.51 (1 H, d); 7.65 (1 H, s); 8.01 (1 H, s); 10.72 (1 H, s).
The synthesis of indol Ind-77 was described in the context of the synthesis of Indol sub-unit 74.
A solution of chloral hydrate (11 g, 0,066 mol) and sodium sulphate (70 g) in water (240 ml) was given a suspension of 3,4-dichloroaniline (10 g, 0,0617 mol) in water (40 ml) and 37% hydrochloric acid (5,3 ml, 0,064 mol). To this mixture a solution of hydroxylamine hydrochloride (13,5 g, 0,195 mol) in water (60 ml) was added. The reaction mixture was boiled for 1 h under reflux, producing a clear reaction solution from which a reaction product was produced already in the heat. The solution was agitated at room temperature for 16 h and obtained after oximeter filtration and washing with water (3 × 50 ml) in a mixture of 91 g (13,1 g) of a yellow solid at 179 °C.
The resulting oxime (13 g, 0.055 mol) was administered in 96% sulphuric acid (60 ml) at 50-60 °C for 15 min. The reaction mixture was then heated to 80 °C for 15 min. After cooling, the solution was slowly poured on ice (500 g). The resulting solid was sucked after 30 min. A mixture of 5,6-dichloro-1H-indol-2,3-dione and 4,5-dichloro-1H-indol-2,3-dione (10,6 g, 90%) was obtained. The two isatines were present in a ratio of 1 to 4.
A solution of 5,6-dichloro-1H-indol-2,3-dione (1.7 g, 7.9 mmol) in a mixture of ethanol/pyridine/acetic acid [15: 5: 2], 39.5 ml] was added to malonic acid monoethylester potassium salt (1.49 g, 8.74 mmol) and boiled for 23 h under reflux. The reaction mixture was compressed and codestilated with toluene (3 × 10 ml). A solid red residue was obtained by stirring in a mixture of ethanol (30 ml) and ethyl acetate (30 ml) for 20 min. The water phase was extracted with ethyl acetate (2 × 20 ml). The organic phases were combined, washed with 2N acid, dried and pressed. The green hydroxy solid was obtained from a solution of 89 °C (213 °C) with a saline point of 20-208 °C.
The solution of the newly prepared (5,6-dichloro-3-hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl) acetic acid ethyl ester (2,13 g, 7,0 mmol) in tetrahydrofuran (15 ml) was placed in an ice bath for 15 min with a 1 M boron/THF solution (28,0 ml, 28,0 mmol) stirred at room temperature for 57 h and agitated for processing in a mixture of ethyl acetate (50 ml) and (50 ml) separated phases and extracted the aqueous phase with ethyl acetate (2,13 g, 7,0 mmol). The organic phases were combined, dried and pressed. The oil was obtained as yellow indentation g.
Indol, CAS No: 120-72-9, commercially available e.g. from Sigma-Aldrich.
7-Azaindol, CAS No: 271-63-6, commercially available, for example, from Sigma-Aldrich.
A 2.5M solution of n-butyllithium in hexane (18 ml, 45 mmol) was added to a solution of benzothiophene (5 g, 37.2 mmol) in diethyl ether (40 ml) under argon for 10 min at -70 °C. After 30 min the reaction mixture was slowly heated to -15 °C (30 min). To this mixture a solution of ethylene oxide (4.88 g, 112 mmol) was added to diethylene ether (20 ml) at -10 °C for 20 min. The ethylene oxide solution was prepared by condensation of the gaseous ethylene oxide at -40 °C and absorption into diethylene. The reaction mixture was slowly heated to room temperature and stirred to 16 °C. The processing was carried out by adding NHL (30 ml) and argon (30 ml) to a refrigerated solution.The aqueous phase was extracted with diethyl ether (2 × 30 ml), the organic phase was combined and washed with 2N HCl (30 ml) and saturated NaCl (30 ml). The organic phase was compressed after drying, with the raw product of the alcohol obtained as a yellow solid. After chromatographic cleaning on silica gel (160 g) with ethylacetate/cyclohexane (1: 5), the alcohol was obtained as a white solid with a melting point of 82-84 °C at a yield of 59%.
Commercially available CAS: 40899-71-6; e.g. Sigma-Aldrich.
Commercially available CAS: 271-89-6 e.g. from Sigma-Aldrich.
KOtBu (0.673 g, 6 mmol) was dissolved in dry DMF (10 ml) with no oxygen. The solution was then mixed with phosphonic acid triethyl ester (0.87 ml, 6 mmol). After 20 min, a solution of benzofuran-3(2H) -on (0.536 g, 4 mmol) was added to this mixture in dry DMF (10 ml, argon atmosphere). The reaction mixture was stirred for 1 h at room temperature and then allowed to cool to 50 ml. The resulting mixture was extracted with diethyl ether (4 x 20 ml). The organic phase was dried with water (4 x 20 ml), washed with SO2 4 and then heated. The product was obtained by means of a cycloxycline glycol filter (4 x 60%) and dissolved in ethyl ether (4 x 0.8 ml) and obtained as a purified product.
LiAlH4 (1,025 g, 37.95 mmol) was suspended in diethyl ether without oxygen. The solution was then slowly added to the solution of the newly produced benzofuran-3-lyssigic acid methyl ester (2,546 g, 13.4 mmol) in diethyl ether (15 ml) and stirred at room temperature for 30 min. The reaction was followed by DC. To complete the hydrolysis of the excess hydride, a mixture of water (2 ml) and diethyl ether (5 ml) was added to the solution as a precautionary droplet. The etheric solution was filtered over silica and then removed with diethyl ether from the filter cake. The solution was then added to the ether in a golden alcohol of 1.93 (8%) without further refining and obtained a bright greenish oil.
Triphenylphosphandibromide (5.52 g, 14.41 mmol) was suspended in acetonitrile (15 ml) with argon, brought to 19 °C in a water bath and transferred within 15 min to 2-benzofuran-3-yl) ethanol (2,11 g, 13.1 mmol) dissolved in acetonitrile (7 ml). During the addition, the temperature of the reaction mixture was maintained between 19 and 21 °C. The treatment was then stopped for 12 h without further cooling. The triphenylphosphan which had fallen off during this time was removed from the reaction mixture by filtration. The resulting phosphan was reduced to red. To remove the phosphan completely, the residue was reduced to cyclohexane (20 g) on approximately 3 ml of diclohexane (15 g) of cyclohexane and washed in a solution containing approximately 20 g (87 ml) of cyclohexane (2 g) of petroleum oil. The resulting oil was dissolved in a solution containing approximately 20 g (87 g) of petroleum cyanide.
Sodium thiosulfate (5,44 g, pentahydrate, 21,9 mmol) was dissolved in water (22 ml) and stirred for 10 min with 3-(2-bromethyl) benzofuran (2,90 g, 12,9 mmol) dissolved in ethanol (40 ml). The reaction mixture was then boiled in the back flow. After 4 h the conversion was completed (DC control). The ethanol contained in the solvent mixture was distilled in a vacuum for processing. The aqueous residue was extracted with diethyl ether (3 × 20 ml), the organic phase was washed with water (2 × 20 ml). The combined aqueous phases were added at the reduction stage. The resulting aqueous residue contains white water (3.63 g) x thiol mol. The conversion was completed without further purification.
The resulting reaction mixture was then coated with diethyl ether (75 ml) and heated under strong stirring at the return stream (7 h) until no solid was observed in the aqueous phase. After cooling the two phases were separated and the aqueous phase was added with diethyl ether (4 × 15 ml). The combined ether phases were further diluted with water (2 × 10 ml) and washed over. The retention of diethyl ether (RN-971-94) was shown to be relatively low in the dilution of the crude oil and was therefore obtained by a dilution of the diethyl ether (RN-1.) and a dilution of the diethyl ether (RN-974-94) with a relative strength of 80%.
Commercially available CAS 1455-18-1 from e.g. Acros Organics.
Tryptamine (1.04 g, 6.5 mmol) was dissolved in a mixture of acetone (20 ml) and triethylamine (1 ml) under nitrogen atmosphere. Benzyl isocyanate (952 mg, 7.15 mmol, 0.88 ml) was rapidly added at 0 °C, then the solution was stirred for 2 h under ice cooling and 2 h under RT. A subsequent DC in chloroform/methanol 20:1 showed only small amounts of tryptamine. The solution was narrowed in one go. The resulting residue was cleaned by flash chromatography with 100 g of silica and chloroform/methanol 20:1→9→14:1.
Other
The yield is 1.72 g (90%)
Tryptamine (1.04 g, 6.5 mmol) was dissolved in a mixture of acetone (20 ml) and triethylamine (1 ml) under nitrogen atmosphere. At 0 °C, phenylisocyanate (852 mg, 7.15 mmol, 0.78 ml) was rapidly dripped, then the solution was stirred for 2 h under ice cooling and overnight at RT. A subsequent DC in chloroform/methanol 20:1 showed only small amounts of tryptamine. The solution was narrowed in i.v. The resulting residue was cleaned by flash chromatography with 100 g of silica and chloroform/methanol 50:1→9:1 mg. Yield: 928 (51 %).
Tryptamine (1.04 g, 6.5 mmol) was dissolved in a mixture of acetone (20 ml) and triethylamine (1 ml) under nitrogen atmosphere. Cyclopentylisocyanate (795 mg, 7.15 mmol, 0.81 ml) was rapidly dripped at 0 °C, then the solution was stirred for 2 h under ice cooling and overnight in RT. A white solid had been extracted from the solution, which was sucked and washed with acetone. This was 641 mg of pure product. The filter was narrowed in i.v. and then stirred with acetone (10 ml). The unsolved white solid was sucked and washed with acetone, thus obtaining another 612 mg of clean product.
Other
Production: 1.25 g (71%)
Tryptamine (950 mg, 5.93 mmol) was presented in a 30 ml bottle of THF and was added to RT with triethylamine (0.82 ml, 5.93 mmol). Cyclopentansulfonyl chloride (1.00 g, 5.93 mmol) was then rapidly added to RT and the 1 d approach was stirred at RT. A subsequent DC in chloroform/methanol showed only small amounts of tryptamine. The approach was narrowed in i.v. 20:1, the resulting residue was absorbed in acetic acid (20 ml) and washed with saturated NaHCO3 solution (2x 20 ml). A precipitate was drained from the solution, according to this, but it was not DC. The organic phase of the product was narrowed with 20 ml (22 ml) NaHCO2 solution (2x 20 ml) and washed with NaSO4 solution.
Other
The yield is 749 mg (43%).
Tryptamine (955 mg, 5.96 mmol) was presented in a 30 ml ABF. Then TEA (888 μL, 6.45 mmol) and benzosulfonic acid chloride (826 μL, 6.45 mmol) were added and stirred for 16 h at RT. The solution was pressed dry once. The residue was collected in EE (20 ml) and washed with saturated NaHCO3 solution (2 x 20 ml) and NaCl solution (2 x 20 ml). The organic phase was dried over Na2SO4 and pressed once. Yield: 1.80 g (100 %).
Tryptamine (640 mg, 4.0 mmol) was presented in a 30 ml ABF. Then TEA (596 μL, 4.3 mmol) and 2-thiophensulfonyl chloride (785 mg, 4.3 mmol) were added and stirred for 5 h at RT. The solution was pressed in a vacuum until dry. The residue was collected in EE (20 ml) and washed with saturated NaHCO3 solution (2 x 20 ml) and NaCl solution (2 x 20 ml). The organic phase was dried over Na2SO4 and pressed in a vacuum. Yield: 1.38 g (100%).
Tryptamine (640 mg, 4.0 mmol) was presented in a 30 ml bottle of THF. Then TEA (596 μL, 4.3 mmol) and nicotinic acid hydrochloride (770 mg, 4.3 mmol) were added and stirred for 5 h at RT. The solution was pressed dry in the IV. The residue was collected in EE (20 ml) and washed with saturated NaHCO3 solution (2 x 20 ml) and NaCl solution (2 x 20 ml). The organic phase was dried over Na2SO4 and pressed in the IV. Yield: 482 mg (45%).
In a sulphur flask with a magnetic agitator, internal thermometer, drip funnel, gas inlet and drainage tube and septum cap, LDA of diisopropylamine (6.7 ml, 48 mmol) and 2.5M n-BuLi solution in hexane (17.6 ml, 44 mmol) was prepared in a dry THF (100 ml) at -5 °C under argon, stirred for 20 min at -5 °C, then cooled to -75 °C and 1-phenylfonyl) troindol (10.3 g, 40 mmol) in dry THF (80 ml) for 2 h so that the internal temperature does not rise above -70 °C. This addition was then added at 90 min. stirred at -5 °C, then stirred in 120 ml (615 ml) of ethylene oxide at -15 °C.The reaction mixture was left overnight in a cold bath. The clear red-brown solution was poured into a saturated NH4Cl solution (100 ml). After adding water (30 ml), phase separation took place. The aqueous phase was extracted with diethyl ether (2 × 50 ml) and the organic phase was washed with 2N HCl (30 ml) and saturated NaCl (30 ml). The organic phase was compressed after drying, with the raw product being a mixture of 2-(1-(phenylsulfonyl) -1-H-indol-2-yl) ethanol, 2-(1-(H-indol-1-yl) ethanol and the starting product. By chromatography [Kiesel G (300 g); Cyclohexan / Ac: 1) ] the starting product could be separated. The starting product was thus classified for the next stage (7).
To separate the phenylsulfonyl residue from 2-(1-(phenylsulfonyl) - 1H-indol-2-yl) ethanol, the mixture just obtained (4,7 g) was dissolved in ethanol (80 ml) and 2M sodium brine (80 ml) and heated to return to the boiling point for 32 h. At the rotary evaporator, the ethanol was removed and the residue was diluted with water (20 ml). The aqueous solution was extracted with ether (3 × 70 ml). The combined organic phases were washed with water (30 ml) and saturated NaCl solution (30 ml). The organic phase was compressed after drying. A dark yellow oil (3.08 g) was obtained, which is related to G (200 g); Cycloacethanol (1.23 g/o) was separated into 1,1% (1,12 g/o) of the 2-hydroxyethyl ethanol by-product, which is obtained from the 16-1,2-hydroxyethyl alcohol (1,1 g/o) and the 14-1,2-hydroxyethyl alcohol (1,1 g/o) by-hydroxyethyl ethanol).
The mixture was then stirred at 0 to -5°C for 30 min. The mixture was then nettrophened at 0 to -5°C and then stirred overnight at room temperature. The mixture was mixed in vacuum and the remainder was mixed with water (50 ml). The mixture was then mixed with Cyclohexan (324 × 30 ml). The components were completely dissolved in the vacuum as 110 g/ m3 of extracted tripropylene (ASP) -nitrophenol (A1O3-nitrophenol). The components were dissolved in the vacuum as 95 g/ m3 of extracted tripropylene.
3-Benzyl-2-triethylsilanyl-1H-indol2-lodaniline (5.48 g, 25.02 mmol), triethyl- ((3-phenylprop-1-inyl) silane (6.34 g, 27.51 mmol), lithium chloride (1.11 g, 26.19 mmol) and sodium carbonate (7.95 g, 75.01 mmol) were combined in dimethylformamide (absolute, 70 ml) in an argon atmosphere. The catalyst ([Pd(dryppf) Cl2 x CH22). 2.05 g, 2.51 mmol) was then added. The solution was stirred at 6 h at 100-106 °C. The black-dry reaction mixture, cooled to room temperature, was then added successively to the water (300 ml) and ethyl gethyl acetate (150 ml): once the mixture was given 60 g/ml. The cyclohexane was completely separated from the mixture. The remaining parts were then separated with ethyl phthalate (30.5 ml) in the oil (e.g. ethyl phthalate) (10.5 ml) and the remaining parts were removed in a vacuum-filter.
3-Benzyl-1H-indol (Ind-108) 3-Benzyl-2-triethylsilanyl-1H-indol (6.37 g, 19.81 mmol) was dissolved in MeOH (119 ml) and dosed with hydrochloric acid (5N, 22 ml, 110 mmol). The reaction mixture was stirred overnight at room temperature. Methanol was distilled, the aqueous residue was extracted with dichloromethane (3 × 20 ml). The combined organic phases were dried with sodium sulphate. After filtration, the volatile components were completely removed in vacuum. The residue (brown solid, 4.97 g) was decrypted from T/hexane (5 + 30 ml). 3.53 g (86 g) 3-Benzyl-1H-indol (H) -H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H
(1:1) Diastereomeric mixtureA suspension of N,N-Dimethyl-N-{4-phenyl-2',3',4',9'-tetrahydrospiro[cyclohexan-1,1'-pyrano[3,4-b]indol]-4-yl}-amin (unpolar diastereomer, see W02004043967) (0.72 g, 2.00 mmol) was administered in concentrated HCl (60 ml) to a clear solution of 2 h of Sn powder (3.00 g, 25.40 mmol) in succession. During addition, a clear solution was obtained, which was stirred for a further 2 h at RT. The treatment was carried out with a concentrated Na2CO3 solution and the remaining solution was dried with Ethoxy-Acetyl (50 ml) The extraction was incomplete, the extraction was carried out in a solution of both ethoxy-acetyl and ethyl-acetyl (32 mg) x 30 ml. The extracts were obtained by means of a filter containing ethyl-acetyl-acetyl (52 mg) and ethyl-acetyl-acetyl (32 ml) x 30 mg.
The solid (0.22 g, 0.60 mmol) was dissolved in boiling EtOH (30 ml) and mixed with citric acid (0.13 mg, 0.67 mmol), dissolved in hot EtOH (5 ml). The ethanol solution was compressed (to about 10 ml) and mixed with ether (10 ml). The precipitate was separated and dried by a fryer. The citrate (Bsp 1) (0.20 g, 60%, Smp: from 114°C) was obtained as a white solid.
The mixture was kept overnight in RT. NaHCO3 was added in portions during stirring and the volatile components were distilled in a vacuum. The residue was dissolved in EtOAc (20 ml) and washed with saturated aqueous NaHCO3 solution (3 x 10 ml). After removal of the solvent from the rotary evaporator, the residue was purified by recrystallization of MeOH (15 ml) base. The free base of the desired product was obtained as a white solid (289 mg, 72 %). This product was washed and dried in a 120 μm (115 μm) suspension of methyl methyl chloride (5 ml) and ethyl chloride (112 μm) (137 μm) (112 μm) (112 μm) (112 μm) and washed with a dry base of methyl chloride (115 μm).
Ketone (Ket-10, 435 mg, 2 mmol) and 3-(H-Indol-3-yl) propane-1-amine (Ind-15, 348 mg, 2 mmol) were dissolved in DCE (20 ml). Then methanosulfonic acid (4 ml) was rapidly added. The solution was stirred for 1 h at RT. The clear red reaction mixture was diluted with H2O (10 ml) and set to pH 11 with 2N NaOH. After phase separation, the aqueous phase was extracted with DCE (3 x 20 ml). The organic extracts were combined, dried over Na2SO4 and the solvent removed at the rotational vapour. The residual was purified by column chromatography (MeOH) and the base product obtained as a free-flowing solid (400 mg,54%).
Other
To produce the citrate, the olefin (380 mg, 1.02 mmol) just obtained was dissolved in hot EtOH (10 ml) and added to EtOH (2 ml) with a hot citric acid (196 mg, 1.02 mmol) solution. The mixture was then stored at 5°C for 16 hours. The ethanol was removed at the rotary evaporator and the desired citrate (Bsp 4) was obtained as a yellow solid (576 mg, 100 %, Smp: 150-155 °C).
Other
The dose of the active substance is calculated by dividing the dose by the dose of the active substance in the dose range from 1 μg/ kg to 1 μg/ kg.The following are the main types of data:
Other
The following is a list of the active substances that may be used in the manufacture of the active substance:
A solution of ketone (Ket-10, 1.1 g, 5.07 mmol) and indole (Ind-16, 1.48 g, 6.0 mmol) was mixed with triethylmethyl ester (1 ml, 5 mmol) of triethyl methanosulfonic acid for 5 min. The reaction mixture was stirred at -78 °C for 60 min. Finally, the mixture was mixed with triethyl silane (0.9 ml, 5.6 mmol). The mixture was partially heated for about 4 h and stirred for another 10 h. 1 N NaOH (40 ml) was added to RT and stirred for 60 min. A precipitation formed, which dissolved when 30 ml of DC (30 ml) was added.After phase separation, the aqueous phase was extracted with DCM (3 x 30 ml), the organic extracts were combined and washed with 1N NaOH (1 x 30 ml) and H2O (2 x 30 ml).After drying with Na2SO4, the solvent was removed from the rotary evaporator and the residue was cleaned column chromatographically (EtOAc, then EtOAc/EtOH (8: 2)), obtaining the desired olefin (134 mg, 7 %. Smp: 163-167 °C).For transfer to the hydrochloride, the olefin (120 mg, 0.31 mmol) was dissolved in ethylmethyl ketone (10 ml), mixed with Me3Cl (76 μl. 0.6 SiSi) and stirred at 3 h. The hydrochloride (B) was then reduced to a white solid (67 mmol, 5 mmol, 6 mmol) (67 mmol, 6 mmol) (62 mmol, 6 mmol)The temperature of the water is between 212 and 216 °C.
The reaction mixture was stirred for 21 h at RT. A brown solid was released. The reaction mixture was stirred with 1N NaOH (20 ml) and stirred at RT for 1 h. The phases were separated and the aqueous phase was extracted with DCM (20 ml). The organic phases were combined, dried over Na2SO4 and the solvent removed after filtration of the dry agent at the rotation. The residue was removed with 2-propane (3 ml) for 10 min, separated by filtration and the residue was removed with 2-propane (3 ml) and water (3 × 2 ml).The olefin was obtained as a yellow solid (87 mg, 20%, Smp: 116-119 °C). It was mixed with EtOH (15 ml) to produce the citrate and heated to 50 °C. The cloudy solution was mixed with citric acid (42 mg, 0.22 mmol), dissolved in warm EtOH (4 ml). The result was a clear solution, which was filtered out by cooling to RT. The mixture was stirred for 16 h at RT 2 and stored at 5 °C. The weighted solution (B 7) was washed with ethanol (5 ml × 5 ml) and the solution was removed by a mixture of ethanol (29 mg × 5 ml) and ethanol (29 mg × 5 ml).The maximum temperature of the product is 210 to 212 °C.
Other
The mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed was approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed were approximately 1 μs/m2 (m, 1 h), and the mean of the measurements performed were approximately 1 μs/m2 μs/m2 (m, 1 h), and the mean of the measurements performed were approximately 1 μs/m2 μs/m2 (m, 1 h, and the mean of the measurements performed were approximately 1 μs/m, and the mean of the measurements performed were approximately 1 μs/m, and the mean of the measurements performed were approximately 1 μs/m, and the measured at a time were approximately 1 μs/m, and the mean of the measured at a time, and the measured were approximately 1 μs/m, and the measured at a time, and the measured at a time, the measured at a time, the measured at a time, the measured at a time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time, the time
Ketone (Ketone-9, 259 mg, 1 mmol) and tryptopholic (Ind-5, 1 mg, 1 mmol) were presented in absolute DCM (50 ml) and added to trifluoromethanesulphonic acid (0.1 ml, 1.1 mmol). It was stirred for 15 h at RT. A light brown precipitate formed. The reaction mixture was stirred with 1N NaOH (20 ml) and stirred for 16 h at RT. After phase centering, the aqueous phase was extracted with DCM (2 × 20 ml). The organic phases were combined and dried over Na24. Removal of the solution from the rotary steam generator produced the desired olefin solvent as a beige solid (40 mg, 991 mg). This was dissolved in SOH (50 mg, 11 ml) and the solvent was dissolved in ethanol (5 mg, 11 ml) at 10 °C. The solution was dissolved in water and dissolved in ethanol (5 mg, 11 ml) at 5 °C. The solution was obtained at 12 °C. The solution was dissolved in ethanol (5 mg, 11 mg, 11 mg, 11 ml) and dissolved in water (5 ml, 11 mg, 12 mg, 12 ml, 12 ml, 2 ml, and 2 ml) at 5 °C. The solution was obtained by dissolving it at 5 mg, 5 mg, 2 mg, 5 mg, 2 ml, and 2 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5 ml, 5
The clear light brown solution was stirred for 20 h at RT. The clear light brown solution was infused with 1 N NaOH (20 ml) and stirred vigorously for another hour. Between the phases a white solid was deposited. It was washed with DCM (20 ml) to obtain the desired olefin (416 mg, 97%, Smp: 255-258 °C). To produce the citrate, a portion of the solid (341 mg, 0,79 mg) was heated in 151 ml (60 °C) of ethanol dissolved in 0.9 mg of ethanol, 10 ml (108 mg, 10 ml) of ethanol dissolved in water and heated at approximately 6 °C. The solution was dissolved in 151 ml (108 mg, 10 ml) of ethanol dissolved in water and heated at approximately 6 °C. The solution was then heated to a temperature of 6 mL (108 mg, 10 ml) and dissolved in 6 ml (108 mg, 10 ml) of ethanol.
A suspension of N,N-Dimethyl-N-{4-phenyl-6'-fluor-1',3',4',9'-tetrahydrospiro[cyclohexan-1,1'-pyrano[3,4-b]indol]-4-yl}amine (unpolar diastereomer, see WO2004043967) (400 mg, 1.06 mmol) (20 ml) was stirred in HCL concentrate for 18 h at RT. The initial cloudy solution cleared over time. The resulting solid was then based on saturated Na2CO3 solution. The resulting solid was diluted via a cold table to obtain the desired olefin (340 mg, 84 mg, S: 216-221 °C). This (340 mg, 0.89 ml) was diluted in 30 ml of isopropol dissolved in a saturated solution containing 30 mmol (180 mg) of isopropol. This was diluted in a vacuum solution containing 10 mg (180 ml) of isopropol dissolved in a vacuum solution containing 42 mg (180 mg) of isopropol dissolved in a vacuum solution containing 10 mg (180 mg) of isopropol dissolved in a vacuum solution containing 10 mg (180 ml) of isopropol.
The ketone (Ket-10, 245.4 mg, 1.13 mmol) was presented with the indole (Ind-28, 270.0 mg, 1.13 mmol) in absolute 1,2-dichloroethane (35 ml). The methane sulphonic acid (220.6 μl, 3.39 mmol) was then added by dripping. The solution was stirred at RT for 16 h. The reaction mixture was then heated to 75 °C and stirred for 7 h. A bright yellow precipitate was produced. It was sucked at room temperature and washed with 1,2-dichloroethane (3 × 2 ml) and diethyl ether (2 × 2 ml) and then dried.
The freshly prepared sulfonate (763 mg, 1.21 mmol) was clearly soluble in water (28 ml). The solution was mixed with 1 N of baking soda (pH 11) and stirred vigorously for one hour. The voluminous precipitation dissolved in dichloromethane (100 ml). The clear phases were separated. The aqueous phase was extracted with dichloromethane (3 × 10 ml). The organic extracts were dried and then combined. The residue was a bright yellow solid (477.5 mg) corresponding to that of the spirotheer and the desired olefin in DC. The separation of the mixture was done by double flash chromatography [60 g of kiesel (50 g each); column: 1.OH/O ether; 1.Ac; 7 ml; 400 ml]:The olefin was obtained at a yield of (20 mg, Fp. 202-207 °C, 4 %).
Other
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements by the mean of the measurements.The number of hours of work per week is calculated by the following formula:
Other
The racemate of the olefin l (20 mg, 0.046 mmol) was heated in ethanol (5 ml) and heated with citric acid (19.3 mg, 0.101 mmol), dissolved in ethanol (1 ml). The mixture was stirred 1 time at RT. No precipitation occurred during cooling. The solution was compressed to approximately 1 ml, stirred with diethyl ether (3 ml) and stirred 2 times.The parent solution was carefully decanted over the deposited solid. The solid was rinsed twice with diethyl ether (2 ml) and the remaining solution was re-pipetitized. The residue was vacuum dried. The citrate of the olefin (Bsp 11) was obtained as a yellow solid at a yield of 98% (28.2 mg, melting point not determined).
The ketone (Ket-10, 1.305 g, 6.0 mmol) was dissolved with the indole (Ind-27, 1.24 g, 6 mmol) in dry dichloromethane (60 ml). In RT, trifluoromethane sulphonic acid (1,19 ml, 6 mmol) was added quickly, with the solution turning brown. The solution was stirred for another 48 h at RT. The reaction was controlled by DC. For processing, the solution was transferred to 5N NaOH (50 ml) and stirred for 30 min. The organic phase was separated. The wet phase was extracted with dichloromethane (5 × 30 ml). The organic phase was dried over Na2SO4 and then re-pressed.The mixture was separated and purified by column chromatography [silica gel 60 (200 g; MeOH (2000 ml) ] and the olefin was obtained as a yellow solid at a yield of 1,23 g (51%).
Other
The mean of the measurements performed was approximately 0.01% for the mean of the measurements performed in the previous two years.
Other
The mean of the measurements is calculated as the mean of the measurements.I'm going to have to go with the other one.
To produce the citrate, the olefin (360 mg, 1 mmol) was dissolved in hot ethanol (50 ml) and added to ethanol (5 ml) with an equally hot solution of citric acid (194 mg, 1 mmol). After cooling to 5°C, the process was stopped for 16 h. The resulting solid was sucked and dried. The desired hemicitrate was obtained at a yield of 276 mg (50%) as a white solid (melting point: 199-203 °C).
Other
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Ketone (Ket-6, 0.220 g, 0.804 mmol) and tryptopholes (Ind-5, 0.130 g, 0.804 mmol) were presented in a mixture of dichloromethane (10 ml) under argon, then mixed with methanesulfonic acid (0.078 ml, 0.881 mmol) and stirred at room temperature overnight.
Other
The yield is 0.07 g, 21.2%
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.01 (2 H, m); 2.19 (1 H, m); 2.24 (6 H, s); 2.73 (2 H, s); 2.91 (2 H, t); 3.34 (1 H, m); 3.53 (2 H, m); 4.71 (1 H, t, OH); 6.25 (1 H, bs); 6.96 (2 H, m); 7.27 (4 H, m); 7.41 (1 H, m); 7.73 (1 H, m); 7.88 (1 H, m); 10.66 (1 H, bs).
Other
The total number of patients with a history of renal failure was estimated at approximately 108,528 in the United States.
The olefin (0.07 g, 0.168 mmol) obtained was dissolved in hot ethanol (2.5 ml) and transferred to room temperature with citric acid (0.033 g, 0.168 mmol), dissolved in hot ethanol (1 ml), then the reaction solution was compressed into a vacuum and a brown solid was obtained.
Other
The test chemical is used to determine the concentration of the test chemical in the test medium.
Ketone (Ket-6, 0.220 g, 0.804 mmol) and indole (Ind-4, 0.194 g, 0.804 mmol) were presented in a flask of dichloromethane (10 ml) under argon, then mixed with methanesulfonic acid (0.078 ml, 0.881 mmol) and stirred at room temperature overnight. The solution was mixed with 1 N NaOH and extracted with dichloromethane (3 x 15 ml), the org. phase was dried over Na2SO4 and compressed in i. a. and then purified by flash chromatography with chloroform/methanol (9:1) Outputs: 0.130 g (37%) 1H-NMR (DMSO-d6): 2.01 H (2,26 m; 7.25 h; 7.74 m; 2.87 m; 3.29 h (1,26 h; 7.73 h; 7.72 h; 7.73 h; 7.86 h (1,72 h); 7.73 h (1,72 h); 7.73 h (1,72 h); 7.86 h (1,72 h); 7.73 h (1,72 h).
Other
The total number of patients treated with the product was approximately 10 in the control group.
The olefin (0.130 g, 0.298 mmol) was dissolved in hot ethanol (2.5 ml) and mixed with citric acid (0.058 g, 0.298 mmol), dissolved in hot ethanol (1.5 ml), then the reaction solution was compressed into a vacuum and a brown solid was left.
Other
The yield is 0.151 g (83%) Example 15; melting point 92-104 °C
The reaction mixture was mixed with 2N NaOH (10 ml) for processing. After separation of the phases, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The resulting raw product (720 mg) was recrystallized from methanol (20 ml). The desired olefin (B 16) was obtained in a crystal of 412 mg (62%) with a melting point of - 168 °C.
Other
The citrate precipitation was analogous to example 15.
3-Methylindol (Ind-10, 262 mg, 2 mmol) was dissolved in dichloromethane (20 ml) together with Ket-10 (434 mg, 2 mmol) and recycled with trifluoromethanesulphonic acid (0.2 ml, 2.3 mmol). The solution was stirred for 3 days at RT. - For processing, the reaction mixture was mixed with 2N NaOH (10 ml). After separation of the phases, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The resulting raw product (720 mg) was recycled with methanol (20 ml). (±) N-N-Dimethyl-N4-methyl-crystalline[13-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H-H
(±) N,N-dimethyl-N-[4-(methyl-1H-indol-2-yl) 1-phenylcyclohex-3-enyl]amine (550 mg, 1.66 mmol) was dissolved in HBr/iron vinegar (33% HBr, 20 ml) and then administered to the RT Sn powder (1 g, 8.5 mmol) for 30 min. After completion of the addition, the reaction mixture was stirred for another 30 min. - For processing, the mixture was reduced to dry by the rotary evaporator. The remaining residue was reduced to basic by the addition of 2 N NaOH (20 ml). The resulting mixture was extracyclically combined with ethyl acetate (43% HBr, 20 ml). The organic residue was reduced to neutral by extracyclically mixing 20 ml of ethyl acetate (44% NSO). The organic residue was reduced to 204 °C by mixing N2-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl (52 mg, 20 ml) and obtained by dissolving 22 N2-methyl-methyl-phenyl-methanol (60 mg, 120 ml) at a temperature of 204 °C.
The methanol parent solution was reduced, and NMR studies of the remaining residue (305 mg, 55% yield) showed that it was predominantly the second, more polar diastereoisomer.
3-Methylindol (Ind-10, 262 mg, 2 mmol) was mixed with Ket-10 (434 mg, 2 mmol) with HBr/iron vinegar (33% HBr, 20 ml) and stirred at RT for 22 h*). The solution was then given to the solution in RT Sn powder (0.5 g) in portions for 30 min. After completion of addition, the mixture was stirred for another 30 min. - The reaction mixture was processed at the rotary evaporator to dry oil. The solution was made with 2N NaOH. The aqueous mixture was dissolved with ethyl acetate (20 mg). The insoluble components of the mixture were separated by a deep-frying process. The filter was further separated with 204 mg (34 ml) of ethyl acetate (34 ml) by a separate method. The solution was dissolved in a solid at 110 °C. The product was dissolved in a mixture of ethyl methylated with methylated methylated methylated (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Ethyl methylated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated) (Elated)
N,N-dimethyl-[4-(3-methyl-1H-indol-2-yl)-1-phenylcyclohexyl]amine (unpolar isomer, 222 mg, 0.68 mmol) was dissolved in 2-propanol (50 ml) at boiling temperature and mixed with citric acid (192 mg, 1 mmol), dissolved in hot isopropanol (2 ml). The solution was cooled to 5 °C (refrigerator) and left to stand for 12 h. The precipitate was separated by a frying process. Example 17 was obtained at a yield of 283 mg (99 %, melting point: 244 - 252 °C).
N,N-Dimethyl-[4-(3-methyl-1H-indol-2-yl)-1-phenylcyclohexyl]amine (polar isomer 290 mg, 0.87 mmol) was dissolved in isopropanol (150 ml) at boiling temperature and mixed with citric acid (254 mg, 1.32 mmol, dissolved in 5 ml of isopropanol). The reaction mixture was stirred for 10 min. After cooling to RT, the reaction mixture was agitated to approximately 80 ml. The solution was stored for 1 h at room temperature and then overnight at 5 °C. The resulting solid was sucked and discarded. The mother's eye was narrowed to dry. The backing was soaked with water (7 ml) and removed for 30 min. The soluble solid was removed at 18 °C (49 °C) and successfully cooled to a melting point of 229 mg (436 °C).
Ketone (Ket-10, 898 mg, 4.13 mmol) and indole (Ind-1, 1.20 g, 4.13 mmol) were dissolved in dichloromethane (50 ml) in abs with argon. Then trifluoromethane sulphonic acid (480 μL/ 5.5 mmol) was quickly added and stirred overnight at RT. The solution was made alkaline with 1 N NaOH and stirred for 15 min at RT. The phases were separated. The aqueous phase was extracted with dichloromethane (three times 20 ml). The organic phase was dried over Na2SO4 and i.e. vacuumed. The residue was cleaned by flash chromatography with CHCl3/MeOH (9:1)
Other
The yield is 1.10 g (55%).
Other
The mean value of the dose of the active substance is 1.63 (2 H, m); 2.09 (6 H, m); 2.48 (2 H, m); 2.64 (2 H, m); 3.00 (2 H, m); 3.69 (2 H, m); 6.24 (1 H, s); 6.97 (2 H, m); 7.20-7.47 (5 H, m); 7.68 (4 H, m); 10.66 (1 H, s).
The olefin (1.10 g, 2.24 mmol) was dissolved in HBr/iron vinegar (55 ml). Tin (2.60 g, 2.24 mmol) was added within 30 min and stirred at RT for 4 h. The solution was mixed with ethanol and stirred at RT overnight. The solution was then pressed in a vacuum, mixed with 5N NaOH and extracted with dichloromethane (three times 20 ml). The organic phase was dried over Na2SO4 and pressed in a vacuum. The residue was cleaned by flash chromatography EE/EtOH (1:2 → MeOH + 1 % TEA).
Other
| 177 mg (16 %) (Mischfraktion) | |
| 432 mg (39 %) polares Diastereomer |
The polar diastereomer (80 mg, 0.162 mmol) was dissolved in hot ethanol (5 ml), citric acid (30 mg, 0.162 mmol) was dissolved in hot ethanol (1 ml) and added, the solution was cooled, compressed in half, the precipitation was vacuumed and vacuum dried.
Other
The following information shall be provided in the form of a summary of the results of the analysis:
Other
The melting point is 108 to 110 °C.
Other
The mean value of the active substance is 1.46 (2 H, m); 1.74 (2 H, m); 1.89 (2 H, m); 2.37 (6 H, s); 2.45-2.65 (4 H, m); 2.97 (2 H, m); 3.75 (2 H, t); 6.89 (2 H, m); 7.13 (1 H, d); 7.46 (6 H, m); 7.64 (4 H, s); 10.44 (1 H, s), citrate.
Ketone (Ket-10, 234 mg, 1.08 mmol) and indole (Ind-2, 219 mg, 1.08 mmol) were dissolved in abs dichloromethane (10 ml) under argon, rapidly transferred to trifluoromethane sulphonic acid (188 μL, 2.16 mmol) and stirred at RT for 16 h. Then alkaline with 1 N NaOH and stirred for 15 min at RT. The phases were separated. The aqueous phase was extracted with dichloromethane (three times 20 ml). The organic phase was dried over Na2SO4 and compressed i.C. The residue was combined by flash vacuum tomatography with CH/EA (1:1:11, EE/EEOH → 1:1), Ethanol (1:1, 1OH + 1%) T.OH. The reactions were purified with 1 N NaOH and compressed over 86 ml (i.e.
The olefin (436 mg/1.08 mmol) was dissolved in HBr/iron vinegar (25 ml), added tin (1.25 g, 1.08 mmol) within 30 min and stirred at RT for 4 h. The solution was added ethanol and stirred at RT overnight. The solution was then dried in the i.Vac. The residue was added 5N NaOH and extracted with dichloromethane (three times 20 ml). The organic phase was dried using Na2SO4 and i.Vac.
Other
| 185 mg (42 %) unpolares Diastereomer | |
| 250 mg (57 %) polares Diastereomer |
The unpolar diastereomer (76 mg, 0.188 mmol) was dissolved in hot ethanol (5 ml), citric acid (36 mg/0.188 mmol) was dissolved in hot ethanol (1 ml) and added, the solution was cooled and etherised, the precipitation was sucked out and dried.
Other
The following table shows the results of the analysis:
Other
The melting point is 245-247 °C
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.77 (5 H, m); 2.35 (6 H, s); 2.65-2.80 (6 H, m); 2.97 (2 H, m); 3.18 (2 H, m); 6.96 (2 H, m); 7.30-7.58 (6 H, m); 7.89 (1 H, s); 10.91 (1 H, s), citrate.
The polar diastereomer (63 mg/ 0.155 mmol) obtained in example 20 was dissolved in hot ethanol (5 ml)/dioxane (5 ml). Citric acid (30 mg/ 0.155 mmol) was dissolved in hot ethanol (1 ml) and added. The solution was cooled and etherised, with precipitation. The precipitation was vacuumed and vacuumed. Yield: 52 mg (e.g. 21.56%)
Other
The mean value of the dose of the active substance is 1.47 (2 H, m); 1.81 (5 H, m); 2.23 (2 H, m); 2.43 (6 H, s); 2.58-2.71 (4 H, m); 2.92 (1 H, t); 3.11 (2 H, m); 3.43 (2 H, m); 6.90 (2 H, m); 7.14 (1 H, m); 7.39 (1 H, d); 7.57 (3 H, m); 7.74 (2 H, m); 8.02 (1 H, s); 10.40 (1 H, s).
The ketone Ket-3 (606 mg, 2.62 mmol) and Ind-6 (410 mg, 2.62 mmol) were dissolved in dichloromethane (40 ml) and mixed with trifluoromethane sulphonic acid (0.256 ml, 432 mg, 2.88 mmol) and stirred at room temperature for 3 days. The reaction mixture formed a bright precipitate. The solution was mixed with water (10 ml) and 1N of baking soda (10 ml) and stirred for 1 h. The phases were separated. The aqueous phase was extracted with dichloromethane (40 ml). The organic phases were combined, washed with water (20 ml), dried and solidified. The residue was oil (950 mg) which was separated at chromatograph temperature [18]; 60 g of ethylene glycol (80 g/ml) was obtained from a single ethanol (3500 mg/ml) at a temperature of 120 °C. The residue was obtained from a 34-35% ethanol (318 g/ml) in a colourless solid.
The ketone Ket-10 (568 mg, 2.62 mmol) and the indol Ind-6 (410 mg, 2.62 mmol) were dissolved in a flask of dichloromethane (40 ml), washed with trifluoromethane sulphonic acid (0.256 ml, 432 mg, 2.88 mmol) and stirred at room temperature for 3 days. A bright precipitate formed in the reaction mixture. The solution was stirred with water (20 ml) and 1N of baking soda (15 ml) and stirred for 30 min. The phases were separated. The aqueous phase was extracted with dichloromethane (30 ml). The organic phases were combined, washed with water (20 ml), dried and pressed. The residual oil (983 mg) was obtained by chromatograph separation at 180 °C. [: 60 g of trichloroethane (120 mg/ 400 ml) ]: 1,24 g of trichloroethane (180 mg/ 800 ml) was obtained from a solution of 1,400 mg (120 mg/ 800 ml) of trichloroethane (180 °C) ]: 1,24 g of trichloroethane (180 mg/ 800 ml) in a solution of 1,16 mg (180 mg/ 800 ml) of trichloroethane (180 mg/ 800 ml) ]: 1,16 mg/ 800 g of trichloroethane (180 °C)
The ketone Ket-4 (395 mg, 2 mmol) was dissolved in dichloromethane (20 ml) together with Ind-7 (398 mg, 2 mmol) and then trifluoromethane sulphonic acid (0.2 ml, 338 mg, 2.25 mmol) was added, turning the solution dark. The solution was stirred for 3 days at RT. The reaction mixture was mixed with 1 N NaOH (10 ml) and stirred for 10 minutes to make the reaction. The colour changed from dark red to light brown. After phase separation, the aqueous phase was extracted with dichloromethane (2 10 ml). The combined organic phases were dried, filtered and pressed in vacuum with sodium triphate. 74 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg; 1 mg;
The ketone ket-10 (599 mg, 2.76 mmol) was dissolved in dichloromethane (20 ml) together with Ind-7 (550 mg, 2.76 mmol) and the colour changed from dark red to light brown. The aqueous phase was extracted with dichloromethane (2 × 10 ml) after P-phase separation. The combined organic phases were extracted with sodium caesium sulfate, filmetrilated and eosinophilized; the vacuum gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous gaseous g
The clear green solution was stirred for 20 h at RT, then reduced to about 0.5 ml and then stirred with diethyl ether (5 ml) until crystallization. Sample 25 was obtained after extraction at a yield of 56% (124 mg) with an indeterminate melting point. The ketone-10 which was already present in the preliminary stage could not be separated from the citrate-10 ketone.
5-Fluor-3-methylindol (Ind-8) (596 mg, 4 mmol) was dissolved with Ket-3 (932 mg, 4 mmol) in dichloromethane (20 ml) and mixed with trifluoromethane sulphonic acid (0.4 ml, 4.6 mmol). The solution was stirred at RT for 22 h. - For processing, the reaction mixture was stirred with 2N NaOH (10 ml). The mixture was stirred for another 20 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over MgSO4 and then compressed. The resulting raw product (1.50 g) was heated in ethanol (10 ml). The solution was clear-cooled and left at 5 °C.The resulting crystalline broth was added with further EtOH (10 ml) and separated by a deep frying. (±)-2-(4-(Dimethylamino)-4-benzylcyclohex-1-enyl)-3-methyl-5-fluor-1H-indol was obtained in a yield of 558 mg (38%, SMP: 62-65 °C) in crystalline form.
Other
(±) 2-(4-(Dimethylamino) -4-benzylcyclohex-1-enyl) -3-methyl-5-fluor-1H-indol (150 mg, 0.41 mmol) was dissolved in methanol (10 ml) under light heating and mixed with citric acid (80 mg, 0.42 mmol) dissolved in methanol (2 ml). The solvent was then compressed in the rotary evaporator. The resulting residue was evaporated with H2O (approximately 5 ml).The resulting product obtained is a yield of 161 mg (70%) in the case of sample 26.
5-Fluor-3-methylindol (Ind-8) (596 mg, 4 mmol) was dissolved in dichloromethane (30 ml) together with ketone Ket-4 (788 mg, 4 mmol) and replaced with trifluoromethanesulphonic acid (400 μl, 4.6 mmol). The solution was stirred at RT for 24 h. For processing, the reaction mixture was stirred with 2N NaOH (30 ml) and replaced with RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 15 ml). The combined organic extracts were obtained by Na2SO4 and then dried. The resulting raw product (1,4 g) was obtained by accrom chromatography [60 gels]; ethyl acetate (± 50 ml) (500 g/l) (dimethylamino-2-methylbutyl-1-butyl) was obtained as a pure white solid (160 mg-14-dimethyl-1-butyl) in a solution of 160 mg (160 g/l) (14-dimethyl-1-butyl) 3-methyl butyl)
Other
(±)-2-(4-(Dimethylamino)-4-butylcyclohex-1-enyl) 3-methyl-5-fluor-1H-indol (160 mg, 0.49 mmol) was dissolved in isopropanol (10 ml) at boiling temperature and mixed with citric acid (94 mg, 0.49 mmol) dissolved in hot isopropanol (2 ml). The solution was cooled to 5 °C and kept in the refrigerator for 16 h. As no solid was missing, isopropanol was distilled on the rotary evaporator.
5-Fluor-3-methylindol (Ind-8) (498 mg, 2 mmol) was dissolved in dichloromethane (20 ml) together with ketone Ket-10 (434 mg, 2 mmol) and replaced with trifluoromethanesulphonic acid (0.2 ml, 2.3 mmol). The solution was stirred at RT for 22 h. - For processing, the reaction mixture was stirred with 2N NaOH (10 ml). The mixture was stirred for another 20 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were obtained by means of MgSO4 and then ecyclically dried. The resulting crude product (710 mg) was obtained in a crystalline form in a dissolving ethanol (18 mg). The solution was cleared and left at 5 °C. The solution was removed at 14 °C. The mixture was removed in a 39 mg (14--59 mg) nitrile-methylphenyl (F-methyl-1-fluorphenol) residue (F-methyl-39-59 mg) in a 17 mg (175 °C) solution.
(±)-2-(4-(Dimethylamino) -4-phenylcyclohex-1-enyl) -3-methyl-5-fluor-1H-indol (150 mg, 0.43 mmol) was dissolved in isopropanol (10 ml) at boiling temperature and mixed with citric acid (100 mg, 0.52 mmol) dissolved in hot isopropanol (5 ml). The solvent volume was reduced to approximately 6 ml, the solution was then cooled to 5 °C (refrigerated) and 12 h was discontinued. The precipitate was separated by a fresh precipitate and then dried. 28 samples were obtained at a yield of 151 (79%, melting point: 88-93 mg) °C.
5-Methoxycatol (Ind-9) (644 mg, 4 mmol) was dissolved in dichloromethane (40 ml) together with ketone Ket-10 (868 mg, 4 mmol) and mixed with trifluoromethanesulphonic acid (0.4 ml, 4.5 mmol). The solution was stirred for 2.5 days at RT. - For processing, the reaction mixture was stirred with 2N NaOH (20 ml) and stirred for 60 min at RT. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried using MgSO4 and then compressed. The resulting raw product (1.2 g) was purified by accromatography [Kiesel gel 60 g (10 g); Cyclohexane/O 1 (100 ml) ].(±)-2-(4-dimethylamino) -4-phenylcyclohex-1-enyl) -3-methyl-5-methoxy-1H-indol was obtained at a yield of 400 mg (27%) as a solid (melting point 175 to 185 °C).
Other
(±)-2-(4-(Dimethylamino) -4-phenylcyclohex-1-enyl) -3-methyl-5-methoxy-1H-indol (150 mg, 0.41 mmol) was dissolved in isopropanol (15 ml) at boiling temperature and mixed with citric acid (80 mg, 0.42 mmol) dissolved in hot isopropanol (2 ml). After cooling the solution, precipitation occurred. To complete the precipitation, the solution was cooled to 5 °C (refrigerator) and left at this temperature for 17 h. The precipitation was separated from a refrigerant and then dried.
3-Methylindol (Ind-10, 524 mg, 4 mmol) was dissolved in dichloromethane (20 ml) together with ketone Ket-3 (932 mg, 4 mmol) and mixed with trifluoromethane sulphonic acid (0.4 ml, 4.6 mmol). The solution was stirred at RT for 22 h. - For processing, the reaction mixture was stirred with 2N NaOH (10 ml). The mixture was stirred for another 10 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over 510 mg SO4 and then ecyclically bound. The resulting raw product (1.28 g) was agitated with methanol (7 mg) which was removed at a temperature of 5 °C. The solid was removed at a viscous concentration of 3 mg (3-47 ml) of F-methyl-3-dimethylaminoxide (3-1%) obtained in a medium solution of approximately 510 mg (1-47 mg) of F-methyl-3-dimethylaminoxide.
(±) 2-(4-dimethylamino) -4-benzylcyclohex-1-enyl) -3-methyl-1H-indol (100 mg, 0.29 mmol) was dissolved in methanol (10 ml) under light heating and transferred to citric acid (58 mg, 0.3 mmol) dissolved in methanol (1 ml), then the solvent was compressed at the rotary evaporator. The resulting residue was rubbed with H2O (approximately 5 ml). A white solid was obtained by frying.
3-Methylindol (Ind-10, 524 mg, 4 mmol) was dissolved in dichloromethane (30 ml) together with ketone Ket-4 (788 mg, 4 mmol) and mixed with trifluoromethanesulphonic acid (0.4 ml, 4.6 mmol). The solution was stirred at RT for 22 h. - For processing, the reaction mixture was stirred with 2N NaOH (10 ml). The mixture was stirred for another 20 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over MgSO4 and then compressed. The resulting raw product (1.21 g) was sachromatically purified (on the basis of: L-ethylacetate) by a semi-steady solution. (±) (((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((
(±)-2-(4-(Dimethylamino) -4-butylcyclohex-1-enyl) -3-methyl-1H-indol (120 mg, 0.39 mmol) was dissolved in methanol (10 ml) under light heating and mixed with citric acid (80 mg, 0.42 mmol) dissolved in methanol (1 ml). As no precipitation occurred after cooling the solution (5 °C), the solvent was compressed in the rotary evaporator. The resulting residue was absorbed in 4 ml of hot isopropanol. After cooling, a sticky precipitation was produced which, when vacuum-dried, sticks to a glassy solid. The first sample was then cooled again when exposed to air, so it was obtained in a 105 mg (53%) citrate solution.
The ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ket
2-amino-3-iodopyridine (3108 mg, 14.13 mmol), 4-dimethylamino-4-phenyl-1-prop-1-ynyl) cyclohexanol (4000 mg, 15.54 mmol), lithium chloride (630 mg, 14.83 mmol) and sodium carbonate (4.49 g, 42.38 mmol) were combined in dimethylformamide (absolute, 60 ml) in an argon atmosphere. The catalyst ([Pdddppf) Cl2 × CH2Cl2], 1154 mg, 1.41 mmol) was then added. The red solution was heated for 5 minutes at 79 °C (temperature of bath); to complete the reaction, another 0.3 g of Aquino-2-iodopyridine (932 mg, 4.24 g, 0.24 mmol × 0.200 mmol) was removed from the water. The liquid was then separated into a vacuum-filter (a liquid containing 0.05 ml of R-O-diesel) and added to the water (a liquid containing approximately 20 mg of D-diesel) at a temperature of 20 °C. The remaining components were added to the water (a liquid containing approximately 0.0 g/mO) and filtered at a temperature of 1.77 °C. The water was then added to the water (a liquid containing approximately 0.0 g/mL) and filtered with water (a liquid containing approximately 0.0 ml of R-diesel) and dissolubleated at a temperature of 20 °C. The remaining components were added to the water (a liquid) and filtered at a temperature of 1.77 °C. The remaining parts were added to the water (a liquid) and filtered at a temperature of 20 °C.
4-Dimethylamino-1- ((3-methyl-1H-pyrrolo[2,3-b]pyridin-2-yl) -4-phenylcyclohexanol (900 mg, 2.58 mmol) was dissolved in methanosulfonic acid (20 ml), added P4O10 (about 1 g), and stirred the lightly coloured (light brown) solution for 3 h at 77 °C (oil bath temperature). The reaction mixture was based on 5M sodium hydroxide solution. Then dichloromethane (30 ml) was added and stirred for 10 min. The phases were separated. The water phase was extracted with dichloromethane (3 × 35 ml) extracted. The combined organic phases were dissolved with natriyl triphosphate and then completely dissolved in a vacuum containing 94 ± 1 mg of dichloromethyl methylphenyl (24-dimethyl-3-phenyl) -4-methyl-3-methyl, 94 mmol; 43 ± 1 ml).
(±) -N,N-dimethyl-N-[4-(3-methyl-1H-pyrrolo[2,3-b]pyridin-2-yl) --1-phenylcyclohex-3-enyl]amine (43 mg, 0.13 mmol) was dissolved in ethanol (10 ml). The dark solution was mixed with citric acid (27 mg, 0.14 mmol). It was stirred at boiling temperature for 1 h. The reaction mixture was cooled to room temperature and reduced to about 3 ml in a vacuum. The plunger was stored at room temperature and 0 °C. The solution was coated with about 5 diethyl ether and left to stand at room temperature for 3 days. It was a solid. The remaining solution was discarded and dried. The solid was vacuumed to about 30 ml. The target compound was obtained by:
Other
The mean time between the onset and the end of the treatment is approximately 1 hour NMR (400 MHz, RT, CD3OD) δ ppm: 2.08 (s, br, 1 ), 2.19 (s, 3H), 2.46 (s, br, 1H), 2.72 (s, 6H), 2.79 (dd, 4H), 2.60-2.85 (including, br, another 2 H) 2.97 (d, br, 1H), 3.68 (d, br, 1H), 6.14 (s, 1H), 7.01 (m, 1H), 7.40-7.60 (m, 2H), 7.73 (d, 2H), 7.84 (dd, 1H), 8.08 (s, br, 1H).
Ketone Ket-3 (693 mg, 3 mmol) and Ind-11 (472 mg, 3.0 mmol) were dissolved in 40 ml of dichloromethane, added to trifluoromethane sulphonic acid (0.293 ml, 495 mg, 3.3 mmol) and stirred at room temperature for 67 h. Since the transposition was not complete, trifluoromethane sulphonic acid (0.586 ml, 990 mg, 6.6 mmol) was added again and stirred at room temperature for 5 h. The solution was stirred with water (20 ml) and 1 N-natron (15 ml) and stirred for 30 min. The phases were separated. The aqueous phase was extra-dried with dichloromethane (30 ml). The organic phases were combined with water (20 ml), dried, washed and soaked with sodium sulphate.The residue was a brown oil (1.17 g) which was chromatographically separated [silica gel 60 (70 g); ethylacetate (500 ml), ethylacetate/ methanol 4:1 (400 ml) ]. (±) 2-(4-(dimethylamino) -4-benzylcyclohex-1-enyle) -3-cyclopropyl-1H-indol was obtained as a colourless solid (100 mg). A resulting mixed fraction of ketone-3 and product was further chromatographically separated ketmally [silica gel 60 (70 g); ethylacetate (500 ml), ethylacetate/ methanol 4:1 (300 ml) ]. In addition to the product (102 mg), another mixed fraction (490 mg) was obtained chromatographically separated again [60 mg); a resulting mixed fraction of ketone-3 and product was further chromatographically separated [silica gel 60 (70 g); ethylacetate: 1 mg (800 ml) ].The mixture (286 mg) was dissolved in ethyl acetate (30 ml), mixed with water (30 ml) and 1N hydrochloric acid (5 ml) and stirred at room temperature for 1 h. A colourless solid formed between the phases was separated by filtration, washed with water (2 × 10 ml) and ethyl acetate (2 × 10 ml). The hydrochloride sample 33 (221 mg, ) was obtained with a melting point of 222-224 °C. Total yield: 39%.
The ketone Ket-4 (592 mg, 3 mmol) and Ind-11 (472 mg, 3.0 mmol) were dissolved in 40 ml of dichloromethane, added to trifluoromethane sulphonic acid (0.293 ml, 495 mg, 3.3 mmol) and stirred at room temperature for 67 h. Since the transposition was not complete, trifluoromethane sulphonic acid (0.586 ml, 990 mg, 6.6 mmol) was added again and stirred at room temperature for 5 h. The solution was reconstituted with water (20 ml) and 1 N of natron oil (15 ml) and stirred for 30 min. The phases were separated. The aqueous phase was reconstituted with dichloromethane (30 mL) extract. The organic phase was reconstituted with water (20 mL) and extracted with nitric acid (5 mL) and exchanged with water. The sample was reconstituted with methanol (34 mg, 34 mL) and ethyl methanol (34 mL) (300 mL) (300 mL) (260 mL) (300 mL) (300 mL) (300 mL) (300 mL)), and was mixed with ethyl methanol (334 mL) (260 mL) (300 mL) (300 mL) (300 mL) (300 mL)), and ethyl ethanol (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL)), and 34 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (300 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3 mL) (3
Variant 1: Ketone Ket-10 (652 mg, 3.0 mmol) and Indol Ind-11 (472 mg, 3 mmol) were dissolved in 40 ml of dichloromethane, mixed with trifluoromethane sulphonic acid (0.293 ml, 495 mg, 3.3 mmol) and stirred at room temperature for 4 days. No turnover was detectable. The solution was mixed with water (20 ml) and 1N of baking soda (15 ml) and stirred for 30 min. The phases were separated. The aqueous phase was extracted with dichloromethane (20 ml). The organic phases were combined, washed with water (20 ml), dried with sodium sulphate and sealed. The residue was a brine oil (1.1 g), which was dissolved in 120 ml (40 ml) of dichloromethane.The aqueous phase was extracted with dichloromethane (20 ml). The organic phases were combined, washed with water (20 ml), dried with sodium sulphate and compressed. The residue was a brown oil (593 mg) that was chromatographically [triple 60 g silica (50 g); chloromethane/methanol 40: 1 (600 ml), methanol/methanol 20: 1 (400 ml) ] separated. The residue was obtained as a solid by 35 percent dilution of a 60 mg solution at 180 °C (302-187 mg).
Variant 2: A solution of Ket-10 and Ind-11 in 1,2-dichloroethane (1.5 mmol, 20 ml) was mixed with trifluoromethane sulphonic acid (0.147 ml, 248 mg, 1.65 mmol) and heated at 70 °C for 8 h. Further trifluoromethane sulphonic acid (0.293 ml, 495 mg, 3.3 mmol) was added and stirred at room temperature for 24 h. The solution was mixed with water (10 ml) and 1 N of baking soda (10 ml) and stirred for 30 min. The phases were separated. The aqueous phase was extracted with chloromethanate (30 ml). The organic ones were mixed, washed with water (20 ml), dried with sodium trichloroethane and pressed. One of the residues was: 60 mg (572 mg) of chloromethanol, a solid of 40 g/m3 (450 ml) of chloromethanol (for example, 1 mg) of chloromethanol (450 mg/m3); the remaining was dissolved in 40 mg (450 mg) of chloromethanol.
3-Cyclohexylmethyl-1H-indol (Ind-12, 640 mg, 3 mmol) was dissolved with ketone Ket-3 (694 mg, 3 mmol) in dichloromethane (40 ml) and then dried with trifluoromethane sulphonic acid (0.396 ml, 4.51 mmol). The solution was stirred at room temperature for 90 h. For processing, the reaction solution was stirred with 5N NaOH (10 ml). The mixture was stirred for another 10 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The dried raw product (1.34 g) was dissolved in diethyl ether oil (30 ml) and dissolved in water at room temperature (2.5 ml). The solution was dissolved at room temperature (20 °C) and obtained as a solution containing 55 mg of diethyl ether (52-61%).
3-Benzyl-1H-indol (Ind-108) (622 mg, 3 mmol) was dissolved in dichloromethane (40 ml) with ketone Ket-3 (694 mg, 3 mmol) and added to trifluoromethane sulphonic acid (0.396 ml, 4.51 mmol). The solution was stirred at room temperature for 81 h. For preparation, the reaction solution was stirred with 5N NaOH (10 ml). The mixture was stirred for another 10 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic extracts were dried over Na2SO4 and then evaporated. The resulting crude product (1.30 g oil) was dissolved in water (550 ml) at room temperature. 1 ml (1024 ml) of NCl was added to water. The solution was added to water at room temperature (25 mg, 37 mg, 8 mg, 8 ml) and some diethyl ether was added.
Ind-12 (640 mg, 3 mmol) was dissolved in ketone Ket-4 (592 mg, 3 mmol) in dichloromethane (40 ml) and trifluoromethane sulphonic acid (0.396 ml, 4.51 mmol) was added. The solution was stirred at room temperature for 90 h. The reaction solution was stirred with 5N NaOH (10 ml) for processing. The mixture was stirred for another 10 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The resulting raw product (1.33 g, brownish point) was melted into diethyl alcohol (30 ml) at room temperature.
3-Benzyl-1H-indol (Ind-108, 622 mg, 3 mmol) was dissolved in dichloromethane (40 ml) with ketone Ket-4 (592 mg, 3 mmol) and added to trifluoromethane sulphonic acid (0.396 ml, 4.51 mmol). The solution was stirred at room temperature for 81 h. The reaction solution was stirred with 5N NaOH (10 ml) for processing. The mixture was stirred for another 10 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic extracts were dried over Na2SO4 and then evaporated. The resulting raw product (1,17 g, oil) was obtained by column cracking [80 g: 60 g: 60 g: 5 g: ethanol/cethylene (100 ml: 397-115 °C) ]; the purified solid was obtained at 40 °C. Example: 39 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: 40 mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg: mg
3-Cyclohexylmethyl-1H-indol (Ind-12) (640 mg, 3 mmol) was dissolved in dichloromethane (40 ml) with ketone Ket-10 (652 mg, 3 mmol) and then dried with trifluoromethane sulphonic acid (0.396 ml, 4.51 mmol). The solution was stirred at room temperature for 90 h. For processing, the reaction solution was stirred with 5N NaOH (10 ml). The mixture was stirred for another 10 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic extracts were dried over Na2SO4 and then dried tightly. The dissolved raw product (1.34 g) was dissolved at room temperature (5 °C). The solution was dissolved at room temperature (2,5 ml) and some water was added to the solution. The solution was dissolved at room temperature (2,5 mL) and some water was added to the solution (2,5 mL) The sample was diethyl ether (2,5 mL) and some water was added at room temperature (2,5 mL) and some water was added to the solution (2,5 mL) and some water was added to the solution (2,5 mL) The sample was dissolved at room temperature (2,5 mL) and some water was added to the solution (2,5 mL) The solution was dissolved at room temperature (2,5 mL (2,5 mL) and some water was added to the solution (2,5 mL) The solution (2,5 mL was added to the solution (2 mL) was dissolved at room temperature (2,5 mL.
3-Benzyl-1H-indol (Ind-108, 622 mg, 3 mmol) was dissolved in dichloromethane (40 ml) with ketone ketone Ket-10 (652 mg, 3 mmol) and mixed with trifluoromethane sulphonic acid (0.396 ml, 4.51 mmol). The solution was stirred at room temperature for 81 h. For processing, the reaction solution was stirred with 5N NaOH (10 ml). The mixture was stirred for another 10 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic extracts were dried over Na2SO4 and then dried. The resulting raw product (1.24 g) was diluted in Toluol (5 ml).
3-Propyl-1H-indol (Ind-13, 797 mg, 5.0 mmol) was dissolved in dichloromethane (60 ml) with ketone Ket-3 (1157 mg, 5.0 mmol) and replaced with trifluoromethane sulphonic acid (0.485 ml, 5.52 mmol). The solution was stirred at room temperature for 88 h. The reaction solution was extracted with water (3 × 40 ml) for processing. The organic phase was then washed with 1 N NaOH solution (40 ml), dried over Na2SO4 and then compressed. The resulting raw product (1.68 mmol) was chromatographically cleaned [metatographically green [kiesel gel 60 (140); ethyl acetate/ethyl alcohol: 20 ml 1260 mg]. 1031% (55 mg) (temperature: 104 °C) was obtained.
3-Propyl-1H-indol (Ind-13) (797 mg, 5.0 mmol) was dissolved in dichloromethane (60 ml) with ketone Ket-4 (987 mg, 5.0 mmol) and added to trifluoromethane sulphonic acid (0.485 ml, 5.52 mmol). The solution was stirred at room temperature for 88 h. The reaction solution was extracted with water (3 × 40 ml) for processing. The organic phase was washed with 1 N NaOH solution (40 ml), dried over Na2SO4 and then pressurised. The resulting crude product (1.44 g of brown oil) was chromatographically treated [silica (140 g), ethyl acetate/methanol 10 1 (550 ml), ethyl acetate/methanol 5 100 ml), ethyl acetate 1 (68 ml), ethyl acetate 2 (1200 mg) ] (480 °C) Example: 43-48 °C).
3-Propyl-1H-indol (Ind-13) (1035 mg, 6.50 mmol) was dissolved in dichloromethane (80 ml) together with ketone ketone Ket-10 (1413 mg, 6.50 mmol) and replaced with trifluoromethane sulphonic acid (0.630 ml, 7.17 mmol). The solution was stirred at room temperature for 88 h. The reaction solution was extracted with water (3 × 40 ml) for processing. The organic phase was then washed with 1 N NaOH solution (40 ml), dried over Na2SO4 and then compressed. The remaining raw product (1.90 g of brown solid) was chromatographically purified [silicon gel (140 g); triethylmethanol/methanol (150 g); trichloroethane (550 ml): 1 100 mg/methanol) (680 °C) ]. Example: 44-168 g (temperature: 16 °C) were obtained.
Example 45: (±)-2-(4-dimethylamino)-4-benzylcyclohex-1-enyl) -3-(2-(pyridin-4-yl) ethyl) -1-H-indol 3-(2-pyridin-4-ylethyl) -1-H-indol (Ind-14, 667 mg, 3 mmol) was dissolved with ketone (Ket-3, 652 mg, 3 mmol) in dichloromethane (45 ml) and dissolved with trifluoromethane sulphonic acid (0.553 ml, 6.3 mmol). The solution was agitated for 67 h, with a brown oil film. For processing, the reaction solution was agitated with 1 N NaOH (10 ml) and THF 154 (10 750 ml). The mixture was agitated for a further 60 min. The post-treatment phase was completed with: Pethyl methanol (1,100 mg, 652 mg, 6 500 ml) (1,510 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml)), and the product was obtained as a white extract of ethylene oxide (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml)), and 31 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,517 g/ml) (1,52 g/ml) (1,52 g/ml) (1,52 g/ml) (1,52 g/ml) (1,52 g/ml
3-(2-pyridine-4-ylethyl) - 1H-indol (Ind-14, 667 mg, 3 mmol) was dissolved in dichloromethane (45 ml) together with the ketone (Ket-4, 592 mg, 3 mmol) and transferred to trifluoromethane sulphonic acid (0.553 ml, 6.3 mmol). The solution was stirred at RT for 67 h, with a brown oil being produced. The reaction solution was agitated with 1 N NaOH (10 ml) and THF (10 ml) for processing. The mixture was stirred for another 60 min. After separation of the phases, the aqueous phase (3 x 10 ml) was extracted with dichloromethane. The combined organic extracts were dried over Na2SO4 and then burned. The resulting product (1,24 g) was obtained by extracting a yellow ethanol gel (100 g/l) (1,60 g/l);The desired product 46 was obtained as a white solid (437 mg, 36%, 145-149 °C) in addition to a bisindol compound (121 mg, 274-282 °C). 1H NMR (400 MHz, CDCl3) δ ppm: 0.93 (t, J = 6.89, Hz, 3H), 1.16-1.60 (m, 6H), 1.63-1.87 (m, 2H), 1.92-2.06 (m, 1H), 2.06-2.51 (m, 9H), 2.95 (t, J = 7.82 Hz, 2H), 3.12 (t, 7.82 Hz, 7.82 Hz), 5.82 (m, 7.24), 7.02-7.53 (m, 7.20), J = 7.02, 1H (m, 7.53), 7.02-7.5 (m, 7.20).The number of hours of operation of the system is determined by the number of hours of operation of the system.
Other
The mean of the measurements of the two samples was calculated using the following formula:
3-(2-pyridine-4-ylethyl) - 1H-indol (Ind-14, 667 mg, 3 mmol) was dissolved in dichloromethane (45 ml) together with the ketone (Ket-10, 652 mg, 3 mmol) and mixed with trifluoromethane sulphonic acid (0.553 ml, 6.3 mmol). The solution was stirred for 64 h at RT, with a brown oil being discharged. The reaction solution was mixed with 1 N NaOH (10 ml) and THF (10 ml) for processing. The mixture was stirred for another 60 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 x 10 ml). The combined organic extracts were extracted from Na2SO4 and pressed approximately. The resulting product (1,34 g) was purified with ethylene glycol (100 g/l);The desired product 47 was obtained as a colourless solid (339 mg, 27%, SmP: 193-198 °C).
Other
The mean of the measurements performed was approximately 0.01% for the mean of the measurements performed in the previous two years.
Other
The mean of the measurements shall be calculated as follows:The number of times the number of people who are in the same group as the number of people who are in the same group is equal to the number of people who are in the same group.
Indol-16 (350 mg, 2 mmol) was dissolved in dichloromethane (40 ml) together with ketone Ket-3 (463 mg, 2 mmol) and replaced with trifluoromethane sulphonic acid (270 μl, 3 mmol). The solution was stirred at RT for 24 h. For processing, the reaction mixture was stirred with 2N NaOH (30 ml) and 20 min at RT. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 15 ml). The combined organic extracts were dried over NaSO24, and then compressed. The resulting raw product (780 mg) was obtained by column chromatography [silicon gel (100 g); 60 ml (500 ml) ].
Other
(±) 3-(2-(4-benzyl-4-dimethylamino) cyclohex-1-enyl) - 1H-indol-3-yl) propane-1-ol (50 mg, 0.13 mmol) was dissolved in isopropanol (4 ml) at boiling temperature and mixed with citric acid (25 mg, 0.13 mmol) dissolved in hot isopropanol (1 ml). The solution was cooled to 5 °C in the refrigerator and left for 16 h. The resulting white precipitate was separated by a frying process. 48 samples were obtained at a yield of 50 mg (67%, melting point 95-98 °C).
Indol-16 (350 mg, 2 mmol) was dissolved in ketone Ket-4 (395 mg, 2 mmol) in dichloromethane (40 ml) and replaced with trifluoromethane sulphonic acid (270 μl, 3 mmol). The solution was stirred at RT for 24 h. For processing, the reaction mixture was stirred with 2N NaOH (30 ml) and 20 min at RT. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 15 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The resulting raw product (710 mg) was obtained by column chromatography [silicon gel (50 g); 60 g; melamine (500 ml) ] (± 3OH-OH-cyclo-32-dimethyl-4-dimethyl-4-dimethyl-4-methyl-4-methyl-4-methyl-4-methyl) in a 34-14-mg solution of 34-methyl-1-butyl-4-butyl-1-4-methyl-1) obtained as a purified solid product.
Other
The solid was dissolved in isopropanol (4 ml) at boiling point and mixed with citric acid (187 mg, 0.97 mmol), dissolved in hot isopropanol (2 ml), the solution was cooled to 5 °C (refrigerator) and left for 16 h. The isopropanol was distilled in the rotary evaporator to obtain Example 49 at an yield of 531 mg (100 %, melting point: 50-54 °C).
Ketone (Ket-10, 461 mg, 2.12 mmol) and indole (Ind-18, 615 mg, 2.12 mmol) were dissolved in dichloromethane (20 ml) in abs with argon. Then trifluoromethane sulphonic acid (230 μL, 2.64 mmol) was added quickly and stirred for 24 h at RT. The approach was made with 1 N NaOH base and stirred for 15 min at RT. The phases were separated, the aqueous phase was extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and vacuum-sealed. The residue was cleaned by flash chromatography with CH:13/OH (9→4→1:1:1).
Other
The yield is 560 mg (54%).
Indol (Ind-19, 668 mg, 2.39 mmol) and ketone (Ket-3, 553 mg, 2.39 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.64 ml, 7.2 mmol). The solution was stirred for 72 h at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (Na2SO4) and pressing the solution i.e. vacuum.
Other
The yield is 395 mg (52; 33%) of the porous solid.
Other
The mean value of the dose of the active substance is 1.23 (2 H, m); 2.06 (2 H, m); 2.41 (6 H, bs); 3.22 (2 H, t); 3.33 (2 H, s); 4.43 (2 H, t); 5.58 (1 H, s); 6.84 (1 H, m); 7.08 (3 H, m); 7.29 (6 H, m); 7.40 (1 H, d); 7.56 (1 H, d); 7.86 (1 H, s); 10.92 (1 H, s).
Indol (Ind-19, 977 mg, 3.5 mmol) and ketone (Ket-4; 690 mg, 3.5 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.93 ml, 10.5 mmol). The solution was stirred at RT for 48 h, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, combining the organic phases with washed water, dried (NaSO24) and compressing the solution i.e. vacuum. The resulting residue was cleared by flash chromatography with EE/OH (1:4) 5 mg: 223 porous solids (3% porous solids),
Other
The mean value of the 1H-NMR (DMSO-d6) is 0.88 (3 H, t); 1.23 (10 H, m); 2.11 (3 H, bs); 2.22 (6 H, bs); 3.22 (2 H, t); 4.43 (2 H, t); 5.62 (1 H, s); 6.86 (1 H, m); 7.20 (4 H, m); 7.41 (1 H, d); 7.61 (1 H, d); 7.86 (1 H, s); 10.83 (1 H, s).
Indol (Ind-19, 600 mg, 2.14 mmol) and ketone (Ket-10, 466 mg, 2.14 mmol) were dissolved in abs. di-chloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.57 ml, 6.4 mmol). The solution was stirred for 72 h at RT, leaving a dark brown oil. After adding 1N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, the phases were separated, the aqueous phase ex-tracted twice with CH2Cl2, the combined organic phases with washed, dried water (Na2O4) and the solution was compressed i.v.
Other
The mean value of the dose of the active substance is 1.61 (2 H, m); 1.91 (2 H, m); 2.08 (6 H, bs); 3.13 (2 H, t); 4.31 (2 H, t); 5.85 (1 H, s); 6.82 (1 H, m); 7.20 (9 H, m); 7.64 (1 H, m); 7.85 (1 H, s); 10.79 (1 H, s).
Indol (Ind-20, 739 mg, 3.00 mmol) and ketone (Ket-3, 694 mg, 3.0 mmol) were dissolved in RT in abs CH2Cl2 (30 ml) and rapidly mixed with trifluoromethanesulphonic acid (1.35 g, 0.80 ml, 9.0 mmol). Then a black oil fell out. The mixture was stirred 2 d at RT. 1 N NaOH (30 ml) was added and the mixture stirred for 20 min. The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (2 x 30 ml). The combined organic extraction phases were washed with water (15 ml), dried with Na2SO4, filtered with dry and vacuum. By flash chromatography, the product was pressed with 50 g/l CH2OH/L ammonium chloride and e.g. 1 N-Cl2O2 (1:1), and the second product was obtained by vacuum extraction with Na2SO4 (1:1), and the second product was vacuum-washed with Na2SO4 (1:1), and vacuum-washed with e.g.
Other
The following table shows the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.37 (2 H, m); 1.49 (4 H, m); 1.95 (2 H, m); 2.31 (6 H, s); 2.41 (8 H, m); 2.80 (4 H, m); 5.91 (1 H, s); 6.83 (1 H, m); 7.20 (7 H, m); 10.73 (1 H, s).
The mixture was stirred 3 days at RT. 1N NaOH (50 ml) was added and the mixture stirred for 20 min. The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (2 x 50 ml). The combined organic phases were washed with water (20 ml), dried with Na2SO4, filtered dry and vacuumed. By flash chromatography, the product was vacuumed with 50 g/l CH2OH/N2SO2 and 1N NaOH/N2SO2 was obtained as a second product, with NaCl2 (Cl2OH) as the first and 2nd products, and vacuumed with NaCl2O2 (Cl2OH) as the second product.
Other
The yield is 1.08 g (56.59%) of colourless solids
Other
The mean value of the 1H-NMR (DMSO-d6) is 0.89 (3 H, t); 1.25-1.61 (10 H, m); 1.79 (2 H, m); 1.96 (2 H, m); 2.21 (6 H, s); 2.39 (8 H, m); 2.83 (2 H, m); 5.97 (1 H, s); 6.81 (1 H, m); 7.16 (2 H, m); 10.79 (1 H, s).
The mixture was stirred at RT for 24 h. 1 N NaOH (30 ml) was added and the mixture stirred for 20 min. The organic phase was separated and the aqueous phase extracted twice with CH2Cl2 (each 30 ml). The combined organic phases were washed with water (15 ml), dried with Na2SO4, filtered and vacuumed. By flash chromatography, the product was pressed with 50 ml of hydrochloric acid and 1 ml of ammonium chloride (9:1/N2SO2) and obtained as a second product, washed with Na2SO4 and vacuumed.
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as the following:
The ketone (Ket-10, 1.73 g, 8.0 mmol) and the indole (Ind-21, 1.82 g, 8.0 mmol) were dissolved in dichloromethane (100 ml). Then the trifluoromethane sulphonic acid was added in portions (total 3.12 ml, 36 mmol within 3 days). For processing, the solution was mixed with 2N NaOH (150 ml) and stirred at room temperature for 20 min. The organic phase was separated and the aqueous phase was extracted with dichloromethane (2 x 2.5 ml). The combined organic phases were dried over Na2SO4 and vacuum-pressed. The residue was cleaned with methanol by flash chromatography.
Other
The following are the most commonly reported effects of the drug:
Indol (Ind-22, 750 mg, 3.25 mmol) and ketone (Ket-3, 752 mg, 3.25 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.87 ml, 9.8 mmol). The solution was stirred for 48 h at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (Na2SO4) and pressing the solution i.e. vacuum. The precipitated residue was cleaned by flash chromatography with EE/OH (1:4)
Other
The following is the list of active substances in the feed additive:
Other
The mean value of the dose of the active substance is 1.37 (1 H, m); 1.97 (3 H, m); 2.31 (6 H, bs); 2.72 (4 H, m); 3.24 (2 H, t); 4.56 (2 H, t); 6.86 (1 H, m); 7.22 (7 H, m); 7.62 (1 H, s); 8.00 (1 H, s); 10.91 (1 H, s).
Indol (Ind-22, 825 mg, 3.58 mmol) and ketone (Ket-4, 707 mg, 3.58 mmol) were dissolved in dichloromethane (25 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.96 ml, 10.8 mmol). The solution was stirred for 48 h at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring continued for 20 min, separating the phases, ex-tracting the aqueous phase twice with CH2Cl2, combining the organic phases with washed, dried water (Na2SO4) and compressing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with EE/OH (1:4)
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as the following: 1H-NMR (DMSO-d6): 0.89 (3 H, t); 1.33 (6 H, m); 1.77 (2 H, m); 1.99 (1 H, m); 2.28 (6 H, bs); 2.38 (2 H, m); 3.25 (2 H, t); 4.54 (2 H, t); 5.83 (1 H, s); 6.87 (1 H, m); 7.22 (2 H, m); 7.64 (1 H, s); 7.98 (1 H, s); 10.92 (1 H, s).
Indol (Ind-22, 600 mg, 2.6 mmol) and ketone (Ket-10, 565 mg, 2.6 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.7 ml, 7.8 mmol). The solution was stirred at RT for 20 h, leaving a dark brown oil. After adding 1N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, washing (Na2SO) and compressing the solution in a vacuum. The dried residue was cleaned by flash chromatography with EE/OH (1:4)
Other
The following is the list of active substances in the feed additive:
Other
The mean value of the dose of the active substance is 1.68 (1 H m); 2.10 (6 H, s); 2.39 (1 H, m); 2.62 (2 H, m); 3.20 (2 H, t); 4.47 (2 H, t); 6.06 (1 H, s); 6.81 (1 H, m); 7.16 (5 H, m); 7.46 (2 H, m); 7.66 (1 H, s); 7.95 (1 H, s); 10.82 (1 H, s).
Tryptamine (Ind-1, 2.43 g, 15.2 mmol) and ketone (Ket-4, 3.0 g, 15.2 mmol) were dissolved in methanol (90 ml) and stirred under argon for 25 h at room temperature. The reaction mixture was then narrowed. The residue was dissolved in 1,2-dichloroethane (150 ml) and rapidly stirred with trifluoroacetic acid (10.4 ml, 15.5 g, 136 mmol) and stirred for 3 days at room temperature. The brown solution was refrigerated with 1 N of sodium chloride (130 ml) and stirred for 20 min. The phases of the solution were separated. The aqueous phase was extracted with 1,2-dichloroethane (2 x 70 ml). The organic particles were washed (50 ml) with water and then added to the solution.The colourless crystals were sucked out and washed with methanol (60 ml) (1.28 g). This was pure nonpolar spiramine. The filtrate was compressed and the resulting brown solid was again mixed with methanol (50 ml) and stirred for 1 h in an ice bath. After sucking and washing with cold methanol (20 ml), 673 mg of the nonpolar spiramine could be obtained. The filtrate was compressed and the residue (2.4 g) chromatographically separated [silicon gel 60 g; methanol (500 ml),The resulting solid (332 mg) was a pure nonpolar product. The nonpolar spiroamine was obtained in a total yield of 44% (2.28 g) with a melting point of 180-182 °C. The polar spiroamine was obtained in a further fraction at a yield of 12% (622 mg) with a melting point of 93-96 °C.
3,3-dimethylbutyric acid (0.246 ml, 238 mg, 1.77 mmol) was dissolved in argon in abs. dichloromethane (5 ml) and transferred to room temperature with the newly produced unpolar spiroamine (200 mg, 0.59 mmol) dissolved in dichloromethane (15 ml) within 30 min. After a reaction time of 24 h, the yellow solution was mixed with water (10 ml) and 1 N of baking soda (5 ml) and stirred 1 time. The phases were separated. The aqueous phase was extracted with dichloromethane (20 ml). The combined phases were washed with water (20), dried and dried. This resulted in a colourless oil (322 mg) which was chromatographed at 60 °C. The oil was obtained from a mixture of ethyl methanol (450 ml) (1400 mg/mL) and isocyanate (440 mg/mL) (148 mg/mL) (150 °C); the oil was obtained from a mixture of ethylene oxide (450 mg/mL) (150 mg/mL) with a colour of ethylene oxide (150 mg/mL) (150 mg/mL)), which was obtained by pressing the oil at a temperature of 140 °C.
The newly produced olefin (82 mg, 0.187 mmol) was dissolved in methanol (20 ml) and added to 5 % (16 mg) of coal with palladium. The reaction mixture was hydrated at room temperature at 3 bar for 4.5 h. The implementation was complete. The catalyst was separated via cellite and the filtrate was narrowed. The solid residue (84 mg) was chromatographically separated [silica gel 60 (20 g); ethylacetate/methanol (4: 1.150 ml), methanol (300 ml). The polarised amide was obtained at a yield of 83% (68 mg).
The newly produced polar amide (47 mg, 0.107 mmol) was dissolved in ethanol (1 ml) and mixed with citric acid (23 mg, dissolved in ethanol (1 ml). As no crystallization occurred after 6 h, the mixture was slowly mixed with diethylether (15 ml) and stirred at room temperature 16. The solvent was decanted. The remaining colourless solid was wetly transferred to the delivery tube and dried. Citrate 62 was obtained at a yield of 69% (46 mg).
Ketone (Ket-10, 234 mg, 1.08 mmol) and indole (Ind-2, 219 mg, 1.08 mmol) were dissolved in abs dichloromethane (10 ml) under argon, rapidly transferred to trifluoromethane sulphonic acid (188 μL/ 2.16 mmol) and stirred at RT for 16 h. Then alkaline with 1 N NaOH and stirred for 15 min at RT. The phases were separated. The aqueous phase was extracted with dichloromethane (three times 20 ml). The organic phase was dried over Na2SO4 and bound i.C. The residue was fused by flash-phase Vak/EEA (1:1:11→EE/OH1:1), ET, (methhanol + 1OH) 1%, T.OH. The reactions were purified with 1 N Na2SO4 and bound i.C. The Vak was fused over 10 ml.
Other
The yield is 86 mg (63.19%)
The substance described in Example 62 (±) -N-(2-(2-(4-butyl-4-dimethylamino-cyclohex-1-enyl) -H-indol-3-yl) ethyl) -3,3-dimethylbutanamide is further specified in Example 64.
A solution of Ind-26 (1.60 g, 7.63 mmol) and Ket-10 (1.65 g, 7.63 mmol) in anhydrous dichloromethane (40 ml) was stirred at room temperature with trifluoromethane sulphonic acid (1.52 g 10.1 mmol) and stirred at room temperature for 16 h. The reaction solution was then stirred with 0.5 m sodium salt (10 ml) and stirred at room temperature for 2 h. The phases were separated and the aqueous phase was extracted with ethyl acetate (3 × 30 ml). The combined organic pings were dried with sodium sulphate and i. Vac.The combined organic phases were dried with sodium sulphate and compressed i.v.
Other
The residue (100 mg, 0.24 mmol) was mixed with DL-methionine (107 ml, 0.72 mmol) in dichloromethane (10 ml) with methanesulphonic acid (69 mg, 0.72 mmol) and stirred at room temperature for 2 h. After adding further methanesulphonic acid (69 mg, 0.72 mmol), the reaction mixture was stirred over the weekend, then mixed with 1 N of baking soda (30 ml) and extracted with dichloromethane (3 × 40 ml).
Other
The following is the list of substances that are considered to be toxic if they are used in the manufacture of the product:
Other
The test chemical is used to determine the concentration of the active substance in the test chemical.The test method is based on the following equations:
A solution of ket-2 (700 mg, 2.44 mmol) and 5-fluorotriptophol (Ind-4) (449 mg, 2.5 mmol) in anhydrous dichloromethane (25 ml) was refrigerated with trifluoromethane sulphonic acid (450 mg, 265 μL, 3 mmol) and stirred overnight at room temperature. For volume control, a sample (0.5 ml) was taken, washed with 0.5 N of baking soda and the organic phase was dried with sodium sulphate. Under refrigeration, trifluoromethane sulphonic acid (450 mg, 265 μL, 3 mmol) was added and the mixture was stirred over the weekend at room temperature. The reaction was then mixed with 0.5 ml of N (10 μL, 2 μL) of baking soda at room temperature and mixed with the organic phase (2 mg, 265 μL, 3 mmol) and dried with extracted sodium sulphate.
Other
The raw product was purified with methanol by flash chromatography (200 g, 20 × 5,7 cm).
Other
The following table shows the results of the analysis of the results of the analysis:
Other
The mean value of the measurements of the test chemical is calculated as the following:
A solution of ket-8 (486 mg, 2 mmol) and 5-fluorotriptophol (Ind-4) (358 mg, 2 mmol) in anhydrous dichloromethane (20 ml) was mixed with trifluoromethane sulphonic acid (399 mg, 232 μL, 2.66 mmol) at 5-10 °C and stirred overnight at room temperature. After adding 0.5 M sodium bromide (10 ml), the phases were separated and the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic phases were dried with sodium sulphate and i. i. compressed. The raw product (596 mg) was purified by flash chromatography (18 g, 20 × 1.5 cm) with ethyl acetate / cyclohexane (1:92:1) and 1 cm of triethylamine (1%) respectively.
Other
The yield is 140 mg (17%)The method of analysis is based on the following equation: the concentration of the active substance in the feed additive is calculated as the sum of the total feed additive and the total feed additive, expressed as a percentage of the feed additive, and the total feed additive and the total feed additive, expressed as a percentage of the feed additive and the total feed additive, expressed as a percentage of the feed additive and the total feed additive.The following are the main components of the test method:
The reaction mixture was hydrated at 40 °C and 3 bar for 4.5 h. The catalyst was separated via cellite and the filtrate was compressed. The solid residue was chromatographically separated [silica gel 60 (30 g); ethylacetate/methanol (20: 1.200 ml), ethylacetate/methanol (10: 1.200 ml), ethylacetate/methanol (4: 1.350 ml), methanol (200 ml). The unpolar diastereoisomer was obtained at a yield of 27 (77%) % with a melting point of 205-213 mg and the polar isomer at 55 mg (155-182 mg) with a melting point of 175 °C.
2- ((4-Benzyl-4- ((dimethylamino) cyclohexyl) -3-methyl-1H-indol-5-carbonitrile (unpolar diastereomer) (72 mg, 0.194 mmol) was dissolved at 60 °C in ethanol (9 ml) and added to an ethanol solution (2 ml) of citric acid (41 mg, 0.213 mmol). A precipitation immediately began. After a reaction time of 16 h at room temperature, the colourless citrate was separated by filtration and washed with ethanol (2 ml). 68 mg was obtained at a yield of 46% (50 mg) with a melting point of 249-255 °C
2- ((4-Benzyl-4- ((dimethylamino) cyclohexyl) 3-methyl-1H-indol-5-carbonitrile (polar diastereomer) (158 mg, 0.425 mmol) was dissolved at 60 °C in ethanol (7 ml) and replaced with an ethanol solution (2 ml) of citric acid (91 mg, 0.47 mmol). After a reaction time of 16 h at room temperature, the colourless citrate was separated by filtration and washed with ethanol (3 ml). Example 69 was obtained at a yield of 51 % (122 mg) with a melting point of 193-195 °C.
(±) 2- ((4-Butyl-4-dimethylaminocyclohex-1-enyl) 3-methyl-1H-indol-5-carbonitrile The ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ket
The reaction mixture was hydrated at 40 °C for 2 h at 3 bar. The conversion was complete. The catalyst was separated via cellite and the filtrate was narrowed. The solid residue (239 mg) was separated chromatographically [silica gel 60 g); ethylacetate/methanol (10 1, 200 ml); ethylacetate/methanol (4 1, 250 ml); methanol (400 ml). 2-Butyldimethylaminoxide-3-methyldimethylaminoxide-5-methyl-5-methyl-5-methyl-1 (H2O) was obtained from a 176-117 mg of polar diisomers (15-168 mg) in a melting point of 17 to 17 °C (117-180 ml) and a polar diisomer of 57 to 17 mg (16-166 ml).
2- ((butyl-4-dimethylaminocyclohexyl) 3-methyl-1H-indol-5-carbonitri (unpolar diastereoisomer) (30 mg, 0,089 mmol) was dissolved in ethanol (3 ml) at 60 °C and mixed with an ethanol solution (2 ml) of citric acid (19 mg, 0,098 mmol). After a reaction time of 20 h, the solution was reduced to 1 ml, mixed with diethyl ether (20 ml) and stirred for 15 min. The colourless citrate was separated by filtration and washed with diethyl ether (2 ml). Sample 70 was obtained at a yield of 45 % (21 mg).
2- ((butyl-4-dimethylaminocyclohexyl) 3-methyl-1H-indol-5-carbonitri (polar diastereoisomer) (144 mg, 0.426 mmol) was dissolved in ethanol (6 ml) at 60 °C and added to an ethanol solution (3 ml) of citric acid (90 mg, 0.47 mmol). After a reaction time of 18 h, the cloudy mixture was reduced to 1 ml, mixed with diethyl ether (20 ml) and stirred for 15 min. The colourless citrate was separated by filtration and washed with diethyl (3 ml). Sample 71 was obtained at a yield of 76 % (171 mg).
For example, 23 (200 mg, 0.562 mmol) was dissolved in methanol (30 ml) and substituted with palladium on charcoal (5 per cent; 75 mg). The reaction mixture was hydrated at 3 bar for 20 h. The implementation was complete. The catalyst was separated via cellite and the filtrate was narrowed. The solid residue (150 mg) was chromatographically separated [silica gel 60 (30 g); ethylacetate/methanate (4: 1,250 ml), methanol (300 ml) ]. 2-(4-dimethylamino-4-phenylcyclohexyl) 3-methyl-1H-indol-5-carbonite (polar diastereomer) was obtained at a yield of 50 per cent (100 mg) with a melting point of 235-240 °C.
2- ((4-dimethylamino-4-phenylcyclohexyl) 3-methyl-1H-indol-5-carbonitrile (polar diastereomer) (95 mg, 0.265 mmol) was dissolved in ethanol (7 ml) and mixed with citric acid (56 mg) dissolved in ethanol (2 ml). As no crystallization occurred after 16 h, the mixture was compressed to 2 ml, mixed with diethyl ether (30 ml) and stirred at room temperature for 10 min. The solvent was decanted. The remaining colourless solid was moistened and dried in the feed tube. Sample 72 was obtained at a yield of 75 % (90 mg) with a melting point of 257-261 °C.
(±) - [1-benzyl-4-(3-methyl-5-trifluorethyl-1H-indol-2-yl) cyclohex-3-enyl]-dimethylamine ketone Ket-3 (393 mg, 1.7 mmol) was dissolved in dichloromethane (20 ml) together with Indol Ind-7 (340 mg, 1.7 mmol) and then trifluoromethanosulfonic acid (0.17 ml, 287 mg, 1.9 mmol) was added, with the approach becoming dark. The reaction was agitated for 3 days at RT. The reaction was followed by DC treatment. The reaction mixture was dissolved with 1 N NaOH (10 mg, 1.7 mmol) and agitated for 10 minutes. The colour changed from dark to light to black. After phase 1 separation, the solution was separated from the mixture by a thin layer of benzyl methyl methacrylate (150 g/m3 × 10 g/m3 × 10 g/m3 × 120 g/m3 × 120 g/m3 × 120 g/m3) and obtained in a vacuum with a mixture of ethyl methacrylate (120 mg/m3−20 g/m3) and ethyl methacrylate (120 g/m3−20 g/m3) in a mixture of ethyl methacrylate) obtained by extraction of ethyl methacrylate and ethyl methacrylate.
(±) - [1-benzyl-4-(3-methyl-5-trifluormethyl-1H-indol-2-yl) cyclohex-3-enyl]-dimethylamine (220 mg, 0,53 mmol) was dissolved in methanol (50 ml) at high temperatures and Pd/C (5 %, 100 mg) was added to argon. At 3 bar, hydrated for 4 h at 40 °C. The catalyst was then sucked through cellite and the filtrate was narrowed. The solid colourless residue was chromatographically separated [silicon gel 60 (30 g); ethyl acetate/methanol (20: 1; 500 ml); (4: 1; 300 ml); (2: 1; 300 ml). N-point: [1-benzyl-dimethylamine-4-methyl-1-dihydroxylamine-2]-dimethylamine-dimethylamine (N-methyl-2-dioxylamine) was obtained from a solid with a polar polarity of 46 mg (29 °C) at a temperature of 180 °C. The isomer was obtained from a solid containing 46 mg (29 °C) of isomeric acid at a temperature of 180 °C.
N-[1-benzyl-4-(3-methyl-5-trifluormethyl-1H-indol-2-yl) cyclohexyl]-N,N-dimethylamine (unpolar diastereoisomer) (46 mg, 0.11 mmol) was dissolved in ethanol (10 ml) and added to citric acid (23 mg, 0.122 mmol) dissolved in hot ethanol (2 ml). After 10 min of stirring, a colourless solid began to emerge at RT. The reaction product was stirred with diethyl ether (5 ml) and stirred 16 times.
N-[1-benzyl-4-(3-methyl-5-trifluormethyl-1H-indol-2-yl) cyclohexyl]-N,N-dimethylamine (polar diastereoisomer) 135 mg, 0.33 mmol) was dissolved in ethanol (20 ml) and mixed with citric acid (70 mg, 0.36 mmol) dissolved in hot ethanol (5 ml). The clear colourless solution was stirred for 24 h and then reduced to approximately half. After another 2 h stirring in RT, the unwanted precipitation was sucked out. 74 samples were obtained at a yield of 76 % (151 mg) with a melting point of 158-165 °C.
For example, 24 (110 mg, 0.29 mmol) was dissolved in methanol (25 ml) under argon atmosphere and replaced with Pd/C (5 %, 50 mg). At 3 bar, the catalyst was hydrated at RT for 3 h. The catalyst was then vacuumed via Celite and the filtrate was narrowed. The solid, colourless residue was chromatographically separated [silica gel 60 (20 g); ethylacetate/methanol (4: 1; 500 ml); (1: 1; 300 ml) ].Butyl-N,N-dimethyl-4- ((3-methyl-5-triformethyl) -1-H-indol-2-yl) hydrohexaneamine (polar diastereomer) was obtained in a yield of 83 mg (75%) as a colourless solid with a melting point of 141-146 °C.
Other
The more unpolar diastereoisomer was isolated as a colourless oil at a yield of 10 mg (9%).
The more polar (1r,4s) -butyl-N,N-dimethyl-4-(3-methyl-5-trifluor-methyl) --1H-indol-2-yl) cyclohexanamine (82 mg, 0.21 mmol) was dissolved in ethanol (10 ml) and mixed with citric acid (44 mg, 0.23 mmol) dissolved in hot ethanol (2 ml). The clear colourless solution was stirred for 24 h and then compressed. After adding diethyl ether (10 ml), the precipitate was stirred for 2 h at RT and then sucked. 75 was obtained in a yield sample of 78% (94 mg) with a melting point of 191-193 °C
The suspension was agitated for approximately 10 min until complete solution. The resulting solution was extracted with dichloromethane (4 x 30 ml). The combined organic phases were dried with Na2SO4 (1,22 g, 10,5 mmol) and then heated at 1 °C. The reaction mixture was stirred for another 1.5 h and then compressed to dry for processing in the rotary evaporator. The remaining residue was obtained by adding 5NOH (40 ml) to the base. The resulting solution was extracted with dichloromethane (4 x 30 ml); the combined organic phases were dried with Na2SO4 (1 °C); the resulting organic phases were heated at 1 °C. The solution was separated from the solid nitroxide (42-50 mg/N) in a 60 mg (14-50 mg) diethyl methacrylate (N-14-50 mg) of ethyl methacrylate (N-14-50 mg/N) in a solution of 400 mg (14-50 mg) diethyl methacrylate (N-14-50 mg) of ethyl methacrylate (N-14-50 mg/N) in a solution of 17 mg (14-50 mg) diethyl methacrylate (N-1) in a solution of 450 mg (14-50 mg/N) of ethyl methacrylate (N-1) in a solution of 13 mg (14-50 mg/N-1) of ethyl methacrylate (N-1) in a solution of 14 mg (14-50 mg/N-1) of ethyl methacrylate (N-1) in a solution of 14 mg (14-50 mg/N-1) of ethyl methacrylate (N-1) in a solution of 14 mg (24-50 mg/N-1) of ethyl methacrylate (N-1) in a solution of 14 mg (24-50 mg/N-1) of ethyl methacrylate (N-1) of ethyl methacrylate (N-1) in a solution of 2-methyl methacrylate (N-1) of 2-methyl methacrylate (N-1) of ethyl methacrylate) of ethyl methacrylate (N-1) of ethyl methacrylate (N-1) is obtained from the solution of the solution of
N,N-dimethyl-4-(3-methyl-5-trifluormethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine (polar diastereomer) (170 mg, 0.42 mmol) was dissolved in ethanol (10 ml) and added to citric acid (89 mg, 0.46 mmol) dissolved in hot ethanol (2 ml). After 30 min of stirring, a colourless solid began to fall out at RT. After 1 h, it was sucked out. Sample 76 was obtained at a yield of 76 % (188 mg) with a melting point of 243-247 °C.
For example, 26 (200 mg, 0.55 mmol) was dissolved in HBr/Ice vinegar (33% HBr, 20 ml). The resulting solution was added to the RT Sn-powder (700 mg, 5.9 mmol) solution and administered in portions for 60 min. After completion of the addition, the reaction mixture was stirred for another 60 min. - For processing, the mixture was added to ethanol (20 ml) and the solvent mixture was reduced to dry by the rotary evaporator. The remaining residue was obtained by adding 5N NaOH (40 ml) base. The resulting solution was extracyclically added to ethanol (700 mg, 5.9 mmol) and acidified (4 x 20 ml). The combined organic phases were sterilized with MgSO4 and then dried. The residual isomeric acid was obtained from ethanol (N-3-methyl-2-methyl-1) in a polar ethanol (1-3-methyl-1) solution of 87 mg (1-3-metyl-1-methyl-1) ethanol (1-3-metyl-1) (1-methyl-1) (1-3-methyl-1) (1-3-methyl-1) (1-3-methyl-1) (1-3-methyl-1) (1-3-methyl-1) (1-3-acethanol) (1-3-methyl-1) (1-3-methyl-1) (1-3-methyl-1) (1-3-methyl-1) (1-3-acethanol) (1-3-methyl-1) (1-3-methyl-1) (1-3-acethanol) (1-3-methyl-1) (1-3-acethanol) (1-3-methyl-1) (1-3-acethanol) (1-3-acethanol) (1-3-acethanol) (1-3-acethanol) (1-3-acethanol) (1-3-acethanol) (1-3-acethanol-1) (1-3-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1-acethanol-1) (1
For example, 26 (137 mg, 0.38 mmol) was dissolved in ethanol (30 ml), converted to catalyst (Pd/coal 5%, 100 mg) and hydrated for 2 h at RT and 3 bar hydrogen pressure. The solid residue (128 mg) obtained after separation of the catalyst and removal of the solvent was column chromatographically purified (carrier: unpolar isomer EtOAc, polar isomer EtOAc/EtOH 2 : 1).
1-Benzyl-4- ((5-fluor-3-methyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (unpolar isomer, 72 mg, 0,2 mmol) was dissolved in isopropanol (5 ml) at boiling temperature and mixed with citric acid (40 mg, 0,21 mmol), dissolved in hot isopropanol (1 ml). The solution was cooled at 5 °C (refrigerator) and left to stand for 17 h. The precipitation was separated by a frying process. 77 mg was obtained at a yield of 87 (94%; melting point: 228-233 °C, crystal conversion point 140 °C).
(1s,4s)-1-benzyl-4-(5-fluor-3-methyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (polar isomer, 80 mg, 0.22 mmol) was dissolved in isopropanol (3 ml) at boiling temperature and mixed with citric acid (60 mg, 0.31 mmol), dissolved in hot isopropanol (2 ml). The solution was cooled to 5 °C (refrigerator) and left to stand at 17 °C. The precipitate was separated by frying. 78 samples were obtained at a yield of 84 mg (68%, melting point: 183-184 °C).
5-Fluor-3-methylindol (Ind-8) (596 mg, 4 mmol) was dissolved in dichloromethane (30 ml) together with ketone Ket-4 (788 mg, 4 mmol) and added to trifluoromethane sulphonic acid (500 μl, 5.63 mmol). The solution was agitated at RT for 24 h. Then, to the solution, triethyl silane (2 ml, 12.4 mmol) was added. The reaction mixture was agitated at RT for 60 h. The reaction mixture was agitated at RT for processing with 2Nrich NaOH (30 ml) and agitated at RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 15 ml). The organic extracts were dissolved in NaSO2 (50 mg, 12.4 mmol) and then agitated. The possible gaseous solid was obtained from two white diethyl methacrylate (26-dimethyl methacrylate) (26-dimethyl methacrylate) (24-dimethyl methacrylate) (26-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-dimethyl methacrylate (24-dimethyl methacrylate) (24-dimethyl methacrylate) (24-methyl methacrylate (24-methyl methacrylate) (24-methyl methacrylate) (24-methyl methacrylate (24-methyl methacrylate) (24-methyl methacrylate (24-methyl methacrylate) (24-methyl methacrylate (24-
1-Butyl-4-(5-fluor-3-methyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (266 mg, 0.8 mmol) was dissolved in ethylmethylketone (30 ml). RT was then dripped with Me3SiCl (205 μl, 1.6 mmol) and stirred.
(±) 2-(4-(Dimethylamino) -4-phenylcyclohex-1-enyl) -3-methyl-5-fluor-1H-indol (free base from example 28) (420 mg, 1.2 mmol) was dissolved in HBr/iron vinegar (33% HBr, 25 ml) and then administered as a portion to RT Sn-powder (1,4 g, 12 mmol) for 40 min. After completion of the addition, the reaction mixture was stirred for another 60 min. - For processing, the mixture was reduced to dry by the rotary evaporator. The remaining residue was reduced to a basic solution by adding 5 N NaOH (40 ml). The resulting solution was heated and extracted with extracyclic methanol (45 ml). The 20 mg of organic methanol were reconstituted with a solid solution of 4-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-1-methyl-methyl-methyl-methyl-methyl (30-34 mg/ ml) at a temperature of 256 °C. The residue was obtained by melting and dissolving it in a solution of 1 mg (30-60 ml) of 2-methyl-1-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl at a temperature of 25 °C.
The ethanol parent solution was compressed, the remaining residue (162 mg) was column chromatographically purified (carrier EtOAc/EtOH 2 : 1) and 4- ((5-fluor-3-methyl-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (polar diastereoisomer) was obtained at a yield of 150 mg (35%).
4- ((Fluor-3-methyl-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (unpolar isomer) (250 mg, 0.71 mmol) was dissolved in isopropanol (300 ml) at boiling temperature and mixed with citric acid (138 mg, 0.72 mmol) dissolved in hot isopropanol (5 ml). The solution was compressed to approximately 130 ml, cooled at 5 °C (refrigerator) and left to stand for 17 h. The precipitation was separated by a F. 80 was obtained at an output of 218 mg (68 mg, melting point: 224-229 °C, starting from crystallization) %.
4- ((Fluor-3-methyl-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (polar diastereoisomer, 150 mg, 0.43 mmol) was dissolved in methanol (5 ml) at boiling temperature and mixed with citric acid (84 mg, 0.44 mmol), dissolved in hot methanol (2 ml). The solution was compressed. The resulting residue was heated with isopropanol (10 ml), leaving the substance largely undissolved. The gel was left at 5 °C for 1 h. The solid was then separated by a fryer. Example 81 was obtained at a yield of 131 % (56 mg, melting point: 190-194 °C).
1-[5-Fluor-1H indol-3-yl) -ethyl]-1H benzimidazole (Ind-19, 977 mg, 3.5 mmol) and ketone (Ket-4, 690 mg, 3.5 mmol) were dissolved in abs. dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.93 ml, 10.5 mmol). The solution was stirred at RT for 48 h, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (((20 ml), stirring continued for 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (NaSO24) and vacuuming the solution. The e.OH. residue was cleaned by flash chromatography (1:4) with EE/Et.
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is calculated by dividing the dose by the mean value of the dose of the active substance.
The solution of the newly produced olefin (450 mg, 0.98 mmol) in HBr/iron vinegar (35 ml) was given tin (1.25 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was reduced to dry and the residue was dissolved in 5N NaOH (50 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over NaSO24, and i.e. vacuum-sealed. The remaining residue was separated by flash chromatography using EE/OH (1:4→OH).
Other
| 304 mg (67 %), unpolares Diastereomer | |
| 119 mg (26 %), polares Diastereomer |
The polar compound (107 mg, 0.232 mmol) was dissolved in hot ethanol (4 ml) and mixed with a solution of citric acid (45 mg, 0.232 mmol) in hot ethanol (3 ml).
Other
The test chemical is used to determine the concentration of the test substance in the test medium.
Other
The mean value of 1H-NMR (DMSO-d6) is 0.92 (3 H, t); 1.07 (2 H, m); 1.23 (4 H, m); 1.34 (2 H, m); 1.48 (2 H, m); 1.62 (2 H, m); 1.80 (2 H, m); 2.08 (1 H, m); 2.57 (10 H, m); 3.17 (2 H, t); (4.46 (2 H, t); 6.85 (1 H, m); 7.24 (4 H, m); 7.52 (1 H, d); 7.63 (1 H, d); 7.79 (1 H, s); 10.77 (1 H, s), citrate.
Olefin sample 54 (836 mg, 1.74 mmol) in HBr/iron vinegar (70 ml) was administered with tin (2.20 g) for 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was compressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and vacuum-pressed. The remaining residue was separated by flash chromatography with EE/OH→Et (9:11:4)
Other
| 244 mg (29 %), unpolares Diastereomer | |
| 367 mg (44 %), polares Diastereomer |
The resulting nonpolar compound (225 mg, 0.468 mmol) was dissolved in hot ethanol (8 ml) and mixed with a solution of citric acid (90 mg, 0.468 mmol) in hot ethanol (5 ml).
Other
The yield is 206 mg (83.65%).
Other
The melting point is between 115 °C and 125 °C.
Other
The mean value of the dose of 1H-NMR (DMSO-d6) is 1.17 (2 H, m); 1.45 (2 H, m); 2.10 (6 H, s); 2.28 (1 H, t); 2.64 (6 H, m); 3.19 (2 H, t); 4.44 (2 H, t); 6.84 (1 H, m); 7.11 (2 H, m); 7.26 (8 H, m); 7.48 (1 H, m); 7.85 (1 H, s); 10.67 (1 H, s), citrate.
The polar compound obtained in example 83 (346 mg, 0.72 mmol) was dissolved in hot ethanol (10 ml) and mixed with a solution of citric acid (138 mg, 0.72 mmol) in hot ethanol (6 ml).
Other
The yield is 348 mg (72%) of porous solid
Other
The mean value of the dose of the active substance is 1.21 (2 H, m); 1.45 (2 H, m); 2.27 (6 H, s); 2.70 (4 H, m); 3.13 (2 H, t); 4.43 (2 H, t); 6.78 (1 H, m); 7.08 (1 H, m); 7.24 (3 H, m); 7.46 (5 H, d); 7.66 (1 H, d); 7.82 (1 H, s); 10.41 (1 H, s), citrate.
Indol (Ind-36, 700 mg, 3.0 mmol) and ketone (Ket-3, 697 mg, 3.0 mmol) were dissolved in RT in abs CH2Cl2 (30 ml) and rapidly mixed with trifluoromethanesulphonic acid (1.36 g, 0.80 ml, 9.0 mmol). Then a black oil was dropped. The mixture was stirred 2 d at RT. 1N NaOH (30 ml) was added and the mixture stirred for 20 min. The organic phase was separated and the aqueous phase was added with CH2Cl2 (2 x 30 ml). The combined organic extraction phases were washed with water (15 ml), dried with Na2SO4, filtered with rock and i.e. vacuum. By flash chromatography, the product was pressed with 50 g/l ammonium chloride and e.g. 1 NSO2 (1:1), and the second product was obtained by pressing with Na2SO4 e.g. 1 NSO2 (1:1), and then with NaCl2 (1:1), and the second product was vacuum-washed with e.g.
Other
The following is the list of active substances:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.40 (2 H; m); 1.67 (4 H; m); 2.01 (4 H; m); 2.31 (6 H; m); 2.45 (5 H; m); 2.75 (4 H; m); 5.89 (1 H; bs); 6.83 (1 H; m); 7.20 (7 H; m); 10.76 (1 H, s).
The olefin (650 mg, 1.46 mmol) obtained was dissolved in HBr/iron vinegar (33% by volume, 30 ml) and mixed with tin (1.90 g) in a portion of the mixture at RT for 30 min. The mixture was stirred for 4 h at RT. Ethanol was added, the solvent mixture was removed i.v. and the residue was dissolved with 5N NaOH (60 ml) and CH2Cl2 (80 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4, filtered and injected i.v. The narrowed residue was cleaned by flash chromatography with chlorine/methanol (20:1:14:1 + 1 % triethylamine respectively).
Other
| 351 mg (54 %), unpolare Verbindung, enthielt Triethylamin | |
| 108 mg (17 %), polare Verbindung, enthielt Triethylamin |
The newly produced nonpolar compound (274 mg, 0.61 mmol) was hot dissolved in ethanol (4 ml) and mixed with a solution of citric acid (118 mg, 0.61 mmol) in ethanol (2 ml).
Other
The yield is 339 mg (85.87%).
Other
The following shall be added to the list of active substances:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.17 (2 H, m); 1.43 (2 H, m); 1.67 (2 H, m); 1.96 (8 H; m); 2.38 (6 H, s); 2.59 (4 H, m); 2.86 (2 H, m); 3.11 (2 H, t); 6.81 (1 H, m); 7.24 (7 H, m); 10.79 (1 H, bs); 11.1 (1 H, bs), citrate.
The polar compound obtained in example 85 (94 mg, 0.21 mmol) was hot dissolved in ethanol (2 ml) and mixed with a solution of citric acid (40 mg, 0.21 mmol) in ethanol (1 ml).
Other
The yield is 76 mg (86.57%); melting point is amorphous solid
Other
The mean value of the active substance is calculated as the sum of the following:
Indol (Ind-36, 1.00 g, 4.3 mmol) and ketone (Ket-4, 849 mg, 4.3 mmol) were dissolved in RT in abs CH2Cl2 (50 ml) and rapidly mixed with trifluoromethanesulphonic acid (1.93 g, 1.15 ml, 12.9 mmol). Then a black oil was dropped. The mixture was stirred 3 d at RT. 1N NaOH (50 ml) was added and the mixture stirred for 20 min. The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (2 x 50 ml). The combined organic action phases were washed with water, washed over Na2SO4, filtered dry and vacuumed. By flash chromatography, the vacuum was pressed with 50 g/l ammonium nitrate and 1N NaOH (1/l chlorine) was obtained as the second product, with the first and second vacuum pressed over Na2SO4 and 1N NaCl2 (Cl2O) as the second product.
Other
The following table shows the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 0.90 (3 H; t); 1.24-1.60 (6 H, m); 1.91 (4 H, m); 2.11 (2 H, m); 2.38 (6 H, s); 2.57 (4 H, m); 5.87 (1 H, bs); 6.83 (1 H, m); 7.22 (2 H, m); 10.82 (1 H, s).
The olefin (640 mg, 1.55 mmol) was dissolved in HBr/iron vinegar (33% by 35 ml) and mixed with tin (2.02 g) in a portion of the mixture at RT for 30 min. The mixture was stirred for 4 h at RT. Ethanol was added, the solvent mixture was removed in one go and the residue was dissolved with 5N NaOH (60 ml) and CH2Cl2 (80 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, washed over Na2SO4, filtered and sealed in one go. The resulting residue was cleaned by flash chromatography with Chlorochloro/methanol (20:14 + 1 % triethylamine) in each case.
Other
| 285 mg (44 %), unpolare Verbindung, enthielt Triethylamin | |
| 174 mg (27 %), polare Verbindung, enthielt Triethylamin |
The resulting nonpolar compound (261 mg, 0.63 mmol) was hot dissolved in ethanol (ml) and mixed with a solution of citric acid (121 mg, 0.63 mmol) in ethanol (ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of 1H-NMR (DMSO-d6) is 0.94 (3 H, t); 1.25-1.55 (10 H, m); 1.98 (6 H, m); 2.38 (6 H, s); 2.57 (4 H, m); 2.97 (1 H, m); 3.09 (2 H, t); 3.13 (2 H, t); 6.82 (1 H, m); 7.30 (2 H, m); 10.89 (1 H, s); 11.1 (1 H, bs), citrate.
The polar compound obtained in example 87 (176 mg, 0.43 mmol) was hot dissolved in ethanol (ml) and mixed with a solution of citric acid (82 mg, 0.43 mmol) in ethanol (ml).
Other
The yield is 138 mg (88.54%); amorphous solid
Other
The mean value of the active substance is calculated as the sum of the following:
Indol (Ind-36, 600 mg, 2.60 mmol) and ketone (Ket-10, 561 mg, 2.60 mmol) were dissolved in RT in abs CH2Cl2 (30 ml) and rapidly mixed with trifluoromethanesulphonic acid (1.16 g, 0.69 ml, 7.7 mmol). A black oil then fell out of the solution. The mixture was stirred at RT for 24 h. 1 N NaOH (30 ml) was added and the mixture stirred for 20 min. The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (2 × 30 ml). The combined organic phases were washed with water (15), dried over Na2SO4, filtered and vacuumed. Flash chromatography of the glitter of the glitter with 50 g of choline (9:1 + 1 ml) and a mixture of triethylene and methanol (9:1 + 1 ml) was obtained.Flash chromatography of the i.v. compressed mixed fractions with 50 g of silica gel and acetonitrile/methanol/aqueous 1 N ammonium chloride solution (9:1:1) obtained the first fraction indole and the purified product as the second fraction.
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.66 (6 H, m); 2.09 (8 H, m); 2.40 (6 H, m); 2.61 (4 H, m); 6.20 (1 H, bs); 6.82 (1 H, m); 7.21 (5 H, m); 7.45 (2 H, m); 10.73 (1 H, s).
The olefin (600 mg, 1.40 mmol) was added to HBr/iron vinegar (33% by volume, 30 ml) at RT for 30 min with tin (1.82 g) in portions. The mixture was stirred for 4 h at RT. Ethanol was added, the solvent mixture was removed i.v. and the residue was dissolved with 5N NaOH (60 ml) and CH2Cl2 (80 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4, filtered and vacuumed i.v. The residue was bleached.
Other
| 352 mg (58 %), unpolare Verbindung, enthielt Triethylamin | |
| 213 mg (35 %), polare Verbindung, enthielt Triethylamin |
The resulting nonpolar compound (295 mg, 0.68 mmol) was hot dissolved in ethanol (7 ml) and mixed with a solution of citric acid (131 mg, 0.68 mmol) in ethanol (2 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the active substance is calculated as the sum of the following:
The polar compound obtained in example 89 (166 mg, 0.38 mmol) was hot dissolved in ethanol (2 ml) and mixed with a solution of citric acid (74 mg, 0.38 mmol) in ethanol (1 ml).
Other
The maximum content of the active substance is the maximum content of the active substance in the feed additive.
Other
The mean value of the dose of 1H-NMR (DMSO-d6) is 1.41 (2 H, m); 1.82 (2 H, m); 1.96 (4 H, m); 2.10 (2 H; s); 2.35 (6 H, s); 2.61 (4 H, m); 3.08 (6 H, t); 3.18 (2 H, m); 6.77 (1 H, m); 7.13 (1 H, m); 7.32 (1 H, m); 7.55 (3 H, m); 7.67 (2 H, m); 10.6 (1 H, s), citrate.
Olefin sample 55 (691 mg, 1.5 mmol) was dissolved in HBr/iron vinegar (33% by 30 ml) and replaced with tin (1.96 g) at RT in portions within 30 min. The mixture was stirred for 4 h at RT. Ethanol was added, the solvent mixture was removed in a vacuum and the residue was dissolved with 5N NaOH (60 ml) and CH2Cl2 (80 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4, filtered and narrowed in a vacuum. The remaining residue was cleaned by flash chromatography with 50 g of silica gel and chlor chloral hydrochloride/methanol (50:1).
Other
The yield is 512 mg (74%) of nonpolar compound; 130 mg (19%) of polar compound.
The newly produced nonpolar compound (420 mg, 0.91 mmol) was hot dissolved in ethanol (4 ml) and mixed with a solution of citric acid (175 mg, 0.91 mmol) in ethanol (2 ml).
Other
The total number of samples of the test chemical is calculated by dividing the total number of samples by the total number of samples of the test chemical.
The polar compound (111 mg, 0.24 mmol) obtained in example 91 was hot dissolved in ethanol (2 ml) and mixed with a solution of citric acid (46 mg, 0.24 mmol) in ethanol (1 ml).
Other
The yield is 80 mg (51%); melting point is amorphous solid
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.50 (4 H, m); 1.72 (8 H, m); 2.13 (4 H, m); 2.46 (2 H, s); 2.90 (6 H, m); 3.02 (3 H, m); 6.77 (1 H, m); 7.14 (2 H, m); 7.23 (5 H, m); 10.61 (H, bs), citrate.
Olefin sample 56 (972 mg, 2.30 mmol) was dissolved in HBr/iron vinegar (33%-ig, 50 ml) and replaced with tin (2.98 g) at RT in portions of 30 min. The mixture was stirred for 4 h at RT. Ethanol was added, the solvent mixture was removed i.e. by vacuum and the residue was dissolved with 5N NaOH (120 ml) and CH2Cl2 (160 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with organic water, dried over Na2SO4, filtered and i.e. by vacuum. The residual residue was narrowed by flash-rock chromatography with 100 g diesel and phenol/methyl phenol (50:1:1OH) The polymer was unlikely to be polymer but was extracted in pure water, and the polymer was combined with trichloroethylene and diethylene chloride, which were extracted from Na3Cl3 and phenol. The phases were separated into polymer and chlorine.
Other
| 472 mg (48 %), unpolare Verbindung | |
| 45 mg (5 %), polare Verbindung |
The newly produced nonpolar compound (444 mg, 1.04 mmol) was hot dissolved in ethanol (5 ml) and mixed with a solution of citric acid (200 mg, 1.04 mmol) in ethanol (2 ml).
Other
The yield is 390 mg (93.61%); amorphous solid
Other
The mean value of 1H (DMSO-d6) is 0.96 (3 H, t); 1.33 (6 H, m); 1.62 (6 H, m); 1.88 (6 H, m); 2.01 (2 H, m); 2.29 (2 H, m); 2.73 (6 H, s); 3.08 (6 H, m); 6.84 (1 H, m); 7.21 (1 H, m); 7.39 (1 H, m); 11.66 (1 H, s), citrate.
The polar compound (43 mg, 0.10 mmol) obtained in example 93 was hot dissolved in ethanol (1 ml) and mixed with a solution of citric acid (19 mg, 0.10 mmol) in ethanol (1 ml).
Other
The following table shows the results of the analysis:
Other
The 1H-NMR (DMSO-d6) is 0.96 (3 H, t); 1.42 (6 H, m); 1.75-1.93 (14 H, m); 2.53-2.70 (10 H, m); 3.16 or 3.34 (4 H, m); 6.84 (1 H, m); 7.28 (1 H, m); 7.40 (1 H, m); 11.22 (1 H, s), citrate (sample also contained TEA x HCl).
Olefin sample 57 (354 mg, 0.8 mmol) was dissolved in HBr/iron vinegar (33%-ig, 15 ml) and replaced with tin (1.03 g) at RT in portions within 30 min. The mixture was stirred for 4 h at RT. Ethanol was added, the solvent mixture was removed i.v. and the residue was dissolved with 5N NaOH (30 ml) and CH2Cl2 (40 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4, filtered and pressed i.v. The flash chromatography of the residue with 50 g of silicon· chloromethane/methanol (20:1 polar) obtained the unpolar dimer, only the dimer was purified by flash chromatography and re-polished with 25 g of chloromethane/methanol (50: 1) polymer.
Other
| 161 mg (45 %), unpolare Verbindung | |
| 109 mg (30 %), polare Verbindung |
The newly produced nonpolar compound (140 mg, 0.31 mmol) was hot dissolved in ethanol (3 ml) and mixed with a solution of citric acid (60 mg, 0.31 mmol) in ethanol (1 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the active substance is calculated as the sum of the following:
The polar compound (93 mg, 0.21 mmol) obtained in example 95 was hot dissolved in ethanol (2 ml) and mixed with a solution of citric acid (40 mg, 0.21 mmol) in ethanol (1 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.50 (4 H, m); 1.72 (8 H, m); 2.13 (4 H, m); 2.46 (2 H, s); 2.90 (6 H, m); 3.02 (3 H, m); 6.77 (1 H, m); 7.14 (2 H, m); 7.23 (5 H, m); 10.61 (H, bs), citrate.
Indol (Ind-38, 600 mg, 2.62 mmol) and ketone (Ket-3, 605 mg, 2.62 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.70 ml, 7.9 mmol). The solution was stirred for 48 h at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (Na2SO4) and compressing the solution i.e. vacuum. The precipitated residue was cleaned by flash chromatography with CH20/ClClOH (1:1).
Other
The yield is 259 mg (22%) of crude oil.
Other
The mean value of the dose of the active substance is 1.96 (2 H, m); 2.32 (6 H, bs); 2.77 (6 H, m); 3.17 (2 H, t); 4.28 (2 H, t); 5.78 (1 H, bs); 6.12 (1 H, s); 6.86 (2 H, m); 7.17 (6 H, d); 7.54 (1 H, s); 10.85 (1 H, s).
The solution of the newly produced olefin (250 mg, 0.565 mmol) in HBr/iron vinegar (25 ml) was given tin (0.70 g) for 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was compressed to dry and the residue was dissolved in 5N NaOH (30 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried with Na2SO4 and i. flash-dried. The remaining phase was separated by back-chromatography with CHCl3/OH (9:1→OH). The unpolar compound was obtained as a vacuum (159 mg) which was then separated by a vacuum-filled solution of CH2CH2H2 and P2CH2H2H2H2H2H2H. The combined organic phase was extracted and dried with NaCl2H2Cl2 and i. flash-dried with HCl2H2H2Cl. The residual was then separated by back-chromatography with HCl3/OH (9:1→OH).
Other
| 85 mg (34 %), unpolares Diastereomer | |
| 37 mg (15 %), polares Diastereomer |
The newly isolated nonpolar compound (63 mg, 0.14 mmol) was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (27 mg, 0.14 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean of the measurements of the 1H-NMR (DMSO-d6) was 1.18 (2 H, m); 1.31 (2 H, m); 1.80 (2 H, m); 2.03 (1 H, m); 2.59 (6 H, s); 2.79 (2 H, m); 3.02 (2 H, t); 4.19 (2 H, t); 6.04 (1 H, s); 6.78 (1 H, m); 7.09 (1 H, m); 7.29 (8 H, m); 11.50 (1 H, s), free base.
The polar compound (37 mg, 0.08 mmol) obtained in example 97 was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (16 mg, 0.08 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.24 (4 H, m); 1.66 (4 H, m); 1.95 (4 H, m); 2.57 (6 H; s); 3.16 (2 H, t); 4.26 (2 H, t); 6.14 (1 H, s); 6.62 (1 H, m); 6.85 (2 H, m); 7.25 (7 H, m); 10.91 (1 H, s), citrate.
Indol (Ind-38, 730 mg, 3.18 mmol) and ketone (Ket-4, 628 mg, 3.18 mmol) were dissolved in dichloromethane (25 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.85 ml, 9.6 mmol). The solution was stirred for 72 h at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (Na2SO4) and closing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CH0Cl3/HMeMe (20:19:1).→
Other
The yield is 402 mg (31%) of porous solid
Other
The mean value of the dose of the active substance is calculated as the following: 1H-NMR (DMSO-d6): 0.89 (3 H, t); 1.12 to 1.68 (6 H, m); 2.00 (4 H, m); 2.69 (6 H, bs); 3.18 (2 H, t); 4.33 (2 H, t); 5.80 (1 H, s); 6.16 (1 H, s); 6.88 (1 H, m); 7.18 (1 H, m); 7.28 (1 H, s); 7.44 (1 H, d); 7.56 (1 H, s); 11.07 (1 H, s).
The solution of the newly produced olefin (385 mg, 0.94 mmol) in HBr/iron vinegar (30 ml) was given tin (1.20 g) for 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was compressed to dry and the residue was dissolved in 5N NaOH (40 ml) and chloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried with Na2SO4 and i.e. pressed. The remaining residue was separated by vacuum chromatography with CHCl:13/OH (9→OHMe) The unpolar compound was obtained as a vacuum (173 mg) which was then separated by a vacuum dissolved in CHCl2 P2H2 and the second phase was washed and dried with HCl2Cl2 P2H2 and i.e. separated by a vacuum.
Other
| 122 mg (32%), unpolares Diastereomer | |
| 46 mg (12 %), polares Diastereomer |
The newly isolated nonpolar compound (104 mg, 0.25 mmol) was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (49 mg, 0.25 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of 1H (DMSO-d6) is 0.95 (3 H, t); 1.23-1.96 (14 H, m); 2.64 (6 H, s); 3.32 (2 H, t); 4.27 (2 H, t); 6.14 (1 H, t); 6.82 (1 H, m); 7.18 (1 H, m); 7.28 (1 H, m); 7.44 (1 H, d); 7.54 (1 H, d); 10.6 (1 H, s), citrate.
The polar compound (46 mg, 0.11 mmol) obtained in example 99 was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (21 mg, 0.11 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of 1H (DMSO-d6) is 0.96 (3 H, t); 1.29 (2 H, m); 1.37-1.83 (11 H, m); 2.57 (7 H, m); 3.12 (2 H, t); 4.24 (2 H, t); 6.14 (1 H, t); 6.83 (1 H, m); 7.20 (2 H, m); 7.45 (1 H, d); 7.52 (1 H, d); 10.82 (1 H, s), citrate.
Indol (Ind-38, 500 mg, 2.18 mmol) and ketone (Ket-10, 473 mg, 2.18 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.58 ml, 6.54 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the organic phases with water, drying (Na2SO4) and closing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OH (9:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as the following:
The solution of olefin (450 mg, 1.05 mmol) in HBr/iron vinegar (30 ml) was given tin (1.31 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was reduced to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (20 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. vacuumed. The remaining residue was separated and purified by flash-Cl chromatography with CHMe3/OH (9:1)
Other
| 178 mg (39 %), unpolares Diastereomer | |
| 209 mg (46 %), polares Diastereomer |
The resulting nonpolar compound (167 mg, 0.387 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (74 mg, 0.387 mmol) in hot ethanol (4 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the active substance is 1.15 (2 H, t), 1.13 (1 H, t), 6.82 (1 H, m), 7.19 (2 H, m), 7.46 (7 H, m), 11.0 (1 H, bs), and the mean value of the active substance is 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (2 H, t), 1.15 (1 H, t), 1.15 (1 H, t), 1.15 (1 H, t), 1.15 (1 H, t), 1.15 (1 H, t, 1.15 (1 H, t), 1.15 (1 H, 1.15 (1 H, t), 1.15 (1 H, 1.15 (1 H, t), 1.15 (1 H, 1.15 (1 H, 1.15 (1 H, t), 1.15 (1 H, 1.15 (1 H, 1.15 (1 H, 1.15 (1 H, 1.15), 1.15 (1 H, 1.15 (1 H, 1.15 (1 H, 1.15), 1.15 (1 H, 1.15 (1 H, 1.15 (1 H, 1.15), 1.15 (1 H, 1.15 (1 H, 1.15 (1 H, 1.15), 1.15 (1 H, 1.15 (1 H, 1.15 (1 H, 1.16).
The polar compound obtained in example 101 (190 mg, 0.44 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (85 mg, 0.44 mmol) in hot ethanol (5 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is 1.34 (2 H, m); 1.58 (2 H, m); 1.91 (2 H, m); 2.40 (6 H; s); 2.61 (5 H, m); 2.99 (2 H, m); 3.09 (2 H, t); 4.23 (2 H, t); 6.15 (1 H, s); 6.76 (1 H, m); 7.10 (2 H, m); 7.54 (7 H, m); 10.5 (1 H, s), citrate.
Indol (Ind-39, 600 mg, 2.62 mmol) and ketone (Ket-3, 605 mg, 2.62 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.70 ml, 7.9 mmol). The solution was stirred for 48 h at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (Na2SO4) and pressing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OH (9:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.42 (1 H, m); 1.95 (1 H, m); 1.99 (1 H, m); 2.27-2.40 (9 H, m); 2.80 (2 H, q); 3.13 (2 H, t); 4.13 (2 H, t); 5.71 (1 H, s); 6.85 (2 H, m); 7.09 (1 H, s); 7.25-7.29 (7 H, m); 7.47 (1 H, s); 10.87 (1 H, s).
The solution of the newly produced olefin (530 mg, 1.2 mmol) in HBr/iron vinegar (30 ml) was given tin (1.5 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (40 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-separated. The residues were separated by CH3/ClOH (9:1MeMe→OH) chromatography.
Other
| 248 mg (46 %), unpolares Diastereomer | |
| 62 mg (12 %), polares Diastereomer |
The resulting nonpolar diastereomer (230 mg, 0.517 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (99 mg, 0.517 mmol) in hot ethanol (4 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.30 (4 H, m); 2.01 (4 H, m); 2.37-2.80 (9 H, m); 2.98 (2 H, t); 4.0 (2 H, t); 6.80 (2 H, m); 7.09 (1 H, s); 7.15-7.41 (8 H, m); 11.0 (1 H, bs), free base.
The polarized diastereomer (62 mg, 0.139 mmol) produced in example 103 was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (27 mg, 0.139 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as the following:
Indol (Ind-39, 800 mg, 3.49 mmol) and ketone (Ket-4, 690 mg, 3.49 mmol) were dissolved in dichloromethane (25 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.93 ml, 10.5 mmol). The solution was stirred for 72 h at RT, leaving a dark brown oil. After adding 1N NaOH (20 ml) and CH2C12 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (Na2SO4) and pressing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OH (9:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as the following:
The solution of the newly produced olefin (528 mg, 1.29 mmol) in HBr/iron vinegar (35 ml) was given tin (1.60 g) for 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was compressed to dry and the residue was dissolved in 5N NaOH (50 ml) and chloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.i. pressed. The remaining residue was separated by vacuum chromatography with CHCl:13/OH (91→1+1%) TEA. The compound was then vacuumed to obtain a nonpolar solution (350 mg) which was then used to filter the liquid from the liquid. The liquid was separated by extraction of CHCl2 and i.i.i. the combined organic phase was washed over HCl2 and i.i.i. pressed with NCl2 and i.i.i. pressed over HCl2 and i.i.i. pressed over NaCl2 and i.i.i. pressed over HCl2 and i.i.i. pressed over NaCl2 and i.i. pressed over NaCl2 and i.i. pressed over HCl2 and i.i.i. pressed over NaCl2 and i. pressed over NaCl2 and i. pressed over NaCl2 and i. pressed with HCl2 and i.i.i.i. pressed over NaCl2 and i. pressed over NaCl2 and i. pressed over NaCl2 and i. pressed with H2 and i. pressed with NaCl2 and i.
Other
| 285 mg (54 %) unpolares Diastereomer | |
| 123 mg (23 %), polares Diastereomer |
The resulting unpolar diastereomer (285 mg, 0.694 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (133 mg, 0.694 mmol) in hot ethanol (5 ml).
Other
The following table shows the results of the analysis:
Other
The mean of the 1H-NMR (DMSO-d6) is 0.96 (3 H, t); 1.37 (6 H, m); 1.73 (4 H, m); 1.94 (5 H, m); 2.71 (6 H, m); 3.08 (2 H, t); 4.12 (2 H, t); 6.85 (2 H, m); 7.24 (3 H, s); 7.54 (1 H, s); 11.4 (1 H, s); bs, free base.
The polar diastereomer (123 mg, 0.30 mmol) obtained in example 105 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (58 mg, 0.3 mmol) in hot ethanol (2 ml).
Other
The yield is 129 mg (106.71%), a porous solid
Other
The mean value of the 1H-NMR (DMSO-d6) is 0.95 (3 H, t); 1.23 (8 H, m); 1.63 (7 H, m); 2.19 (6 H, m); 3.05 (2 H, t); 4.09 (2 H, t); 6.81 (2 H, m); 7.21 (3 H, m); 7.41 (1 H, s); 10.8 (1 H, s), free base.
Indol (Ind-39, 667 mg, 2.91 mmol) and ketone (Ket-4, 631 mg, 2.91 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.78 ml, 8.7 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring continued for 20 min, separating the phases, double-treating the aqueous phase with CH2Cl2ex, combining the organic phases with washed, dried water (Na2SO4) and compressing the solution i.e. vacuum. The solution was cleaned by flash chromatography with CH13/ClOH (9:1→MeCl4:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.71 (1 H, m); 2.18 (8 H, m); 2.39 (1 H, d); 2.58 (1 H, s); 2.83 (1 H, d); 2.98 / 2 H, m); 3.95 (2 H, m); 6.02 (1 H, s); 6.83 (2 H, m); 7.04 (1 H, s); 7.18-7.50 (8 H, m); 10.82 (1 H, s).
The solution of the newly produced olefin (900 mg, 2.1 mmol) in HBr/iron vinegar (50 ml) was given tin (2.54 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (80 ml) and dichloromethane (50 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-tighted. The remaining residue was separated by CHCl3/OH (9:1→Me1:4) chromatography.
Other
| 198 mg (22 %), unpolares Diastereomer | |
| 157 mg (17 %), polares Diastereomer |
The resulting nonpolar diastereomer (172 mg, 0.4 mmol) was dissolved in hot dioxin (5 ml) and mixed with a solution of citric acid (77 mg, 0.4 mmol) in hot dioxin (4 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.48 (4 H, m); 2.10 (7 H, bs); 2.74 (3 H, m); 3.05 (2 H, t); 4.10 (2 H, t); 6.83 (2 H, m); 7.20-7.52 (9 H, m); 10.95 (1 H, s), free base.
The sample 107 (144 mg, 0.33 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (64 mg, 0.33 mmol) in hot ethanol (4 ml).
Other
The following table shows the results of the analysis:
Other
The mean of the 1H-NMR (DMSO-d6) is 1.40 (2 H, m); 1.62 (2 H, m); 1.90 (6 H, s); 2.71 (3 H, m); 3.01 (2 H, t); 4.07 (2 H, t); 6.73 (1 H, m); 6.85 (1 H, s); 7.11-7.43 (9 H, m); 10.47 (1 H, s), free base.
Indol (Ind-40, 668 mg, 2.39 mmol) and ketone (Ket-3, 553 mg, 2.39 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.64 ml, 7.2 mmol). The solution was stirred for 72 h at RT, leaving a dark brown oil. After adding 1N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 20 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (Na2SO4) and closing the solution i.e. vacuum.
Other
The yield is 395 mg (33%) of porous solid
Other
The mean value of the dose of the active substance is 1.23 (2 H, m); 2.06 (2 H, m); 2.41 (6 H, bs); 3.22 (2 H, t); 3.33 (2 H, s); 4.43 (2 H, t); 5.58 (1 H, s); 6.84 (1 H, m); 7.08 (3 H, m); 7.29 (6 H, m); 7.40 (1 H, d); 7.56 (1 H, d); 7.86 (1 H, s); 10.92 (1 H, s).
The solution of the newly produced olefin (395 mg, 0.8 mmol) in HBr/iron vinegar (30 ml) was given tin (1.00 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was reduced to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-concentrated. The remaining residue was separated by EE/OH (9:1→1:4) chromatography.
Other
The following table shows the results of the analysis:
The resulting unpolar diastereomer (155 mg, 0.313 mmol) was dissolved in hot ethanol (4 ml) and mixed with a solution of citric acid (60 mg, 0.313 mmol) in hot ethanol (2 ml).
Other
The maximum content of the active substance shall be as follows:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.60 (2 H, m); 1.75 (2 H, m); 2.43 (6 H, s); 2.63 (6 H, m); 3.05 (2 H, t); 3.20 (1 H, m); 4.36 (2 H, t); 6.79 (1 H, m); 6.91 (1 H, m); 7.08 to 7.44 (8 H, m); 7.55 (1 H, d); 7.61 (1 H, s); 10.46 (1 H, s), citrate.
The polar diastereomer (56 mg, 0.11 mmol) obtained in example 109 was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (22 mg, 0.11 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.11 (2 H, m); 1.58 (2 H, m); 1.73 (2 H, m); 2.11 (2 H, m); 2.39 (6 H, s); 2.58 (4 H, m); 3.10 (2 H, bs); 3.21 (2 H, t); 3.45 (1 H, m); (4.45 (2 H, t); 6.85 (1 H, m); 7.19 (9 H, m); 7.60 (2 H, m); 7.76 (1 H, s); 10.83 (1 H, s), citrate.
For a solution of example 82 (450 mg, 0.98 mmol) in HBr/iron vinegar (35 ml), tin (1.25 g) was added within 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was reduced to dry and the residue was dissolved in 5N NaOH (50 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. vacuum-sealed. The remaining residue was separated by flash chromatography with EE/OH (1:4→OH).
Other
| 304 mg (67 %), unpolares Diastereomer | |
| 119 mg (26 %), polares Diastereomer |
The resulting nonpolar diastereomer (275 mg, 0.597 mmol) was dissolved in hot ethanol (10 ml) and mixed with a solution of citric acid (115 mg, 0.597 mmol) in hot ethanol (5 ml).
Other
The yield is 165 mg (42%) of porous solid
Other
The mean value of the 1H-NMR (DMSO-d6) is 0.97 (5 H, m); 1.06 (4 H, m); 1.42 (4 H, m); 1.82 (4 H, m); 2.07 (1 H, m); 2.59 (10 H, m); 3.19 (2 H, t); 4.45 (2 H, t); 6.83 (1 H, m); 7.21 (4 H, m); 7.62 (2 H, d); 7.77 (1 H, s); 10.99 (1 H, s), citrate.
The solution of sample 59 (356 mg, 0.8 mmol) in HBr/iron vinegar (30 ml) was given tin (1.00 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (40 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and pressed i.e. vacuum. The remaining residue was separated by flash chromatography with EE/OH (1:41:2 + 1 TEA→ %).
Other
| 237 mg (66 %), unpolares Diastereomer | |
| 73 mg (20 %), polares Diastereomer |
The resulting nonpolar diastereomer (234 mg, 0.525 mmol) was dissolved in hot ethanol (10 ml) and mixed with a solution of citric acid (101 mg, 0.525 mmol) in hot ethanol (5 ml).
Other
The yield is 173 mg (112.61%); the melting point is 262-167 °C.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.34 (4 H, m); 2.11 (2 H, m); 2.46 (1 H, m); 2.56 (2 H, m); 2.75 (6 H, s); 2.92 (2 H, m); 3.14 (2 H, t); 4.44 (2 H, t); 6.79 (1 H, m); 7.13 (2 H, m); 7.28 (5 H, m); 7.55 (1 H, s); 7.90 (1 H, s); 11.41 (1 H, s), which is hemicitrate.
The polar diastereomer (73 mg, 0.163 mmol) obtained in example 112 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (31 mg, 0.163 mmol) in hot ethanol (2 ml).
Other
The yield is 79 mg (113.76%), a porous solid
Other
The mean value of the dose of the active substance is 1.64 (4 H, m); 1.89 (4 H, m); 2.47 (11 H, m); 3.22 (2 H, t); 4.55 (2 H, t); 6.85 (1 H, m); 7.27 (7 H, m); 7.65 (1 H, s); 8.01 (1 H, s); 10.98 (1 H, s), citrate.
The solution of sample 60 (440 mg, 1.07 mmol) in HBr/iron vinegar (30 ml) was given tin (1.40 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (40 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and pressed i.e. with a vacuum. The remaining residue was separated by flash chromatography with EE/OH (1:41:2 + 1 TEA→ %).
Other
| 265 mg (60 %), unpolares Diastereomer | |
| 134 mg (30 %), polares Diastereomer |
The resulting nonpolar diastereomer (245 mg, 0.595 mmol) was dissolved in hot ethanol (10 ml) and mixed with a solution of citric acid (114 mg, 0.595 mmol) in hot ethanol (5 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the active substance is 1.03 (3 H, t); 1.33 (6 H, m); 1.57 (2 H, m); 1.70 (2 H, m); 1.99 (2 H, m); 2.16 (2 H, m); 2.66 (11 H, m); 3.21 (2 H, t); 4.53 (2 H, t); 6.85 (1 H, m); 7.21 (2 H, m); 7.64 (1 H, s); 8.02 (1 H, s); 11.43 (1 H, s), which is a half-citrate.
The polar diastereomer (130 mg, 0.315 mmol) obtained in example 114 was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (61 mg, 0.315 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.03 (3 H, t); 1.35 (6 H, m); 1.86 (8 H, m); 2.65 (11 H, m); 3.22 (2 H, t); 4.54 (2 H, t); 6.85 (1 H, m); 7.26 (2 H, m); 7.65 (1 H, s); 8.05 (1 H, s); 10.90 (1 H, s), citrate.
The solution of sample 61 (730 mg, 1.7 mmol) in HBr/iron vinegar (70 ml) was given tin (2.10 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was compressed to dry and the residue was dissolved in 5N NaOH (70 ml) and dichloromethane (70 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. vacuum-pressed. The remaining residue was separated by flash chromatography with EE/OH (9:1→OH).
| 181 mg (25 %), unpolares Diastereomer | |
| 265 mg (36 %), polares Diastereomer |
The resulting nonpolar diastereomer (168 mg, 0.389 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (75 mg, 0.389 mmol) in hot ethanol (3 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.47 (4 H, m); 2.04 (2 H, m); 2.12 (6 H, s); 2.67 (7 H, m); 3.21 (2 H, t); 4.54 (2 H, t); 6.83 (1 H, m); 7.30 (7 H, m); 7.64 (1 H, s); 8.01 (1 H, s); 10.8 (1 H, s), citrate.
The polar diastereomer (248 mg, 0.574 mmol) obtained in example 116 was dissolved in hot ethanol (8 ml) and mixed with a solution of citric acid (110 mg, 0.574 mmol) in hot ethanol (6 ml).
Other
The yield is 262 mg (73%) of porous solid
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.33 (2 H, m); 1.53 (2 H, m); 1.80 (2 H, m); 2.29 (6 H, s); 2.57 (5 H, m); 2.89 (2 H, m); 3.19 (2 H, t); 4.50 (2 H, t); 6.77 (1 H, m); 7.13 (2 H, m); 7.45 (5 H, s); 7.67 (1 H, s); 7.98 (1 H, s); 10.5 (1 H, s), citrate.
After 10 min, precipitation was lost. The solution was stirred for 18 h at RT. - For preparation, the mixture was mixed with NaHCO3 solution (20 ml) and stirred for 30 min. The solid at the phase limit (156 mg) was removed. and stirred in a mixture of NaHCO3 solution (20 ml) and methanol (2 ml) 3 d. At the time of rotation, the methanol was removed and the residual methanol (5 x 10 ml) was added to the mixture.The combined organic phases were dried with MgSO4 and then compressed. The resulting residue was decrystallized from methanol (1 ml). Example 118 was obtained as a greenish/beige solid at a yield of 62 mg (31%, melting point 227-235 °C).
Other
The mean of the measurements performed was approximately 0.01% for the mean of the measurements performed in the previous two years, i.e. 0.01% for the mean of the measurements performed in the previous two years.The number of times the number of samples is calculated is the number of samples of the sample.
The solution of the free base of Bsp 128 (polar diastereoisomer, 340 mg, 0.94 mmol dry dichloromethane (40 ml) was given to RT by stirring and moisture excretion of about 1 M solution of BBr3 in dichloromethane (5 ml, about 5 mmol). The solution was stirred for 18 h at RT. - For processing, the mixture was mixed with water (10 ml) and the resulting mixture was added to a saturated NaHCO3 solution (30 ml). The mixture was stirred for 2 h at RT, then the mixture was separated by a frying. The phases of the filtrate were separated. The water was extra-dried with dichloromethane (2 x 20 ml). The organic phases were mixed with MgSO4 and then evaporated at the rotation excretion.A further product (90 mg) was isolated by column chromatographic purification [silica gel 60 G (10 g; EtOAc/EtOH 1 : 1 (100 ml) ] and, after recrystallization of the combined product fractions (methanol, 3 ml), sample 119 was obtained as an ochre solid at a yield of 92 mg (28%, melting point 164-169 °C).
Other
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Other
The test chemical is used to determine the concentration of the active substance in the test chemical.The number of times the number of samples is calculated is the number of samples of the sample.
The ketone ket-3 (462 mg, 2 mmol) was dissolved in dichloromethane (25 ml) together with indol Ind-43 (430 mg, 2 mmol) and the ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ket
(±) -N-[1-benzyl-4- ((3-methy) -5-thifluormethoxy-1H-indol-2-yl) cyclohex-3-enyle] -N,N-dimethylamine (230 mg, 0.53 mmol) was dissolved in methanol (40 ml) and ethanol (10 ml) at high temperatures and transferred to argon with Pd/C (5 %, 100 mg). At 3 bar, the catalyst was hydrated for 4 h at 40 °C. The catalyst was then sucked through cellulite and the filler gel was ejected. The solid colourless residue (227 mg) was chromatographically separated [60 g uncoated with silica (30 mg); ethyl acetate/methanol (20 ml; 400 ml; 400 ml; 500 ml) : (2; 300 ml). 1-benzyl-N-dimethylamine (-dimethyl-4-dimethyl-methyl-methyl-hydroxy-o-o-o-o-thersal) was obtained as a colourless solid from a diethyl (175 mg) oxalate (7 mg) in a colourless solution of 175 mg (2-hydroxy-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o
1-Benzyl-N,N-dimethyl-4-(3-methyl-5-trifluormethoxy) -1-H-indol-2-yl) cyclohexanamine (polar diastereoisomer) (159 mg, 0.37 mmol) was dissolved in ethanol (8 ml) under heating and replaced with citric acid (78 mg, 0.4 mmol) dissolved in hot ethanol (5 ml). After about 30 min a precipitation started to fall. The cap was stirred for 20 h and the precipitation was deflected. The filter was narrowed down to half and combined with diethyl ether (10 ml). After another 2 h of rubbing at RT, the failed precipitation was combined.
The ketone ket-4 (513 mg, 2.6 mmol) was dissolved in dichloromethane (30 ml) together with indol Ind-43 (560 mg, 2.6 mmol) and then trifluoromethane sulphonic acid (0.26 ml, 439 mg, 2.86 mmol) was added. The solution was stirred 3 days at RT. The reaction was followed by DC. To separate the ketone, water (15 ml) was added and the mixture stirred vigorously for 10 min. After phase separation, the organic phase was stirred with water (15 ml). The procedure was performed three times. The organic phase was then stirred with 1 NOH (10 mg) of NaOH and stirred for 10 min. After phase separation, the insulin was obtained with phase 1 dichloromethane; the extract was obtained from 60 mg (2 × 10 mm) of ethyl methacrylate (N1-methyl methacrylate) and extracted in a 500 ml (11-mm) of vacuum-filled ethanol (31-methacrylate) (11-methacrylate) (11-methacrylate) (11-methacrylate) (11-methacrylate) (11-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-methacrylate) (13-metha
The light brown solid residue (341 mg) was chromatographically separated [silica gel (30 ml); ethylclosyl/methanol (1: 500; 1 : 2; 300 ml) ]. 1-butylnethylnethylnethylnethyl-4-methylnethylnethylnethyl-1-methoxy-2-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-o-
1-Butyl-N,N-dimethyl-4-(3-methyl-5-trifluormethoxy) -1-H-indol-2-yl) cyclohexanamine (unpolar diastereoisomer) (28 mg, 0.07 mmol) was dissolved in ethanol (5 ml) in heat and mixed with citric acid (15 mg, 0.08 mmol) dissolved in hot ethanol (1 ml). The clear colourless solution was stirred for 24 h and then compressed to approximately 0.5 ml. After addition of diethyl ether (5 ml) was stirred for 1 h at RT and then the precipitate was sucked. Sample 121 was obtained at an output of 75 % (31 mg) with a melting point of 246-253 °C.
1-Butyl-N,N-dimethyl-4-(3-methyl-5-trifluormethoxy) -1-H-indol-2-yl) cyclohexanamine (polar diastereoisomer) (230 mg, 0.58 mmol) was dissolved in ethanol (15 ml) in heat and mixed with citric acid (122 mg, 0.64 mmol) dissolved in hot ethanol (2 ml). The clear colourless solution was agitated for 24 h and then compressed to approximately 0.5 ml. Addition of diethyl ether (5 ml) was agitated for 1 h at RT and then the precipitate was sucked. Sample 122 was obtained at an output of 74% (252 mg) with a melting point of 166 to 168 °C.
The ketone Ket-10 (313 mg, 1.44 mmol) was dissolved in dichloromethane (15 ml) together with Ind-43 (310 mg, 1.44 mmol) and then trifluoromethane sulphonic acid (0.144 ml, 1.6 mmol) was added. It was stirred 3 days at RT. For processing, the reaction mixture was mixed with 1N NaOH (10 ml) and stirred for 10 min. After phase separation, the aqueous phase was extracted with dichloromethane (2 × 10 ml). The combined organic phases were dried, filtered and vacuum-stripped with sodium sulphate. 676 of a light brown solid was obtained, which was chromatographically separated (silicon 60 mg (30 g); ethyl acetate/methylamine; 1 ml).
(±) N,N-dimethyl-N-trifluormethoxy-1H-indol-2-yl) -methyl-phenylcydohex-3-enyl]amine (350 mg, 0.84 mmol) was stirred with HBr/ice vinegar (33 % HBr, 18 ml) until completely dissolved, then administered to the RT tin powder (0.98 g, 8.4 mmol) in portions for 30 min. After completion of the addition, the reaction mixture was stirred further 1.5 h and then obtained for processing on the rotary steam table to dry ethanol. The remaining residue was obtained by addition of 5 N NaOH (40-1) to the base. The solution was obtained by separation of 1 g of dichloromethane: 1 g of ethanol (30 g, 8.4 ml). The solid was extracted from ethanol (42 mg, 28-24-8) and obtained in a solvent containing 52 mg (221 mg, 28-24-8) ethanol (42 mg, 28-39 ml) and the remaining residue was obtained by dissolving it in a solvent containing 150 mg (221 mg, 28-24-8) ethanol (43 mg, 28-39 mg, 28-24-8) ethanol (42 mg, 28-24-8) and 150 ml (24-0) ethanol (42-methoxy-methyl-methyl-methyl-methyl-methyl) ethanol (42 mg, 28-2) at 60 °C).
N,N-dimethyl-4-(3-methyl-5-(trifluormethoxy)-1H-indol-2-yl)-1-phenylcyclohexanamine (unpolar diastereoisomer) (132 mg, 0.317 mmol) was dissolved in ethanol (10 ml) and added to citric acid (67 mg, 0.349 mmol) dissolved in hot ethanol (2 ml). After 30 min of stirring, a colourless solid began to precipitate at RT. After 20 h of stirring, it was sucked out.
N,N-dimethyl-4-(3-methyl-5-(trifluormethoxy)-1H-indol-2-yl) -phenylcyclohexanamine (polar diastereoisomer) (151 mg, 0.36 mmol) was dissolved in ethanol (10 ml) and mixed with citric acid (77 mg, 0.4 mmol) dissolved in hot ethanol (2 ml). After 20 h of agitation at RT, the resulting colourless solid was removed. Sample 124 was obtained at a yield of 50% (109 mg) with a melting point of 198-199 °C.
5-Methoxycatol (Ind-9, 806 mg, 5 mmol) was dissolved with Ket-4 (985 mg, 5 mmol) in dichloromethane (40 ml) and mixed with trifluoromethane sulphonic acid (0.65 ml, 7.5 mmol). The solution was stirred at RT for 24 h. - For processing, the reaction mixture was mixed with 2N NaOH (20 ml) and mixed at RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 × 20 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The crude product was obtained at a yield of 1.69 g (99%) as a yellowish oil and was used in the next reaction without further purification.
(±) N-[1-Butyl-4-(5-methoxy-3-methyl-1H-indol-2-yl) cyclohex-3-enyl]-N,N-dimethylamine (1.5 g, 4.4 mmol) was suspended in HBr/iron vinegar (33% HBr, 20 ml) and then administered to the RT Sn-powder (2,6 g, 22 mol) in portions for 30 min. After completion of the addition, the reaction mixture was stirred for another 24 h. - For processing, the mixture was diluted with EtOH (20 ml) and obtained at the rotary vapour until dry. The remaining residue was obtained by adding 5 N NaOH (100 g) of basic acid. The residue was obtained by adding 60 g (50 g) of ethanol (50 g) of polar methanol (450 g) to 60 g (400 ml) of methanol (400 g) of methanol (400 g) of methanol (400 g) to 1 ml (150 g) of methanol (400 g) of methanol (400 g) to 1 ml) of extracted methanol (150 g) to 1 g (150 g) of methanol (150 g) (acethanol) (150 g) was obtained by purified from a secondary methanol (150 mg) of methanol (150 g) (150 g (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 ml) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (1
1-Butyl-4- ((5-methoxy-3-methyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (unpolar diastereomer) (50 mg, 0.14 mmol) was dissolved in hot isopropanol (20 ml) and mixed with isopropanolic citric acid solution (28 mg, 0.14 mmol in 2 ml). The mixture was stirred at room temperature for 2 h. The white solid was suctioned. Sample 125 was obtained at a yield of 56 mg (71%) with a melting point of 115-121 °C.
1-Butyl-4- ((5-methoxy-3-methyl-1H-indol)-2-yl) N,N-dimethylcyclohexanamine (polar diastereomer) (125 mg, 0.36 mmol) was dissolved in hot isopropanol (30 ml) and mixed with isopropanolic citric acid solution (70 mg, 0.36 mmol in 2 ml). The mixture was stirred at room temperature for 2 h. The precipitated solid was sucked. Sample 126 was obtained at a yield of 130 mg (65 %).
The free base from sample 29 (385 mg, 1.07 mmol) was suspended in HBr/iron vinegar (33% HBr, 15 ml). The free base was then administered to the RT Sn powder (1.8 g, 15 mmol) in portions for 30 min. After completion of the addition, the reaction mixture was stirred for another 30 min at RT. A clear solution was obtained. - For processing, the mixture was diluted with EtOH (20 ml) and dried at the rotary evaporator. The remaining residue was made basic by adding 5N NaOH (60 ml). The resulting aqueous mixture was added with dichloromethane (4 x 20 ml). The organic phases were washed with water (50 ml) and the remaining residue was removed by adding a mixture of NaOH (60 ml) and a mixture of NaOH (60 ml) to the solution.The resulting residue (360 mg) was boiled in boiling methanol (30 ml) with some solvent. The mixture was RT and refrigerated for 17 h to complete crystallisation. 4-(5-Methoxy-3-methyl-1H-indol-2-yl) N,N-dimethylphenyl-1-hydrohexane ((163 mg (42%)), unpolar diastereoisomer) was separated by filtration as a white solid at a melting point of 156-163 °C (from isopropanol). The methanol parent ether was pressurised and obtained by accromatography [60 g (10 g); 60 g (10 g); OOH/OH: 1 ml) 1 . The ether was obtained by purification in a white solid at a melting point of 227-22% (22%), as from a polar ether.
4- ((Methoxy-3-methyl-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (unpolar diastereomer) (156 mg, 0.43 mmol) was dissolved in isopropanol (10 ml) at boiling temperature and mixed with citric acid (82 mg, 0.43 mmol) dissolved in hot isopropanol (1 ml). During cooling, precipitation failed. To complete the precipitation, the solution was cooled (refrigerated) to 5 °C and left at 17 h. The precipitate was separated by a fryer and then dried.
4- ((Methoxy-3-methyl-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (polar diastereomer, 82 mg, 0.22 mmol) was dissolved in isopropanol (10 ml) at boiling temperature and mixed with citric acid (41 mg, 0.22 mmol) dissolved in hot isopropanol (1 ml). During cooling, precipitation failed. To complete the precipitation, the approach was cooled (refrigerated) to 5 °C and left at this temperature at 17 h. The precipitation was separated by an F and then dried.
The free base from sample 30 (280 mg, 0.81 mmol) was dissolved in ethanol (30 ml), added to the catalyst (Pd/coal 5%, 200 mg) and hydrated for 3 h (sample after 1 h: hardly transition) at RT and 3 bar hydrogen pressure. The solid residue (270 mg) obtained after separation of the catalyst and removal of the solvent was separated column chromatographically (solvent: EtOAc). 1-benzyl-N,N-dimethyl-4- ((3-methyl-1H-indol-2-aminyl) hexanocyclohexane (unpolar diastereoisomer) was obtained at a yield of 71 (25%) %, which is the yield of a more polar diastereoisomer at 145 mg (51%) %.
1-Benzyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl) cyclohexanamine (polar isomer, 130 mg, 0.38 mmol) was dissolved in isopropanol (4 ml) at boiling temperature and mixed with citric acid (80 mg, 0.41 mmol), dissolved in hot isopropanol (2 ml). The solution was cooled to 5 °C (refrigerator) and left to stand for 17 h. The precipitate was separated by a deep frying.
1-Benzyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine, citrate (2:1), unpolar diastereomer 1-Benzyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine (unpolar isomer, 68 mg, 0.20 mmol) was dissolved at boiling temperature in methanol (30 ml) and dissolved with citric acid (60 mg, 0.31 mmol), dissolved in hot methanol (5 ml). The solution was refrigerated at 5 °C (refrigerated) and left to stand at 17 °C. The precipitation was separated by a frost.
3-Methylindol (Ind-10, 524 mg, 4 mmol) was dissolved in dichloromethane (30 ml) together with ketone Ket-4 (788 mg, 4 mmol) and added to trifluoromethane sulphonic acid (0.4 ml, 4.6 mmol). The solution was agitated at RT for 24 h. Then triethyl silane (2 ml, 12.6 mmol) was added to the solution. The reaction mixture was agitated at RT for 60 h. - The reaction mixture was agitated at 2N NaOH (10 ml) for further 20 min. After separation of the phases, the aqueous phase was extracycled with dichloromethane (3 x 20 ml). The dried organic extracts were extracted by heating and dissolving them in 230 mg SO4 and then heated. The gaseous product was obtained by removing the polymers (1,8 mg) from the triethyl isomethyl isomethyl (1-2 mg) (12-methyl isobutyl butyl (12-methyl isobutyl) (12-methyl isobutyl) (12-methyl isobutyl) (12-methyl isobutyl) (12-methyl isobutyl) (12-methyl isobutyl isobutyl) (12-methyl isobutyl) (12-methyl isobutyl isobutyl (12-methyl) (12-methyl isobutyl) (12-methyl isobutyl isobutyl) (12-methyl isobutyl (12-methyl isobutyl) (12-methyl isobutyl isobutyl isobutyl isobutyl) (12-methyl isobutyl isobutyl (12-methyl isobutyl) (12-methyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl isobutyl is
For example, 31 (free base, 210 mg, 0.68 mg) was presented with the catalyst (5% Pd/C, 100 mg) in methanol (50 ml) and hydrated at RT and 3 bar hydrogen pressure. After 1 hour of reaction time, no or almost no turnover was observed. After 6 hours of hydration at RT, no starting product was detectable. - For processing, the catalyst was separated by a fryer and washed with methanol (2 x 20 ml). After removal of the solvent, a residue of 198 mg was obtained.
1-Butyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl) cyclohexanamine (unpolar diastereomer, 102 mg, 0.33 mmol) was dissolved in isopropanol (4 ml) at boiling temperature and mixed with citric acid (62 mg, 0.32 mmol), dissolved in hot isopropanol (1 ml). The solution was cooled at 5 °C in the refrigerator and left for 3 h. The precipitation was separated by a frying process. The hemicitrate of the unpolar isomer Bsp 131 was obtained at a yield of 108 mg (80 %, melting point: 208-211 °C).
1-Butyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl) cyclohexanamine (polar diastereomer, 200 mg, 0.63 mmol) was dissolved in isopropanol (2 ml) at boiling temperature and mixed with citric acid (120 mg, 0.63 mmol), dissolved in hot isopropanol (1 ml). After cooling the solution, a sticky precipitate was produced which solidified to a glassy solid when vacuum-dried. The substance was absorbed in H2O (6 ml) and agitated. The resulting solid was separated by a fryer. The citrate of the polar isomer B 132 was obtained in a yield of 152 mg (59 °C, melting point: 124-129 °C).
The free base from sample 33 (210 mg, 0.567 mmol) was dissolved in methanol (35 ml) and added to coal with palladium (5 per cent; 90 mg). The reaction mixture was hydrated at 3 bar for 5 h. The catalyst was separated via cellite and the filtrate was narrowed. The solid residue (185 mg) was chromatographically separated [silicon gel 60 (40 g); ethylacetate/methanol 10 : 1 (250 ml), ethylacmethanol 4 / methanol 4 : 1 (250 ml) ]. 1-benzyl-4-[[3-cyclopropyl-1H-indolyl-2-) N,N-dimethylcyclohexanamine (polar diastereoisomer) was obtained in a 50% solution (105 mg) with a melting point of 65 °C. The untreated diastereoisomer was obtained in a 60 mg/polar diesel solution (44 mg/polar diastereoisomer) with a further purified byproduct of this mixture (20 mg/polar diastereoisomer) and obtained in a mixture of 43 mg/polar diastereoisomer (20 mg/polar diastereoisomer) and a dilute of 60 mg/polar diesel (20 mg/polar diastereoisomer) [26 mg/polar diastereoisomer] was obtained in a mixture of 26 mg/polar diesel (20 mg/polar diastereoisomer] with a dilute of 43 mg (2,4 mg/polar diastereoisomer] obtained in a dilute solution (20 mg/polar diesel (20 mg/polar diastereoisomer) and a dilute of 40 mg (2,4 mg/polar diesel (20 mg/polar diesel (20 mg/polar diastereoisomer) [26 mg/polar diesel] obtained in a dilute.
1-Benzyl-4-(3-cyclopropyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (unpolar isomer) (41 mg, 0.11 mmol, impure) was dissolved at 60 °C in ethanol (7 ml) and added to an ethanol solution (3 ml) of citric acid (24 mg, 0.12 mmol). After a reaction time of 2 h at room temperature, the colourless solid was separated by filtration and washed with ethanol (2 ml) and diethyl ether (2 ml).
1-Benzyl-4-(3-cyclopropyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (polar isomer) (105 mg, 0.29 mmol) was dissolved at 40 °C in ethanol (5 ml) and mixed with an ethanol solution (3 ml) of citric acid (62 mg, 0.32 mmol). After a reaction time of 16 h at room temperature, no salt was lost. The reaction mixture was pressed. The residue was dissolved in ethanol (1.5 ml). Then diethyl ether (20 ml) was added. After 30 minutes, the colourless solid was separated by filtration and washed off with diethyl ether (2 × 3 ml). The citrate (B 134) was isolated in a 56% (91 mg) spray.
The reaction mixture was hydrated at 3 bar for 4 h. Since no transition was visible, catalyst was added again (Pd/C, 5 per cent, 144 mg) and hydrated at 3 bar for 2 h. After 2 h no conduit was detectable. The catalyst was separated via cellite and the filtrate was isolated. The solid residue (297 mg) was chromatographically separated [silicon 60 (50); methanol (600 ml). 1-butyl-4-cyclopropyl-1-butyl-2-indol-2-N-N, 1-n-cyclohexane (dimethyl dimethyl) diethyl) diethylamine (dimethyl) was obtained from a melting point of 62 °C (209 °F) with a further 62% diethyl (27-29 mg).
Other
1-Butyl-4-(3-cyclopropyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (polar diastereomer) (135 mg, 0.398 mmol) was dissolved in trichloromethane (15 ml) and methanol (10 ml) and added to propane-2-ol with a 5N hydrochloric acid (0.16 ml, 0.8 mmol). The purple solution was compressed and added to diethyl ether (40 ml). After 30 min, the hydrochloride was separated by filtration and washing with diethyl ether (2 × 2 ml) as a purple solid. The sample was obtained at a yield of 135 56% (84 mg) with a melting point of 274-276 °C.
The solid residue (306 mg) was chromatographically separated [silica 60 (45 g); ethyl acetate/methanol 4 : 1 (500 ml); methanol 124 mg). The reaction mixture was hydrated at 3 bar for 5 h. Since the implementation was not complete, a further catalyst (40 mg) was added and hydrated for a further 16 h. The catalyst was separated via cellite and the filtrate was narrowed. The solid residue (306 mg) was chromatographically separated [silica 60 (45 g); ethyl acetate/methanol 4 : 1 (500 ml); methanol (200 ml). 4-Cyclopethyl-1H-indol-2-yl) N, N-dimethyl-1-phenyl (polar diethyl) diethyl) diethyl (polar diethyl) diethyl) was obtained from 0.5% ethanol at 64 °C. The solid was separated from the ethanol at a temperature of 62 °C. The ethanol was then dissolved in a solution of 30 mg (268 ml) of ethanol (26-dimethyl-methyl) diethyl (146 mg) diethyl and ethanol (26-dimethyl) diethyl (146 mg) diethyl) at a temperature of 56 °C. The ethanol was then dissolved in a solution of 56 mg (268 °C) ethanol (26-dimethyl-methyl) diethyl (26-methyl) diethyl (246 mg (26-dimethyl) diethyl) and ethanol (146 mg (246 ml) diethyl (146 mg (26-dimethyl) diethyl) diethyl) at a temperature of 56 °C.
Methyl 2- ((1H-indol-3-yl) acetate (Ind-47, 757 mg, 4 mmol) was dissolved in dichloromethane (80 ml) together with ketone Ket-10 (868 mg, 4 mmol) and replaced with trifluoromethane sulphonic acid (540 μl, 6 mmol). The solution was stirred at RT for 16 h. For processing, the reaction mixture was stirred with 2N NaOH (50 ml) and replaced with RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 × 20 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The resulting raw product (1,52 g) was obtained by column heating [cycloheatography]; 60 g (100 g) of methyl methyl methyl phenol (± 300 ml) was obtained as a purified solid of 2-dimethyl-1-methyl (1-3-dimethyl) phenol (60 mg) in the form of 60 ± 300 g (1-36-dimethyl) methyl-1-3-methyl (1-3-methyl) phenol (60 mg) obtained as a purified product.
(±) -Methyl 2-((2-(4-dimethylamino) -4-phenylcyclohex-1-enyl) -1-H-indol-3-yl) acetate (936 mg, 2.4 mmol) was dissolved in HBr/iron vinegar (33% HBr, 30 ml) and then administered to the RT Sn powder (2,88 g, 24 mmol) in 1 hour portion-by-portion approach. After completion of the addition, the reaction mixture was stirred for a further 16 h at RT. For processing, the mixture was diluted with EtOH (10 ml) and pressed to dry at the rotary steam. The remaining residue was made by adding 2 N NaOH (100 mg) to the base of the vinegar. The resulting product was extracted with dichloromethane. The resulting product was extracted from a polymeric diethyl methacrylate (NOOH) of 60 × 40 mg (2,2 to 3,00 mg (2,2 to 3,00 mg) by weight. The product was obtained from a polymeric diethyl methacrylate (NOOH) of 60 mg (2,2 to 1,00 mg (2,2 to 1,00 to 1,400 ml) by weight) and obtained by extracting methanol from a purified oil.
Methyl 2-(2-(4-(dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) acetate (unpolar diastereomer) (290 mg, 0.74 mmol) was dissolved in hot dichloromethane (150 ml) and added to citric acid (143 mg, 0.74 mmol). The clear solution was left for 16 h at 4 °C. The discarded colourless solid was sucked and dried. Sample 137 was obtained at a yield of 250 mg (67%) with a melting point of 226-229 °C.
Other
The mean of the measurements is calculated as the mean of the measurements of the two samples taken at the same time.
Other
The following are the most commonly reported abnormalities in the treatment of the disease:
[Methyl 2-(2-(4-dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) acetate (polar diastereomer) (200 mg, 0.51 mmol) was dissolved in hot dichloromethane (100 ml) and added to citric acid (99 mg, 0.96 mmol). The clear solution was left for 16 h at 4 °C. The discarded colourless solid was sucked and dried. Sample 138 was obtained at a yield of 170 mg (57%) with a melting point of 190-193 °C.
Other
The measurement of the frequency of the measurement is based on the following equations:
Other
The following are the most commonly reported abnormalities in the treatment of the disease:
The product was dissolved as a hydrobromide. It was filtered and washed with water (33 × 5 ml). To the pink, wet solid (5.0 g) was added 1 N NaOH (50 g) at room temperature, and the mixture was further diluted with extracted chloroplasts (3 30 g) and stirred for another 20 min. The organic naphthalene was further diluted with water (300 g) at 5 °C. The product was dissolved as a hydrobromide. It was filtered and washed with water (2 5 mg × 5 ml). The pink, wet solid (5.0 g) was added to the solution with NaOH (50 g). The mixture was further diluted with extracted diethyl methacrylate (3 30 g) after extraction. The organic naphthalene was further diluted with 48 g of benzoyl triethyl phthalate (42 g × 48 g) at 120 °C. The solution was completely removed from the solution with methacrylate (1 60 mg × 1 ml) and dissolved in a vacuum (160 mg × 1 ml) of methacrylate (160 mg × 1 g) and dimethyl methacrylate (1 60 mg/ml) at 60 °C. The best part of this solution was removed from the solution with methacrylate (1 60 mg/ml) and dissolved in a white (160 mg (260 mg/ml) (160 × 1 g/ml) of methacrylate (160 mg/ml) (160 g/ml/ml/g/g (260 g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g/g
1-Benzyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl) N,N-dimethylcyclohexanamine (unpolar diasteroisomer, 285 mg, 0.641 mmol) was dissolved in hot ethanol (12 ml) and mixed with an equally hot ethanolic citric acid solution (135 mg, 0.703 mmol in 2 ml). The mixture was then stirred overnight at room temperature, then filtered and washed with some ethanol.
1-Benzyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl) N,N-dimethylcyclohexanamine (polar diastereomer) (92 mg, 0.215 mmol) and citric acid (44 mg, 0.229 mmol) were dissolved in hot ethanol (0.5 ml). For a clear solution, diethyl ether (10 ml) was slowly added at room temperature. The mixture was stirred at room temperature overnight. A white solid was produced, which was filtered and washed with diethyl ether.
For example, 37 (750 mg, 1.64 mmol) was dissolved in hydrogen bromide/iron vinegar (33% HBr, 40 ml). Then tin powder (1,950 g, 16.43 mmol) was added to the solution at room temperature for 40 min. The solution was stirred for another 20 min. The mixture was then diluted with water (300 ml). The solution was stirred for 1 h at 5 °C. The product was dissolved as hydrobromide. It was filtered and washed with water (2 × 5 ml). Pink, moist solid (5.0 g) was added 1 N NaOH (50) to the solution. The mixture was combined with dried dichloromethane (3 × 30 ml). The organic naphthalene was filtered with P2SO4 and then filtered.The volatile components of the filtrate were completely removed in a vacuum. The solid (615 mg) was stirred with methanol (6 ml) overnight at room temperature. 1-benzyl-4-(3-benzyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (unpolar diastereoisomer) was obtained as a beige solid. It was filtered and washed with methanol (2 × 1 ml) and diethyl ether (2 × 1 ml) (277 mg). The fillet was narrowed (330 mg). After chromatographic separation of this oil [silicon 60 (40 g); ethyl acetate (1500 ml) ] further quantities of unpolar diastereoisomer (61 mg, total: 49% at 140 °C-143 °C) and polar diastereoisomer (207 mg, 30 mg) were obtained.
1-Benzyl-4-(3-benzyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (unpolar diasteroisomer) (304 mg, 0.719 mmol) was dissolved in a mixture of dichloromethane (4 ml) and ethanol (2 ml) and added to ethanolic citric acid solution (145 mg, 0.755 mmol in 4 ml). The solution was compressed to approximately 2 ml. The solid was vacuumed and washed with ethanol (2 × 0.5 ml).
1-Benzyl-4-(3-benzyl-1H-indol-2-yl) N,N-dimethylcyclohexanamine (polar diasteroisomer) (85 mg, 0.201 mmol) and citric acid (43 mg, 0.224 mmoi) were dissolved in ethanol (2 ml). For a clear solution, diethyl ether (20 ml) was slowly added at room temperature. The mixture was stirred at room temperature for 1 h. A beige solid was released, which was filtered and washed with diethyl ether (2 × 1 ml). 142 samples were obtained at a yield of 69% (76 mg) with a melting point of 110-115 °C.
The solution was dissolved in hydrogen bromide/iron vinegar (33% HBr, 40 ml) and then added to the solution at room temperature in tin powder (2,150 g, 18.1 mmol) for 40 min, stirring the solution for another 20 min. The mixture was then diluted with water (250 ml) and stirred for 1 h at 5 °C. The solution was dissolved as a hydrobromide. It was filtered and washed with water (25% HBr, 40 ml). To the beige wet solid (5.0 g) was added 1 N NaOH (50 ml). The mixture was combined with chloroplast (360 g, 18.1 mmol) and extracyclic chloroplast (360 g, 30 g, 164-60 g) The organic compounds obtained were:
1-Butyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl) N,N-dimethylcyclohexanamine (unpolar diastereoisomer) (277 mg, 0.702 mmol) and citric acid (142 mg, 0.739 mmol) were dissolved in hot ethanol (20 ml). A solid was precipitated at room temperature. The mixture was left overnight at 5 °C, then filtered and washed with some ethanol. Example 143 was obtained at a yield of 72% (298 mg) with a melting point of 228-232 °C.
1-Butyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl) N.N-dimethylcyclohexanamine (polar diastereomer) (135 mg, 0.342 mmol) and citric acid (71 mg, 0.370 mmol) were dissolved in hot ethanol (4 ml). For a clear solution, diethyl ether (26 ml) was slowly dripped at room temperature. The mixture was stirred at room temperature overnight. The white solid was filtered and washed with diethyl ether. was obtained at a yield of 50 % (101 mg) with a melting point of 268-272 °C. This product was identified as hydrochloride.
For example, 39 (438 mg, 1.133 mmol) was dissolved in hydrogen bromide/iron vinegar (33% HBr, 25 ml). Tin powder (1,345 g, 11.330 mmol) was then added to the solution at room temperature for 40 min, and the solution was stirred for another 20 min. The mixture was then diluted with water (100 ml). The solution was stirred for 1 h at 5 °C. The product was dissolved as hydrobromide. It was filtered and washed with water (2 × 5 ml). The wet yellow solid (4.0 g) was added 1 N NaOH (50 ml). The mixture was extracted with dichloromethane (3 × 30 ml) P. The organic Na2SO4 was combined with dihydromethane (3 × 30 ml) P. The organic Na2SO4 was dried and filtered.Err1:Expecting ',' delimiter: line 1 column 703 (char 702)
4- ((benzyl) - 1-H-indol-2-yl) -butyl-N,N-dimethylcyclohexanamine (unpolar diastereoisomer, 121 mg, 0.311 mmol) dissolved in hot ethanol (2 ml) and mixed with ethanolic citric acid solution (63 mg, 0.328 mmol in 1 ml). The mixture was stirred at room temperature for 2 h. The precipitated solid was sucked out and washed with diethyl ether (2 × 1 ml). 145 samples were obtained at a yield of 61% (111 mg) and a melting point of 1671 °C.
4- ((Benzyl-1H-indol-2-yl) 1-butyl-N,N-dimethylcyclohexanamine (polar diastereoisomer, 157 mg, 0.404 mmol) was dissolved in diethyl ether (10 ml) and mixed with ethanolic citric acid solution (83 mg, 0.432 mmol in 0.5 ml). The mixture was stirred at room temperature for 2 h. The resulting solid was sucked out and washed with diethyl ether (2 × 1 ml). Example 146 (beige solid) was obtained at a yield of 55 % (130 mg) at a melting point of 90-95 °C (HPLC purity of about 88%)
For example, 40 (913 mg, 2,033 mmol) was dissolved in hydrogen bromide/iron vinegar (33% HBr, 46 ml). Tin powder (2,415 g, 20,344 mmol) was then added to the solution at room temperature for 40 min in portions and the solution was stirred for another 20 min. The mixture was then diluted with water (300 ml). The solution was stirred for 1 h at 5 °C. The product was dissolved as hydrobromide. It was filtered and washed with water (2 × 5 ml). To the pink wet solid (5.7 g) 1 N NaOH (50 ml) was added. The mixture was combined with extra-dry dichloromethane (3 × 30 ml). The organic nahas were dried with P2SO4A yellow solid (776 mg) was left behind. After chromatographic separation of this mixture [silica gel 60 (80 g); ethyl acetate (500 ml), ethyl acetate/methanol 20 : 1 (525 ml), ethyl acetate/methanol 5 : 1 (600 ml), ethyl acetate/methanol 2 : 1 (600 ml) ] and the polar diastereoisomer (269 mg, 32%, Schmp.: 195-198 °C) were obtained as white solids.
Other
The nonpolar diastereomer was further purified by mixing with methanol (15 ml) and stirring overnight, then filtration. The residue was washed with methanol (3 × 1 ml). The white solid was obtained at a yield of 40% (336 mg) with a melting point of 206-209 °C).
4-3-((Cyclohexylmethyl)-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (unpolar diastereomer) (294 mg, 0.706 mmol) and citric acid (141 mg, 0.734 mmol) were dissolved in hot ethanol (7 ml). A solid precipitate was obtained at room temperature. The mixture was stirred overnight at room temperature, then filtered and washed with some ethanol.
4-((Cyclohexylmethyl)-1H-indol-2-yt) N,N-dimethyl-1-phenylcyclohexanamine (polar diastereomer) (245 mg, 0.588 mmol) and citric acid (122 mg, 0.635 mmol) were dissolved in hot ethanol (2 ml). For a clear solution, diethyl ether (12 ml) was slowly dripped at room temperature. The mixture was stirred overnight at room temperature. The white solid was filtered and washed with diethyl ether.
The product was dissolved as a hydrobromide. It was filtered and washed with 205 (23% HBr, 40 ml). The beige fatty solid (4,3 g) was returned to 1 N NaOH (50) at room temperature, and the mixture was extracted with 30 g of ethylene glycol (30,060 g, 17,353 mmol) and stirred for another 20 min. The organic compounds obtained were: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl methacrylate: benzoyl metha
4- ((Benzyl-1H-indol-2-yl) N.N-dimethyl-1-phenylcyclohexanamine (unpolar diastereoisomer) (146 mg, 0.357 mmol) was dissolved in a mixture of dichloromethane (4 ml) and ethanol (0.5 ml) and mixed with ethanolic citric acid solution (73 mg, 0.380 mmol in 3.5 ml). The solution was compressed to approximately 2 ml. The resulting solid was extracted and washed with ethanol (2 × 0.5 ml).
4- ((Benzyl-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (polar diastereoisomer) (150 mg, 0.367 mmol) was dissolved in dichloromethane (10 ml) and mixed with ethanolic citric acid solution (77 mg, 0.401 mmol in 10 ml). The solution was reduced to approximately 2 ml. The resulting solid was extracted and washed with ethanol (2 × 0.5 ml) and diethyl ether (2 × 0.5 ml).E.g. 150 was obtained at a yield of 74% (163 mg) at a melting point of 140-143 °C.
(±) -Dimethyl- ((1-phenyl-4- ((3-pyridine-2-ylmethyl-1H-indol-2-yl) cyclohex-3-enyl]amine To a solution of Ind-49 (2.17 g, 10.4 mmol) and Ket-10 (2.70 g, 12.5 mmol) in anhydrous dichloromethane (80 ml) was given trifluoromethane sulphonic acid (3.95 g, 2.30 ml, 26 mmol) under ice-cooling. The reaction mixture was stirred 2 d at room temperature and then stirred with 0.5 M sodium chloride (50 ml) and 2 h at room temperature. The phases were separated, the aqueous phase was extracted with dichloromethane (3 × 30 ml) and the organic phase was dried with vanadium triphosphate. The product was purified by a flash methanol (7.6 × 20 g) and e.g. (6.45 cm) (9 g) was purified with methanol.
Other
The following shall be added to the list of products:
Other
The mean time between the onset and the onset of treatment is approximately 1 minute and 5 minutes, and the mean time between the onset and the onset of treatment is approximately 1 minute and 6 minutes.
(±) -Dimethyl-[1-phenyl-4-(3-pyridine-2-ylmethyl-1H-indol-2-yl) cyclohex-3-enyl]amine (200 mg, 0.49 mmol) was dissolved by stirring for one hour at room temperature in a 33% solution of hydrogen bromide in ice vinegar. The solution was then stirred with tin powder (622 mg) in portions for 30 min. The mixture was then stirred overnight at room temperature. The mixture was stirred with ethanol (10 ml) and compressed into i. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. a. aThe unpolar and polar diastereomers could be separated and were precipitated as hydrochloride due to the chloroform used. To obtain the free base, sodium hydrocarbonate solution was added to each and extracted with dichloromethane (3 × 10 ml).
Other
The combined organic phases were dried with sodium sulphate and compressed i.v. yield: 25 mg (12%) of yellowish amorphous solid
Other
The mean value of the dose for each dose group is given by the following formulae:The time interval between the first and second measurements is given by the following equations: 16 (s, 2H); 6.86 (t, 1H, J = 7.4 Hz); 6.96 (t, 1H, J = 7.5 Hz); 7.06-7.16 (m, 2H); 7.22-7.43 (m, 7H); 7.59 (dt, 1H, J = 7.7 and 1.8 Hz); 8.44 (d, 1H, J = 3.9 Hz); 10.77 (s, 1H).
Other
The test chemical is used to determine the concentration of the test chemical in the test medium.
Other
The mean value of the dose for each dose group is given as follows: 1.48 (t, 2H, J = 12.3 Hz); 1.65 (t, 4H, J = 12.1 Hz); 1.92 (s, 6H); 2.77 (d, 2H, J = 11.3 Hz); 3.03 (t, 1H, J = 11.8 Hz); 4.11 (s, 2H); 6.83 (t, 1H, J = 7.3 Hz); 6.91 (t, 1H, J = 7.0 Hz).The following are the most commonly used frequencies: 0 Hz, 7.03 (d, 1H, J = 7.8 Hz), 7.13 (dd, 1H, J = 7.9 and 4.9 Hz); 7.17 (d, 1H, J = 7.9 Hz), 7.30 (d, 2H, J = 7.6 Hz); 7.36-7.46 (m, 4H); 7.59 (dt, 1H, J = 7.6 and 1.8 Hz); 8.45 (d, 1H, J = 3.8 Hz); 10.45 (s, 1H).
Ketone-10 (1.9 g, 8.75 mmol) and Indol Ind-50 (1.66 g, 8.75 mmol) were dissolved in HBr/iron vinegar (33% HBr, 50 ml) and agitated at RT for 16 h. Then, for the RT approach, Sn-powder (10.5 g, 87.5 mmol) was administered in 2 h portions. After completion of the addition, the reaction mixture was agitated at RT for another 48 h. For processing, the mixture was diluted with EtingeOH (20 ml) and evaporated to dry at the rotary evaporator. The resulting product was purified by column chromatography [silicon 60 (300 g); meOH (3000 ml] 3-[2-dimethylphenyl-4-cyclohexanol) 3-hydroxyethyl ester (119-hydroxyethyl ester) was obtained as a white solid (12 mg) obtained from a 4 per cent dilution.
3-[2- ((4-Dimethylamino-4-phenylcyclohexyl) - 1H-indol-3-yl]propionic acid (polar diastereomer) (419 mg, 1.08 mmol) was dissolved in ethyl acetate (50 ml). In RT, Me3SiCl (276 μl, 1.16 mmol) was dripped and stirred for 16 h. The solvent was distilled in the rotary evaporator and obtained as white solid sample 153 (458 mg, Fp. 242-245 °C. 100 %).
For example, 42 (956 mg, 2.57 mmol) was dissolved in methanol (60 ml), added to Pd/C (5%, 300 mg) and hydrated at 3 bar 3 h at 40 °C under stirring. For processing, the catalyst was filtered via Celite and the methanol removed in vacuum. After chromatographic separation of the remaining residue, the remaining methanol was obtained by chromatographic separation (834 mg of yellow oil) [silicon yellow 60 (70 g); cyclohexane/ethylacetate 2 : 1 (450 ml), cyclohexane/ethylacetate 1 : 1 (1000 ml), ethylacetate (500), ethylacetate 1 1 1 (300 ml) ] from a single coloured solid (432 mg). This was obtained in ethylacetate (32 ml) and then filtered with ethylacetate (38 ml) and suspended at two temperature levels (20 °C) and obtained as a single coloured solid (2,2 mg, 22 mg, 23 mg, 22 mg, 23 mg, and 0,5 mg) from a suspension of ethylacetate (2,2 mg, 23 mg, 22 mg and 2 mg) and a suspension of ethylacetate (2,2 mg, 22 mg, 23 mg, and 2 mg).
Other
1-Benzyl-N.N-dimethyl-4-(3-propyl-1H-indol-2-yl) cyclohexanamine (200 mg, 0.534 mmol) and citric acid (105 mg, 0.547 mmol) were dissolved in hot methanol (6 ml). The clear solution was vacuum-pressed. The residue was stirred with ethyl acetate (5 ml) overnight, then filtered and washed with diethyl ether (2 × 2 ml). 156 samples were obtained at a yield of 61% (185 mg) at a melting point of 250-265 °C (sublimation point above 230 °C).
After chromatographic separation of the remaining residue (769 mg of yellow oil) [silica gel 60 (70 g); ethyl acetate/methanol 100: 1 (500 ml), ethyl acetate/methanol 20: 1 (525 ml), ethyl acetate/methanol 10:1 (1100 ml), ethyl acetate/methanol 5:1 (350 ml), ethyl acetate/methanol 1:1 (300 ml), ethanol 1:1 (350 ml) ], a medium oil (550 mg) was obtained and a solid was obtained. This was then obtained from a diethyl ether (10 ml) at a temperature of 78 °C. The solid was obtained from a white, diethyl ether (172 mg, ethanol, butyl acetate, 1-2,2 mg, ethanol, 1-47 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, 12 mg, and mg, and mg, and mg, and mg, and mg, and mg, and mg, respectively. This solid was obtained from the remaining residue was obtained in a diethyl ether (569 gels,
1-Butyl-N,N-dimethyl-4-(3-propyl-1H-indol-2-yl) cyclohexanamine (1 diastereomer) (73 mg, 0.214 mmol) and citric acid (43 mg, 0.224 mmol) were dissolved in hot methanol (5 ml). The clear solution was compressed in a vacuum. The residue was stirred with diethyl ether (15 ml) overnight, then filtered and washed with diethyl ether (2 × 1 ml). 158 samples were obtained as a white solid at a yield of 71 % (81 mg) with a melting point of 83-90 °C.
The solution was dissolved in hydrogen bromide/iron vinegar (33% HBr, 70 ml) for 20 min. After separation of the phases, the aqueous phase (3 with dichloromethane 20 ml) was extracted. The combined organic extracts were dried over Na2SO4 for 1 hour and the solution was stirred for 1 hour. The mixture was then diluted with dichloromethane (250 ml). Under cooling, 3N sodium hydroxide solution (750 ml) was added. The solution was stirred for 20 min at room temperature. After separation of the phases, the aqueous phase (3 with dichloromethane 20 ml) was extracted. The combined organic extracts were dried over Na2SO4 and then e-propaneated at 177 °C (976 mg). The polar solvent of this compound: Glycyl methacrylate (550 mg/mL): 60 g (150-150 mg/mL) (150-150 mg/mL) (150-150 mg/mL) (150-150 mg/mL) (150-150 mg/mL) (150-150-150 mg/mL) (150-150-150 mg/mL) (150-150-150 mg/mL) (150-150-150-150 mg/mL) (150-150-150-150 mg/mL) (150-150-150-150 mg/mL) (150-150-150-150-150 mg/mL) (150-150-150-150-150 mg/mL) (150-1/mL) (150-150-150-150-1/mL) (150-1/mL) (150-1/mL) (150-150-1) (150-1) (150-1) (150-150-1/mL) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (150-1) (120 mg/m (150-1) (150-1) (120-1) (120-1) (120-150-1)
N,N-dimethyl-1-phenyl-4-(3-propyl-1H-indol-2-yl) cyclohexanamine (unpolar diastereoisomer) (155 mg, 0.430 mmol) was dissolved in hot methanol (80 ml) and mixed with methanol citric acid solution (85 mg, 0.442 mmol in 5 ml) and stirred for 2 h at 0 to 5 °C and then filtered. 159 samples were obtained as white solids at a yield of 77 % (182 mg) and a melting point of 243-249 °C.
N,N-dimethyl-1-phenyl-4- ((3-propyl-1H-indol-2-yl) cyclohexanamine (polar diastereoisomer) (248 mg, 0.688 mmol) and citric acid (136 mg, 0.707 mmol) were dissolved in methanol (5 ml). The clear solution was compressed in a vacuum. The residue was stirred with ethyl acetate (5 ml) for 1 h, then filtered and washed with diethyl ether.
A solution of olefin sample 45 (335 mg, 0.769 mmol) in methanol (40 ml) was added to the catalyst (110 mg, 5% Pd/C) and hydrated at 3 bar 4 h at 40 °C under stirring. For processing, the catalyst was filtered and the methanol removed in a vacuum. After chromatographic separation of the remaining residue [silica gel 60 (40 g): ethyl acetate/methanol (10: 1.550 ml), ethylac/methanol (1: 1.550 ml), ethyl acetate/methanol (1: 2.480, 480 ml), methanol (750 ml) ], the nonpolar diastereoisomer (93 mg, 27%, Schemper: 233-237 °C) and the polar diastereoisomer (150 mg, 44-203 °C: 20-34% Schemper: 198°C) were obtained as white solids.
The mean of the measurements is calculated as the mean of the measurements of the two samples taken at the same time.
Other
The following are the most commonly used medicinal products:
The mean value of the measurement of the effect of the measurement on the concentration of the substance in the sample is calculated by multiplying the mean value of the measurement by the mean value of the measurement of the concentration of the substance in the sample.
Other
The following are the most commonly reported effects of the drug:
The newly produced unpolar diastereomer (70 mg, 0.160 mmol) was dissolved in a mixture of methanol (2 ml) and chloroform (2 ml) and mixed with citric acid (33 mg, 0.172 mmol), dissolved in methanol (2 ml). The clear solution was compressed in a vacuum. The residue was dissolved in hot ethanol (4 mi).
Other
The following is a list of the most commonly used methods of measuring the frequency of the radio frequency spectrum:
The polar diastereomer (135 mg, 0.308 mmol) and citric acid (60 mg, 0.312 mmol) obtained in example 161 were dissolved in methanol (4 ml). The clear solution was compressed in a vacuum and the residue dissolved in hot isopropanol (10 ml). The mixture was stirred at 5 °C for 2 h. The desired citrate was obtained as a white solid which was filtered and washed with diethyl ether. The product was obtained at a yield of 61% (119 mg) with a melting point of 122-150 °C.
Other
The mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour, and the mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour.
A solution of olefin sample 46 (390 mg, 0.971 mmol) in methanol (40 ml) was added to the catalyst (140 mg, 5% Pd/C) and hydrated at 3 bar 2 h at 40 °C under stirring. For processing, the catalyst was filtered and the methanol removed in a vacuum. After chromatographic separation of the remaining residue [silica gel 60 (50 g); ethyl acetate/methanol (5: 1.250 ml), ethyl acetate/methanol (1: 1.450 ml), methanol (1800 ml) ], the unpolar diastereoisomer (89 mg, 23%, Schmp: 210-250 °C, sublimated over 200 °C) and the polar diastereoisomer (221 mg, 56 mg, Schmp: 2012 °C) were obtained as white solids.
The mean value of the measurement of the effects of the test chemical on the human body is calculated by dividing the mean value of the measurement of the effects of the test chemical by the mean value of the measurement of the effects of the measurement of the test chemical on the human body.
Other
The following are the most commonly reported effects of the drug on the brain:
Other
To produce the citrate, the newly obtained nonpolar diastereomer (63 mg, 0.156 mmol) and citric acid (31 mg, 0.161 mmol) were dissolved in hot methanol (20 ml). The clear solution was compressed in a vacuum, and the residue dissolved in hot ethanol (2 ml). Ethylacetate (8 ml) and diethyl ether (30 ml) were slowly added to the solution in RT. The desired citrate turned out to be a white solid. The vegetable was stirred overnight in RT, then filtered and washed with diethyl ether. The yellow powder was washed in a 61% (57 mg) solution with a melting point of 184-187 °C.
The mean of the measurements performed in the controlled dose range was approximately 0.01% for the controlled dose, and the mean of the controlled dose was approximately 0.01% for the controlled dose.
The polar diastereomer (234 mg, 0.580 mmol) and citric acid (113 mg, 0.588 mmol) obtained in example 163 were dissolved in hot methanol (20 ml). The clear solution was compressed in a vacuum, and the residue dissolved in hot ethanol (4 ml). Ethylacetate (6 ml) and diethylether (20 ml) were slowly added to the solution at RT. The mixture was stirred at RT overnight. The desired citrate turned out to be a yellow powder, which was filtered and washed with diethylether. The product was obtained at a yield of 76% (261 mg) with a melting point of 97-103 °C.
The solution was then added slowly under refrigeration so that the temperature did not exceed 25 °C. The mixture was stirred for 20 minutes. The phases were separated. The liquid phase was obtained with dichloromethane (50 g, 4.8 mmol) and the solution stirred for 1 h. The organic compound was dissolved in a solid state of 250 ml (250 mg/ ml): ethyl methanol (1,260 mg/ ml), ethyl methanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,230 mg/ ml), ethanol (2,260 mg/ ml), ethanol (2,230 mg/ ml), ethanol (2,230 mg/ ml), ethanol (2,250 mg/ ml), ethanol (2,250 mg/ ml), ethanol (2,250 mg/ ml), ethanol (2,250 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2,2 mg/ ml), ethanol (2, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, ethanol, et
The mean value of the measurement of the dose of the active substance is calculated by dividing the dose by the dose of the active substance in the dose range from 1 μg/ kg to 1 μg/ kg.
Other
The mean of the measurements is calculated as the mean of the measurements of the two samples taken at the same time.
The mean of the measurements is calculated as the ratio of the mean value of the measurements to the mean value of the measurements.
Other
The following is a list of the active substances that may be used in the administration of the active substance:
To produce the desired citrate, the newly obtained nonpolar diastereomer (122 mg, 0.288 mmol) and citric acid (57 mg, 0.297 mmol) were dissolved in methanol (200 ml) under high heat. The solution was reduced to 10 ml and left overnight at 5 °C. The failed citrate was sucked and washed with methanol (2 x 0.5 ml). The white solid was obtained at a yield of 86% (153 mg) with a melting point of 198-203 °C, and 273-278 °C.
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Other
The following are the most commonly reported effects of the drug:
The polar diastereomer (58 mg, 0.137 mmol) and citric acid (28 mg, 0.146 mmol) produced in example 165 were dissolved in methanol (80 ml) under heating conditions. The solution was reduced to 10 ml and left overnight at 5 °C. The failed citrate was sucked out and washed with methanol (2 x 0.5 ml). The white solid was obtained at a yield of 65% (55 mg) with a melting point of 223-225 °C.
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Indol (Ind-54, 0.850 g, 3.08 mmol) and ketone (Ket-10, 668 mg, 3.08 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.82 ml, 9.24 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (15 ml) and CH2Cl2 (20 ml), stirring continued for 60 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, combining the organic phases with washed, dried water (Na2SO4) and compressing the solution i.e. vacuum. The solution was cleaned by flash chromatography with CHCl3/OH (9:1) Me.
Other
The yield is 777 mg (53%) of porous solid
Other
The mean value of the dose of the active substance is 1.74 (1 H, m); 2.12 (8 H, m); 2.37 (2 H, m); 2.56 (1 H, m); 2.98 (2 H, t); 3.18 (2 H, t); 3.49 (3 H, s); 6.08 (1 H, s); 6.88 (1 H, t); 7.01 (1 H, m); 7.22 (6 H, m): 7.44 (4 H, m); 7.61 (1 H, d); 10.66 (1 H, s).
The solution of the newly produced olefin (770 mg, 1.62 mmol) in HBr/iron vinegar (40 ml) was given tin (1.92 g) for 30 min and stirred at RT for 5 h. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-tight. The remaining residue was separated by CHCl:13/MeOH (20:1 → 1:1) chromatography.
Other
| 223 mg (29 %), unpolares Diastereomer | |
| 176 mg (23 %), polares Diastereomer |
The resulting unpolar diastereomer (200 mg, 0.42 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (80 mg, 0.42 mmol) in hot ethanol (5 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is 1.48 (4 H, m); 2.18 (8 H, m); 2.72 (7 H, m); 3.16 (4 H, m); 3.52 (3 H, s); 6.98 (2 H, m); 7.01 (2 H, m); 7.16 (2 H, m); 7.44 (9 H, m); 10.67 (1 H, s).
Other
Citrate (ethanol)
The polar diastereomer (168 mg, 0.35 mmol) obtained in example 167 was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (68 mg, 0.35 mmol) in hot ethanol (3 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.35 (2 H, m); 1.54 (2 H, m); 2.00 (2 H, m); 2.37 (6 H; s); 2.61 (2 H, m); 2.83 (4 H, m); 3.14 (4 H, m); 3.53 (3 H, s); 6.88 (3 H, m); 7.19 (3 H, m); 7.49 (7 H, m); 10.36 (1 H, s).
Other
Citrate (ethanol)
3-(2-Pyridine-2-yl-ethyl) - 1H-indol (Ind-55, 444 mg, 2.0 mmol) and ketone (Ket-10, 434 mg, 2.0 mmol) were dissolved in a mixture of dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.54 ml, 6.0 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (10 ml) and CH2Cl2 (10 ml), stirring continued for 30 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, drying (NaSO24) and narrowing the solution i.e. vacuum. The resulting solution was cleaned with CHOH (93/Cl) by flash chromatography (9:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.75 (2 H, m); 2.12 (8 H, m); 2.40-2.69 (3 H, m); 2.90 (2 H, m); 3.06 (2 H, m); 6.15 (1 H, bs); 6.89 (1 H, m); 6.98 (1 H, m); 7.09 (1 H, m); 7.22 (5 H, m); 7.39 (1 H, m); 7.49 (2 H, m); 7.64 (1 H, m); 8.52 (1 H, m); 10.58 (1 H, s).
The solution of the newly produced olefin (300 mg, 0.71 mmol) in HBr/iron vinegar (15 ml) was given tin (0.9 g) and stirred for 20 min at RT for 3 h. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (20 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-tight. The remaining residue was separated by CHCl:13/OH (9:1/Me → 4:1) chromatography.
Other
| 141 mg (47 %), unpolares Diastereomer | |
| 58 mg (19 %), polares Diastereomer |
The resulting nonpolar diastereomer (116 mg, 0.27 mmol) was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (53 mg, 0.27 mmol) in hot ethanol (3 ml).
Other
The maximum content of the active substance is the maximum content of the active substance.
The mean value of the dose of the active substance is 1.42 (2 H, m); 1.56 (2 H, m); 2.01 (2 H, m); 2.15 (6 H, s); 2.64-2.77 (6 H, m); 3.04 (2 H, t); 3.45 (2 H, t); 6.93 (2 H, m); 7.14 (2 H, m); 7.42 (6 H, s); 7.62 (1 H, m); 8.49 (1 H, m); 10.49 (1 H, s).
Other
Citrate (ethanol)
The polar diastereomer (58 mg, 0.14 mmol) obtained in example 169 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (27 mg, 0.14 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.40 (2 H, m); 1.58 (2 H, m); 1.88 (2 H, m); 2.41 (6 H, m); 2.54-2.66 (4 H, m); 2.76 (1 H, m); 2.99 (6 H, m); 6.87 (2 H, m); 7.04 to 7.23 (3 H, m); 7.41 (1 H, m); 7.61 (6 H, m); 10.30 (1 H, s).
Other
Citrate (ethanol), porous solid
4-[2- ((4-benzyl-4-dimethylaminocyclohex-1-enyl) -H-indol-3-yl]butanoic acid 4- (((1H-indol-3-yl)butanoic acid (Ind-56, 813 mg, 4 mmol) was dissolved in dichloromethane (80 ml) together with ketone ketone 3 (926 mg, 4 mmol) and substituted with trifluoromethanesulfonic acid (540 μl, 6 mmol). The solution was agitated at RT for 48 h. The reaction mixture was agitated at H2O (20 ml) for processing. After separation of the organic phase, the aqueous solution was extracted with dichloromethane (3 x 20 mg, 4 mmol). The organic extracts were obtained as NaOH2SO4 and subsequently e-glycol. The product was purified by a raw methyl methyl nitrate (1,32-dimethyl-1,3-methyl-1,3-ohl) (1,31-milligram) (1,34-dimethyl-1,3-ethyl-1-3-ethyl) (1,34-milligram) (1,31-methyl-1) (1,34-methyl-1) (139 ml) [R) ]; the organic extract was purified by a raw methyl nitrate (1,3-methyl nitrate (1,3-methyl-1) (1,3-methyl-1 (R) (1,34-dimethyl-1) (1-3-methyl-1) (1,34-methyl-1) (1,34-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl) (1,34-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl) (1,34-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl-methyl
The catalyst was removed by a deep fryer with a 1 cm layer of cellite. It was thoroughly rinsed with methanol (500 ml). The solvent was distilled under vacuum. 4-benzyl-4-dimethylamino (cyclohexyl) - 1H-indol-3-yl) butanoic acid was obtained at a yield of 260 mg (86%) as a solid (one of the two possible diasteroids).
4-(2-(4-Benzyl-4- ((dimethylamino) cyclohexyl) -1-H-indol-3-yl) butanoic acid (260 mg, 0.6 mmol) was dissolved in ethyl acetate (50 ml). In RT, Me3SiCl (153 μl, 1.2 mmol) was then dripped and stirred 1. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried. Example 171 (197 mg, Fp. 90-93 °C, 70%) was obtained as a white solid (purity < 95%).
4- ((Indol-3-yl) butyric acid (Ind-56, 1,626 g, 8 mmol) was dissolved with ketone Ket-10 (1,736 g, 8 mmol) in dichloromethane (160 ml) and replaced with trifluoromethane sulphonic acid (1,08 ml, 12 mmol). The solution was stirred at RT for 16 h. For processing, the reaction mixture was stirred with H2O (40 ml) and replaced with RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 30 ml). The combined organic extracts were obtained by Na2SO4 and then dried. The resulting raw product (2 g) was obtained by accrom chromatography [60 g (100 g); 1 g (1000 g) OH) ± 0.
(±) -4-[2-(4-Dimethylamino-4-phenyl-cyclohex-1-enyl) -1-H-indol-3-yl]butanoic acid (500 mg,1.2 mmol) was added to a mixture of methanol (50 ml) with palladium as catalyst (Pd/C, 5%,200 mg) and hydrated at RT for 6 h (hydrogen pressure: 3 bar). The catalyst was removed with a fryer with a 1 cm high layer of cellite. It was thoroughly rinsed with methanol (500 ml). The solvent was desaturated in a vacuum. 4-[2-(dimethylamino-4-phenyl-cyclohexyl) -1-H-phenyl-butanoic acid was obtained in a single 340 mg (68%) white solid (two possible diasteroids).
4-[2- ((4-Dimethylamino-4-phenylcyclohexyl) -H-indol-3-yl]butanoic acid (340 mg, 0.81 mmol) was dissolved in ethyl acetate (50 ml). RT was then dripped with Me3SiCl (207 μl, 1.62 mmol) and stirred for 16 h. The solvent was distilled at the rotary evaporator.
4- ((H-indol-3-yl) butan-1-ol (Ind-57) (797 mg, 4.21 mmol) was dissolved in dichloromethane (80 ml) together with ketone Ket-10 (914 mg, 4.21 mmol) and substituted with trifluoromethanesulphonic acid (540 μl, 6 mmol). The solution was stirred at RT for 24 h. For processing, the reaction mixture was stirred with 5N NaOH (30 ml) and for 20 min at RT. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 30 ml). The combined organic extracts were dried over Na2SO4 and then ecycled. The resulting product (2 g) was obtained by column glycolography [60 g/l]; 60 g/l (100 g/l) (14-dimethylamino-1-1-1-1) was obtained from 600 g/l (32-dimethylamino-1) (1 mmol-1) (1 mmol-1) (1 mmol-1) (3 mmol-1) (1 mmol-1) (1 mmol-1) (3 mmol-1) in a white solution.
(±) -4-[2-(4-Dimethylamino-4-phenylcyclohex-1-enyl) -1-H-indol-3-yl]butanol (600 mg, 1.54 mmol) was dissolved in HBr/iron vinegar (33 % HBr, 10 ml) and then administered to the Sn RT powder (1.81 g, 15.4 mmol) in 2 h portions. After completion of the addition, the reaction mixture was stirred for another 16 h at RT. For processing, the mixture was diluted with EtOH (10 ml) and pressed to a dry level at the rotary steam. The remaining residue was made more basic by adding 5N NaOH (40 ml) to the solution. The resulting organic compound was extracted with dichloromethane (39 mg x 30 ml). The solids were combined in 60 mg (32 ml) of 4-dimethylamino-3-methyl (14-dimethyl-1-phenyl) -4-ohydroxyethylene (SO4) and purified by extracting 173 ml (50 ml) of diethyl (1-dimethyl-1-methyl) -4-butanol (SO4) from the raw material.
4-[2-(4-Dimethylamino-4-phenylcyclohexyl)-1H-indol-3-yl]butan-1-ol (unpolar diastereomer) (170 mg, 0.43 mmol) was dissolved in ethyl acetate (50 ml). In RT, Me3SiCl (108 μl, 0.86 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried. Example 173 (170 mg, Fp. 223-226 °C, 91%) was obtained as a white solid.
The ketone Ket-3 (463 mg, 2 mmol) and Ind-57 (379 mg, 2 mmol) were dissolved in HBr/iron vinegar (33% HBr, 2 ml) and stirred at RT for 24 h. The ketone Ket-3 (463 mg, 2 mmol) and Ind-57 (379 mg, 2 mmol) were then administered to the RT Sn powder (2,4 g, 20 mmol) in 1 hour portion-by-portion doses. After completion of the addition, the reaction mixture was stirred at RT for a further 16 h. For processing, the mixture was diluted with EtOH (10 ml) and pressed dry in the rotary evaporator. The remaining residue was neutralized by addition of solid NaHCO3 and dissolved with H2O (40 ml) (50 ml). The remaining white-cyclic acid mixture was extracted with nitrous oxide (4 ml). The organic naphtha oxide was dissolved in 120 g/mol (80 mg/mL) of acyl methacrylate (80 mg/mL) and purified by a white-acyl diethyl nitrate (80 mg/mL) (120 mg/mL) and dissolved in 80 mg/m2 (80 mg/mL) of acyl methacrylate (80 mg/mL) (120 mg/mL) (120 mg/mL) and dissolved in 80 mg/m2 (80 mg/mL) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (120 mg/l) (140 ml) (140 mg/l) (120 mg/l) (140 ml) (140 mg/l) (140 mg/l) (1l) (140 mg/l) (1l) (1l) (1l) (1l) (1l) (1l) (1l) (1l) (1l) (1l) (1l)
4-(2-(4-Benzyl-4- ((dimethylamino) cyclohexyl) -1-H-indol-3-yl) butyl acetate (nonpolar diastereomer) (120 mg, 0.27 mmol) was dissolved in ethyl acetate (10 ml) and dripped to RT Me3SiCl (68 μl, 0.54 mmol) and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
4-(2-(4-Benzyl-4- ((dimethylamino) cyclohexyl) -1-H-indol-3-yl) butyl acetate (polar diastereomer) (87 mg, 0.19 mmol) was dissolved in ethyl acetate (7 ml). In RT, Me3SiCl (49 μl, 0.39 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
The ketone Ket-4 (395 mg, 2 mmol) and Ind-57 (379 mg, 2 mmol) were dissolved in HBr/iron vinegar (33% HBr, 2 ml) and stirred at RT for 24 h. The remaining residue was neutralized by addition of solid NaHCO3 and dissolved at RT H2O for 40 ml. The resulting white residue was extracted with 120 ml of 120 ml (24 oz) of 120 ml (24 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (30 oz) of 120 ml (50 oz) of 120 ml (50 oz) of 120 ml (50 oz) of 120 ml (50 oz) of 120 ml (50 oz) of 120 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50 oz) of 200 ml (50 oz) of 200 ml) of 200 ml (50) (50 oz) of 200 ml) (50 oz) of 200 ml (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50) (50)
Acetic acid-4-[2-(4-butyl-4-dimethylaminocyclohexyl) -1-H-indol-3-yl]butyl ester (polar diastereomer) (124 mg, 0.3 mmol) was dissolved in ethyl acetate (50 ml). In RT, Me3SiCl (76 μl, 0.39 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
Acetic acid 4-[2-(4-butyl-4-dimethylaminocyclohexyl) -1-H-indol-3-yl]butyl ester (unpolar diastereomer) (206 mg, 0.5 mmol) was dissolved in ethyl acetate (50 ml). In RT, Me3SiCl (126 μl, 1 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried. Example 177 (150 mg, Fp 128-131 °C, 67 % was obtained as a white solid
The ketone Ket-10 (434 mg, 2 mmol) and Ind-57 (379 mg, 2 mmol) were dissolved in HBr/iron vinegar (33% HBr, 1.75 ml) and stirred at RT for 24 h. The remaining residue was neutralized by addition of solid NaHCO3 and dissolved with 40 ml H2O (50 ml). The remaining dry solution was extracted with extracyclic acetic acid (4 g, 20 mmol) at RT. The organic naphtha was dissolved in a white solid containing 120 mg (22-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethyl) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol) (24-dimethylphenol (24-dimethyl) (24-dimethylphenol) (24-dimethyl) (24-dimethyl) (24-dimethyl) (24-dimethyl
4-(2-(4-(Dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) butyl acetate (unpolar diastereomer) (234 mg, 0.54 mmol) was dissolved in ethyl acetate (50 ml). In RT, Me3SiCl (136 μl, 1.08 mmol) was then dripped. The mixture was stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried. 178 sample (155 mg, pH 238-241 °C, 61%, NMR purity < 95%) was obtained as a white solid.
4-(2-(4-(Dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) butyl acetate (polar diastereomer) (112 mg, 0.26 mmol) was dissolved in ethyl acetate (20 ml). In RT, Me3SiCl (65 μl, 0.52 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
The free base from sample 48 (300 mg, 0.77 mmol) was dissolved in HBr/iron vinegar (33% HBr, 10 ml). The resulting aqueous mixture was then added to the RT Sn powder (906 mg, 7.7 mmol) for 1 hour. After completion of the addition, the reaction mixture was stirred for another 16 h at RT. For processing, the mixture was diluted with EtOH (10 ml) and compressed to dry at the rotary evaporator. The remaining residue was formed by adding 2N NaOH (40 ml) base. The resulting aqueous mixture was extracted with dichloromethane (4 x 20 ml). The combined organic phases were treated with Na2SO4 and further agitated. The resulting product was obtained by 60 mg (250 mg) of benzoyl (3-dimethyl-1-methyl-1-methyl) (12-dimethyl-14-methyl) (12-dimethyl-1) (125 mg) (12-dimethyl-1) (12-dimethyl-1) (12-dimethyl-1) (14-dimethyl-1) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl (14-dimethyl) (14-dimethyl) (14-dimethyl) (14-dimethyl (14-dimethyl) (14-dimethyl) (14-dimethyl) (1
The nonpolar diastereomer (129 mg, 0.33 mmol) was dissolved in isopropanol (4 ml) at boiling temperature and mixed with citric acid (64 mg, 0.33 mmol) dissolved in hot isopropanol (2 ml). The solution was refrigerated to 5 °C and left for 16 h. The resulting white precipitate was separated by a deep frying process.
The free base from sample 49 (300 mg, 0.85 mmol) was dissolved in HBr/iron vinegar (33% HBr, 20 ml). The remaining residue was obtained by adding 2N NaOH (80 ml) base. The remaining aqueous mixture was extracted with dichloromethane (4 x 20 ml). The combined organic phases were agitated over 111 Na2SO4 and further agitated. The resulting product was obtained by a polarised solution of 54 mg (300 mg) of 3-dimethyl methacrylate (34-dimethyl butylenedioxylamine) (1-47 mg) in a 60 mg (1500 mg) solution of 3-dimethyl methacrylate (OH) as a crude oil.
3-(2-(4-butyl-4- ((dimethylamino) cyclohexyl) -1-H-indol-3-yl) propane-1-ol (polar diastereomer) (54 mg, 0.15 mmol) was dissolved in ethyl acetate (5 ml). In RT, Me3SiCl (38 μl, 0.3 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 3 ml) and then dried. Example 181 (57 mg, pH 128-132 °C, 95%) was obtained as a white solid.
3-(2-(4-butyl-4- ((dimethylamino) cyclohexyl) -1-H-indol-3-yl) propane-1-ol (unpolar diastereomer) (110 mg, 0.25 mmol) was dissolved in ethyl acetate (10 ml). In RT, Me3SiCl (63 μl, 0.5 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
Indol lnd-16 (701 mg, 4 mmol) was dissolved in dichloromethane (80 ml) together with ketone ketone Ket-10 (868 mg, 4 mmol) and mixed with trifluoromethane sulphonic acid (540 μl, 6 mmol). The solution was stirred at RT for 24 h. For processing, the reaction mixture was stirred with 5N NaOH (30 ml) and mixed at RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 30 ml). The combined organic extracts were dried over Na2SO4 and then pressed tightly. The resulting raw product (1. g) was obtained by column chromatography [silicon gel 60 g (100 g); (500 ml) OH) ± ± 0.3 (± 0.32-dimethylamino-2-phenyl-1-pyrol) was purified from a white solid (6-56 mg) in a 9-55% white solution of dimethylamino-1-pyrol (6-65-pyrol) 1-1.6 mg.
(±) 3-[2-(4-Dimethylamino-4-phenylcyclohex-1-enyl) -1-H-indol-3-yl]propan-1-ol (500 mg, 1.335 mmol) was dissolved in HBr/iron vinegar (33 % HBr, 10 ml) and then administered to the RT Sn-powder (1,57 g, 13.35 mmol) in 2 h portions. After completion of the addition, the reaction mixture was stirred for a further 16 h at RT. For processing, the mixture was diluted with etheric OH (10 ml) and pressed to dry at the rotary steam. The remaining residue was made more basic by adding 5 N NaOH (40%) to the solution. The resulting mixture was extracted with dichloromethane oxide (20 ml). The solid product was obtained from polymers of P-methyl (160 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, 120 mg, and 120 ml) of diethyl (1-methyl-1-3-methyl) was obtained by extraction of white diethylene oxide (24-diol) and obtained by extraction of white diethylene oxide (260 mg, 120 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 mg, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml, 200 ml
3-(2-(4-(Dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) propane-1-ol (polar diastereomer) (130 mg, 0.35 mmol) was dissolved in ethyl acetate (15 ml). In RT, Me3SiCl (88 μl, 0.7 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
3-(2-(4-(Dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) propane-1-ol (unpolar diastereomer) (160 mg, 0.43 mmol) was dissolved in ethyl acetate (20 ml). In RT, Me3SiCl (108 μl, 0.86 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
The ketone Ket-10 (434 mg, 2 mmol) and Ind-16 (350 mg, 2 mmol) were dissolved in HBr/iron vinegar (33% HBr, 2 ml) and stirred at RT for 24 h. The resulting residual was neutralized by addition of solid NaHCO3 and dissolved at RT H2O. The resulting cyclic compound was added to the RT Sn powder (2,4 g, 20 mmol) for 1 h. After completion of the addition, the reaction mixture was stirred at RT for a further 16 h. For processing, the mixture was diluted with EtOH (10 ml) and reduced to dry at the rotary evaporator. The remaining residue was neutralized by addition of solid NaHCO3 and dissolved at RT H2O for 40 ml. The resulting aqueous solution was dissolved with extracyclic acetic acid (4 x 30 ml). The organic compound NaOH was dissolved at RT H2O. The solid was obtained from a white powder (50 mg/l) of diethyl methacrylate (50 mg/l) and dissolved in a white powder (50 mg/l) of diethyl methacrylate (50 mg/l methacrylate) containing 60 to 40 mg/l methacrylate (24- (24- to 400 mg/l methacrylate) of diethyl methacrylate (80 to 60 mg/l methacrylate) and dissolved in a white powder (50 to 400 mg/l methacrylate) of diethyl methacrylate (50 to 400 to 400 mg/l methacrylate) of diethyl methacrylate (80 to 400 to 400 to 400 mg/l methacrylate) of diethyl methacrylate (80 to 400 to 400 to 400 mg/l methacrylate) of diethyl methacrylate (H2O) and obtained by means of a white powder (associated diethyl methalic acid) of diethyl methalic acid) as a diethyl methalic acid (SO4) as a white powder (associated with diethyl methalic acid) as a diethyl methalic acid) as a diethyl methalic acid (SO4) (SO4) as
3-(2-(4-(Dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) propyl acetate (polar diastereomer) (60 mg, 0.16 mmol) was dissolved in ethyl acetate (20 ml). In RT, Me3SiCl (40 μl, 0.32 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (1 x 5 ml) and then dried.
Other
The mean of the measurements performed was approximately 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m2 (m, 2 H), 1 μs/m3 (m, 2 H), 1 μs/m3 (m, 2 H), 1 μs/m3 (m, 2 H), 1 μs/m3 (m, 2 H), 1 μs/m3 (m, 2 H), 1 μs/m3 (m, 2 H), 1 μs/m3 (m, 2 H), 1 μs/m3 (m), 1 μs/m3 (m), 1 μs/m3 (m), 1 μs/m3 (m), 1 μs/m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3 (m3), 1 μs/m3), 1 μs/m (m3), 1 μs/m3 (m3), 1 μs/m (m3), 1 μs/m3 (m3), 1 μs/m (m3), 1 μs/m (m3), 1 μs/m (m3
Other
The following are the most commonly reported effects of the drug on the brain:
3-(2-(4-(Dimethylamino) -4-phenylcyclohexyl) -1-H-indol-3-yl) propyl acetate (unpolar diastereomer) (190 mg, 0.51 mmol) was dissolved in ethyl acetate (50 ml). In RT, Me3SiCl (128 μl, 1.02 mmol) was then dripped. The mixture was stirred for 1 h. A white precipitate was produced. The precipitate was sucked out, washed with ethyl acetate (2 x 5 ml) and then dried.
The indole (Ind-61, 3.00 g, 12.4 mmol) and the aminoketone (Ket-10, 2.70 g, 12.4 mmol) were dissolved in dichloromethane (160 m), trifluoromethane acid (3.0 ml) was added and stirred overnight at RT. The solution was transferred to 3.5N NaOH (50 ml), the aqueous phase was separated, the organic phases were extracted with CH2Cl2 (twice 140 ml), combined, dried (Na2SO4) and i.e. vacuumed. The residue was cleaned by flash chromatography with MeOH/esterification (1:1)
Other
Production: 3.30 g (57%)
Other
The mean value of the dose of the active substance is calculated as the following:
The olefin (1.50 g, 3.00 mmol) was dissolved in ice vinegar (50 ml) in 33 percent HBr. Tin powder (3.56 g, 30 mmol) was added in portions within one hour under ice cooling. After 1 h, the approach was narrowed down to a vacuum. After adding 5N NaOH (100 ml) and CH2Cl2 (50 ml), the aqueous phase was separated, extracted with CH2Cl2 (twice 50 ml), the organic phases were combined, dried (Na2SO4) and narrowed down to a vacuum. The residue was cleaned by flash chromatography with methanol/esterification (1:1) and both the polar and the nonpolar diasters were obtained.
Other
| 350 mg (27 %) Unpolareres Diastereomer | |
| 484 mg (37 %) Polareres Diastereomer |
The newly obtained nonpolar diastereomer is given as example 187. 1H-NMR (DMSO-d6): 1.47 (2 H, m); 1.68 (2 H, m); 2.13 (8 H, m); 2.46 (2 H, m); 2.87 (4 H, m); 3.51 (2 H, t); 6.98 (2 H, m); 7.38 (7 H, m); 10.76 (1 H, bs).
The polar diastereomer obtained in example 187 is used as example 188.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.48 (2 H, m); 1.66 (4 H, m); 1.99 (6 H, s); 2.59 (4 H, m); 2.81 (4 H, m); 3.50 (2 H, m); 6.91 (2 H, m); 7.17 (1 H, m); 7.38 (6 H, m); 10.42 (1 H, bs).
The amino ketone (Ket-10, 2.58 g, 11.9 mmol) was dissolved with the indole (Ind-62, 3.28 g, 11.9 mmol) in dichloromethane (200 ml). Then, at room temperature, the trifluoromethane sulphonic acid (3.62 ml, 41.7 mmol) was rapidly added. The solution was stirred at room temperature for 24 h. For processing, the solution was mixed with 2N NaOH (200 ml) and stirred at room temperature for 20 min. The organic phase was separated and the aqueous phase was extracted with dichloromethane (2 25 ml). The combined organic phases were dried over Na2SO4 and i.e. dried to a single dry volume. The raw product was pressed with flash chromatography using Cycloxanone/EEEE1→ (2:1:1→) and the product was first fully purified with methanol.
Other
The yield is 2.22 g (40%)
Other
The mean value of the 1H-NMR (CDCl3) is 1.80 (4 H, m); 2.09 (8 H, m); 2.64 (4 H, m); 2.87 (2 H, m); 3.09 (2 H, m); 6.22 (1 H, s); 6.48 (1 H, t); 6.61 (1 H, d); 7.02 (4 H, m); 7.26 (4 H, m); 7.45 (3 H, m); 10.69 (1 H, s).
The solution of the newly produced olefin (2.00 g, 4.2 mmol) in HBr/iron vinegar (85 ml) was added with tin (5.00 g) for 20 min. The reaction mixture was then stirred at room temperature for 2 h. The mixture was mixed with ethanol and i.e. compressed to dry. The residue was mixed with 5N NaOH (120 ml) and extracted with dichloromethane (3 x 50 ml). The combined organic phases were dried over Na2SO4. The raw product was purified by flash chromatography and (3 cyclohexan/EE:1→1 and methanol) to obtain the non-volatile product with cyclohexan/EE (1:1) and the polar product with methanol.
Other
| 0.140 g (7 %), unpolares Diastereomer | |
| 0.650 g (33 %), polares Diastereomer |
The resulting nonpolar diastereomer (0.140 g, 0.293 mmol) was dissolved in hot ethanol (4 ml) and mixed at room temperature with citric acid (0.056 g, 0.29 mmol), dissolved in hot ethanol (2 ml). The solution was stirred at room temperature for 2 h. Since no precipitation could be observed, the solution was compressed in a vacuum and the residue was stirred with ether.
Other
The yield is 74 mg (e.g. 189.8%) of porous solid
Other
The mean of the measurements of the 1H-NMR (DMSO-d6) was 1.66 (6 H, m); ); 2.11 (6 H, m); 2.58 (4 H, m); 2.63 (4 H, m); 2.88 (4 H, m); 6.41 (2 H, m); 6.63 (1 H, m); 6.95 (3 H, m); 7.34 (6 H, m); 10.64 (1 H, s), citrate.
The polar diastereomer (0.650 g, 1.36 mmol) obtained in example 189 was dissolved in hot ethanol (20 ml) and mixed at room temperature with citric acid (0.260 g, 1.36 mmol), dissolved in hot ethanol (10 ml). The solution was stirred at room temperature for 2 h. Since no precipitation could be observed, the solution was compressed in a vacuum and the residue stirred with ether.
Other
The following table shows the results of the analysis:
Other
The mean value of the active substance is calculated as the following: 1H-NMR (DMSO-d6): ): 1.52 (2 H, m); ); 1.80 (6 H, m); 2.36 (6 H; s); 2.64 (4 H, m); 2.86 (4 H, m); 2.97 (4 H, m); 6.50 (1 H, t); 6.62 (1 H, d); 6.91 (2 H, m); 7.03 (1 H, m); 7.17 (1 H, m); 7.54 (6 H, m); 10.46 (1 H, s), citrate.
3-[2-(1H-Indol-3-yl) -ethyl) -3-H-(1,2,3) triazole-4-carboxylic acid methyl ester (320 mg, 1.18 mmol) and 4-dimethylamino-4-phenyl cyclohexanone (256 mg, 1.18 mmol) were dissolved in abs. dichloromethane (15 ml) and rapidly added to trifluoromethane sulphonic acid (0.21 ml, 2.4 mmol). The solution was stirred overnight at RT, leaving a dark oil. After addition of 1 N NaOH (10 ml) and CH2Cl2 (10 ml) was stirred for another 20 min, the phases separated, the duration of the phase was extra-dry with CH2Cl2 extra-dry, the organic phase was washed with water, washed with e-solid (Na2SO24) and e-solid (Na2SO3) The solution was cleaned with a vacuum cleaner (9°C).
Other
The yield is 245 mg (44%).
Other
The mean value of the dose of the active substance is calculated as the following:
Other
The total number of patients with a history of renal failure was estimated at approximately 108,500.
The solution of the newly produced olefin (218 mg, 0.46 mmol) in HBr/iron vinegar (10 ml) was given tin (0.60 g) for 20 min and stirred at RT for 3 h. The solution was mixed with ethanol, the solvent mixture was pressed to dry and the residue was dissolved in 5N NaOH (20 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase ex-tracted twice with CH2Cl2, the combined organic phases were washed with water and dried over NaSO24. The dichloromethane phase was sucked (soaked) over cellular water and the solution was vacuum-pressed. The residue was cleaned by flash chromatography using CHCl3/OHMe (20:1:1:1).
Other
| 70 mg (32 %) unpolares Diastereomer | |
| 39 mg (18 %) polares Diastereomer |
The resulting unpolar diastereomer (66 mg, 0.14 mmol) was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (27 mg, 0.14 mmol) in hot ethanol (2 ml).
Other
The following information shall be provided in the form of a summary of the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.40 (4 H, m); 2.04 (8 H, m); 2.58 (1 H, m) 2.72 (2 H, m); 3.26 (2 H, t); 3.79 (3 H, s); 4.60 (2 H, t); 6.94 (2 H, t); 7.38 (6 H, m); 7.47 (1 H, m); 8.73 (1 H, s); 10.73 (1 H, bs), free base.
The polar diastereomer (39 mg, 0.082 mmol) obtained in example 191 was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (16 mg, 0.082 mmol) in hot ethanol (2 ml).
Other
The following shall be added to the list of active substances:
Other
The mean of the 1H-NMR (DMSO-d6) is 1.39 (4 H, m); 1.64 (2 H, m); 1.98 (6 H, m); 2.50 (1 H, m); 2.71 (2 H, m); 3.22 (2 H, t); 3.85 (3 H, s); 4.57 (2 H, t); 6.92 (2 H, t); 7.17 (1 H, m); 7.42 (6 H, m); 8.72 (1 H, s); 10.40 (1 H, bs), free base.
Indol (Ind-64, 1.05 g, 4.0 mmol) and ketone (Ket-10; 868 mg, 4.0 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (1.06 ml, 12.0 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (30 ml), stirring continued for 30 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, washing (Na2SO) and sealing the solution i. i. Vacuum. The dried residue was cleaned by flash chromatography with CH203/OHClMe:1.
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.83 (1 H, m); 2.16 (7 H, m); 2.57 (1 H, m); 2.72 (4 H, m); 2.88 (2 H, m); 3.80 (4 H, s); 6.22 (1 H, s); 6.98 (2 H, s); 7.26 (8 H, m); 7.47 (3 H, m); 10.66 (1 H, s).
The solution of the newly produced olefins (588 mg, 1.27 mmol) in HBr/iron vinegar (30 ml) was given tin (1.50 g) and stirred at RT for 30 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-tight. The remaining residue was separated by CHCl:13/MeOH (20:1 → 9:1) by vacuum chromatography.
Other
| 304 mg (52 %), unpolares Diastereomer | |
| 108 mg (18 %), polares Diastereomer |
The resulting nonpolar diastereomer (264 mg, 0.57 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (109 mg, 0.57 mmol) in hot ethanol (5 ml).
Other
The total volume of the product shall be calculated as follows:
Other
The mean value of the dose of the active substance is calculated as the following:
Other
Citrate (ethanol)
The polar diastereomer (93 mg, 0.20 mmol) obtained in example 193 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (38 mg, 0.20 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.50 (2 H, m); 1.80 (2 H, m); 1.98 (2 H, m); 2.32 (6 H, s); 2.58 (4 H, m); 2.96 (6 H, m); 4.15 (4 H, s); 6.91 (2 H, s); 7.15-7.34 (5 H, m); 7.43-7.65 (5 H, m); 10.48 (1 H, s).
Other
Citrate (ethanol), porous solid
Indol (Ind-65, 1.10 g, 4.0 mmol) and ketone (Ket-10, 868 mg, 4.0 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (1.06 ml, 12.0 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1N NaOH (20 ml) and CH2Cl2 (30 ml), stirring for another 30 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, washing (Na2SO4) and sealing the solution i.e. vacuum. The dried residue was cleaned by flash chromatography with CHCl (203/OHCl:1).
Other
The yield is 637 mg (33%) of porous solid
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.75 (2 H, m); 1.94 (2 H, m); 2.11 (6 H, s); 2.55-2.89 (8 H, m); 3.82 (1 H, m); 6.22 (1 H, s); 6.91 (13 H, m); 10.62 (1 H, s).
The solution of the olefins (600 mg, 1.26 mmol) in HBr/iron vinegar (30 ml) was given tin (1.50 g) and stirred at RT for 30 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4, and i.e. pressed.
Other
| 207 mg (34 %), unpolares Diastereomer | |
| 128 mg (21 %), polares Diastereomer |
The resulting unpolar diastereomer (195 mg, 0.41 mmol) was dissolved in hot ethanol (10 ml) and mixed with a solution of citric acid (78 mg, 0.41 mmol) in hot ethanol (3 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is calculated as the following:
Other
Citrate (ethanol)
The polar diastereomer (102 mg, 0.21 mmol) obtained in example 195 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (41 mg, 0.21 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The total number of samples of the active substance is calculated by dividing the total number of samples by the total number of samples of the active substance.
Indol (Ind-66, 1.00 g, 4.7 mmol) and ketone (Ket-10, 1.01 g, 4.7 mmol) were dissolved in RT in a CH2Cl2 (50 ml) solution and rapidly mixed with trifluoromethane sulphonic acid. A black oil then fell out. The mixture was stirred for 24 h at RT, 1 N NaOH (50 ml) was added and the mixture stirred for 20 min. The organic phase was separated and the aqueous phase was extracted with CH2Cl2 (2 x 50 ml). The combined organic phases were washed with water (20 ml), dried over Na2SO4, filtered and vacuumed. The residue was cleaned by flash chromatography with chlorochloroethane/methanol (9 + 1 / 1 %) triethylamine.
Other
The yield is 789 mg (41%), yellow solid
Other
The mean value of the dose of the active substance is 1.75 (4 H, m); 2.09 (8 H, m); 2.62 (6 H, m); 2.82 (4 H, m); 6.19 (1 H, s); 6.97 (2 H, m); 7.21-7.48 (7 H, m); 10.62 (1 H, s).
The olefin (666 mg, 1.6 mmol) was dissolved in 33% HBr/iron vinegar (35 ml) and added to the mixture with tin (2.10 g) in a portion of 30 min. The mixture was stirred for 4 h at RT. Ethanol was added, the solvent mixture was removed i.v. and the residue was dissolved with 5N NaOH (70 ml) and CH2Cl2 (100 ml). The phases were separated, the aqueous phase was extracted with CH2Cl2 (2x), the combined organic phases were washed with water, dried over Na2SO4, filtered and injected i.v. The remaining residue was cleaned by flash chromatography with chlorine/methanol (20:1 → 9:1).
Other
yield: 544 mg (82%) nonpolar compound, contained triethylamine and impurity
Other
259 mg (39%) polar compound, contained triethylamine and impurity The citrate was converted into ethanol as a yellow solid by conversion of the unpolar diastereomer with a molar amount of citric acid.
Other
The following is the list of active substances and mixtures:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.57 (4 H, m); 1.94 (4 H, m); 2.08 (8 H, m); 2.58 (4 H, m); 2.83 to 3.41 (10 H, m); 6.99 (2 H, m); 7.41 (6 H, m); 7.51 (1 H, m); 10.88 (1 H, s).
The polar diastereomer obtained in example 197 with a molar amount of citric acid in ethanol had little precipitation, and the citrate was a yellow solid after the addition of ether.
Other
The following is the list of active substances in the active substance:
Other
The mean value of the dose of the active substance is calculated as the following:
The solution of sample 58 (0.209 g, 0.488 mmol) in HBr/iron vinegar (10 ml) was given Sn powder (0.57 g) within 20 min. The reaction mixture was then stirred at room temperature for 2.5 h. The mixture was mixed with ethanol and compressed to dry in 1 vacuum. The residue was mixed with 5N NaOH (20 ml) and extracted with dichloromethane (3 x 20 ml), the organic phase was dried with Na2SO4, compressed in 1 vacuum and the residue was cleaned by flash chromatography with chloroform/methanol (15:1)
Other
The yield is 0.05 g (24%)
Other
The resulting reduction product (0.050 g, 0.116 mmol) was dissolved in hot ethanol (1.4 ml) and mixed with citric acid (0.022 g, 0.116 mmol), dissolved in hot ethanol (0.865 ml).
Other
The yield is 0.055 g; melting point is 214-215 °C.
Other
The mean value of the dose of the active substance is calculated as the following:
Indol (Ind-68, 1.23 g, 5.05 mmol) and ketone (Ket-10, 1.09 g, 5.05 mmol) were presented in CH2Cl2 (60 ml) with argon and mixed with trifluoromethane sulphonic acid (1.77 ml, 20.2 mmol). The solution was stirred overnight at RT. For processing, the solution was mixed with 1 N NaOH and mixed for 30 min. The phases were separated and the aqueous phase was extracted with CH2Cl2 (3 x 20 ml). The organic phase was dried over Na2SO4 and vacuumed. The residue was cleaned by flash chromatography with CHCl3/OH (1:1) Me.
Other
The yield is 382 mg (17%)
Other
The mean value of the dose of the active substance is calculated as the following:
Other
The total number of patients treated with the product was approximately 10 in the control group.
The olefin (375 mg, 0.847 mmol) was presented in HBr/iron vinegar (18 ml), mixed with tin (988 mg) for 30 min and stirred in RT for 3 h. The solution was diluted with ethanol, mixed in RT for 20 min and pressed in the vacuum. The residue was mixed with 5N NaOH and extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and pressed in the vacuum. The residue was cleaned by flash chromatography with CHCl3/MeOH (9:1)
Other
The yield is 160 mg (43%).
Other
When converted with a molar amount of citric acid into ethanol, the citrate was obtained as a white solid.
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.53 (4 H, m); 2.06 (6 H, m); 2.54-2.69 (10 H, m); 2.81 (10 H, m); 6.96 (2 H, s); 7.29 (2 H, m); 7.40 (5 H, m); 10.72 (1 H, s).
Indol (Ind-69, 1.05 g, 4.56 mmol) and ketone (Ket-10, 0.99 g, 4.56 mmol) were dissolved in RT in CH2Cl2 (50 ml) and rapidly mixed with trifluoromethane sulphonic acid (2.05 g, 2.2 ml, 13.7 mmol), then a black oil was released. The mixture was stirred for 3 days at RT. After adding 1 N NaOH (50 ml), the mixture was stirred for 20 min, then the organic phase was separated and the aqueous phase was ex-tracted with CH2Cl2 (2 x 50 ml). The combined organic phases were washed with water (20 ml), dried over Na2SO4, filtered and vacuumed.
Other
The resulting residue was purified by flash chromatography with 100 g of silica gel and chloroform/methanol (9:1).
Other
The yield is 644 mg (33%)
Other
The mean value of the dose of the active substance is 1.78 (2 H, m); 2.11 (6 H, s); 2.37 (8 H, m); 2.80 (4 H, d); 3.59 (4 H, d); 6.19 (1 H, s); 6.94 (2 H, m); 7.21-7.50 (7 H, m); 10.64 (1 H, s).
The olefin (617 mg, 1.4 mmol) obtained was dissolved in 33% HBr/iron vinegar (30 ml) and then mixed with tin (1.87 g) in RT for 30 min. The mixture was stirred for 4 h in RT. Ethanol was added, the solvent mixture was removed in the vacuum and the residue was dissolved in 5N NaOH (60 ml) and CH2Cl2 (90 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4, filtered and the solution was pressed in the vacuum.
Other
The remaining residue was cleaned by flash chromatography with chloroform/methanol (9:1 → 4:1).
Other
| 334 mg (54 %), unpolare Verbindung | |
| 119 mg (19 %), polare Verbindung |
The conversion of the newly obtained nonpolar diastereomer with a molar amount of citric acid into ethanol produced the citrate as a colourless solid.
Other
The yield is 346 mg, nonpolar compound; melting point 234-242 °C.
Other
The mean value of the dose of the active substance is 1.63 (4 H, m); 2.11 (8 H, m); 2.55-2.91 (14 H, m); 3.68 (4 H, m); 6.96 (2 H, m); 7.37 (7 H, m); 10.71 (1 H, s).
The polar diastereomer obtained in example 201 is converted from ethanol to a molar amount of citric acid, leaving the citrate as a colourless solid.
Other
The mean value of the dose of the active substance is calculated as the following:
Indol (Ind-70, 650 mg, 2.5 mmol) and ketone (Ket-10, 542 mg, 2.5 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.66 ml, 7.5 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (10 ml) and CH2Cl2 (20 ml), stirring for 30 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the combined organic phases with water, washing (Na2SO) and compressing the solution in a vacuum. The dried residue was cleaned by flash chromatography with CHCl3/OH (9:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.H-NMR (DMSO-d6): 2.09 (10 H, m); 2.41 (2 H, m); 3.19 (2 H, m); 4.29 (2 H, m); 5.83 (1 H, s); 6.89-7.28 (7 H, m); 7.41 (6 H, m); 7.65 (1 H, s); 10.64 (1 H, bs).
Other
The following information is provided in the summary of the product characteristics and the manufacturer's specifications:
The solution of the newly produced olefin (429 mg, 0.93 mmol) in HBr/iron vinegar (20 ml) was given tin (1.20 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. pressed. The remaining residue was separated by vacuum chromatography with CHCl:13/OH (20 MeMe → 9:1).
Other
| 165 mg (38 %), unpolares Diastereomer | |
| 144 mg (33 %), polares Diastereomer |
The resulting nonpolar diastereomer (143 mg, 0.31 mmol) was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (59 mg, 0.31 mmol) in hot ethanol (3 ml).
Other
The maximum content of the active substance shall be as follows:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.19 (4 H, m); 1.89 (2 H, m); 2.09 (6 H, s); 2.33 (2 H, t); 2.67 (4 H, m); 3.21 (2 H, t); 4.45 (2 H, t); 7.00 (2 H, m); 7.14 (2 H, m); 7.32 to 7.61 (9 H, m); 7.84 (1 H, s); 10.55 (1 H, s).
Other
Citrate (ethanol)
The polar diastereomer (135 mg, 0.27 mmol) obtained in example 203 was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (52 mg, 0.27 mmol) in hot ethanol (3 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.61 (2 H, m); 2.33 (2 H, m); 2.41 (6 H, s); 2.63-2.83 (6 H, m); 3.18 (2 H, t); 4.43 (2 H, t); 6.93 (3 H, m); 7.20 (3 H, m); 7.42-7.67 (7 H, m); 7.83 (1 H, s); 10.33 (1 H, s).
Other
Citrate (ethanol), porous solid
Indol (Ind-71, 490 mg, 2.32 mmol) and ketone (Ket-10, 503 mg, 2.32 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.62 ml, 7 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1N NaOH (10 ml) and CH2Cl2 (20 ml), stirring for 90 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the organic phases with water, drying (Na2SO4) and closing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OHMe (4:1)
Other
Production: 311 mg (33%) of oil from hardwood
Other
The mean value of the dose of the active substance is 1.68 (2 H, m); 1.88 (1 H, m); 2.08 (6 H, s); 2.38 (1 H, d); 2.60 (2 H, d); 3.06 (2 H, m); 4.02 (2 H, m); 6.00 (1 H, s); 6.78-7.03 (4 H, m); 7.19-7.48 (8 H, m); 10 70 (1 H, s).
Other
The following are the most commonly used medicines:
The solution of the newly produced olefin (300 mg, 0.708 mmol) in HBr/iron vinegar (15 ml) was given tin (0.90 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (20 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over NaSO24, and i.e. vacuumed. The remaining residue was separated by flash chromatography with CHCl3/OH (20:1→Me1:1)
Other
| 111 mg (38 %), unpolares Diastereomer | |
| 33 mg (11 %), polares Diastereomer |
The resulting nonpolar diastereomer (87 mg, 0.21 mmol) was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (40 mg, 0.21 mmol) in hot ethanol (2 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, calculated as follows:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.46 (4 H, m); 2.03 (6 H, s); 2.10 (1 H, m); 2.70 (3 H, m); 3.08 (2 H, t); 4.13 (2 H, t); 6.85 (1 H, s); 6.99 (2 H, m); 7.15 (1 H, s); 7.25 to 7.49 (8 H, m); 10.74 (1 H, s), (free base).
Other
Citrate (ethanol)
The polar diastereomer (33 mg, 0.08 mmol) obtained in example 205 was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (15 mg, 0.08 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.39 (2 H, m); 1.51 (2 H, m); 1.60 (2 H, m); 1.99 (6 H; s); 2.69 (3 H, m); 3.04 (2 H, t); 4.08 (2 H, t); 6.91 (3 H, m); 7.18 (2 H, m); 7.42 (7 H, m); 10.40 (1 H, s), (free base).
Other
Citrate: (ethanol) porous solid
Indol (Ind-72, 800 mg, 3.77 mmol) and ketone (Ket-10, 819 mg, 3.77 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (1.0 ml, 11.3 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for another 30 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the organic phases with water, drying (Na2SO4) and closing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OH (9MeMe: 1)
Other
The following is the list of substances that are to be used in the preparation of the product:
Other
The mean value of the dose of the active substance is 1.70 (2 H, m); 2.11 (8 H, m); 2.63 (2 H, m); 3.17 (2 H, t); 4.25 (2 H, t); 6.08 (1 H, s); 6.94 (2 H, m); 7.32 (5 H, m); 7.48 (2 H, m); 7.99 (1 H, s); 8.28 (1 H, s); 10.74 (1 H, s).
The solution of the newly produced olefin (450 mg, 1.09 mmol) in HBr/iron vinegar (25 ml) was given tin (1.3 g) for 30 min and stirred at RT for 6 h. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. pressed. The remaining residue was separated by CHCl:13/OH (20 MeMe → 9:1) by flash chromatography.
Other
| 191 mg (42 %), unpolares Diastereomer | |
| 131 mg (29 %), polares Diastereomer |
The resulting nonpolar diastereomer (174 mg, 0.42 mmol) was dissolved in hot ethanol/ dioxan (1:1, 10 ml) and mixed with a solution of citric acid (81 mg, 0.42 mmol) in hot ethanol (3 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is 1.47 (4 H, m); 2.01 (2 H, m); 2.36 (6 H, s); 2.58-2.64 (6 H, m); 3.12 (2 H, t); 4.33 (2 H, t); 6.92 (2 H, m); 7.15 (1 H, m); 7.39-7.64 (6 H, m); 8.00 (1 H, s); 8.21 (1 H, s); 10.43 (1 H, s).
Other
Citrate (ethanol/dioxane)
The polar diastereomer (120 mg, 0.29 mmol) obtained in example 207 was dissolved in hot ethanol (5 ml) and mixed with a solution of citric acid (56 mg, 0.29 mmol) in hot ethanol (3 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is calculated as the following:
Other
Citrate (ethanol)
Indol (Ind-73, 542 mg, 2.33 mmol) and ketone (Ket-10, 503 mg, 2.33 mmol) were presented in CH2Cl2 (50 ml) with argon and mixed with trifluoromethane sulphonic acid (612 μl, 6.99 mmol). The solution was stirred overnight at RT. To prepare the solution, 1 N NaOH was added and stirred for 30 min. The phases were separated, the aqueous phase was extracted with CH2Cl2 (3 x 20 ml), the organic phase was dried with Na2SO4 and vacuumed. The residue was cleaned by flash chromatography with CHCl3/OH (1:1) Me.
Other
The yield is 417 mg (42%).
Other
The mean value of the dose of the active substance is calculated as the following:
The olefin (417 mg, 0.96 mmol) obtained was presented in HBr/iron vinegar (30 ml), mixed with tin (1.13 g) for 30 min and stirred in RT for 3 h. The solution was diluted with ethanol, stirred in RT for 20 min and then pressed in i.v. The residue was mixed with 5N NaOH, extracted with CH2Cl2 (3 x 20 ml), the organic phase was dried using Na2SO4 and pressed in i.v. The residue was cleaned by flash chromatography with CHCl3/OH (4:1 → 1:1).
Other
The following information shall be provided in the form of a summary of the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as the following:
The mean value of the dose of the active substance is calculated as follows:
Other
The newly obtained nonpolar diastereomer (86 mg, 0.198 mmol) was dissolved in hot ethanol (5 ml), citric acid (37 mg, 0.198 mmol) was dissolved in hot ethanol (1 ml) and added, the solution was cooled to RT, precipitation was eliminated, precipitation was vacuum dried.
Other
The following is the list of active substances and mixtures:
The polar diastereomer (119 mg, 0.274 mmol) obtained in example 209 was dissolved in hot ethanol (5 ml). Citric acid (51 mg, 0.274 mmol) was dissolved in hot ethanol (1 ml) and added. The solution was cooled to RT, with precipitation.
Other
The following is the list of active substances and mixtures:
Indol (Ind-74, 620 mg, 2.72 mmol) and ketone (Ket-10, 592 mg, 2.72 mmol) were dissolved in dichloromethane (15 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.73 ml, 8.2 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1N NaOH (10 ml) and CH2Cl2 (20 ml), stirring continued for 60 min, separating the phases, ex-tracting the aqueous phase twice with CH2Cl2, combining the organic phases with washed, dried water (Na2SO4) and compressing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OH (9:1) Me.
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.74 (2 H, m); 2.13 (8 H, m); 2.42 (3 H, s); 2.61 (2 H, m); 3.31 (2 H, m); 4.63 (2 H, t); 6.07 (1 H, s); 6.90 (1 H, m); 7.01 (1 H, m); 7.24 (5 H, m); 7.50 (2 H, m); 10.76 (1 H, s).
The solution of the newly produced olefin (418 mg, 0.98 mmol) in HBr/iron vinegar (30 ml) was given tin (1.20 g) for 20 min and stirred at RT for 3 h. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-tight. The remaining residue was separated by CHCl3/MeOH (20:1→9:1) chromatography.
Other
| 91 mg (22 %), unpolares Diastereomer | |
| 139 mg (33 %), polares Diastereomer |
The resulting nonpolar diatheromer (91 mg, 0.212 mmol) was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (41 mg, 0.212 mmol) in hot ethanol (2 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is 1.46 (2 H, m); 1.65 (2 H, m); 2.17 (4 H, m); 2.28 (8 H; s); 2.41 (3 H, s); 2.93 (2 H, m); 4.77 (2 H, t); 6.98 (2 H, m); 7.27 (1 H, d); 7.43 (4 H, m); 7.55 (2 H, m); 10.92 (1 H, s), citrate.
The polar diastereomer (133 mg, 0.31 mmol) produced in example 211 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (60 mg, 0.31 mmol) in hot ethanol (2 ml).
Other
The yield is 103 mg (212.53%), a porous solid
Other
The mean value of the active substance is calculated as the following: 1H-NMR (DMSO-d6): ): 1.40 (4 H, m); ); 1.88 (2 H, m); 2.41 (9 H; m); 2.57 (4 H, m); 3.01 (2 H, m); 3.34 (2 H, m); 4.73 (2 H, t); 6.91 (2 H, m); 7.13 (1 H, m); 7.39 (1 H, m); 7.53 (5 H, m); 10.45 (1 H, s), citrate.
Indol (Ind-75, 615 mg, 2.9 mmol) and ketone (Ket-10, 632 mg, 2.9 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.77 ml, 8.7 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1N NaOH (20 ml) and CH2Cl2 (20 ml), stirring continued for 60 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, combining the organic phases with water, washing, drying (Na2SO4) and closing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OH (9:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.74 (2 H, m); 2.11 (9 H, m); 3.13 (2 H, t); 3.85 (1 H, m); 4.18 (2 H, t); 6.01 (1 H, s); 6.19 (1 H, s); 6.90 (1 H, m); 7.01 (1 H, m); 7.22 to 7.49 (9 H, m); 10.68 (1 H, s).
The solution of the newly produced olefin (230 mg, 0.56 mmol) in HBr/iron vinegar (10 ml) was given tin (0.8 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (20 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-separated. The remaining residue was separated by CHCl3/MeOH (9:1) chromatography.
Other
| 48 mg (21 %) unpolares Diastereomer | |
| 47 mg (20 %) polares Diastereomer |
The resulting unpolar diastereomer (48 mg, 0.116 mmol) was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (22 mg, 0.116 mmol) in hot ethanol (2 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is calculated as the following:
Other
Citrate (ethanol)
The polar diastereomer (47 mg, 0.114 mmol) obtained in example 213 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (22 mg, 0.114 mmol) in hot ethanol (2 ml).
Other
The following table shows the percentage of the total production of the product:
Other
The mean value of the dose of the active substance is 1.41 (2 H, m); 1.61 (2 H, m); 1.95 (2 H, m); 2.14 (2 H, m); 2.61 (6 H, s); 2.66-2.70 (5 H, m); 3.03 (2 H, t); 4.23 (2 H, t); 6.17 (1 H, d); 6.93 (2 H, m); 7.14 (1 H, m); 7.41 to 7.60 (6 H, m); 7.68 (2 H, m); 10.39 (1 H, s).
Other
Citrate (ethanol), hard oil
Indol (Ind-76, 500 mg, 2.35 mmol) and ketone (Ket-10, 511 mg, 2.35 mmol) were dissolved in dichloromethane (20 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.62 ml, 7.0 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1 N NaOH (20 ml) and CH2Cl2 (20 ml), stirring for 60 min, separating the phases, extracting the aqueous phase twice with CH2Cl2, washing the organic phases with water, drying (Na2SO4) and closing the solution i.e. vacuum. The resulting residue was cleaned by flash chromatography with CHCl3/OH (9:1).
Other
Production: 327 mg (34%) of colourless oil
Other
The mean value of the dose of the active substance is 1.70 (2 H, m); 2.14 (6 H, m); 2.37 (2 H, m); 2.65 (2 H, m); 3.23 (2 H, t); 4.45 (2 H, t); 6.04 (1 H, s); 6.95 (2 H, m); 7.21-7.51 (7 H, m); 7.67 (1 H, s); 7.94 (1 H, s); 10.74 (1 H, s).
The solution of the newly produced olefin (300 mg, 0.73 mmol) in HBr/iron vinegar (20 ml) was given tin (0.90 g) for 20 min and stirred at RT for 5 h. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. flash-tight. The remaining residue was separated by CHCl:13/MeOH (20:1 → 9:1) chromatography.
Other
| 96 mg (32 %), unpolares Diastereomer | |
| 77 mg (26 %), polares Diastereomer |
The resulting nonpolar diastereomer (84 mg, 0.20 mmol) was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (39 mg, 0.20 mmol) in hot ethanol (2 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, calculated as the following:
Other
The mean value of the dose of the active substance is 1.47 (4 H, m); 2.02 (2 H, m); 2.12 (6 H, s); 2.57-2.83 (6 H, m); 3.21 (2 H, t); 4.55 (2 H, t); 6.97 (2 H, m); 7.39 (7 H, m); 7.65 (1 H, s); 8.02 (1 H, s); 10.70 (1 H, s).
Other
Citrate (ethanol)
The polar diastereomer (73 mg, 0.17 mmol) obtained in example 215 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (34 mg, 0.17 mmol) in hot ethanol (2 ml).
Other
The following table shows the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.40 (2 H, m); 1.58 (2 H, m); 1.88 (2 H, m); 2.40 (6 H, m); 2.57 (8 H, m); 2.99 (1 H, m); 3.20 (2 H, t); 4.54 (2 H, t); 6.91 (1 H, m); 7.14 (1 H, m); 7.42 to 7.67 (8 H, m); 7.95 (1 H, s); 10.45 (1 H, s).
Other
Citrate (ethanol), porous solid
Indol (Ind-77, 900 mg, 3.96 mmol) and ketone (Ket-10, 860 mg, 3.96 mmol) were dissolved in dichloromethane (40 ml) and rapidly mixed with trifluoromethane sulphonic acid (1.06 ml, 12 mmol). The solution was stirred overnight at RT, leaving a dark brown oil. After adding 1N NaOH (20 ml) and CH2Cl2 (40 ml), stirring continued for 60 min, separating the phases, ex-tracting the aqueous phase twice with CH2Cl2, combining the organic phases with water, washing, drying (Na2SO4) and closing the solution i.e. vacuum. The resulting solution was cleaned by flash chromatography with CHCl3/OH (9:1).
Other
The following table shows the results of the analysis:
Other
The mean value of the dose of the active substance is 1.69 (2 H, m); 2.02-2.32 (11 H, m); 2.61 (2 H, m); 3.19 (2 H, m); 4.36 (2 H, m); 6.02 (1 H, s); 6.90 (1 H, m); 7.01 (1 H, m); 7.22 (5 H, m); 7.48 (2 H, m); 10.78 (1 H, s).
The solution of the newly produced olefin (670 mg, 1.57 mmol) in HBr/iron vinegar (40 ml) was given tin (1.90 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (40 ml) and dichloromethane (30 ml). The phases were separated, the aqueous phase was extracted twice with CH2Cl2, the combined organic phases were washed with water, dried over Na2SO4 and i.e. pressed. The remaining residue was separated by flash chromatography with CHCl:13/OH (9:1→MeMe1:1)
Other
| 107 mg (16 %), unpolares Diastereomer | |
| 145 mg (22 %), polares Diastereomer |
The resulting nonpolar diastereomer (103 mg, 0.24 mmol) was dissolved in hot ethanol (2 ml) and mixed with a solution of citric acid (46 mg, 0.24 mmol) in hot ethanol (2 ml).
Other
The yield is 86 mg (217.58%) and the melting point is 198-199 °C.
Other
The mean value of the active substance is 1.40 (2 H, m); 1.59 (2 H, m); 1.97 (3 H, s); 2.10 (2 H, m); 2.25 (6 H, s); 2.57-2.74 (4 H, m); 3.31 (2 H, t); 4.52 (2 H, t); 6.96 (2 H, m); 7.39 (7 H, m); 10.86 (1 H, s), citrate.
The polar diastereomer (130 mg, 0.30 mmol) obtained in the following sample 217 was dissolved in hot ethanol (3 ml) and mixed with a solution of citric acid (58 mg, 0.30 mmol) in hot ethanol (2 ml).
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the active substance is 1.41 (2 H, m); 1.50 (2 H, m); 1.96 (3 H, s); 2.05 (2 H, m); 2.37 (6 H, s); 2.61 (2 H, m); 3.02 (2 H, m); 3.17 (2 H, t); 4.50 (2 H, t); 6.93 (2 H, m); 7.16 (1 H, m); 7.29 (1 H, m); 7.51 (3 H, m); 7.68 (2 H, m); 10.48 (1 H, s), citrate.
For example, 220 (1.70 g, 4.2 mmol) was suspended in methanol (35 ml), added to a solution of KOH (800 mg, 14.4 mmol) in water (7 ml) and boiled under reflux. After 16 h, another KOH (2.66 g, 47 mmol) was added in solid form and stirred at RT for 72 h. The precipitate was vacuumed. The precipitate was washed with water and dissolved. The aqueous solution was extracted six times with CHCl3, dried, filtered and compressed over the organic phase Na2SO4.
Other
The following is the list of active substances and their metabolites:
Other
The dose of the active substance is administered with the following doses: 1H-NMR (DMSO-d6): 1.47 (2 H, m); 1.70 (4 H, m); 1.93 (6 H, s); 2.78 (4 H, m); 2.92 (1 H, t); 3.51 (2 H, m); 4.57 (1 H; s); 6.91 (2 H, m); 7.15 (1 H, m); 7.38 (6 H, m); 10.31 (1 H, bs).
2-(2-(4-(Dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)ethyl acetate 2-(1H-indol-3-yl) ethanol (Ind-5, 6.44 g, 40 mmol) and Ket-10 (8.68 g, 40 mmol) were dissolved in 33% HBr/Iron Vinegar (35 ml) under argon and ice cooling and stirred for 3 days at RT.
Other
The amount of NaHCO3 (93.7 g, 1.12 mol) needed to neutralize HBr was added in solid portions and stirred for 3 h at 40 °C until no gas was formed. The acetic acid was removed in vacuum, the residue was added with acetic acid and stirred with saturated NaHCO3 solution for 1 h at 40 °C until no gas was formed. The aqueous phase was separated and extracted three times with acetic acid.The combined organic phases were washed with saturated NaHCO3 solution and water and dried with Na2SO4.The organic phase was filtered, vacuum-tighted and cleaned by flash chromatography with 500 g of silica gel and chloroform/methanol (20:1).
Other
The following shall be added to the list of active substances:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.72 (2 H, m); 1.98 (3 H, s); 2.14 (7 H, m); 2.58 (1 H, m); 2.77 (1 H, m); 3.01 (2 H, m); 4.08 (2 H; t); 6.22 (1 H, bs); 6.94 (2 H, m); 7.31 (4 H, m); 7.45 (3 H, m); 10.7 (1 H, bs).
Other
The following information is provided for the purpose of the assessment:The Bible says that "they will be like the dew that drips down from heaven, and like the dew that drips down from heaven".
2-(2-(4-(Dimethylamino) -4-phenylcyclohex-1-enyl) -1-H-indol-3-yl) ethyl acetate (6.80 g, 16.9 mmol) was dissolved in acetic acid (300 ml), 10% palladium/activated carbon (2.10 g) and hydrated with hydrogen for 16 h at 50 °C and 3 bar, then further hydrated at RT for 16 h, and then the catalyst was filtered via cellite.
Other
The acetic acid was removed in the vacuum, and the resulting diastereomer enzyme mixture (6.24 g, 90%) was slightly contaminated and was therefore washed with ether.
Other
The following table shows the results of the analysis:
Other
The mean value of the 1H-NMR (DMSO-d6) is 1.51 (2 H, m); 1.70 (3 H, m); 1.90-1.99 (10 H, m); 2.79 (2 H, m); 2.89 (3 H, m); 4.08 (2 H; t); 6.88 (2 H, m); 6.95 (1 H, m); 7.31 (6 H, m); 10.44 (1 H, bs).
The ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ket
Other
The total number of active substances in the active substance shall be calculated as follows:
4-dimethylamino-3-iodopyridine (2331 mg, 10.60 mmol), 4-dimethylamino-4-phenyl-1-prop-1-ynyl) cyclohexanol (3000 mg, 11.66 mmol, diastereomeric mix), lithium chloride (472 mg, 11.13 mmol) and sodium carbonate (3369 mg, 31.79 mmol) were combined in dimethylformamide (absolute, 45 ml) in an argon atmosphere. The catalyst ([Pddddppf) CH2Cl2], 865 mg, 1.06 mmol) was then added. The colourless red solution was heated for 4 h at 100 °C (oil temperature), the sodium chloride (472 mg, 11.13 mmol) and sodium carbonate (3369 mg, 31.79 mmol) were combined in dimethylformamide (absolute, 45 ml) in an argon atmosphere. The solid was first dissolved in a vacuum: 1, 500 ml (50 ml × 1,500 ml) of the sodium chloride was removed from the solution; the remaining sodium chloride was then separated into a solution of 1 500 ml (3200 ml) of diethyl chloride (1 500 ml) and sodium chloride (1 500 ml (3200 ml) was added to the solution, and the remaining components were added to the solution as a powder.
The light brown solution was stirred for 3 h at 77 °C (oil bath temperature). The reaction mixture was added water (10 ml) and based with sodium hydroxide solution (5 M). Then dichloromethane (30 ml) was added and 10 min. The dissolved phenylenediol was separated. The liquid phase was extracted with an anthracycline (3 35 × 35 ml). The organic phenylenediol was combined with the non-organic phenylenediol (N2-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-N3-
The reaction mixture was agitated overnight at room temperature. The reaction mixture was then injected into the dry steam and the residue was added to 5N sodium hydroxide solution (20 ml). The dimethylphenylmethyl-3-enyl]amine suspension was added to diethyl methanol (20 ml) and agitated for 10 min. The solution was then separated from the polarised polymer by a highly insoluble, highly polarised polymer: 60 g (0.50 mm × 0.50 mm) of diethyl methanol (120 mg/ml) and the residue was completely separated from the vacuum mixture (1-3-milligrams) of diethyl methanol (1-1,3 ml) and the residual isomers were dissolved in a vacuum (1-1,3 ml) and the residual isomers were removed from the polymer.
Dimethyl-4- ((3-methyl-1H-pyrrolo[3,2-c]pyridin-2-yl)-1-phenylcyclohexanamine (unpolar diastereoisomer) (20 mg, 0.06 mmol) was suspended in ethanol (5 ml) and stirred with citric acid (13 mg, 0.07 mmol). The reaction mixture was stirred strongly at boiling temperature for 1 h, then cooled to room temperature and compressed in vacuum to about 3 ml. The solution was left overnight at room temperature. A colourless solid was dropped. The precipitation was completed by dissolving with diethyl ether (5). The mixture was left dry at room temperature for 3 h. The remaining solution was dissolved. The solid was stirred with diethyl ether (10 ml) and dissolved in vacuum as a light liquid at 103 °C (28-101 mg) for 22 hours.The dose of the active substance is calculated by dividing the dose by the dose of the active substance in the dose range from 1 mg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg
N,N-Dimethyl-4-(3-methyl-1H-pyrrolo[3,2-c]pyridin-2-yl)-1-phenylcyclohexanamine (polar diastereoisomer) (78 mg, 0.23 mmol) was suspended in ethanol (5 ml) and stirred with citric acid (49 mg, 0.26 mmol) and boiled for 1 h. The reaction mixture was cooled to room temperature and left overnight at room temperature. A colourless solid was precipitated. The precipitation was completed by distillation with diethyl (5 ml). The mixture was left at room temperature for 3 hd. The above solution was distilled. The solid was washed with diethyl (10 mmol/l) and brine for 1 h. The resulting solution was obtained by distillation at vacuum (H2H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O) at 1.68 (H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O), H2O) at 1.68), H2 (H, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O) at 1.), H2 (H, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O, H2O
Other
The following are the parameters for the determination of the concentration of the active substance in the feed additive:
The solution was then steamed in vacuum to dry and the residue was transferred to 5 N sodium hydroxide solution (20 ml). The light suspension was extracted with dichloromethane (3 × 20 ml). Insoluble constituents in the form of a grey powder were combined. The organic phases were dried with sodium sulphate. The volatile components were then completely removed. The best solution was vacuum separated: chloropyrol (N-dimethyl ethanol) (E-methyl ethanol) (E-methyl ethanol) (E-methyl ethanol) (E-methyl ethanol) (E-methyl ethanol) [1,2-5,4-5,3-milligrams]; and N-dimethyl ethanol (E-methyl ethanol) [1,2-5,4-milligrams]; and the best solution was extracted in vacuum (1,5 g/mL); the best solution was chloropyrol (N-dimethyl ethanol) (E-methyl ethanol) (E-methyl ethanol) [1,2-5,3-milligrams]; and the best solution was chloropyrol (E-methyl ethanol) [1,2-5,3-milligrams]; and the best solution was chloropyrol (E-methyl ethanol) [1,2-methyl ethanol] (E-methyl ethanol) [1,2-milligrams; and N-methyl ethanol) [1,2-methyl ethanol [1,2-methyl ethanol] [1,2-methyl ethanol] [1,2-methyl ethanol; and the best solution was extracted in vacuum [1,3-methyl ethanol] [1,2-methyl ethanol [1,2-methyl ethanol] [1,2-methyl ethanol; and N-methyl ethanol [1,2-methyl ethanol [1,2-methyl ethanol] [1,2-methyl ethanol] [1,2-methyl ethanol; and N-methyl ethanol [1,2-methyl ethanol] [1,2-methyl; the best solution [1,2-methyl ethanol [1,2-methyl ethanol] [1,2-methyl ethanol] [1,2-methyl] [1,2-methyl] [1,2-methyl] [1,2-methyl] [1,2-methyl
N,N-dimethyl-4-(3-methyl-1H-pyrrolo[2,3-b]pyridin-2-yl)-1-phenylcyclohexanamine (unpolar diastereomer) (70 mg, 0.18 mmol) was suspended in ethanol (10 ml) and mixed with citric acid (44 mg, 0.23 mmol). It was stirred vigorously in the boiling water for 1 h. The reaction mixture was cooled to room temperature and left overnight. The remaining solution was separated from the colourless precipitate and discarded.
N,N-dimethyl-4-(3-methyl-1H-pyrrolo[2,3-b]pyridin-2-yl)-1-phenylcyclohexanamine (polar diastereomer) (100 mg, 0.30 mmol) was suspended in ethanol (10 ml) and mixed with citric acid (63 mg, 0.32 mmol). It was stirred strongly in boiling water for 1 h. The reaction mixture was cooled to room temperature and stored overnight. It fell from a colourless solid. The remaining solution was separated from the colourless precipitate and discarded. 114 mg (0.22 mmol; 72%) were isolated.
The olefin (500 mg, 1.9 mmol) obtained in example 240 was dissolved in HBr/iron vinegar (33% HBr, 20 ml) and transferred to RT in portions with Sn powder (1.4 g, 12 mmol) within 30 min. After completion of the addition, the reaction mixture was stirred for another 14 hours. - For processing, the mixture was compressed to dry in the rotary evaporator. The remaining residue was made basic by addition of 5N NaOH (40 ml). The resulting solution was mixed with dichloromethane and extracted (4 × 20 ml). The combined organic phases were dried with MgSO4 and then sealed. The resulting residue (442 mg) was polymerized into a column of ether (1; LOH: 1.OOH/OOH: 1.OOH: 2.OOH: 1.OOH: 2.OOH: 10%, 1.OOH: 1.OOH: 1.OOH: 12%, 1.OOH: 126-138 °C. This method obtained the ether diameters of ether, 126-150 mg, 126-138 °C. This method was used to purify and diametrically diametrically diametrically diametrically, 12-14 μg, 126-150 °C.
The polar diastereoisomer of amine (157 mg, 0.47 mmol) was dissolved in isopropanol (5 ml) at boiling temperature and mixed with citric acid (96 mg, 0.5 mmol) dissolved in hot isopropanol (5 ml). The volume of solvent was reduced to about 5 ml. The remaining solution was cooled to 5 °C (refrigerator) and left for 17 h. The precipitation was separated by a deep frying. The citrate of polar amine was obtained at a yield of 135 mg (54 %, melting point: 169-171 °C).
The unpolar diastereoisomer of amine (146 mg, 0.44 mmol) obtained in example 225 was dissolved in isopropanol (10 ml) at boiling temperature and mixed with citric acid (96 mg, 0.5 mmol) dissolved in hot isopropanol (1 ml). The solution was cooled (refrigerated) to 5 °C and left to stand for 17 h. The precipitation was separated by a frying process. The hemicitrate of the unpolar amine was obtained in a yield of 167 mg (88 %, melting point 184-185 °C).
1H-indol (351 mg, 3 mmol) was dissolved in dichloromethane (20 ml) together with ketone (Ket-10, 651 mg, 3 mmol) and replaced with trifluoromethanesulphonic acid (0.3 ml, 3.4 mmol). After about 30 min, precipitation failed. The solution was stirred for 17 h at RT. The solution was then stirred with triethyl silane (1 ml, 6.2 mmol) and then stirred for another 2 days at RT. As precipitation was present throughout, the solution was stirred with triethyl ethanol (10 ml) until a clear solution was obtained. The resulting solution was stirred with triethyl silane (1 ml, 6.2 mmol) and stirred for 20 mmol (probably about 20 mmol) (this treatment is not recommended for use in patients with severe liver disease).- the reaction mixture was mixed with 2N NaOH (10 ml) for processing. The mixture was stirred for another 10 min and mixed with saturated NH4Cl (30 ml) to facilitate phase separation. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 × 20 ml). The combined organic extracts were dried over MgSO4 and then compressed. The resulting raw product (1.12 g) was mixed with ethyl acetate (approximately 20 ml) and the insoluble parts were separated by a separate F-ring.The resulting solution was compressed, the residue was purified by column chromatography (transfer agent: EtOAc) and one of the two possible isomers was obtained at a yield of 140 mg (11%, melting point 210-214 °C, after recrystallization from 2-propanol).
Other
The amine (120 mg, 0.38 mmol) obtained was dissolved in isopropanol (10 ml) at boiling temperature and mixed with citric acid (80 mg, 0.4 mmol) dissolved in hot isopropanol (4 ml). Immediately after the addition of the acid, precipitation failed. To complete the precipitation, the approach was cooled to 5 °C (refrigerator) and left for 12 h. The precipitation was separated by a deep fryer and then dried.The desired product was obtained at a yield of 111 mg (71%, melting point 197-201 °C and above) as hemicitrate.
7-Azaindol (Ind-86) (637 mg, 5.39 mmol) and Ketone Ket-3 (1,247 g, 5.39 mmol) were dissolved in 2N KOH/MeOH (50 ml) and boiled at the back flow for 16 h. For processing, MeOH was distilled and the reaction mixture was mixed with H2O (60 ml). The aqueous phase was extracted with dichloromethane (3 × 30 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The residue was crystallized from MeOH (20 ml).
Other
The mean of the measurements performed was approximately 0.01% for the same frequency range as the mean of the measurements performed for the same frequency range.
7-Azaindol (Ind-86) (591 mg, 5 mmol) and Ket-4 (987 mg, 5 mmol) were dissolved in 2N KOH/MeOH (50 ml) and boiled at the return stream for 16 h. For processing, MeOH was distilled and the reaction mixture was added to H2O (100 ml). The aqueous phase was extracted with dichloromethane (4 × 30 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The residue was recrystallized from MeOH (20 ml).
Other
The mean of the measurements performed was approximately 0.015 mm/s2 (see Figure 1).
Other
The following is a list of the active substances that may be used in the active substance:
7-Azaindol (Ind-86) (294 mg, 2.49 mmol) and Ket-10 (540 mg, 2.58 mmol) were dissolved in 2N KOH/MeOH (20 ml) and boiled at the return stream for 10 h. For processing, MeOH was distilled and the reaction mixture was added to H2O (40 ml). The aqueous phase was extracted with dichloromethane (3 x 20 ml). The combined organic extracts were dried over Na2SO4 and then concentrated. (±) -3-(4-dimethylamino) -4-phenylcyclohexene-1-yl) -1-H-pyrrolo[2,3-b]pyridine was obtained at a yield of 740 (94%) mg as a base solid.
(±) -3-(4-(Dimethylamino) -4-phenylcyclohex-1-enyl) -1-H-pyrrolo[2,3-b]pyridine (640 mg, 2 mmol) was dissolved in isopropanol (20 ml) at boiling temperature and mixed with citric acid (385 mg, 2 mmol) dissolved in hot isopropanol (5 ml). The solution was left at 5 °C for 16 h. The resulting white precipitate was separated by a deep frying.
Other
The dose of the active substance is calculated by dividing the dose by the dose of the active substance in the dose range from 1 mg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg/ kg
1H-indol (468 mg, 4 mmol) was dissolved in dichloromethane (40 ml) together with ketone (Ket-10, 868 mg, 4 mmol) and mixed with trifluoromethane sulphonic acid (0.4 ml, 4.6 mmol). The solution was stirred at RT for 20 h. - For processing, the reaction mixture was stirred with 2N NaOH (20 ml). The mixture was stirred for another 20 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The resulting raw product (1.2 g) was mixed with ethyl acetate (approximately 10 ml) which was separated by a solvent separating the insoluble fractions.The resulting clear solution was purified by column chromatography (solvent: EtOAc) to obtain a mixture (230 mg) containing small amounts of an isomer (probably a substitution in the 2-position of the indol) in addition to the desired product.
Other
The olefin (158 mg, 0.5 mmol) obtained was dissolved in isopropanol (20 ml) at boiling temperature and mixed with citric acid (100 mg, 0.52 mmol) dissolved in hot isopropanol (4 ml). Immediately after the addition of the acid, precipitation occurred. To complete the precipitation, the approach was cooled to 5 °C (refrigerator) and stopped for 12 h.The precipitate was separated by a frying process and then dried, resulting in the desired product at a yield of 109 mg (52% melting point 98-102 °C).
The resulting white solid is sucked out and rinsed with H2O (3 × 5 ml). After drying the solid, the desired olefin is obtained at a yield of 250 mg (39 %). To produce the hydrochloride, the olefin (250 mg, 0.785 mmol) is dissolved in ethyl methyl ketone and 1,85 N (1,85 NOH/HCl) ether (0.65 ml) at a melting point of 193 °C. The resulting white solid is obtained by melting 26 mg (37 %) of the desired olefin at a melting point of 195 °C.
The reaction mixture was mixed with ice (30 g) for processing, resulting in a colourless solid which was suspended and stirred for 30 minutes in 1 N of sodium (10 ml) and trichloroethane (30 ml). The organic phase was separated and the water phase was separated with 151 ml of hydrochloric acid (30 ml) added. The organic extracts were dried and obtained by pressing the oil at 75 °C (295 °F) to obtain a clear colour: 0.4 mg (0.8 mg) of diethyl ethanol (44 ml) The solid was obtained by pressing 1 mg (49 ml) of isopropyl ethanol (44 ml) in a solution of 1 mg (1,5 mg) of diethyl ethanol (44 ml) and 1 mg (1,5 ml) of hydrochloric acid (44 ml) in a solution of 1 mg (1,5 mg) of diethyl ethanol (44 ml) and obtained by pressing the oil with a solution of 0.2 mg (1,5 mg) of hydrochloric acid (44 ml) and 1 ml (1,5 mg) of hydrochloric ethanol (44 ml) in a solution of 0.4 mg (1,5 mg) of diethyl ethanol (44 ml) and 1 mg (1,5 mg (1,5 ml) of hydrochloric ethanol (44 ml) in a solution of 0.4 mg (1 mg) of diethyl ethanol (44 mg) and 1 ml (1 ml) of hydrochloric ethanol (44 mg (1 ml) in a solution of hydrochloric ethanol (44 mg) obtained by pressing the organic extract of 0.4 ml of hydrochloric ethanol (44 mg (1 ml) and 1 ml) in a solution of hydrochloric ethanol (44 mg (2 mg (1 ml) at a solution of diethyl ethanol (44 mg (1 ml) at a solution of diethyl ethanol (44 mg) at a solution of diethyl ethanol (44 mg (1 mg) and 1 mg (2 mg (2 mg) at a solution of diethyl ethanol (44 mg) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml) (1 ml)
The ketone (Ket-11, 218 mg, 1 mmol) was dissolved in absolute dichloromethane (5 ml) under argon, together with 2-benzo[b]thiophen-2-ylethanol (Ind-89, 178 mg, 1 mmol). The solution was then added methanosulfonic acid (3 ml). The solution was stirred 3 days at RT. The reaction mixture was mixed with ice (5 g) and water (30 ml) for processing. After neutralization with NaHCO3 (4.4 g, 52 mmol) and addition of 5N NaOH (1 ml), dichloromethane (10 ml) was added. The organic phase was separated and the aqueous phase was extracted with dichloromethane (2 × 30 ml). The extracts were organised into three groups: a 3-dimensional (375 mg) and a 3-dimensional (3 mmol) ethanol (35 mg/methanol) extract.The desired olefin was obtained as a colourless oily compound at a yield of 26%.
Other
The olefin (100 mg, 0.264 mmol) was dissolved in ethanol (5 ml) and added to 5N isopropanolic hydrochloric acid (0.104 ml, 0.52 mmol). After 2.5 h the clear solution was reduced to 3 ml, added to diethyl ether (30 ml) and stirred for 1.5 h. The hydrochloride was obtained as a colourless solid at a yield of 67 % (73 mg).
1-Phenylsulfonyl-1H-indol (Ind-90, 1.2 g, 4.66 mmol) was dissolved in dry THF and then dried for another hour at -5 °C (ice/cooking salt mixture) and removed from the refrigeration phase at 5 d RT for 30 min. The reaction mixture was stirred at 0 °C for 2 h before the ketone (Ket-10, 986 mg, 4.66 mmol) was dissolved in dry THF (10 ml) and added, maintaining the temperature for 15 min. The reaction mixture was then dried for another hour at 0 °C (ice/cooking salt mixture) and removed from the refrigeration phase at 5 d RT. - The solution was mixed with saturated L-Cl (30 mg) for 2 h. The reaction product was then dissolved in 60 ml of ethanol (10 mg) (109 ml) (10.3 mg) and obtained by extraction of ethylene glycol (10.4 mg) from the organic solvent. The product was then obtained by extraction of ethylene glycol (10.4 mg) in water (20 ml) and extraction of ethylene glycol (10.3 mg) from the organic solvent.
4- (((1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine, citrate (1:1) : Polar diastereomer The olefin (450 mg, 1.42 mmol) just isolated was dissolved in HBr/iron vinegar (33% HBr, 20 ml). It was then administered to the RT Sn powder (2 g, 16.95 mmol) in portions for 2 h. After completion of the addition, the reaction mixture was stirred for another 60 min. - For processing, the mixture was diluted with EtOH (20 ml) and removed to dry at the rotational evaporation. The remaining residue was made basic by adding 5N NaOH (60 ml). The mixture was mixed with 20 × Phasmethyl chloride (50 ml) in extra water, which was added to the RT.After it was shown that purification by recrystallization was only partially possible, the resulting raw product (400 mg) was purified by column chromatography [60 g (10 g) of silica gel; ethyl acetate, ethyl acetate/ethanol 2 : 1, methanol (250 ml total) ]; the non-polar product was obtained at a yield of 106 mg (23 %, melting point 159-164 °C) and the polar product at a yield of 135 mg [30 %, melting point 205-211 °C (from 2-propanol) ].
Other
The polar diastereomer (68 mg, 0.21 mmol) just isolated was dissolved in isopropanol (5 ml) at boiling point and dissolved in hot isopropanol (1 ml) with citric acid (59 mg, 0.3 mmol).The precipitation was removed by a fryer and then dried, thus obtaining the desired product as citrate at a yield of 83 mg (76% melting point: from 194-197 °C).
The unpolar diastereomer (100 mg, 0.31 mmol) isolated in example 235 was dissolved in isopropanol (5 ml) at boiling temperature and mixed with citric acid (60 mg, 0.31 mmol) dissolved in hot isopropanol (2 ml). Immediately after the addition of the acid, precipitation failed. To complete the precipitation, the approach was cooled to 5 °C (refrigerator) and left to stand for 17 h. The precipitation was separated by a fritter and then dried. The desired result was obtained in a yield of 103 mg (79 %, melting point: from 2333 °C to 232 °C) as hemicrate.
For example, 228 (540 mg, 1.63 mmol) was distilled in methanol (100 ml) with palladium catalyst (Pd/C, 5%, 216 mg) and hydrated at RT for 36 h (hydrogen pressure: 3 bar). The catalyst was removed with a fry with a 1 cm layer of cellite. The fry was thoroughly washed with methanol (1000 ml). The solvent was distilled under vacuum. 1-benzyl-N,N-dimethyl-4-(1H-pyrrolo[2,3-b]pyridin-3-yl) cyclohexaneamine was obtained as a white solid at a yield of 350 mg (65%) from a mixture of the two diistereoisers.
The diastereoisomer enzyme mixture (350 mg, 1.05 mmol) was dissolved in ethyl acetate (100 ml). In RT, Me3SiCl (265 μl, 2.1 mmol) was dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 × 5 ml) and then dried.
Other
For example, 237 (350 mg, Fp. 215-219 °C, 90%) was obtained as a white solid.
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Other
The following are the most commonly used methods for the determination of the concentration of the active substance in the food:
For example, 229 (500 mg, 1.68 mmol) was distilled in methanol (100 ml) with palladium catalyst (Pd/C, 5%, 200 mg) and hydrated at RT (hydrogen pressure: 3 bar) for 36 h. The catalyst was removed with a fry with a 1 cm layer of cellite. The fry was thoroughly washed with methanol (1000 ml). The solvent was distilled under vacuum. 1-Butyl-N,N-dimethyl-4-(1H-pyrrolo[2,3-b]pyridine-3-yl) cyclohexaneamine was obtained at a yield of 428 mg (85%) as a white solid. It was obtained as only one of two possible diastereoisers.
1-Butyl-N,N-dimethyl-4-(1H-pyrrolo[2,3-b]pyridine-3-yl) cyclohexanamine (425 mg, 1,42 mmol) was dissolved in ethyl acetate (100 ml). RT was then dripped with Me3SiCl (358 μl, 2,84 mmol) and stirred for 1 h. A white precipitate was produced. The precipitate was sucked, washed with ethyl acetate (2 × 10 ml) and then dried.
Other
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Other
The following are the parameters to be taken into account for the determination of the concentration of the active substance:
A solution of benzo[b]furan (Ind-92, 612 mg, 5.12 mmol) in dry THF (40 ml) was cooled to -8 °C under an argon stream. Then tert-butyllithium (6.22 mmol, 4.14 ml of a 1.5 M pentane solution) was gently dripped so that a reaction temperature of -5 °C was not exceeded. After completion of the addition, the reaction mixture was stirred for 2 h at -5 °C. Then a solution of ketone (Ketone-3, 1.198 g, 5.18 mmol) was stirred in dry THF (10 ml) at 0 °C. The mixture was stirred at 0 °C for 1 h and then at room temperature for 4 days. This was done by using a suitable solution of ammonium chloride (20 ml) to prepare the mixture.The organic phase was separated and the aqueous phase was extracted with dichloromethane (4 × 30 ml). The combined organic phases were dried with sodium sulphate. The solvent was then removed in a vacuum. The purification was carried out by flash chromatography (silica gel, cyclohexane/EtOAc (8: 2)). 380 mg (21%) of cyclohexanol with a melting point of 121 to 124 °C was obtained
Other
A solution of newly isolated cyclohexanols (250 mg, 0.72 mmol) in hydrobromic acid (5 ml, 48%) was heated at the return flow for 15 min. The cooled reaction mixture was set to a pH of 9 with 5N NaOH solution. The mixture was then extracted with dichloromethane (4 x 10 ml). The combined organic phases were dried using sodium sulphate.The solvent was then removed in vacuum and purified by flash chromatography (silica gel, cyclohexane/EtOAc (1: 1)), resulting in 170 mg (71%) of the desired olefin.
Other
To produce the hydrochloride, the olefin (170 mg, 0,512 mmol) just isolated was dissolved in ethyl methyl ketone (5 ml), mixed with chlorotrimethyl silane (105 mg, 0,769 mmol) and stirred for 45 min at room temperature in an open reaction vessel. The resulting solid was sucked out. The hydrochloride was obtained at a yield of 160 mg (61%) as a white solid with a melting point of 115 °C to 119 °C.
3-Methylbenzofuran (354 mg, 3 mmol) was dissolved in dichloromethane (25 ml) together with ketone (Ket-10, 651 mg, 3 mmol) and mixed with trifluoromethane sulphonic acid (0.3 ml, 3.4 mmol). The solution was stirred at RT for 20 h. - For processing, the reaction mixture was stirred with 2N NaOH (10 ml). The mixture was stirred for another 20 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 x 20 ml). The combined organic extracts were dried over MgSO4 and then pressed. The resulting raw product (950 mg) was chromatographically purified (L:O) The olefin was weighed in 348 mg (35 mg) of olive oil as a viscous adhesive.
Other
The olefin (331 mg, 1 mmol) was dissolved in isopropanol (10 ml) at boiling temperature and mixed with citric acid (192 mg, 1 mmol) dissolved in hot isopropanol (5 ml). The solution was kept at 5 °C for 15 h. The resulting crystals were separated by a fryer. The crystals dissolved in the air. They were therefore quickly filled into a test tube and then dried in a vacuum. The desired citrate was obtained at a yield of 185 mg (35%) as a glassy solid.
The ketone (Ket-10, 2.06 g, 9.5 mmol) was presented under argon together with 2-benzofuran-3-yl) ethanthyl (Ind-94, 1.70 g) in absolute dichloromethane (25 ml). The solution was then stirred 4 days at RT. The solution was transferred to H2O (15 ml) for processing. The aqueous phase was separated and extracted with dichloromethane (3 × 20 ml). The combined organic phases were washed with 2N H2SO4. The dichloromethane phase was closed at the rotation valve. The yellow, sticky residue was washed with diethyl ether (3 × 10 ml). The solution was washed off with a residual residue of 2N (20 ml).The resulting mixture was extracted with diethyl ether (3 × 15 ml), the etheric phase was dried with sodium sulphate and compressed in the rotary evaporator, and the resulting residue was obtained by column chromatography (silica gel 60 (100 g); ethyl acetate, ethanol (9: 1)), the desired olefin i as a viscous oil at a yield of 381 mg (10% on the ketone used).
Other
The olefin (350 mg, 0.928 mmol) just isolated was dissolved in boiling ethanol (8 ml), mixed with a solution of citric acid (178 mg, 0.928 mmol) in hot ethanol (2 ml), stirred for 10 min and allowed to come to RT, and then brought to 5 °C in the refrigerator.The result was a white precipitate, the consistency of which was not stable at room temperature, so the ethanol was poured at about 5 °C and the remaining solid residue was vacuum dried.
3-Methylbenzo[b]thiophen (Ind-95, 0.27 ml, 2 mmol) was dissolved in dichloromethane (20 ml) together with ketone (Ket-10, 434 mg, 2 mmol) and mixed with trifluoromethane sulphonic acid (0.2 ml, 2.3 mmol). The solution was stirred for 2 days at RT, with a brown oil falling out. - For processing, the reaction mixture was mixed with 2N NaOH (10 ml). The mixture was stirred for another 20 min. After phase separation, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over MgSO4 and then re-pressed. The resulting raw product (856 mg) was crystallised with a sealing agent (Latograph: Octomethane) at 49 °C. The solution was obtained in a solid state at 380 °C. The solution was obtained by pressing 39 mg (2-54 mg) of methanol (395 mg) into a liquid crystalline.
Other
The olefin (295 mg, 0.85 mmol) just isolated was dissolved in methanol (30 ml) at boiling temperature and mixed with citric acid (163 mg, 0.85 mmol) dissolved in hot methanol (2 ml).
Example 243: N,N-dimethyl-4-(3-methylbenzo[b]thiophen-2-yl)-1-phenylcyclohexanamine, citrate (1:1) One of 2 possible diastereomers of 3-methylbenzo[b]thiophen (Ind-95, 0.27 ml, 2 mmol) was dissolved with ketone (Ket-10, 434 mg, 2 mmol) in HBr/iron vinegar (33% HBr, 20 ml) and stirred for 50 h at RT. Then Sn powder (1 g, 8.5 mmol) was added to the solution in RT portions for 30 min. After completion of the addition, the reaction mixture was stirred for another 20 h. - For processing, the mixture was diluted at the rotation until dry. The resulting solution was dissolved by 5 ml (4 x NOH) of chlorine and made into a solution containing 20 ml (4 x chlorine).The combined organic phases were dried and then compressed with MgSO4. The resulting residue (552 mg) was column chromatographically purified (conductor: 1.EtOAc; 2.EtOAc/EtOH 2:1), thus obtaining one of the two possible diastereoisomeric reduction products at a yield of 200 mg (28%) in addition to olefin (120 mg).
Other
The isolated reduction product (224 mg, 0.64 mmol) was dissolved in methanol (5 ml) at boiling temperature and replaced with citric acid (124 mg, 0.64 mmol) dissolved in hot methanol (2 ml). As no precipitation occurred, the solvent was withdrawn. The resulting solid residue was treated with dichloromethane. The desired product (271 mg, 78%) was obtained as citrate with a melting point of 178 to 179 °C.
The free base from sample 230 (300 mg, 0.95 mmol) was distilled in methanol (40 ml) with palladium catalyst (Pd/C, 5%, 120 mg) and hydrated at RT (hydrogen pressure: 3 bar) for 36 h. The reaction was monitored by DC. The catalyst was removed with a fry with a 1 cm layer of cellite. The fry was thoroughly washed with methanol (1000 ml). The solvent was distilled in a vacuum. The resulting raw product (310 mg) was purified by column chromatography [silicon 60 (20OH); whey (500 ml) ]. N,N-dimethyl-1-phenyl-4-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydroloxanone-hydrone-hydroloxanone-hydroloxanone-hydrone-hydroloxanone-hydrone-hydroloxanone-hydrone-hydrone-hydroloxanone-hydrone-hydrone-hydroloxanone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydrone-hydroneThe solid (180 mg, 0.56 mmol) was dissolved in isopropanol (10 ml) at boiling point and mixed with citric acid (108 mg, 0.56 mmol) dissolved in hot isopropanol (3 ml). The method was stopped at 5 °C for 16 h. The resulting white precipitate was separated by a frying process. Sample 244 was obtained at a yield of 173 mg (60 %, melting point 130-133 °C).
Other
The mean of the measurements of the two samples was approximately 1 μs/m2 at 1H NMR (300 MHz, DMSO-d6) δ ppm: 1.18-1.45 (m, 2H), 1.84-2.15 (m, 4H), 2.40 (s, 6H), 2.52-2.67 (m, 4H), 2.78-3.02 (m, 3H), 6.82-6.96 (m, 1H), 7.00 (S, 1H), 7.39-7.59 (m, 3H), 7.59-7.77 (m, 3H), 8.03-8.18 (m, 1H), 11.24 (s, 1H)
Other
The following is a list of the active substances in the active substance, as defined in Annex I to Regulation (EC) No 1831/2003:
Dimethylamine (324 mg, 2.36 mmol; 33 per cent in ethanol, 0.76 g/ml) was added to a suspension of sample 247 (115 mg, 0.40 mmol) in ethanol (15 ml) at room temperature. The reaction mixture was stirred for 9 h at 59 °C (oil bath temperature). The reaction mixture was then completely removed from volatile components in a vacuum. The residue was dissolved with diethyl ether (3 ml). The mixture was stored for 3 days at 0 °C. A precipitation failed. The remaining solution was decanted. Sample 244 (smp. 54-57 °C) was obtained as a colourless solid in a 50 per cent (64 mg, 0.15 mmol) dissolved solution.
The free base from example 17 (unpolar diastereomer, 279 mg, 0.84 mmol) was dissolved in dimethylformamide/tetrahydrofuran (20 ml, 1:1), and the clear light yellow solution was added to sodium hydride (60% suspension in mineral oil, 70 mg, 1.75 mmol). A bright solid then fell out of the reaction mixture. It was stirred for 1 h at 57 °C (oil bath temperature). Then the epichlorohydrin (163 mg, 1.76 mmol; 1.183 g/ml) was added at this temperature. It was stirred for 1 h at 57 °C (oil bath temperature). Then the reaction mixture was stirred with water (30 ml) and diethyl (20 ml) The mixture was stirred for 10 min. The methyl was then quickly separated.The aqueous phase was extracted with ethyl acetate (2 x 20 ml). The combined organic phases (ethyl acetate and diethyl ether) were washed with saturated sodium chloride solution (3 × 10 ml), dried and filtered with sodium sulphate. The volatile components were then completely removed in vacuum, leaving 406 mg (±) -N.N-dimethyl-4- (((3-methyl ((-1-oxiran-2-ylmethyl) - 1H-indolyl-2-) --1-phenylcyclohexane. The raw product was resold without further purification.
Other
(±) -N,N-dimethyl-4-(3-methyl-1- ((oxiran-2-ylmethyl) -H-indol-2-yl) -phenylcyclohexanamine (62 mg. 0,16 mmol) was dissolved in boiling ethanol (5 ml). Citric acid (34 mg, 0,18 mmol) was then added. The clear solution was stirred at boiling point 3. The reaction mixture was then cooled to room temperature and left to stand at this temperature for 24 h.A colourless microcrystalline precipitate was obtained, which was filtered and washed with ethanol (2 × 5 ml) to obtain 69 mg (0.12 mmol; 75%) sample 247 (SMP: 175-178 °C).
The free base from sample 17 (unpolar diastereomer, 176 mg, 0.53 mmol) was presented in an argon atmosphere in dry dimethylformamide (15 ml) and mixed with sodium hydride (60% suspension in mineral oil, 21 mg, 0.53 mmol). The reaction mixture was stirred at room temperature for 1 h and then cooled to 0 °C in an ice bath. Methyliodide (150 mg, 0.06 ml, 1.06 135 mmol, 2.28 g/ml) was added to the yellow solution, and instantaneous de-discoloration was initiated. The reaction mixture was heated at room temperature within 2 h and dried overnight at room temperature. For processing, the reaction mixture was stirred with 2 N/L sodium hydroxide (10 ml) solution (108 ml) and 10 mg of hydrogen oxide (10 °C). The sample was vacuumed and left to stand for 24 hours (the next day, the mixture was dried at room temperature).
After 10 min, precipitation failed. The solution was stirred at RT for 24 h. - For preparation, the mixture was mixed with NaHCO3 solution (15 ml) and stirred for 24 h. The organic phase was separated and the aqueous phase extracted with dichloromethane (3 × 10 ml). The combined organic phases were dried over Na2SO4 and then compressed. 2-butyl-4-dimethylaminoxyl-3-methyl-1 (dimethylaminoxyl-1) was obtained in a yield of 107 mg (99 × 5%) of 2-methyl-1-methyl-1 (dimethylaminoxyl-1) in a solution of 0.05% by weight.
Other
2-(4-butyl-4- ((dimethylamino) cyclohexyl) 3-methyl-1H-indol-5-ol (unpolar diastereomer, 107 mg, 0.32 mmol) was dissolved in hot isopropanol (50 ml) and mixed with isopropanolic citric acid solution (62 mg, 0.32 mmol in 2 ml). The mixture was stirred at room temperature for 2 h. The white solid was extracted and obtained sample 249 at a yield of 47 mg (27%) with a melting point of 197-208 °C
For solution To a solution of the free base of sample 126 (polar diastereoisomer, 263 mg, 0.77 mmol) in dry dichloromethane (40 ml) a 1 M solution of BBr3 in dichloromethane (0.66 ml, 0.66 mmol) was administered to RT by stirring and moisture excretion. After 10 min a precipitation occurred. The approach was agitated at RT for 24 h. - For preparation the mixture was stirred with NaHCO3 solution (15 ml) and agitated again for 24 h. The solid at the phase boundary (100 mg) was separated. The mixture was mixed in an organic solution. NaHCO3-L solution (20 mg) and ethyl sulphate (10 ml) were stirred for 1 h. The organic phase was separated. The backing was pressed with dimethyl sulphate (5 ml × 10 ml) and obtained by extracting 35 mg (34 ml) of ethyl sulphate (5-34 mg) from a 2-methyl methyl methyl methyl extract and mixing it with Na-SO4-methyl phenol (14-methyl phenol) and extracted from it with a 2-methyl phenol (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl) (14-methyl (14-methyl) (14-methyl) (14-methyl (14-methyl) (14-methyl) (14-methyl (14-methyl) (14-methyl (14-methyl) (14-methyl (14-methyl) (14-methyl (14-methyl) (14-methyl) (14-methyl (14-methyl) (14-methyl (14-methyl) (14-methyl (14-methyl) (14-methyl) (14-methyl (14-methyl) (14-methyl (14-methyl) (14-methyl (14-methyl) (14-methyl) (14-
2-(4-butyl-4- ((dimethylamino) cyclohexyl) -3-methyl-1H-indol-5-ol (polar diastereoisomer) (135 mg, 0.41 mmol) was dissolved in hot isopropanol (30 ml) and mixed with isopropanolic citric acid solution (79 mg, 0.41 mmol in 3 ml). The mixture was stirred at room temperature for 2 h. The beige solid was sucked and obtained sample 250 at a yield of 160 mg (74%) with a melting point of 145-159 °C.
Ind-14 (667 mg, 3 mmol) was dissolved in dichloromethane (45 ml) with ketone Ket-12 (671 mg, 3 mmol) and replaced with trifluoromethane sulphonic acid (0.660 ml, 7.43 mmol). The solution was stirred at RT for 64 h, with a brown oil being removed. For processing, the reaction solution was stirred with 1N NaOH (30 ml) and methanol (10 ml). The mixture was stirred for another 60 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 × 10 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The resulting product (1.33 g) was seeded at 29 °C; 60 g of ethylene glycol (100 g/m3): ethanol (150 mg/m3): 1 200 g/m3), obtained as a solid at 29 °C.
Ind-14 (667 mg, 3 mmol) was dissolved in dichloromethane (45 ml) with ket-13 (706 mg, 3 mmol) and added to trifluoromethane sulphonic acid (0.660 ml, 7.43 mmol). The solution was agitated at RT for 64 h, with a brown oil being removed. For preparation, the reaction solution was agitated with 1 N NaOH (30 ml) and methanol (10 ml). The mixture was agitated for another 60 min. After separation of the phases, the aqueous phase was coated with dichloromethane (3 x 10 ml). The extra organic compounds were dried over Na2SO4 and then pressed. The resulting product (1.33 g) was obtained by crystallisation at 23 °C; 60 g of ethylene glycol (100 mg/ ml) was obtained from methyl methanol (1,5-2,5 mg/ ml) at 25 °C. The product was purified from methyl methanol (2,5-2 mg/ ml) at 25 °C. The solution was obtained as a clear yellow solution of ethylene glycol (1,5-2 mg/ ml) at 25 °C. The product was obtained from methyl methanol (1,5-2 mg/ ml) at 25 °C.
Ind-14 (667 mg, 3 mmol) was dissolved in dichloromethane (45 ml) together with ket-14 (671 mg, 3 mmol) and replaced with trifluoromethane sulphonic acid (0.613 ml, 6.9 mmol). The solution was stirred at RT for 64 h, with a brown oil being omitted. For processing, the reaction solution was stirred with 1N NaOH (30 ml) and methanol (10 ml). The mixture was stirred for another 60 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 x 10 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The resulting raw product (1.35 g) was sequenated [90 g]; 60 g (90 g/ml): 1 g/methanol (2400 mg/ml): 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/ml: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 g/m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 1 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m: 2 m:
Ind-14 (667 mg, 3 mmol) was dissolved in dichloromethane (45 ml) with Ket-15 (610 mg, 3 mmol) and replaced with trifluoromethane sulphonic acid (0.613 ml, 6.9 mmol). The solution was stirred at RT for 64 h, with a brown oil being removed. For preparation, the reaction solution was stirred with 1N NaOH (30 ml) and methanol (10 ml). The mixture was stirred for another 60 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 x 10 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The resulting product (1.47 g) was sequenated [90 g]; 60 g (methanol: 1 g/ 200 ml): ethanol (178 g/ 47 g/ 200 ml): 1 g/ 25 g/ 16 °C. The resulting product was purified as a clear ethanol (178 g/ 47 g/ 16 °C. 1 g/ 47 g/ 17 °C. 1 g/ 200 g/ 17 °C. 1 g/ 47 g/ 17 °C. 1 g/ 47 g/ 17 °C. 1 g/ 17 °C. 1 200 g/ 17 °C. 1 g/ 17 °C. 1 200 g/ 17 °C. 1 200 g/ 17 °C. 1 °C. 1 200 g/ 16 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C. 1 °C.
Ind-10 (686 mg, 5.24 mmol) was dissolved in dichloromethane (40 ml) together with Ket-12 (1.17 g, 5.24 mmol) and replaced with trifluoromethanesulphonic acid (0.5 ml, 5.6 mmol). The solution was stirred at RT for 20 h. - For preparation, the reaction mixture was stirred with H2O (20 ml) with no sticky precipitation. The mixture was stirred for 10 min, then the aqueous phase containing small amounts of unchanged ketone (< 100 mg) was separated. The organic phase and the adhesive were added. NaHCO3 solution (20 ml) was added. The solvent was stirred at RT for 60 min until all the remaining solvent was dissolved. The organic phase was dissolved with 20 ml (3 x) of the extra water chloromethane.The combined organic extracts were washed with water, dried with MgSO4 and then compressed. The resulting raw product (2 g) was purified by column chromatography [silica gel 60 G (10 g; EtOAc (100 ml) ]. (±)-2-(4-dimethylamino) -4- (thiophen-2-yl) -cyclohex-1-enyl) -3-methyl-1H-indol was obtained as a solid (melting point 183-192 °C) at a yield of 882 mg (50 %).
Other
(±)-2-(4-(Dimethylamino)-4-(thiophen-2-yl) -cyclohex-1-enyl) -3-methyl-1H-indol (168 mg, 0.5 mmol) was dissolved in isopropanol (15 ml) at boiling temperature and mixed with citric acid (102 mg, 0.53 mmol) dissolved in hot isopropanol (2 ml). After adding the acid, precipitation was not observed. To complete the precipitation, the solution was cooled to 5 °C (refrigerator) and kept at this temperature for 17 hours.The precipitation was separated by a fryer and then dried, so that sample 255 was obtained at a yield of 163 mg (61% as solid).
The free base from sample 255 (436 mg, 1.3 mmol) was absorbed in HBr/iron vinegar (33% HBr, 30 ml) and then given to RT for the approach in 4 h Sn powder (4 g, 33 mmol) in portions. After completion of the addition, the reaction mixture was stirred for another 18 h at RT. - For processing, the mixture was diluted with EtOH (20 ml) and the solvent volume at the rotational vapour reduced to approximately 10 ml. The remaining residue was given to 200 ml. The hydrogen residue was separated by filtration and then mixed with 2 N NaOH (50 ml). The resulting dry point was extracyclically mixed with methanol (4 g). The organic pollutant was mixed with 60 g (50 ml) of hydrogen at 60 °C. The residue was obtained from a white crystalline solution of methanol (N 2-methanol) (180 mg) and obtained by melting it in a white crystalline solution of 70 mg (22-methanol) (180 mg (22-methanol) (180 mg) and dissolved in a white crystalline solution of methanol (210 mg (24-methanol) (180 mg) (180 mg) (128 g (24-methanol) (180 mg) (180 mg)), and dissolved in a white crystalline solution of methanol (22-methanol).
N,N-Dimethyl-4-(3-methyl-1H-indol-2-yl)-1-(thiophen-2-yl) cyclohexanamine (unpolar diastereomer) (91 mg, 0.27 mmol) was dissolved in isopropanol (4 ml) at boiling temperature and mixed with citric acid (60 mg, 0.31 mmol) dissolved in hot isopropanol (1 ml). Immediately precipitation occurred. To complete precipitation, the solution was cooled to 5 °C (refrigerator) and left at 2 °C. The precipitation was separated by an F and then dried. 256 samples were obtained at a yield of 81 mg (68 %, melting point: 196-198 °C).
N,N-Dimethyl-4-(3-methyl-1H-indol-2-yl)-1-(thiophen-2-yl) cyclohexanamine (polar diastereomer) (64 mg, 0.19 mmol) was dissolved in isopropanol (4 ml) at boiling temperature and mixed with citric acid (52 mg, 0.27 mmol) dissolved in hot isopropanol (1 ml). The solvent was removed and the residue was incorporated into methanol (10 ml). The solution was then dissolved with water (3 ml) and the methanol was removed from the rotary evaporator. The precipitate thus obtained was separated by a F-trap and then dried.
The ketone Ket-14 (800 mg, 3.58 mmol) and Ind-10 (470 mg, 3.58 mmol) were dissolved in dichloromethane (50 ml) and mixed with trifluoromethane sulphonic acid (0.953 ml, 1.61 g, 10.74 mmol) and stirred at room temperature for 18 h. The solution was mixed with water (20 ml) and 1 N sodium nitrate solution (15 ml) and stirred for 1 h. The phases were separated. The aqueous phase was extracted with dichloromethane (2 × 20 ml). The organic phases were combined, washed with water (20 ml), dried with sodium sulphate and browned. The residue was a narrow oil (1.24 g) which was chromatographically [60 g] gelised (100 g); ethyl acetate/methanol (600 ml), a solid obtained from methanol (48 mg) was extracted from a 36% more colourful example.
3-Methylindol (Ind-10, 393 mg, 3 mmol) was dissolved in dichloromethane (25 ml) together with Ket-15 (609 mg, 3 mmol) and mixed with trifluoromethanesulphonic acid (0.4 ml, 4.5 mmol). The solution was stirred at RT for 24 h. - For processing, the reaction mixture was stirred with 2N NaOH (20 ml) and mixed at RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The raw product (() N-methyl-N-4-[3-methyl-1H-indol-2-phenyl-cyclohexamine-3-±) -amines) was dissolved in 945 mg (99%) without further oil extraction and obtained as a by-product of the next reaction.
(±) -N-methyl-N-[4-(3-methyl-1H-indol-2-yl) -phenylcyclohex-3-enyl]amine (900 mg, 2.8 mmol) was dissolved in HBr/iron vinegar (33% HBr, 30 ml) and then administered to the RT Sn-powder (1.66 g, 14 mmol) in portions for 20 min. After completion of the addition, the reaction mixture was stirred at 9 d (likely with a much shorter reaction time) to produce a clear solution. - The mixture was diluted with (20OH) and dissolved organically at the rotation to steam until dry. The leveling resistance was obtained by adding 5 NaNOH (50 ml) to the solution. The resulting mixture was mixed with 20 ml (4 ml) of ethyl ether extracted from the water (50 ml) and mixed with 20 ml (50 ml) of ethyl ether extracted from the water.The raw product (1 g) was obtained as a mixture of base and hydrobromide and was separated by column chromatography [silica gel 60 (50 g); ethylacetate (250 ml), methanol (250 ml) ]. The non-polar product (259 g) was obtained as a hydrobromide at a yield of 67 mg (6%) with a melting point of 288-298 °C. The polar product (N-methyl-4-methyl-1H-indol-2-yl) -phenylcyclohexanamine) was isolated as a base at a yield of 390 mg (39%).
Other
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements by the mean of the measurements.The number of people who are in the labour force is not limited to the number of people who are employed in the labour force.
Other
The following is a list of the active substances in the active substance, as defined in Annex I to Regulation (EC) No 396/2005 and in the active substance, as defined in Annex II to that Regulation:
N-Methyl-4-(3-methyl-1H-indol-2-yl) -phenylcyclohexanamine (polar diastereomer) (390 mg, 1.22 mmol) was dissolved in hot isopropanol (250 ml) and mixed with ethanolic citric acid solution (234 mg, 1.22 mmol in 5 ml). The mixture was stirred at room temperature for 2 h. The precipitated solid was sucked out. Sample 260 was obtained at a yield of 270 mg (43% white solid) with a melting point starting at 189 °C.
Other
The following is a list of the active substances that may be used in the active substance:
For example, 263 (450 mg, 1.3 mmol) was suspended in HBr/Ice vinegar (33% HBr, 15 ml) and then administered to RT Sn-powder (771 mg, 6.5 mmol) in portions for 10 min. After completion of the addition, the reaction mixture was stirred for 48 h at RT. A clear solution was obtained. - For processing, the mixture was diluted with EtOH (20 ml) and evaporated at rotational vapour to dry. The remaining residue was made basic by adding 5N NaOH (30 ml). The resulting aqueous mixture was extracycled with dichloromethane (4 x 20 ml). The dried organic phases were mixed with water (50 ml) and then watered with NaOH. The product containing 1.4% isocyanate (N2SO4) was obtained from a 130 mg (130 mg-29 mg) (130 mg) (130 mg) (2- to 2.00 mg) (130 mg) (130 mg) (130 mg) (130 mg) (2- to 2.00 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 mg) (130 (2 mg) (130 mg) (130 mg) (130 (2 mg) (130 mg) (130 (2) (130 mg) (130 mg) (130 (2) (130 mg) (130 mg) (130 (2) (130 mg) (130 mg) (130 (2) (130 mg) (130 (2) (130 mg) (130 mg) (130 (2) (130 mg) (130 (2) (130 (2) (130 mg) (130 (2) (130 mg) (130 (2) (130 mg) (130 (2) (130
1- ((3-fluorphenyl) N,N-dimethyl-4- ((3-methyl-1H-indol-2-yl) cyclohexanamine (unpolar diastereoisomer) (120 mg, 0.34 mmol) was dissolved in hot isopropanol (110 ml) and mixed with ethanolic citric acid solution (66 mg, 0.34 mmol in 3 ml). The mixture was stirred at room temperature for 2 h. The precipitated solid was sucked out. Sample 261 was obtained at a yield of 90 mg (59%, white solid) with a melting point of 228-237 °C.
Other
The mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory was approximately 0.01% and the mean of the measurements performed in the laboratory were approximately 0.01% and 0.01% and the mean of the measurements performed in the laboratory were performed in the laboratory were performed in the laboratory were approximately 0.0 and 0.0%.
Other
The following are the active substances which may be used in the active substance:
1- ((3-fluorphenyl) N,N-dimethyl-4- ((3-methyl-1H-indol-2-yl) cyclohexanamine (polar diastereoisomer) (120 mg, 0.34 mmol) was dissolved in hot isopropanol (50 ml) and mixed with ethanolic citric acid solution (66 mg, 0.34 mmol in 3 ml). The mixture was stirred at room temperature for 2 h. The failed solid was extracted and sample 262 was obtained at a yield of 64 mg (42%) with a melting point of 276-285 °C.
Other
The mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour, and the mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour.
Other
The following substances are to be classified in the same category as the active substance:
3-Methylindol (Ind-10, 393 mg, 3 mmol) was dissolved in dichloromethane (25 ml) together with Ket-13 (705 mg, 3 mmol) and mixed with trifluoromethane sulphonic acid (0.4 ml, 4.5 mmol). The solution was stirred at RT for 24 h. - For processing, the reaction mixture was stirred with 2N NaOH (20 ml) and mixed at RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (2 x 20 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The raw product was obtained in a yellowish oil yield of 1 g (100 ppm). The oil was dissolved in hot ethanol (10 ml). The mixture was completely crystallized and dissolved in a liquid solution of 17 to 266 mg (473 to 17 °C) in a glass filtered glass filter.
Other
The mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour, and the mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour.
(±) N-[1-benzyl-4-(5-methoxy-3-methyl-1H-indol-2-yl) cyclohex-3-enyl]-N,N-dimethylamine 5-methoxycatol (Ind-9, 806 mg, 5 mmol) was dissolved with ket-3 (1,15 g, 5 mmol) in dichloromethane (40 ml) and added to trifluoromethanesulphonic acid (0,65 ml, 7,5 mmol). The solution was agitated at RT for 24 h. - For processing, the reaction mixture was mixed with 2N NaOH (20 ml) and agitated at RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (3 x 20 ml). The organic extracts were pressurised over NaSO2 and then e2SO4 e. The product was dissolved in a second reaction (98%) and obtained as a pure product from the next reaction without further addition of oil.
(±) N-[1-benzyl-4-(5-methoxy-3-methyl-1H-indol-2-yl) cyclohex-3-enyl]-N,N-dimethylamine (1.97 g, 5.26 mmol) was suspended in HBr/acetic acid (33% HBr, 30 ml) and then administered to the RT Sn powder (3.12 g, 26.3 mmol) for 30 min. After completion of the addition, the reaction table was stirred for another 48 h. - For final processing, the mixture was diluted with ethanol (20 ml) and obtained by evaporation at the rotary evaporator to a dry acetic acid. The remaining residue was obtained by adding 5 N NaOH (100 ml) to the base crystal. The preserved mixture was mixed with 20 × 10 N N N-dimethylamine (0.5 mmol) of polychlorinated ethanol (150 mg/mL) and dissolved in water as a liquid. The residue was then dissolved in a water filter (150 mg/mL) and treated with ethylene glycol (150 mg/mL) (150 mg/mL) and dissolved in water as a liquid. The remaining residue was then removed in a glass filter containing 60 mg (150 mg/mL) of ethanol (150 mg/mL) and dissolved in water as a liquid.
After 10 min, precipitation failed. The solution was stirred for 24 h. - The gem was moved to a solution of NaHCO3 (15 ml) and stirred organically for 48 hours. The phase was separated and the aqueous phase was combined with extracted dichloromethane (3 × 10 ml) by stirring and moisture extraction. The organic nahas were then pressed together in 63 ml (50 × 10 ml) of 2-dimethyl-3-methyl-3-methyl-3-methyl-3-methyl-3-methyl (SO4) and obtained in a 63 mm thick solution (50 × 10 ml) of 2-dimethyl-3-methyl-3-methyl-3-methyl.
2- ((4-Benzyl-4- ((dimethylamino) cyclohexyl) -3-methyl-1H-indol-5-ol (polar diastereomer) (63 mg, 0.173 mmol) was dissolved in hot isopropanol (10 ml) and mixed with isopropanolic citric acid solution (34 mg, 0.173 mmol in 2 ml). The mixture was stirred at room temperature for 2 h. The white solid was sucked. Sample 264 was obtained at a yield of 55 mg (57%) with a melting point of 165°C to 173°C.
Other
The mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour, and the mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour.
After 10 min, precipitation failed. The solution was stirred for 24 h. - For processing, the cream was transferred to a NaHCO3 solution (20 ml) and 48 ml was added. The organic phase was separated and the dilute phase was extracted with a thick dichloromethane (3 x 10 ml). The organic phase was then obtained by pressing the nearby P2SO2 into a 29% (24-dimethyl-4-methyl-3-oyl) diisocyanate (61 ml) of 2-dimethyl-4-oyl.N-[1-benzyl-4-(5-hydroxy-3-methyl-1H-indol-2-yl) cyclohexyl) -N,N-dimethylamine (unpolar diastereoisomer) (291 mg, 0.8 mmol) was dissolved in hot isopropanol (30 ml) and mixed with isopropanolic citric acid solution (154 mg, 0.8 mmol in 2 ml). The mixture was stirred at room temperature for 2 h. The white solid was suctioned. Sample 265 was obtained at a yield of 300 mg (67%) with a melting point of 224-239 °C.
Other
The following are the most commonly reported effects of the drug on the body:The Commission has also been asked to submit a proposal for a directive on the protection of workers from the risks related to exposure to ionising radiation.
Other
The following is a list of the active substances that may be used in the active substance:
The mixture was then diluted with dichloromethane (100 ml), then 5 N NaOH solution (60 ml) was added slowly under infusion so that the temperature did not exceed 25 °C. The mixture was stirred for 30 minutes. The phases were separated. The aqueous phase was extracted with dichloromethane NaCl (0.633 g, 5.33 mmol) for 40 min. The combined organic phases were filtered with Na2SO4 and obtained by filtration of the trioxide: the best vacuum-cleaned solids were: a white solid (44-50 mg/ml), a white solid (44-50 mg/ml) (16-50 mg/ml), a white solid (16-50 mg/ml) (14-50 mg/ml) (14-50 mg/ml) (14-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-50 mg/ml) (16-60 mg/ml) (16-60 mg/ml) (16-60 mg/ml) (16-60 mg/ml) (16-60 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-75-160 mg/ml) (16-60 g) (16-75-160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (160 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g) (150 g)
2-(butyl-4-(pyrrolidine-1-yl)cyclohexyl) -3-(2-(pyridin-4-yl) ethyl) -1-H-indol (unpolar diastereoisomer, 80 mg, 0.186 mmol) was dissolved in dichloromethane (1 ml) and added to citric acid (40 mg, 0.208 mmol), dissolved in ethyl acetate (6 ml). During addition of the acid, precipitation occurred. The mixture was then stirred for 2 h at 23 °C and then filtered. The precipitation was washed with ethyl acetate (2 x 0.5 ml). Sample 266 was obtained as a white solid at a yield of 94% (109%) with a melting point of 132-139 mg °C.
Other
The mean of the measurements is calculated as the ratio of the mean of the measurements to the mean of the measurements.
Other
The following are the most commonly used medicinal products:
2-(butyl-4-(pyrrolidine-1-yl)cyclohexyl) -3-(2-(pyridin-4-yl) ethyl) -1-H-indol (polar diastereoisomer, 44 mg, 0.102 mmol) was dissolved in dichloromethane (0.5 ml) and replaced with citric acid (22 mg, 0.114 mmol), dissolved in ethyl acetate (4 ml). During addition of the acid, precipitation occurred. The mixture was then stirred for 2 h at 23 °C, then filtered and washed with ethyl acetate (2 0.5 ml) precipitation. Example 267 was obtained as a coloured solid at a yield of 93 × 59 % (59 × 59%) with a melting point of 105-112 mg °C.
Other
The mean of the measurements performed was approximately 0.01% and the mean of the measurements performed was approximately 0.01% and the mean of the measurements performed was approximately 0.01% and 0.02% respectively.
Other
The following are the most commonly reported abnormalities of the test chemical:
Indol (Ind-10, 525 mg, 4 mmol) was dissolved with ketone (Ket-16, 917 mg, 4 mmol) in dichloromethane (80 ml) and mixed with trifluoromethane sulphonic acid (0.54 ml, 6 mmol). The solution was stirred at RT for 24 h. For processing, the reaction mixture was stirred with 5N NaOH (40 ml) and mixed at RT for 20 min. After separation of the organic phase, the aqueous phase was extracted with dichloromethane (2 x 30 ml). The combined organic extracts were dried over Na2SO4 and then compressed. The raw product was purified by column chromatography [60 gels (50); gels (500 ml) ] but still contained the edon (Keton) 40 mg. This was obtained by the next reaction without further refinement.
The olefin (730 mg, 2.11 mmol) was dissolved in HBr/iron vinegar (33% HBr, 20 ml) and then given to RT Sn powder (2.5 g, 21 mmol) in portions for 40 min. After completion of the addition, the reaction mixture was stirred for 16 h at RT to obtain a clear solution. - For processing, the mixture was diluted with EtOH (20 ml) and reduced to dry e at the rotary evaporator. The remaining residue was made basic by adding 5N NaOH. The resulting aqueous mixture was extracted with dichloromethane (4 x 30 ml). The dehydrated organic phases were treated with water (50 ml) and then watered with NaOH (302 mg) The resulting product was obtained from a 60 mg (260 mg) of polar ether and obtained from a 220 mg (264 mg) of unrefined methanol (500 mg) [60 g/mol] by means of a purified methanol diisolider.
To produce the citrate, the newly produced polar diastereomer (165 mg, 0.48 mmol) was dissolved in hot methanol (100 ml) and mixed with citric acid (185 mg, 0.96 mmol). The clear solution was left for 16 h at 4 °C. The white citrate was sucked and dried. The citrate (Example 268) was obtained at a yield of 180 mg (67%) with a melting point of 150-155 °C.
Other
The mean of the measurements performed was approximately 0.01% for the two samples, and the mean of the measurements performed was approximately 0.01% for the two samples.
Other
The following are the most commonly reported effects of the drug:
To produce citrate, the unpolar diastereomer (220 mg, 0.63 mmol) produced in Example 268 was dissolved in hot methanol (150 ml) and mixed with citric acid (243 mg, 1.26 mmol).The clear solution was left for 16 hours at 4 °C. The white citrate was sucked and dried.The citrate (Example 269) was obtained at a yield of 183 mg (54%) and a melting point of 165 to 167 °C.
Other
The mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour, and the mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour.
Other
The following are the most commonly reported effects of the drug:
Lindol (Ind-14, 667 mg, 3 mmol) was dissolved in dichloromethane (45 ml) with ketone (Ket-16, 688 mg, 3 mmol) and added to trifluoromethane sulphonic acid (0.613 ml, 6.9 mmol). The solution was stirred at RT for 64 h, with a brown oil being removed. The reaction solution was stirred with 1 N NaOH (30 ml) and methanol (10 ml) for processing. The mixture was stirred for another 60 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 x 10 ml). The combined organic extracts were dried over Na2SO4 and then dried. The resulting raw product (1,42 ml) was seeded with gelling gel [Kylecetat: 60 °C: 60 g/m3 (390 °C: 1 mg/m3 / 100 ml); the refined solid was obtained as methanol (1,515 °C: 1 mg/m3 / 100 ml); the methanol (1,215 °C: 1 mg/m3 /m3 /m3) was obtained as methanol (1,215 °C: 1 mg/m3); the methanol (1,215 °C: 1 mg/m3 /m3) was obtained as methanol (1,215 °C: 1 mg/m3); the refined solid was obtained as methanol (1,215 °C: 1 mg/m3 /m3 /m3); the obtained raw product was obtained as methanol (1,215 °C: 1 mg/m3 /m3 /m3 /m3 /m3); the resulting oil (120 °C: 1 mg/m3 /m3 /m3 /m3 /m3 /m3 /m3 /m3); the resulting oil (120 °C: 1 °C: 1 °C: 1 °C: 1 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2 °C: 2
The olefin (288 mg, 0.66 mmol) was suspended in HBr/iron vinegar (33% HBr, 10 ml) and then administered to the RT Sn powder (797 mg, 6.6 mmol) in 30 min. After completion of the addition, the reaction mixture was stirred at RT for 24 h. For processing, the mixture was diluted with EtOH (20 ml) and compressed to dry in the rotary evaporator. The remaining residue was made basic by adding 5N NaOH (75 ml) and stirred with dichloromethane (70 ml). This mixture was stirred at room temperature for 2 h. The organic phase was separated and the aqueous phase was added with dichloromethane (3 x 30 ml).The combined organic phases were dried and then compressed with Na2SO4. The resulting raw product (196 mg) was purified by column chromatography [silica gel 60 (20 g; methanol (150 ml) ]. The unpolar diastereoisomer was obtained at a yield of 100 mg (35%). The polar diastereoisomer was isolated at a yield of 36 mg (12%).
Other
The resulting polar diastereomer (36 mg, 0.08 mmol) was dissolved in dichloromethane (50 mi). In RT, Me3SiCl (20 μl, 0.16 mmol) was added and stirred for 1 h. Since the precipitated solid was hygroscopic, the solvent was removed at the rotary evaporator.The resulting solution is a white solid.
Other
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements by the mean of the measurements.
The nonpolar diastereomer (100 mg, 0.23 mmol) produced in example 270 was dissolved in dichloromethane (150 ml). In RT, Me3SiCl (50 μl, 0.4 mmol) was then dripped and stirred for 1 h. Since the precipitated solid was hygroscopic, the solvent was removed at the rotary evaporator. The nonpolar hydrochloride (example 271) (108 mg, Fp. 242-245 °C, yield 100%) was a white solid.
Other
The following are the most commonly used methods for the determination of the concentration of the active substance in the feed additive:
The ketone (Ket-17, 800 mg, 3.58 mmol) and the skatol (Ind-10, 470 mg, 3.58 mmol) were dissolved in dichloromethane (50 ml) and mixed with trifluoromethane sulphonic acid (0.953 ml, 1.61 g, 10.74 mmol) and stirred at room temperature for 18 h. The solution was mixed with water (20 ml) and 1N of baking soda (15 ml) and stirred for 1 h. The phases were separated. The aqueous phase was extracted with dichloromethane (2 x 20 ml). The organic phases were combined, washed with (20 ml) water, dried with sodium sulphate and pressed. The residue was a gel oil (1.24 g) which could be obtained from a chromatograph [60 g]; the methanol (100 g / 1 ml) was determined at a concentration of methanol (400 mg/ 500 ml) and was obtained from a 36 per cent pure colourless oil.
Variant 1: The olefin (211 mg, 0.627 mmol) had been dissolved in methanol (30 ml) and added to coal with palladium (5 per cent, 50 mg). The reaction mixture was hydrated at 3 bar for 3.5 h. The catalyst was separated via cellite and the filtrate was pressed. The residue (200 mg, light brown oil) was chromatographically separated [silicon gel 60 (20 g); ethylacetate/methanol 10 : 1 (200 ml), ethylacetate/methanol 4 : 1 (200 ml), methanol (200 ml). The nonpolar diastereoisomer was obtained at a yield of 10 % (20 mg) the polar diastereoisomer at a yield of 67 % (143 mg).Variant 2: The olefin (180 mg, 0.535 mmol) was dissolved in HBr/ice vinegar (33% HBr, 10 ml) at room temperature for 1 h. The tin powder (64 mg, 0.535 mmol) was then added to the solution in 10 min. After completion of the addition, the reaction mixture was stirred for another 30 min. The solution was placed in water (20 ml) under ice cooling and stirred for 15 min at room temperature. The beige solid that had fallen out was soaked, washed with water (4 × 5 ml) and dichloromethane (2 x 5 ml). The hydrobromide of the diastereoisomer mixture was obtained at a yield of 69% (155 mg).The salt was taken in a mixture of dichloromethane (30 ml), water (20 ml) and 1N sodium salts (2 ml) and stirred at room temperature for 30 min. The phases were separated. The aqueous phase was extracted with dichloromethane (20 ml). The organic phases were combined, dried and compressed with sodium sulphate. The residue (107 mg, beige oil) was chromatographically separated [silica 60 (20 g); ethylac gel/methanol 10 : 1 (200 ml), ethylac/methanol 4 : 1 (200 ml), methanol (200 ml). The nonpolar diastereoisomer was obtained at a yield of 31% (56%) and the polar diastereoisomer at a yield of 17 mg (31%) mg.Both diastereoisomers were present as colourless salts on chromatography.
The newly produced polar diastereomer (105 mg, 0.29 mmol) was dissolved in ethanol (5 ml) and replaced with an ethanol solution (2 ml) of citric acid (63 mg, 0.326 mmol). After a reaction time of 16 h at room temperature, the citrate (Example 272) was separated as a colourless solid by filtration and washed with diethyl ether (2 × 2 ml). The salt was obtained at a yield of 51% (80 mg) with a melting point of 239-240 °C.
Other
The mean of the measurements performed in the laboratory was approximately 0.98, 0.98, 0.98, 0.98, 0.98, 0.98, 0.98, 0.98, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.90, 0.9.
After completion of the addition, the now reddish solution was temporarily lightened (15 min) at room temperature, with the solution becoming lighter. The ketone (2394 mg, 13.81 mmol, 97%) was dissolved in absolute tetrahydrofuran (50 ml) and cooled to -78 °C. The solution was then slowly dripped to lithium diisopropylamide (17.95 mmol, 9.9 ml, 1.8 M). After completion of the addition, the now reddish solution was temporarily lightened (15 min) at room temperature, with the solution becoming lighter. The ketone (Ket-10, 3000 mg, 13.81 mmol) was dissolved in red tetrahydrofuran (50 ml) and cooled to -78 °C. The solution was slowly returned to the organopropyl compound produced in situ. The 10 ml was cooled and dissolved in a clear water: the solution was removed from the vacuum. The remaining 50 g of the ammonium was dissolved in a white solution of 60 mg (10.0 ml) (10.0 ml) (10.0 ml) (10.0 ml) (10.0 g/ml) (10.0), and the remaining 50 g/ml (10.0 were dissolved in a white solution of ammonium chloride (10.0 mg/ ml) (10.0). The resulting water was dissolved in a white solution of ammonium chlorophyll phenol (10.0 (e) (10.0 g/ml) (10.0 g/ml) (10.0 (e) (10.0 g/ml) (10.0). The remaining 50 g/ml was removed from the vacuum was dissolved in a white solution of ammonium chlorophyll.
4-dimethylamino) -4-phenyl-1- ((5-tetrahydro-2H-pyran-2-yloxy) pent-1-ynyl) cyclohexanol (700 mg, 1.82 mmol), 2-amino-3-iodopyridine (363 mg, 1.65 mmol), lithium chloride (74 mg, 1.73 mmol) and sodium carbonate (525 mg, 4.95 mmol) were dissolved in dimethylformamide (20 ml) under argon atmosphere. The solution was then passed through argon for 10 min and then the catalyst ([Pdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdpdp
The newly prepared alcohol (662 mg, 1.39 mmol) was dissolved in methanol sulphonic acid (45 ml) and P4O10 (approximately 2 g) was added. The red-coloured reaction mixture was stirred for 3 h at 73°C (oil bath temperature). The colour of the reaction mixture had not changed. The reaction solution was given 5N sodium hydroxide solution (130 ml), water (70 ml) and dichloromethane solution (40 ml) under ice cooling and stirred for 10 min. The phases were then separated. The aqueous phase was extracted with dichloromethane (2 x 30 ml). The combined organic phases were dried over sodium sulphate, filtered and then filtered in liquid form. The composition was completely removed. The remaining parts were removed from the vacuum bath (478 mg) and placed in a vacuum bath with a yellowish powder of ethylene oxide (1,58 ml) and an ultra-low temperature of 1.08 °C. The resulting oil was then removed in a vacuum bath (478 mg) and placed in a vacuum bath with a yellowish powder of ethylene oxide (1,58 mg) and an ultrasonic filtered solution of 74 ml.
The reaction mixture was evaporated in a vacuum until dry and the light brown residue was dissolved with 5N sodium hydroxide solution (20 ml) and dichloromethane (20 ml). The mixture was filtered, the resulting solid was dissolved in methanol (5 ml) and combined with the organic phase. The aqueous phase was separated and extracted with sodium chloride (2 × 20 ml). The organic substances were combined and then dissolved on the sodium chloride chains.The yellow filtrate was fully evaporated (706 mg) and chromatographically separated [silica gel 60 (200 g); chloroform/ethanol 19:1 (500 ml), 9:1 (1000 ml), 4:1 (1000 ml), methanol (500 ml) ] A diastereoisomer of the desired alcohol was obtained as a yellow powder at a yield of 24% (83 mg, 0.22 mmol).
Other
The alcohol (76 mg, 0.20 mmol) produced was introduced into ethanol (5 ml) and the cloudy, faint yellow solution was heated to boiling temperature.The solution was cooled to 5°C in the refrigerator and left for 16 h. Colorless precipitation occurred. The remaining solution was removed and the residue dried in a vacuum. 67 mg (0.12 mmol, 59%) of the target compound (sample: 220-223 °C) could be isolated.
Other
The dose of the active substance is calculated by dividing the dose by the dose of the active substance in the dose range from 1 hour NMR (400 MHz, RT, DMSO-D6) δppm: 1.64 (pst, br, 2H), 1.80 (psd, br, 2H), 1.86-2.20 (m, 4H), 2.46 (s, br, 6H), 2.63 (dd, 4H), 2.67-2.78 (m, br, 2H), 2.88-3.13 (m, br, 2H), 2.46 (t, 2H), 4.16 (t, 1H), 6.93 (dd, 1H), 7.51-7.63 (m, 2H), 6.93 (dd, 1H), 7.51-763 (m, 2H), 6.93 (dd, 1H), 7.51-763 (m, 2H), 7.63 (t, 2H), 7.63 (t, 1H), 7.63 (m, 2H), 7.63 (t, 1H), 7.63 (m, 2H), 7.63 (t, 2H), 7.63 (t, 2H), 7.63 (t, 2H), 7.63 (t, 1H), 7.63 (t, 1H), 7.63 (t, 1H, and 7.63 (t, 2H).The number of cases of the disease is estimated at approximately 3H), 7.71 (psd, 2H), 7.79 (dd, 1H), 8.04 (dd, 1H), 11.22 (s, 1H), in addition to 1.5 to 4.5 (very br).
Other
The following is a list of the active substances that may be used in the active substance:
Methylamine (49 mg, 1.59 mmol; 2M in tetrahydrofuran, 0.79 ml) was added to a suspension of the polar epoxide (220 mg, 0.57 mmol) in ethanol (15 ml) at room temperature. Since no reaction occurred at room temperature, the reaction mixture was stirred for 5 h at 59 °C (oil bath temperature). The reaction mixture was then compressed in a vacuum for about 5 ml. A colourless solid was released. Diethyl ether (3 ml) was added. The mixture was stored for 3 days at 0 °C. The remaining solution was decanted. The polar product could be quantitatively obtained (234 mg, 0.57 mmol).
The polar amino alcohol (298 mg, 0.71 mmol) was presented in boiling ethanol (15 ml). The citric acid (150 mg, 0.78 mmol) was then added and the clear solution stirred at boiling temperature for 3 h. The reaction mixture was then cooled to room temperature and left at that temperature for 24 h. A colourless microcrystalline precipitation was produced. The precipitation was filtered and washed with ethanol. The desired product (Example 274) was obtained as a colourless solid (Smp: 173-180 °C) at a yield of 60 % (260 mg, 0.43 mmol).
Other
The mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour, and the mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour.
Other
The following is a list of the active substances that may be used in the active substance:
Indol (Ind-100, 820 mg, 2.8 mmol) and ketone (Ket-10, 608 mg, 2.8 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (1.00 ml, 11.2 mmol). The solution was stirred for 3 days at RT, leaving a dark brown oil. After adding 1 N NaOH (50 ml) and CH2Cl2 (20 ml), the oil was stirred for 1 h until dissolved. The phases were separated, the aqueous phase was extracted three times with CH2Cl2, the combined organic phases were washed with water, dried (Na2SO4) and the solution was i.e. vacuum treated. The remaining residue was flash chromatographed with 50 g CH1OH (1⁄3) g g/mol and purified (9:1:1:1:1:1).
The solution of the newly produced olefin (871 mg, 1.77 mmol) in HBr/iron vinegar (35 ml) was given tin (2.27 g) for 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was reduced to dry and the residue was dissolved in 5N NaOH (100 ml) and dichloromethane (150 ml). The phases were separated, the aqueous phase was extracted with CH2Cl2, the combined organic phases were washed with water, dried with Na2SO4 and i.e. compressed. The remaining residue was separated by flash chromatography with 50 g of kieselgel and CH→Cl3/OH→OH→OH→OH→OH (20:19:14:11:1) and the diisomers were then added to the solution, and the organic phases were then washed with 1 ml of CH2OH and i.e. 7 ml of Na2SO2 (i.e. 7 NCl2 and i.e. 7 NCl2), respectively.
Other
| 126 mg (14 %), unpolares Diastereomer | |
| 189 mg (22 %), polares Diastereomer |
The newly produced nonpolar diastereomer (108 mg, 0.22 mmol) was hot dissolved in ethanol (10 ml) and mixed with a solution of citric acid (42 mg, 0.22 mmol) in ethanol (0.5 ml).
Other
The mean value of the dose of the active substance is calculated as the following: 1.64-1.71 (4H, m); 2.20 (8H, s); 2.59-2.75 (4H, m); 2.74-2.86 (6H, m); 2.91-2.99 (1H, m); 3.17-3.23 (2H, m); 4.19 (2H, d); 5.94 (1H, t); 6.32 (1H, t); 6.90-7.01 (2H, m); 7.17-7.49 (12H, m); 10.62 (1H, s); 11.10 (4H, bs).
The polar dieastereomer (175 mg, 0.35 mmol) produced in example 275 was hot dissolved in ethanol (5 ml) and mixed with a solution of citric acid (68 mg, 0.35 mmol) in ethanol (0.5 ml).
Other
The mean value of the dose of the active substance is calculated as the following: 1.44-1.54 (2H, m); 1.79-1.92 (4H, m); 2.30 (6H, s); 2.49-2.61 (4H, m); 2.76 (2H, s); 2.93-2.96 (3H, m); 3.17-3.18 (2H, m); 4.24 (2H, d); 5.93 (1H, t); 6.34 (1H, t); 6.87-6.94 (2H, m); 7.14-7.34 (6H, m); 7.41-7.61 (6H, m); 10.37 (1H, s); 11.10 (4H, bs).
Indol (Ind-101, 600 mg, 2.15 mmol) and ketone (Ket-10, 467 mg, 2.15 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.76 ml, 8.6 mmol). The solution was stirred for 3 days at RT, leaving a dark brown oil. After adding 1 N NaOH (40 ml) and CH2Cl2 (30 ml), the oil was stirred for 2 h until dissolved. The phases were separated, the aqueous phase was extracted with CH2Cl2 (3x 40 ml), the combined organic phases were washed with water (10 ml), dried (Na2SO4) and the solution was narrowed to e.g. Vak. The returned solution was purified by flash chromatography with 100 g CH27OH (40 ml) and 9 g CH27OH (93/90 mg) (Cl3): 9 g/mL) cleaning solution.
The solution of the newly produced olefin (638 mg, 1.33 mmol) in HBr/iron vinegar (25 ml) was given tin (1.50 g) and stirred at RT for 20 min. The solution was mixed with ethanol, the reaction mixture was reduced to dry and the residue was dissolved in 5N NaOH (75 ml) and chloroform (175 ml). After 2 h the phases were separated, the aqueous phase was extracted with CHCl3 (3x 100 ml), the combined organic phases were washed with water (30 ml), dried with Na2SO4 and i.e. vacuum. The remaining residue was separated by flash chromatography with 50 g of silicon gel and CHCl3 (20:19:19:11:14).The unpolar diastereomer was replaced by 1 N NaOH (10 ml) and extracted 7 times with CH2Cl2. The organic phase was dried (Na2SO4,) and i. Vak. compressed. 28 mg of a non-crystalline solid was obtained, which was not further studied. The aqueous phase was replaced with acetic acid (40 ml), but the phases did not separate again.The organic phase was dried with Na2SO4 and compressed in vacuum.
| 62 mg (10 %), unpolares Diastereomer | |
| 261 mg (41 %), polares Diastereomer |
The resulting nonpolar diastereomer (61 mg, 0.13 mmol) was hot dissolved in a mixture of ethanol (10 ml) and methanol (2 ml), mixed with citric acid (24 mg, 0.13 mmol) and reheated. The solubility of the substance was visibly improved by the addition of citric acid, so the solvent was removed until the solution was cloudy. The precipitation which had been left after being kept in the refrigerator was washed off and washed with ether.
Other:
The polar diastereomer (236 mg, 0.49 mmol) produced in example 277 was heated in ethanol (5 ml) and mixed with citric acid (94 mg, 0.49 mmol). The solution was briefly heated again. As there was little precipitation, the solution was compressed in half and kept overnight in the refrigerator. The precipitation was sucked out and washed with ether.
Other
The mean value of the dose of the active substance is calculated as the following: 1.44-1.53 (2H, m); 1.79-1.87 (4H, m); 2.25 (6H, s); 2.49-2.62 (4H, m); 2.78-2.96 (5H, m); 3.23-3.28 (2H, m); 6.11 (1H, t); 6.87-6.95 (3H, m); 7.15-7.25 (3H, m); 7.41-7.59 (8H, m); 8.42 (1H, s); 10.39 (1H, s); 11.10 (4H, bs).
Indol (Ind-102, 1.21 g, 4.5 mmol) and ketone (Ket-10, 968 mg, 4.5 mmol) were dissolved in dichloromethane (50 ml) and rapidly mixed with trifluoromethane sulphonic acid (1.58 ml, 17.8 mmol). The solution was stirred for 3 days at RT, leaving a dark brown oil. After adding 1N NaOH (80 ml) and CH2Cl2120 ml, the oil was stirred for 3 h until dissolved. The phases were separated, the aqueous phase was extracted with CH2Cl2 (3x 80 ml), the combined organic phases were washed with water, dried (Na2SO24) and the solution was vacuumed. The resulting bleach was cleaned by flash chromatography using 100 g CH1OH (1:1/1 g CH1OH) and purified.
Other
The yield is 1.39 mg (66%)
The solution of the newly produced olefin (1.37 g, 2.91 mmol) in HBr/iron vinegar (50 ml) was given tin (3.28 g) for 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (80 ml) and dichloromethane (170 ml). The phases were separated, the aqueous phase was extracted with CH2Cl2 (3×80 ml), the combined organic phases were washed with water (20 ml), dried over Na2SO4 and i.e. vacuum dried. The remaining residue was flash-chrographed with 100 g→→Cl3 and CH3 gel (20:19:1:1:1:1:1:1:1:1).
Other
The following is the list of active substances in the active substance:
The resulting nonpolar diastereomer (109 mg, 0.23 mmol) was hot dissolved in ethanol (10 ml) and methanol (5 ml), mixed with citric acid (44 mg, 0.23 mmol) and briefly heated to boil.
Other
The mean value of the dose of the active substance is calculated as the following: 1.20-1.28 (2H, m); 1.43-1.57 (4H, m); 2.14-2.17 (2H, m); 2.23 (6H, s); 2.60-2.74 (4H, m); 2.74-2.95 (5H, m); 3.13-3.18 (2H, m); 3.82 (1H, qu); 5.66 (1H, t); 5.77 (1H, d); 6.90-7.00 (2H, m); 7.31-7.50 (7H, m); 10.63 (1H, s); 11.10 (4H, bs).
The polar diastereomer (274 mg, 0.58 mmol) obtained in example 279 was hot dissolved in ethanol (5 ml) and methanol (2 ml), mixed with citric acid (111 mg, 0.58 mmol) and briefly heated to boil.
Other
The mean value of the dose of the active substance is calculated as the following: 1.25-1.32 (2H, m); 1.44-1.61 (6H, m); 1.77-1.83 (4H, m); 1.91-1.97 (2H, m); 2.36 (6H, s); 2.52-2.64 (4H, m); 2.72 (2H, t); 2.90-3.00 (3H, m); 3.11-3.16 (2H, m); 3.87-3.92 (1H, m); 5.67 (1H, t); 5.80 (1H, d); 6.86-6.94 (2H, m); 7.15 (1H, d); 7.41 (1H, d); 7.54-7.66 (5H, m); 10.36 (1H, s); 11.10 (4H, bs).
Indol (Ind-103, 736 mg, 2.5 mmol) and ketone (Ket-10, 547 mg, 2.5 mmol) were dissolved in dichloromethane (30 ml) and rapidly mixed with trifluoromethane sulphonic acid (0.89 ml, 10.1 mmol). The solution was stirred for 3 days at RT, leaving a dark brown oil. After adding 1 N NaOH (40 ml) and CH2Cl2 (30 ml), the oil was stirred for 2 h until dissolved. The phases were separated, the aqueous phase was extracted with CH2Cl2 (3x 40 ml), the combined organic phases were washed with water (10 ml), dried (netNa2SO4) and the solution was vacuumed. The resulting vacuum was bleached by flash chromatography using 100 g CH3OH (93/Cl1) and cleaned.
Other
Production: 1.04 g (84%)
The solution of the newly isolated olefin (464 mg, 0.94 mmol) in HBr/iron vinegar (20 ml) was given tin (1.07 g) for 20 min and stirred at RT for 4 h. The solution was mixed with ethanol, the reaction mixture was pressed to dry and the residue was dissolved in 5N NaOH (50 ml) and dichloromethane (150 ml). The phases were separated, the aqueous phase was extracted with CH2Cl2 (3 x 50 ml), the combined organic phases were washed with water, dried over Na2SO4 and i.e. pressed. The remaining residue was separated by flash chromatography with 25 g of Kisel gel and CHCl3·OH3/Me (100:1:111:1) and thus the diethyl ester was pressed according to the vacuum and the organic phase was extracted with 1 ml of N2SO2 (10 x 7 nm) and the organic residue was washed with water and i.e. dried.
Other
| 177 mg (38 %), unpolares Diastereomer | |
| 203 mg (44 %), polares Diastereomer |
The newly isolated nonpolar diastereomer (155 mg, 0.31 mmol) was hot dissolved in a mixture of ethanol (5 ml) and methanol (15 ml), mixed with citric acid (60 mg, 0.31 mmol) and reheated.
Other
The yield is 126 mg (72%)
Other
The mean value of the dose of the active substance is calculated as the following:
The polar diastereomer (176 mg, 0.36 mmol) isolated in example 281 was hot dissolved in ethanol (5 ml) and methanol (15 ml), mixed with citric acid (68 mg, 0.36 mmol), briefly heated to boil and placed in the refrigerator.
Other
The mean value of the dose of the active substance is calculated as the sum of the following:
Ketone (Ket-10, 1.33 g, 6.15 mmol) and indole (Ind-104, 1.85 g, 6.15 mmol) were dissolved in 40 ml of dichloromethane under argon. Then trifluoromethane sulphonic acid (1.07 ml, 12.3 mmol) was added rapidly and stirred at RT for 16 h. For processing, the approach was made with 1 N NaOH basic and stirred for 15 min at RT. The phases were separated. The aqueous phase was extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and i.e. vacuum sealed. The residue was then dried with CH3/MeesaOH (9:1, 10 ml) of the desiccated solid, which was not dissolved. This vacuum was removed and i.e. solids were dissolved.
The olefin (1.14 g/ 2.28 mmol) obtained was dissolved in HBr/iron vinegar (55 ml). Within 30 min, tin (2.64 g/ 2.28 mmol) was added and stirred at RT for 4 h. The solution was mixed with ethanol and stirred at RT overnight (actually 20 min). The solution was then compressed i.e. to dry, mixed with 5N NaOH and extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and compressed i.e. to dry. The residue was cleaned by EE-Et/OH (2:1) flash chromatography.
Other
The following table shows the results of the analysis:
Other
285 mg (25%) polar
The polar diastereomer (280 mg/ 0.558 mmol) was dissolved in hot ethanol (5 ml), citric acid (106 mg/ 0.558 mmol) was dissolved in hot ethanol (1 ml) and administered, the solution was cooled at RT, precipitation was not received, precipitation was suctioned and vacuum dried.
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is calculated as the following: 1.40-1.49 (2H, m); 1.72 (2H, d); 1.85 (2H, t); 2.22 (6H, s); 2.40-2.59 (4H, m); 2.70-2.74 (2H, m); 2.82-2.93 (5H, m); 6.83-6.92 (2H. m); 7.12-7.23 (2H, dd); 7.42 (1H, t); 7.49-7.64 (7H, m); 7.80 (2H, d); 10.38 (1H, s); 11.42 (4H, bs).
Ketone (Ket-10, 975 mg, 4.5 mmol) and indole (Ind-105, 1.38 g, 4.5 mmol) were dissolved in dichloromethane (40 ml) in abs with argon. Then trifluoromethane sulphonic acid (781 μL, 9.0 mmol) was added quickly and stirred at RT for 16 h. For processing, the approach was made with 1 N NaOH basic and stirred for 15 min at RT. The phases were separated. The aqueous phase was extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and i.e. vacuumed. The residue was purified by flash chromatography CHCl3/MeOH (15:1, 1:1, +OH1 % TEA).
Other
The yield is 1.26 g (55%).
The olefin (1.26 g, 2.49 mmol) was dissolved in HBr/iron vinegar (50 ml). Within 30 min, tin (2.88 g, 2.49 mmol) was added and stirred at RT for 3 h. The solution was mixed with ethanol and stirred at RT for 10 min. The solution was then bound to dry in a vacuum, mixed with 5N NaOH and extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and bound at vacuum. The residue was separated by flash chromatography CHCl3/OH (20:1, 4:1, MeOH+ 1 % TEA).
Other
| 268 mg (22 %) unpolareres Diastereomer | |
| 262 mg (20 %) polareres Diastereomer |
The newly obtained nonpolar diastereomer (268 mg/ 0.528 mmol) was dissolved in hot ethanol (15 ml) and methanol (5 ml). Citric acid (101 mg/ 0.528 mmol) was dissolved in hot ethanol (1 ml) and administered. The approach was cooled at RT, with no precipitation. The precipitation was sucked and vacuum dried. Yield: 232 mg (62 %); melting point: 233-235 °C.
Other
The mean and standard deviation of the mean and standard deviation of the two samples (DMSO-d6) are as follows: 1.51-1.64 (4H, m); 2.11 (8H, s); 2.57-2.72 (4H, m); 2.80-2.97 (7H, m); 6.88-7.00 (2H, m); 7.13-7.15 (1H, m); 7.29-7.45 (7H, m); 7.55-7-56 (1H, m); 7.87-7.94 (2H, m) 10.65 (1H, s); 11.1 (4H, bs).
The polar diastereomer (262 mg/ 0.516 mmol) obtained in example 284 was dissolved in hot ethanol (15 ml) and methanol (5 ml). Citric acid (98 mg/ 0.516 mmol) was dissolved in hot ethanol (1 ml) and added. The approach was cooled at RT, with no precipitation. The precipitation was sucked out and vacuum dried.
Other
The yield is 229 mg (63 %); the melting point is 143 °C to 145 °C.
Other
The mean value of the dose of the active substance is calculated as the sum of the following:
Ketone (Ket-10, 392 mg, 1.81 mmol) and indole (Ind-106, 482 mg, 1.81 mmol) were dissolved in dichloromethane (40 ml) with argon. Then trifluoromethane sulphonic acid (471 μL, 5.43 mmol) was added quickly and stirred for 16 h at RT. The approach was made with 1 N NaOH basic and stirred for 15 min at RT. The phases were separated. The aqueous phase was extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and i.
Other
The yield is 277 mg (33%).
The olefin (333 mg/ 0.716 mmol) was dissolved in HBr/Iron vinegar (25 ml). Tin (828 mg/ 0.716 mmol) was added within 30 min and stirred at RT for 3 h. The solution was mixed with ethanol and stirred at RT for 10 min. The solution was then compressed to dry in a vacuum, mixed with 5N NaOH and extracted with dichloromethane (3 x 20 ml). The organic phase was dried over Na2SO4 and compressed at the vacuum. The residue was cleaned by flash chromatography CHCl3/OHCl (50:1).
Other
| 91 mg (27 %) unpolareres Diastereomer | |
| 248 mg (74 %) polareres Diastereomer, leicht verunreinigt |
The resulting nonpolar diastereomer (86 mg/ 0.184 mmol) was dissolved in hot ethanol (8 ml), citric acid (35 mg/ 0.184 mmol) was dissolved in hot ethanol (1 ml) and added, the solution was pressed dry and etherised, the precipitation was sucked out and dried.
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean value of the dose of the active substance is calculated as the sum of the following:
The polar diastereomer (248 mg/ 0.531 mmol) obtained in example 286 was dissolved in hot ethanol (10 ml) and methanol (5 ml). Citric acid (101 mg/ 0.531 mmol) was dissolved in hot ethanol (1 ml) and added. The approach was cooled at RT, with no precipitation. The precipitation was sucked out and vacuum dried.
Other
The maximum content of the active substance is the maximum content of the active substance, expressed as a percentage of the total active substance.
Other
The mean and standard deviation of the mean and standard deviation of the two samples (DMSO-d6) are as follows: 1.41-1.54 (2H, m); 1.78-1.83 (2H, m); 2.08-2.20 (2H, m); 2.38 (6H, s); 2.49-2.62 (4H, m); 2.86-3.16 (5H, m); 3.40-3.45 (2H, m); 6.88-6.93 (2H, m); 7.14-16 (1H, m); 7.48-7.59 (5H, m); 7.72 (2H, d); 8.24-8.27 (1H, m); 8.69-8.71 (1H, m); 8.99-9.03 (2H, m); 10.42 (1H, s); 11.45 (4H, bs).
2-(2-(4-dimethylamino-4-pheny-cyclohexyl)-1H-indo) -3-yl]ethanol (sample 219, 3.20 g, 8.8 mmol) was dissolved in RT in abs CH2Cl2 (50 ml) and replaced with tetrabromethane (4.39 g, 13.2 mmol) and then added to RT triphenylphosphate (3.61 g, 12.6 mmol). The solution was stirred at 2.5 h RT and then administered i.v. Flash chromatography of the residue with 300 g of silica gel and acetic acid/ethanol (1:2) yielded 1.98 g of contaminated product, which was diluted with 1 N NaOH and extra-dried with CH3Cl. The organic phase was pressed over Na2Cl4 and e.g. 1.5 g of vacuum (47%)
The newly produced bromide (868 mg, 2.0 mmol) was dissolved in 2N NH3 solution in ethanol (15 ml) and stirred in a pressure vessel for 7 h at 100 °C. The solution was compressed i.v. The resulting residue was washed with ethanol and then dried i.v.
Other
The following information shall be provided in the form of a summary of the results of the analysis:
Other
The mean value of the dose of the active substance is calculated as the following:
The newly produced 4-(3-(2-aminoethyl)-1H-indol-2-yl) N,N-dimethyl-1-phenylcyclohexanamine (200 mg, 0.55 mmol) was suspended in a CH2Cl2 (5 ml) flask. Triethylamine (78 μL, 0.63 mmol) and benzoyl chloride (73 μL, 0.63 mmol) were added to RT and solution 1 d was stirred in RT. The solution was diluted with water and extracted three times with CH2Cl2. The organic phase was dried over Na2SO4 and i.a. vacuumed. The resulting residue was corrected by flash chromatography with 50 g of kieselgel and ether/ethanol (1:2:1:1:1:1:1:1).
Other
The following table shows the results of the analysis:
Since the spectrum of the compound indicated a salt, it was added (119 mg, 0.26 mmol) with 1 N NaOH and extracted several times with CH2Cl2, the organic phase was then dried with Na2SO4 and compressed in vacuum.
Other
The following information is provided for the purpose of the calculation:
Other
The mean value of the dose of the active substance is calculated as the following: 1.40-1.55 (2H, m); 1.74-1.84 (4H, m); 2.31 (6H, s); 2.49-2.63 (4H, m); 2.89-2.93 (5H, m); 3.36-3.42 (2H, m); 6.87-6.95 (2H, m); 7.14-7.16 (1H, m); 7.45-7.61 (9H, m); 7.86-7.89 (2H, m); 8.61 (1H, t); 10.40 (1H, s); 11.10 (4H, bs).
For example, 252 (257 mg, 0.58 mmol) was dissolved in HBr/iron vinegar (33% HBr, 15 ml). The solution was then given to the RT Sn powder (2 g, 16.8 mmol) in portions for 60 min. The solution was stirred overnight (18 h) in RT. The yellow solid was separated by a fryer. The filter cake was washed with ice vinegar (10 ml), heated in ethanol (10 ml) for boiling and then separated by filtration. The solid was stirred with 2N (10 ml) NaOH and ethylacetate (20 ml) and stirred for 20 min. The solid at the border of the phasoregenerator was dried.The solid (13-phenyldihydroxyethylamine, N-dimethyldihydroxylamine, N-dimethyldihydroxylamine, N-dimethyldihydroxylamine, and F-dihydroxylamine) was separated by means of a polarized solution (15 mg) and a diethyldioxane (12-methyldioxane, N-dioxylamine, and diethyldioxylamine) was used.The resulting mixture was base-based with 5N NaOH (10 ml) and extracted with ethyl acetate (5 x 20 ml). The combined organic phases were washed with (50 ml) water, dried over MgSO4 and then pressed. The residue was purified by column chelatography [silica 60 g (10 g); ether O/OH 1 : 1 (150 ml) ]. Example 289 (polar diastere) was obtained in a white solid of 30 mg (11 x 20 ml) washed with a solution of 21 °C (118 g) as pure as white solids.The mean of the measurements of the two samples is calculated as the mean of the measurements of the two samples.
Other
The following is a list of the active substances that may be used in the active substance:
1- ((3-fluorphenyl) N,N-dimethyl-4-(3-(2- ((pyridine-4-yl) ethyl) -1-H-indol-2-yl) cyclohexanamine (polar diastereomer, 140 mg, 0.36 mmol) was heated in isopropanol (100 ml) for boiling. The remaining particles were separated by a deep fryer. The resulting solution was mixed with citric acid (160 mg, 0.83 mmol) dissolved in hot isopropanol (3 ml). The solvent volume was reduced to approximately 20 ml at the rotational evaporation, then the mixture was cooled to 5 °C (cooling point) and left at this temperature. The resulting mixture was then separated by means of a high-pressure method (41 °C) in a vacuum of approximately 240 °C (441 °F) and dried in a vacuum of approximately 240 mg.
Other
The following is a list of the most commonly used methods of determining the concentration of a substance in a sample:
The solution was then diluted with dichloromethane (50 ml) and made alkaline by icing with 5N sodium hydroxide solution (50 ml). The phases were separated. The remaining phase was extracted with chloromethane (3 x 30 ml). The combined organic phases were purified with Na2SO4 and then filtered. The fluorinated phosphates of the filter were obtained: the best part of the filter was completely removed from the vacuum: a solid: a 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (24-5%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5% (25%), 2-5% (-1), 2-5%), 2-5% (25%), 2-5% (-1), 2-5%), 2-5% (-1), 2-5% (-1), 2-5%), 2-5% (-1), 2-5% (-1), 2-5% (-1), 2-%, 2-%, 2-%, 2-%, 2-%, 2-%, 2-%, 2-, and 2-, and 2-), and 2-), and 2-5% (-1), and 2-, and 2-), and 2-), and 2-, and 3-).
N-Methyl-1-phenyl-4-(3-(2-(pyridine-4-yl) ethyl) -1-H-indol-2-yl) cyclohexanamine (unpolar diastereoisomer) (178 mg, 0.43 mmol) was dissolved in ethanol (20 ml) under heating and added to citric acid (100 mg, 0.52 mmol), dissolved in ethanol (4 ml). The solution was stirred for 17 h, then compressed to about 3 ml and mixed with diethyl ether (5 ml) until crystallized. The discoloured precipitate was sifted and washed with diethyl ether (5 ml).
Other
The mean of the measurements performed was approximately 0.01% for the same frequency range as the mean of the measurements performed for the same frequency range.
Other
The following are the active substances which may be used in the active substance:
N-Methyl-1-phenyl-4-(3-(2-(pyridine-4-yl) ethyl) -1-H-indol-2-yl) cyclohexanamine (polar diastereoisomer) (97 mg, 0.284 mmol) was dissolved in ethanol (10 ml) at high temperatures and added to citric acid (55 mg, 0.284 mmol), dissolved in ethanol (2 ml). After 1 hour of stirring at room temperature, a colourless solid began to precipitate. This was filtered and washed with diethyl ether (5 ml).
Other
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Other
The following is a list of the active substances that may be used in the active substance:
The reaction mixture was hydrated at 3 bar for 3.5 h. The catalyst was separated via cellite and the filtrate was narrowed. The residue (200 mg, light brown oil) was chromatographically separated (silica gel 60 (20 g); ethylacetate/methanol 10:1 (200 ml). Ethylacetal/methanol 4:1 (200 ml), methanol (200 ml). 2-(4-butyl- ((pyrrolidin-1-yl) cyclohexyl) 3-methyl-1H-indol (unpolar diastereoisomer) was obtained in a colourless solution of 10 mg (20%) polar diastereoisomers of Chromat after a saline dialysis (143 mg) of 67 mg.Example 2: 258 (180 mg, 0.535 mmol) was dissolved in HBr/ice vinegar (33% HBr, 10 ml) for 1 h at room temperature. Tin powder (64 mg, 0.535 mmol) was then added to the solution in 10 min. After completion of the addition, the reaction mixture was stirred for another 30 min. Under ice cooling, the solution was mixed with water (20 ml) and stirred for 15 min at room temperature. The beige solid that had fallen out was de-soaked, washed with water (4 × 5 ml) and dichloromethane (2 × 5 ml). The hydrobide of the diastereoisomer mixture was obtained at a yield of 69 % (155 mg).The salt was taken in a mixture of dichloromethane (30 ml), water (20 ml) and 1N sodium salts (2 ml) and stirred at room temperature for 30 min. The phases were separated. The aqueous phase was extracted with dichloromethane (20 ml). The organic phases were combined, dried and compressed with sodium sulphate. The residue (107 mg, beige oil) was chromatographically separated [silica 60 (20 g); ethylac gel/methanol 10 : 1 (200 ml), ethylac/methanol 4 : 1 (200 ml), methanol (200 ml). The nonpolar diastereoisomer was obtained at a yield of 31% (56%) and the polar diastereoisomer at a yield of 17 mg (31%) mg.Both diastereoisomers were present as colourless salts on chromatography.
The salt of the unpolar diastereomer (76 mg) was taken in a mixture of dichloromethane (30 ml), water (20 ml) and 1 N of sodium chloride (1 ml) and stirred at room temperature for 1 h. The phases were separated. The aqueous phase was extracted with dichloromethane (20 ml). The combined organic phases were dried and compressed with sodium sulphate. The residue (beige oil, 75 mg, 0.221 mmol) was dissolved in ethanol (5 ml) and replaced with an ethanol solution (1.5 ml) of citric acid (46 mg, 0.24 mmol). A drop was immediately visible. After 30 minutes, diethyl ether (15 ml) was added.
Other
The mean of the measurements performed in the controls was approximately the same as the mean of the measurements performed in the controls.
1-benzolsulfonyl-1H-indol (504 mg, 2 mmol) was dissolved in dichloromethane (20 ml) together with the ketone (Ket-10.434 mg, 2 mmol) and substituted with trifluoromethane sulphonic acid (0.2 ml, 2.3 mmol). The approach was stirred for 15 h at RT. Since the implementation was not complete according to DC, the mixture was stirred for another 3 d. - For processing, the reaction solution was stirred with 2N NaOH (10 ml). The mixture was stirred for another 20 min. After separation of the phases, the aqueous phase was extracted with dichloromethane (3 x 20 ml). The combined organic extracts were dried over Na2O4 and then pressed. The product was obtained from a crystalline solution of Na2O4 (917 mg) obtained from a crude seed extract (Litrometallic acid: 440 mg, 165-167 mg, 16-17 °C: 165-167 °C: 23-178 mg) obtained in a semi-pure form of a crystalline compound.
The olefin (300 mg, 0.66 mmol) was dissolved in HBr/iron vinegar (33% HBr, 10 ml) (not all the substance was dissolved, so a larger amount of HBr appears to be appropriate). The olefin was then administered in RT Sn powder (0.8 g, 7 mmol) for 40 min. After completion of the addition, the reaction mixture was stirred for another 3 h. - The mixture was diluted to dry on the rotary steamer for processing. The remaining residue was made basic by adding 5 N (20 ml NaOH). The resulting solution was mixed with dichloromethane and extracted (4 x 20 ml). The organic phases were mixed with MgSO4 and then dried.The resulting residue (290 mg) was purified by column chromatography (medium: 1) EtOAc; 2) EtOAc/EtOH 2:1; 3) EtOH. The unpolar diastereoisomer, which passed in the thin-film chromatogram when using EtOAc near the solvent front, was obtained at a yield of 29 mg (9%) in the form of a yellowish oil. The more polar diastereoisomer, which remained in the thin-film chromatogram when using EtOAc near the starting spot, was obtained at a yield of 132 mg (43%) as a white solid (at 139-142 °C). The starting product was recovered at 40%.
Other
The test chemical is used to determine the concentration of the active substance in the test chemical.The following are the main characteristics of the product:
Other
The mean of the measurements is calculated as the mean of the measurements of the two samples.
The more polar diastereomer obtained in example 294 is further shown in example 295.
Other
The mean value of the measurement is calculated as the mean value of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement of the measurement
Other
The following are the most commonly reported effects of the drug:
Example 296: (±)-2-(4-dimethylamino)-4-phenycyclohex-1-enyl) 3--(methyl) -(1-(oxiran-2-ylmethyl) -1-H-indol): Diastereomeric mixtureThe free base of Example 16 (350 mg, 1.06 mmol) was presented in dimethylformamide/tetrahydrofuran (20 ml, 1 : 1). The clear light yellow solution was mixed at room temperature with sodium hydride (60% suspension in mineral oil, 110 mg, 2.75 mmol). The reaction mixture was first gas. A brighter solid then fell out of the reaction mixture. It was stirred for 1 h at 57°C (oil temperature). Then the water was stirred at this temperature to the desired temperature (255 mg, 0.75 ml, 2.18 ml; 1.55 ml of diethyl) and the reaction mixture was added to the water (20°C).The mixture was stirred for 10 min. The phases were then separated. The aqueous phase was extracted with ethyl acetate (2 × 20 ml). The combined organic phases were washed with saturated aqueous NaCl solution (3 × 10 ml), dried with sodium sulphate and filtered. The volatile components were then completely removed in vacuum. A bright yellow oil was left, which still contained dimethylformamide. The oil crystallized overnight into a colourless solid. This did not dissolve in methanol. The solid was de-filtered and vacuum dried (100, 0,26 ml; 24 % diastereoisomer). Both filters were separated into roughly 60 mm of chromium and 5 g of ethyl acetate (1 500 mg/ml); ethanol (1 500 g/mc); ethanol (1 500 mg/mc); ethanol (1 500 g/mc); ethanol (1 500 mg/mc); ethanol (1 500 g/mc); ethanol (1 500 mg/mc); ethanol (1 500 g/mc); ethanol (1 500 g/mc); ethanol (1 500 g/mc); ethanol)2 (500 ml) ] Another epoxide (200 mg, 0.52 mmol; 49 %; both diastereoisomers, c. 147-150 °C) was isolated.
Other
The mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour, and the mean of the measurements performed was approximately 0.01% for the first time in the period from 1 hour to 1 hour.
Other
The following are the most commonly reported effects of the drug:The following table shows the total number of units of the product:
The free base of the polar skatole derivative sample 18 (500 mg, 1.50 mmol) was presented in dimethylformamide/tetrahydrofuran (20 ml, 1 : 1) and the clear light yellow solution was added to sodium hydride (60% suspension in mineral oil, 210 mg, 3.13 mmol). The reaction mixture was gas. A bright solid then fell out of the reaction mixture. It was stirred for 1 h at 57 °C (oil bath temperature). Then, at this temperature, the epichlorin (290 mg, 0.122 ml, 3.13 mmol; 1.183 g/ml) was added. The reaction mixture began to boil. It was stirred at 57 °C (oil bath temperature) for 1 h. Then the reaction mixture was stirred with water (30 ml) and diethyl (20 ml).The mix was stirred for 10 min. The phases were then separated. The aqueous phase was extracted with ethyl acetate (2 × 20 ml). An attempt was made to extract the aqueous phase with dichloromethane. This was unsuccessful. No epoxide could be extracted. The combined organic phases (ethyl acetate and diethyl ether) were washed with saturated aqueous NaCl solution (3 × 10 ml), dried and filtered with sodium sulfate. The volatile components in the powder were then completely removed. An attempt was made to chromatographically separate the back [Kiel gel 60 (150), ethyl acetate g/methanol 1 (1500 ml): 1]. 215 mg (0.37 mmol/l) was produced as a vacuum-insulated polar compound of colourless metals.
The resulting polar derivative (50 mg, 0.129 mmol) was dissolved in boiling ethanol (3 ml). Citric acid (27 mg, 0.14 mmol) was added. The clear solution was stirred in the boiling water for 30 min. The reaction mixture was then cooled to room temperature and left to stand for 24 h. A colourless microcrystalline precipitate was produced. It was filtered and washed with ethanol (2 × 5 ml). 52 mg (0.090 mmol; 69%) of polar citrate (temperature 182-184 °C) was obtained.
The suspension was dissolved at room temperature with dimethylamine (35 mg, 0.78 mmol; 33 per cent in ethanol, 0.14 ml; 0.76 g/ml). As no reaction occurred at room temperature, the reaction mixture was stirred for 10 h at 59 °C (oil bath temperature). The reaction mixture was then compressed in vacuum to dry. The amino alcohol was isolated slightly contaminated as a bright yellow oil (120 mg, 0.26 mmol; 67%) and thus used to form citrate.
Other
The solution of the newly produced amino alcohol (110 mg, 0.26 mmol) in boiling ethanol (3 ml) was added with citric acid (54 mg, 0.28 mmol). The clear solution was stirred at boiling temperature for 30 min. The reaction mixture was then cooled to room temperature. A bright yellow solid was produced. It was filtered and washed with ethanol (3 × 1 ml). 48 mg (0.08 mmol; 30%) of citrate (sample 298) (Smp. 170-173 °C) was isolated.
Dimethylamine (37 mg, 0.82 mmol; 33 per cent in ethanol, 0.15 ml; 0.76 g/ml) was added to the free base of the polar epoxide sample 297 (160 mg, 0.41 mmol) in ethanol (15 ml) at room temperature. Since no reaction occurred at room temperature, the reaction mixture was stirred for 4 h at 59 °C (oil bath temperature) and overnight at room temperature. The reaction mixture was then compressed in vacuum to about 5 ml. A colourless solid was released. This was filtered. 132 mg (0.30 mmol; 74%) of the polar amino alcohol was isolated.
The solution of the polar amino alcohol (112 mg, 0.26 mmol) in boiling ethanol (3 ml) was added to a solution of citric acid (55 mg, 0.284 mmol). The clear solution was stirred in the boiling water for 30 min. The reaction mixture was then cooled to room temperature and left to stand for 24 h. A colourless microcrystalline precipitate was already released from the warm ethanol. This precipitate was filtered and dried in a vacuum. 128 mg (0.21 mm; 79%) of polar citrate (Example 299) was isolated.
The sub-gas was the ketone (Ket-10, 217 mg, 1 mmol) presented with 2-Indol-1-yl-ethanol (Ind-107, 161 mg, 1 mmol) in absolute dichloromethane (10 ml). Then the trifluoromethane sulphonic acid trimethylsilyl ester (0.2 ml, 1.03 mmol) was added. The solution was stirred at RT for 24 h. The clear purple solution was mixed with 1N of baking soda (10 ml) for processing, after which a discoloration was obtained. The p-hases were separated. The aqueous phase was extracted with dichloromethane (2 × 10 ml). The combined organic phases were dried with water, washed over SO2 4 and pressed. The product was obtained by chromatography: a bright greenish yellow colour obtained from 30 mg of methanol (10 × 400 mg) in a pure yellow oil.
A solution of the newly isolated olefin (104 mg, 0.3 mmol) in ethyl methyl ketone (5 ml) was given chlorotrimethyl silane (0.06 ml, 0.45 mmol) and stirred at room temperature for 2 h. The reaction mixture turned red. The hydrochloride (Example 300) was obtained as a salmon-coloured solid at a yield of 68% (81 mg) with a melting point of 217-219 °C.
Other
The mean of the measurements performed was approximately 0.01% and the mean of the measurements performed was approximately 0.01% and the mean of the measurements performed was approximately 0.01% and 0.02% respectively.
The olefin N,N-dimethyl-1-phenyl-4-(1-(phenylsulfonyl) -H-indol-2-yl) cyclohex-3-enamine (150 mg, 0.33 mmol) obtained by example 294 was dissolved in ethanol (20 ml) at boiling temperature and added to citric acid (65 mg, 0.34 mmol) dissolved in hot ethanol (3 ml). As no precipitation occurred even after cooling the solution, the solvent was added to the rotary evaporator. The residue was dissolved in isopropanol (12 ml) at boiling temperature. The cooling resulted in a sticky melting point which was crystallised after drying and standing for a long time. The product was then separated with F-metals and obtained as a solid at a melting point of 171 °C (63 °C) (example: 30 mg) (Citrat) and obtained as a product obtained from a melted product at a temperature of 171 °C (63 °C) (example: 30 mg) (200 °C).
Other
The mean of the measurements of the two samples is calculated as the mean of the measurements of the two samples.
Other
The following is a list of the active substances that may be used in the active substance:
After completion of the addition, the reaction mixture is stirred for 2 h at 0 °C. Then a solution of 4-benzyl-4-dimethylaminocyclohexanone (Ket-3, 880 mg, 3.81 mmol) is added to the dry phase (7F) at - 5 °C. The solution is gently dripped with tert-butyllithium (4.19 mmol, 2.47 ml of a 1.7 M pentane solution) so that the reaction temperature does not exceed 0 °C. The reaction is then heated with cyclohexanone (36 mg/o) for 2 h at 0 °C. The solution is then dissolved in a liquid containing only 1 ml of organic disulfide and dissolved in a vacuum solution of 45 mg/o3 (26 ml/o3), which is then obtained by dissolving the extracted methanol in a liquid.
A solution of the newly produced cyclohexanol (500 mg, 1.53 mmol) in hydrobromic acid (5 ml, 48%) was heated at the return flow for 15 min. The cooled reaction mixture was set to a pH of 9 with 5N NaOH solution. The mixture was then extracted with dichloromethane (4 → 10 ml). The combined organic phases were dried with sodium sulphate and then the solvent was removed in a vacuum. The purification was carried out by flash chromatography [Kieselgel, Cyclohexan/OAc: 1) ]. 230 mg (44%) of the desired olefin was obtained.
To produce the hydrochloride, the olefin (220 mg, 0.638 mmol) obtained was dissolved in ethylmethyl ketone (5 ml), mixed with chlorotrimethyl silane (105 mg, 0.96 mmol) and stirred for 1 h at room temperature in an open reaction vessel. The resulting solid was sucked out. The hydrochloride (302) was obtained at a yield of 160 mg (66%) as a white solid with a melting point of 244-246 °C.
After completion of the addition, the reaction mixture was stirred for 24 h at RT. A clear solution was obtained. - For processing, the mixture was diluted with EtOH (20 ml) and reduced to dry by rotational evaporation. The remaining residue was made basic by adding 5N NaOH (75 ml) and dissolved in ethyl acetate (70 ml). This mixture was dissolved at room temperature. The organic phase was separated and the hot phase was dissolved in ethyl acetate (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol) (diethyl ethanol
N,N-dimethyl-4-(3-(2-(pyridine-4-yl)ethyl)-1H-indol-2-yl)-1-(thiophen-2-yl)cyclohexanamine (unpolar diastereoisomer) (60 mg, 0.13 mmol) was dissolved in ethyl acetate (20 ml). In RT, Me3SiCl (25 μl, 0.2 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried. Example 303 (59 mg, Fp. 199-204 °C, yield 90%) was a white solid.
Other
The mean of the measurements performed by the patient was approximately 1 μs/ m2 at the time of administration.
N,N-dimethyl-4-(3-(2-(pyridine-4-yl)ethyl)-1H-indol-2-yl)-1-(thiophen-2-yl)cyclohexanamine (polar diastereoisomer) (43 mg, 0.1 mmol) was dissolved in ethyl acetate (20 ml). In RT, Me3SiCl (19 μl, 0.15 mmol) was then dripped and stirred for 1 h. A white precipitate was produced. The precipitate was vacuumed, washed with ethyl acetate (2 x 5 ml) and then dried.
Other
The mean of the measurements performed was approximately 0.01% and the mean of the measurements performed was approximately 0.01% and 0.02% respectively.
3-Methylindol (Ind-10, 367 mg, 2.8 mmol) was dissolved in dichloromethane (25 ml) together with ketone Ket-18 (750 mg, 3.3 mmol) and mixed with trifluoromethanesulphonic acid (0.4 ml, 4.5 mmol). The solution was stirred at RT for 24 h. - For processing, the reaction mixture was stirred with 2N NaOH (20 ml) and mixed for 20 min at RT. After separation of the organic phase, the aqueous phase was extracted with ethyl acetate (2 x 20 ml). The combined organic extracts were dried over Na2SO4 and then pressed. The raw product ((±)-2-(4-(Mylamino) -4- ((4-methyl-2-methylhexyl) -3-methyl-hydroxyl) -1-methyl-1) was dissolved in 9 mg (99%) of ethyl-140 (99%) without further oil extraction and obtained in the next reaction.
(±)-2-(4-(Methylamino) -4- (methylthiazol-2-yl) cyclohex-1-enyl) -3-methyl-1H-indol (935 mg. 2,7 mmol) was suspended in HBr/iron vinegar (33% HBr, 40 ml) and then administered to the RT Sn powder (1,6 g, 13.8 mmol) in portions for 30 min. After completion of the addition, the reaction mixture was stirred for another 24 h at RT. - For processing, the mixture was diluted with EtOH (20 ml) and compressed to dry at the rotary vapour. The remaining return phase was made basic by adding 5N NaOH (100 ml) and stirred with ethyl acetate (18 ml) at room temperature. The phases were separated and extracted with ethyl acetate (4 × 20 ml).The combined organic phases were washed with water (30 ml), dried with Na2SO4 and then compressed. The resulting residue (1 g) was purified by column chromatography [silica gel 60 (70 g); EtOAc (400 ml), methanol (400 ml) ]. Sample 305 was obtained as yellow oil at a yield of 416 mg (30 %). Sample 306 was obtained as yellow oil at a yield of 249 mg (18 %).
Other
The mean of the measurements performed was approximately 1 μs/m2 at 1H NMR (300 MHz, DMSO-d6) δ ppm: 1.66-1.87 (m, 3H), 1.89-2.01 (m, 3H), 2.15 (s, 3H), 2.17 (s, 3H), 2.31-2.39 (m, 1H), 2.42-2.47 (m, 3H), 2.56-2.72 (m, 2H), 2.82-2.98- (m, 1H), 6.83-7.01 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.24 (m, 2H), 7.08-7.08, 7.08, 7.08, 7.09, 8.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 9.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.09, 10.The first two are:
The mean of the measurements is calculated by multiplying the mean of the measurements by the mean of the measurements.
Other
The following are the most commonly used methods for the determination of the concentration of the active substance in the feed additive:
Ket-10 (8.8 g, 40.48 mmol) and Ind-5 (6.52 g, 40.48 mmol) were presented in a solution of dichloromethane (250 ml) at 0 °C. Then trifluoromethane sulphonic acid silyl ester (8.76 ml, 44.52 mmol) was rapidly added to the solution of dichloromethane (10 ml) and stirred under ice for 20 min. The solution was stirred overnight in RT. The reaction mixture was mixed with 1N NaOH (120 ml) for processing and stirred for 10 min in RT, further turning yellow and precipitating. Ice was stirred for 20 min, the precipitated solution was dried, re-salted in ethanol, and i.e. vacuumed.
Other
This mixture was used for further synthesis.Other
Other
The mixture (8.63 g. 23.88 mmol) was presented in concentrated HCl (730 ml) and stirred overnight. Then tin (35.1 g, 303.33 mmol) was added in 2 portions (always a precipitate, which was reduced after prolonged stirring, and the end of the course the amount of niobium was reduced from 500 g/m2 to 1500 g/m2 of white water after processing. The mixture was then mixed with RT 2 (orange and white water) and dissolved in 5 ml of RT 2 (orange and white water).The phases were separated. The aqueous phase was extracted with CH2Cl2 (3 x 100 ml). The organic phase was dried with Na2SO4 and compressed i.v. (only 412 mg of product isolated). The cellite was boiled with CH2Cl2 (2 x 100 ml) and ethanol (3 x 100 ml) and then filtered. The filtrates were compressed i.v. The solid residue was decrystallized from toluene.
Other
The yield (307) is 4.29 g (49%,
The dose of the active substance is administered to the patient at the same time as the dose of the active substance, and the dose is administered to the patient at the same time as the dose of the active substance.
The following examples have been identified by HPLC-MS analysis:
Other
| 363.2 | |
| 403.2 | |
| 375.2 | |
| 403.2 | |
| 428.1 | |
| 379.2 | |
| 286.3 | |
| 333.3 | |
| 288.3 | |
| 370.2 | |
| 311.2 | |
| 379.2 | |
| 399.2 | |
| 363.2 | |
| 329.3 | |
| 304.2 | |
| 316.2 | |
| 345.3 | |
| 311.3 | |
| 371.2 | |
| 337.3 | |
| 312.3 | |
| 427.2 | |
| 421.2 | |
| 393.3 | |
| 387.3 | |
| 368.2 | |
| 407.2 | |
| 373.2 | |
| 339.3 | |
| 314.3 | |
| 298.2 | |
| 389.2 | |
| 355.3 | |
| 490.2 | |
| 440.3 | |
| 402.2 | |
| 438.3 | |
| 409.2 | |
| 448.3 | |
| 405.2 | |
| 372.2 | |
| 372.2 | |
| 338.3 | |
| 338.3 | |
| 358.2 | |
| 415.2 | |
| 415.2 | |
| 381.2 | |
| 401.2 | |
| 365.2 | |
| 365.2 | |
| 331.3 | |
| 351.2 | |
| 351.3 | |
| 431.2 | |
| 397.2 | |
| 397.2 | |
| 417.2 | |
| 417.2 | |
| 343.3 | |
| 343.3 | |
| 363.2 | |
| 318.2 | |
| 347.3 | |
| 347.3 | |
| 313.3 | |
| 313.3 | |
| 373.2 | |
| 373.2 | |
| 339.3 | |
| 314.3 | |
| 429.3 | |
| 429.2 | |
| 423.2 | |
| 423.2 | |
| 395.3 | |
| 395.3 | |
| 389.3 | |
| 389.3 | |
| 415.3 | |
| 415.3 | |
| 409.2 | |
| 409 | |
| 391.2 | |
| 375.2 | |
| 341.3 | |
| 341.3 | |
| 361.3 | |
| 316.3 | |
| 359.3 | |
| 419.2 | |
| 405.2 | |
| 433.2 | |
| 447.2 | |
| 447.2 | |
| 413.3 | |
| 41.3 | |
| 433.3 | |
| 433.2 | |
| 391.2 | |
| 357.3 | |
| 357.3 | |
| 377.3 | |
| 377.3 | |
| 363.2 | |
| 405.2 | |
| 289.3 | |
| 289.3 | |
| 289.3 | |
| 334.3 | |
| 274.3 | |
| 272.3 | |
| 272.3 | |
| 378.2 | |
| 379.1 | |
| 274.3 | |
| 274.3 | |
| 332.3 | |
| 287.3 | |
| 333.2 | |
| 303.2 | |
| 350.2 |
The compounds of the invention were examined in a receptor binding assay with 3H-nociceptin/orphanine FQ on membranes of recombinant CHO-ORL1 cells, using the test system presented by Ardati et al. (Mol. Pharmacol., 51, 1997, p. 816-824), where the concentration of 3H-nociceptin/orphanine FQ was 0.5 nM. The binding assays were performed with 20 μg of membrane protein per 200 μl of approach in 50 mM of hepas, pH 7.4, 10 mMCl2 and 1 mM MgTA. The binding to the ORL1 receptor was performed using 1 nanometer of W-SGAAD (Pharma-sham, once known as Kiiburg), measured by free-floating inhibition of the antibodies, and is expressed as 1 μg/mL in the inhibition table in RT-W (see Appendix 1).
The receptor affinity for the human μ-opioid receptor was determined in a homogeneous approach in microtiter plates by dilution series of the compound to be tested with a receptor membrane preparation (15-40 μg protein per 250 μl incubation approach) of CHO-K1 cells expressing the human μ-opioid receptor (RB-HOM receptor membrane preparation from NEN, Zaventem, Belgium) in the presence of 1 nmol/l of the radioactive ligand [3H] naloxone (NET719, NEN, Zaventem, Belgium) and 1 mg of WGA-SPA-Beads (WAT-SPA-Beads from Amersham/Pharmacia, Germany) used in a total volume of 90 μl of T-Bobulinum at a temperature of 0.05 μl and a volume of 0.05 μl.To determine non-specific binding, an additional 25 μmol/l naloxone was added. At the end of the 90 minute incubation period, the microtiter plates were decentrifuged at 1000 g for 20 minutes and the radioactivity measured in a β-counter (Microbeta-Trilux, PerkinElmer Wallac, Freiburg, Germany). The percentage of displacement of the radioactive ligand from its binding to the human opioid receptor was determined at a concentration of the test substances of 1 μmol/l and reported as the percentage inhibition (% inhibition) of the specific B. Partial displacement was calculated from the displacement rate due to the different concentrations of the compounds at IC50 general inhibition concentrations, which gives a 50% displacement of the radioactive ligand.The conversion using the Cheng-Prusoff relation yielded Ki values for the test substances.
The mice were individually placed in a test cage and the tail base exposed to the focused heat beam of an electric lamp (tail-flick type 50/08/1.bc. Labtec, Dr. Hess). The lamp intensity was adjusted so that the time from the lighting of the lamp to the sudden flickering of the tail (pain latency) in untreated mice was 3 to 5 seconds. Before the solutions containing the compound or solutions of the invention were applied, the mice were pre-tested twice within five minutes and the mean of these measurements was calculated as the mean of the previous test.
The solutions of the compound of the invention of the general formula I and the comparator solutions were then administered intravenously. Pain measurements were carried out 10, 20, 40 and 60 minutes after each intravenous application. The analgesic effect was determined as an increase in pain latency (% of the maximum possible antinociceptive effect) according to the following formula:
The time T0 is the latency time before application, the time T1 is the latency time after application of the combination of active substances and the time T2 is the maximum exposure time (12 seconds).
The analgesic effect of the test compounds was assessed in the tail-flick test on the rat according to the method of D'Amour and Smith (J. Pharm. Exp. Ther. 72, 74 79 (1941) using female Dawley tongue weighing between 134 and 189 g. The animals were placed individually in special test cages and the base of the tail exposed to a focused heat beam from a lamp (tail-flick type 50/08/1.bc, Labtec, Dr. Hess). The lamp intensity was adjusted so that the time from the light being turned on to the tail suddenly shaking away (painful flick) in untreated animals was 2.5-5 seconds. The animals were placed in special test cages and the tail base was exposed to a focused heat beam from a lamp (tail-flick type 50/08/1.bc, Labtec, Dr. Hess). The lamp intensity was adjusted so that the time from the light being turned on to the tail suddenly shaking away (painful flick) in untreated animals was 2.5-5 seconds. Other
Other
T0 is the latency time before and T1 is the latency time after application of the substance, T2 is the maximum exposure time (12 sec).
To determine dose dependence, the test compound was administered at 3-5 logarithmically increasing doses, each containing the threshold and maximum dose, and ED50 was determined by regression analysis at maximum dose 20 minutes after intravenous administration.
The following values were determined as an example:
Other
| 0.0012 | 0.0044 | 99% MPE bei 100µg/kg (Maus) | |
| 58% | 0.1100 | ||
| 0.0200 | 0.0092 | ||
| 66% | 0.0240 | ||
| 2 | 40% | ||
| - | - | ||
| 39% | 0.0370 | ||
| 37% | 0.0330 | ||
| 49% | 0.3200 | ||
| 10% | 23% | ||
| 3 | 0.0360 | ||
| - | 64% | ||
| 16% | 51% | ||
| 0.0009 | 0.0004 | 79% MPE bei 100 µg/kg (Maus) | |
| 0.0140 | 0.0130 | ||
| 70% | 89% | ||
| 100% | 102% | ||
| 53% | 60% | ||
| - | 62% | ||
| 87% | 96% | ||
| 73% | 0.1400 | ||
| 27% | 53% | ||
| - | 61% | ||
| 58% | 93% | ||
| 12% | 39% | ||
| 35% | 58% | ||
| 75% | 89% | ||
| 96% | 100% | ||
| 35% | 60% | ||
| - | 30% | ||
| 26% | 50% | ||
| 17% | 41% | ||
| - | 20% | ||
| - | 13% | ||
| 11% | - | ||
| 55% | 78% | ||
| - | - | ||
| 29% | 40% | ||
| 50% | 73% | ||
| 48% | 0.5300 | ||
| 17% | 37% | ||
| 16% | 97% | ||
| 78% | 101% | ||
| 62% | 92% | ||
| 64% | 95% | ||
| 74% | 98% | ||
| 36% | 61% | ||
| 35% | 100% | ||
| 88% | 100% | ||
| 89% | 95% | ||
| 31% | 90% | ||
| 80% | 98% | ||
| 66% | 83% | ||
| 90% | 92% | ||
| 84% | 96% | ||
| 52% | 97% | ||
| 52% | 86% | ||
| 78% | 96% | ||
| 79% | 98% | ||
| 63% | 99% | ||
| 65% | 98% | ||
| - | 21% | ||
| 46% | 98% | ||
| 13% | 83% | ||
| 46% | 98% | ||
| 68% | 97% | ||
| 10% | 50% | ||
| 38% | 54% | ||
| 18% | 60% | ||
| 57% | 67% | ||
| - | 21% | ||
| 18% | 24% | ||
| - | 75% | ||
| 55% | 90% | ||
| 92% | 102% | ||
| 94% | 0.0012 | ||
| 24% | 0.5600 | ||
| 38% | 74% | ||
| 102% | 97% | ||
| - | - | ||
| 81% | 100% | ||
| 32% | 68% | ||
| 99% | 100% | ||
| 19% | 41% | ||
| 98% | 100% | ||
| 27% | 36% | ||
| 89% | 100% | ||
| 26% | 64% | ||
| 99% | 99% | ||
| 91% | 98% | ||
| 100% | 101% | ||
| 87% | 91% | ||
| 57% | 98% | ||
| 19% | 48% | ||
| 98% | 100% | ||
| 10% | 34% | ||
| 99% | 99% | ||
| 50% | 57% | ||
| 80% | 99% | ||
| - | 42% | ||
| 99% | 100% | ||
| 14% | 38% | ||
| 99% | 98% | ||
| 37% | 43% | ||
| 62% | 99% | ||
| 23% | 53% | ||
| 101% | 100% | ||
| 72% | 98% | ||
| 55% | 83% | ||
| 99% | 100% | ||
| 38% | 62% | ||
| 99% | 100% | ||
| 42% | 55% | ||
| 87% | 94% | ||
| 19% | 56% | ||
| - | - | ||
| 30% | 94% | ||
| - | 16% | ||
| 29% | 77% | ||
| 67% | 65% | ||
| 69% | 97% | ||
| - | 61% | ||
| 70% | 94% | ||
| 27% | 38% | ||
| 15% | 51% | ||
| 68% | 93% | ||
| 97% | 99% | ||
| 62% | 85% | ||
| 63% | 83% | ||
| 18% | 35% | ||
| 18% | 27% | ||
| 32% | 28% | ||
| 98% | 99% | ||
| 52% | 72% | ||
| - | 10% | ||
| 11% | 21% | ||
| 35% | 37% | ||
| 28% | 47% | ||
| 61% | 79% | ||
| - | 12% | ||
| 95% | 95% | ||
| 62% | 87% | ||
| 73% | 87% | ||
| 18% | 29% | ||
| 93% | 94% | ||
| 27% | 26% | ||
| 98% | 100% | ||
| 76% | 92% | ||
| 84% | 99% | ||
| 11% | 41% | ||
| - | 76% | ||
| 17% | 54% | ||
| 95% | 98% | ||
| - | 29% | ||
| 77% | 98% | ||
| 87% | 100% | ||
| 100% | 102% | ||
| 84% | 99% | ||
| 99% | 101% | ||
| 98% | 100% | ||
| 99% | 99% | ||
| 45% | 84% | ||
| 99% | 101% | 100% MPE bei 100 µg/kg (Ratte) | |
| 88% | 95% | ||
| 36% | 88% | ||
| 83% | 99% | ||
| 99% | 100% | ||
| 55% | 90% | ||
| 67% | 96% | ||
| 66% | 81% | ||
| 99% | 100% | ||
| 99% | 95% | ||
| 38% | 66% | ||
| 86% | 98% | ||
| 64% | 91% | ||
| 99% | 101% | 100% MPE bei 100µg/kg (Ratte) | |
| 79% | 82% | ||
| 99% | 101% | ||
| 69% | 65% | ||
| 98% | 101% | ||
| 100% | 100% | ||
| 41% | 68% | ||
| 100% | 98% | ||
| 76% | 87% | ||
| 99% | 100% | ||
| 71% | 86% | ||
| 98% | 101% | ||
| 96% | 96% | ||
| 100% | 101% | ||
| 95% | 99% | ||
| 100% | 100% | ||
| 78% | 80% | ||
| 99% | 95% | ||
| 99% | 0.0003 | ||
| 100% | 0.0003 | ||
| 72% | 0.1100 | ||
| 99% | 101% | 96% MPE bei 100 µg/kg (Ratte) | |
| 87% | 98% | ||
| 99% | 101% | 100% MPE bei 100 µg/kg (Ratte) | |
| 87% | 94% | ||
| 99% | 0.0003 | 100% MPE bei 10µg/kg (Ratte) | |
| 56% | 0.4500 | ||
| 100% | 99% | ||
| 63% | 65% | ||
| 100% | 102% | ||
| 73% | 65% | ||
| 99% | 100% | ||
| 82% | 89% | ||
| 100% | 102% | ||
| 72% | 89% | ||
| 99% | 100% | ||
| 43% | 43% | ||
| 54% | 60% | ||
| 23% | 62% | ||
| 81% | 97% | ||
| 35% | 88% | ||
| 80% | 95% | ||
| 31% | 59% | ||
| 15% | 26% | ||
| 40% | 89% | ||
| 50% | 67% | ||
| 32% | 80% | ||
| 12% | 49% | ||
| 37% | 72% | ||
| 16% | 13% | ||
| 27% | n. d. | ||
| 65% | 0.2100 | ||
| - | 31% | ||
| 47% | 65% | ||
| 96% | 101% | ||
| 22% | 36% | ||
| 74% | 64% | ||
| - | n. d. | ||
| - | 20% | ||
| 56% | 0.0320 | ||
| - | 42% | ||
| - | 14% | ||
| 39% | 62% | ||
| 95% | 97% | ||
| 95% | 97% | ||
| 67% | 91% | ||
| 63% | 97% | ||
| 15% | 54% | ||
| n. d. | 92% | ||
| n. d. | 67% | ||
| n. d. | 35% | ||
| n. d. | 85% | ||
| n. d. | 64% | ||
| n. d. | 99% | ||
| n. d. | 29% | ||
| n. d. | 20% | ||
| 91% | 101% | ||
| 68% | 73% | ||
| 94% | 99% | ||
| 23% | 11% | ||
| 40% | 38% | ||
| - | 35% | ||
| - | 58% | ||
| 73% | 97% | ||
| 58% | 78% | ||
| 77% | 79% | ||
| 94% | 97% | ||
| 20% | 49% | ||
| 90% | 97% | ||
| - | 15% | ||
| 67% | 88% | ||
| 57% | 57% | ||
| 13% | 67% | ||
| 21% | 25% | ||
| 29% | 64% | ||
| 14% | 42% | ||
| 23% | 43% | ||
| 24% | 52% | ||
| 20% | 0.8100 | ||
| 32% | 18% | ||
| 0.1300 | 0.1033 | ||
| 99% | 99% |
3 g of one of the substituted indole derivatives of the invention, here example 1, is dissolved in 1 l of water for injection at room temperature and then adjusted to isotonic conditions by addition of anhydrous glucose for injection.
Claims (16)
- Substituted heteroaryl derivatives of the general formula I whereinA represents N or CR7-10, wherein A represents N at most twiceW represents O, S or NR4 with the proviso that if W represents O or S, A denotes CR7-10;one of the radicals B or C represents H; C1-8-alkyl, in each case saturated or unsaturated, branched or unbranched, mono- or polysubstituted or unsubstituted, COR12; SO2R12; aryl, C3-8-cycloalkyl or heteroaryl bonded via C1-3-alkyl and in each case mono- or polysubstituted or unsubstituted, aryl-, or heteroaryl, in each case mono- or polysubstituted or unsubstituted; C3-8-cycloalkyl, in each case mono- or polysubstituted or unsubstituted; and the other particular radical B or C represents wherein represents a single bond or a double bond,R1 and R2 independently of one another represent H; C1-5-alkyl, in each case saturated or unsaturated, branched or unbranched, mono- or polysubstituted or unsubstituted; C3-8-cycloalkyl, in each case mono- or polysubstituted or unsubstituted; aryl or heteroaryl, in each case mono- or polysubstituted or unsubstituted; or aryl, C3-8-cycloalkyl or heteroaryl, bonded via C1-3-alkyl and in each case mono- or polysubstituted or unsubstituted; or the radicals R1 and R2 together represent CH2CH2OCH2CH2, CH2CH2NR11CH2CH2 or (CH2)3-6, wherein R11 denotes H; C1-5-alkyl, in each case saturated or unsaturated, branched or unbranched, mono- or polysubstituted or unsubstituted: C3-8-cycloalkyl, in each case mono- or polysubstituted or unsubstituted; aryl-, or heteroaryl, in each case mono- or polysubstituted or unsubstituted; or aryl, C3-8-cycloalkyl or heteroaryl, bonded via C1-3-alkyl and in each case mono- or polysubstituted or unsubstituted; C(O)phenyl, C(O)heteroaryl, C(O)C1-5-alkyl, in each case substituted or unsubstituted; andR3 represents C1-8-alkyl, in each case saturated or unsaturated, branched or unbranched, mono- or polysubstituted or unsubstituted: C3-8-cycloalkyl, in each case mono- or polysubstituted or unsubstituted; aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted; aryl, heteroaryl or C3-8-cycloalkyl, bonded via C1-3-alkyl group and in each case unsubstituted or mono- or polysubstituted;R4 represents H; C1-5-alkyl, saturated or unsaturated, branched or unbranched, unsubstituted or mono- or polysubstituted; aryl, or heteroaryl, in each case substituted or unsubstituted; aryl, heteroaryl or cycloalkyl, bonded via a C1-3-alkyl group and in each case mono- or polysubstituted or unsubstituted; COR12; SO2R12, wherein R12 denotes H; C1-5-alkyl, in each case saturated or unsaturated, branched or unbranched, mono- or polysubstituted or unsubstituted; C3-8-cycloalkyl, in each case saturated or unsaturated, mono- or polysubstituted or unsubstituted; aryl-, or heteroaryl, in each case mono- or polysubstituted or unsubstituted; or aryl, C3-8-cycloalkyl or heteroaryl, bonded via C1-3-alkyl and in each case mono- or polysubstituted or unsubstituted; OR13; NR14R15;R7, R8, R9 and R10 independently of one another representH, F, Cl, Br, I, NO2, CF3, OR13, SR13, SO2R13, SO2OR13, CN, COOR13, NR14R15, NHC(O)NHR13, NHC(O)R13, NH(CNR13)NHR13, SO2NHR13; C1-5-alkyl, C3-8-cycloalkyl, unsubstituted or mono- or polysubstituted; aryl-, or heteroaryl, unsubstituted or mono-or polysubstituted; or aryl, C3-8-cycloalkyl or heteroaryl, bonded via C1-3-alkyl and unsubstituted or mono- or polysubstituted; wherein R13 denotes H; C1-5-alkyl, in each case saturated or unsaturated, branched or unbranched, unsubstituted or mono- or polysubstituted; C3-8-cycloalkyl, in each case saturated or unsaturated, unsubstituted or mono- or polysubstituted; aryl-, or heteroaryl, unsubstituted or mono- or polysubstituted; or aryl, C3-8-cycloalkyl or heteroaryl, bonded via C1-3-alkyl and unsubstituted or mono- or polysubstituted; or R7, R8 and R9 have the abovementioned meaning and R10 together with B represents -CH2CH2CH2- and R10 and B therefore form a six-membered ring,R14 and R15 independently of one another denote H; C1-5-alkyl, in each case saturated or unsaturated, branched or unbranched, unsubstituted or mono- or polysubstituted; or C3-8-cycloalkyl, in each case saturated or unsaturated, unsubstituted or mono- or polysubstituted: aryl-, or heteroaryl, unsubstituted or mono- or polysubstituted; or aryl, C3-8-cycloalkyl or heteroaryl, bonded via C1-3-alkyl and unsubstituted or mono- or polysubstituted: or R14 and R15 together form CH2CH2OCH2CH2. CH2CH2NR16CH2CH2 or (CH2)3-6, wherein R16 denotes H; C1-5-alkyl, saturated or unsaturated, branched or unbranched, unsubstituted or mono- or polysubstituted; wherein the expression "cycloalkyl" or "C3-8-cycloalkyl" represents cyclic hydrocarbons having 3, 4, 5, 6, 7 or 8 carbon atoms, wherein the hydrocarbons can be saturated or unsaturated (but not aromatic), unsubstituted or mono- or polysubstituted, and wherein saturated or unsaturated (but not aromatic) cycloalkyls in which one or two carbon atoms are replaced by a hetero atom S, N or O are also included, and wherein a cycloalkyl ring can also be condensed with a further ring, which can be saturated, unsaturated (also aromatic), wherein the expression "aryl" represents aromatic hydrocarbons, these aryl radicals can also be condensed with further saturated, (partially) unsaturated or aromatic ring systems, and each of these aryl radicals can be unsubstituted or mono- or polysubstituted, wherein the substituents on the aryl can be identical or different and can be in any desired and possible position of the aryl. wherein the expression "heteroaryl" represents a 5-, 6- or 7-membered cyclic aromatic radical which contains at least 1, if appropriate also 2, 3, 4 or 5 hetero atoms chosen from the group consisting of nitrogen, oxygen and sulfur, wherein the hetero atoms are identical or different and the heterocyclic ring can be unsubstituted or mono- or polysubstituted; in the case of substitution on the heterocyclic ring, the substituents can be identical or different and can be in any desired and possible position of the heteroaryl; and wherein the heterocyclic ring can also be part of a bi- or polycyclic system, wherein the abovementioned C1-8-alkyls, C1-5-alkyls, C1-3-alkyls or C1-3-alkylenes or C3-8-cycloalkyl radicals can in each case be mono- or polysubstituted by F, Cl, Br, I, -CN, NH2, NH-C1-6-alkyl, NH-C1-6-alkyl-OH, N(C1-6-alkyl)2, N(C1-6-alkyl-OH)2, NO2, SH, S-C1-6-alkyl, S-benzyl, OCF3, O-C1-6-alkyl, OH, O-C1-6-alkyl-OH, =O, C1-6-alkyl, benzyl, O-benzyl, O-phenyl, C(=O)C1-6-alkyl, CO2H, NHC(=O)C1-6-alkyl, OC(=O)C1-6-alkyl, CO2-C1-6-alkyl, wherein the abovementioned aryl or heteroaryl radicals can in each case be mono- or polysubstituted by F, Cl, Br, I, CN, NH2, NH-C1-6-alkyl, NH-C1-6-alkyl-OH, N(C1-6alkyl)2, N(C1-6-alkyl-OH)2, NO2, SH, S-C1-6-alkyl, OH, O-C1-6-alkyl, O-C1-6alkyl-OH, C(=O)C1-6-alkyl, CO2H CO2-C1-6-alkyl, CF3, OCF3, C1-6-alkyl or phenoxy, in the form of the racemate; of the enantiomers, diastereomers, mixtures of the enantiomers or diastereomers or of an individual enantiomer or diastereomer; of the bases and/or salts of physiologically acceptable acids.
- Heteroaryl derivatives according to claim 1, whereinR1 and R2 independently of one another represent H; C1-5-alkyl, saturated or unsaturated, branched or unbranched, mono- or polysubstituted or unsubstituted;or the radicals R1 and R2 together form a ring and denote CH2CH2OCH2CH2, CH2CH2NR11CH2CH2 or (CH2)3-6.wherein R11 denotes H; C1-5-alkyl, saturated or unsaturated, branched or unbranched, mono- or polysubstituted or unsubstituted.
- Heteroaryl derivatives according to claim 1 or 2, whereinR1 and R2 independently of one another represent CH3 or H, wherein R1 and R2 do not simultaneously denote H.
- Substituted heteroaryl derivatives according to claim 1, whereinR3 denotes butyl, phenyl, thiophenyl, thiazolyl, cyclopentyl, cyclohexyl, naphthyl, benzyl, benzofuranyl, 1,2,4-triazolyl, benzimidazolyl, benzodioxanyl, benzodioxolanyl, pyridyl or benzothiophenyl, in each case unsubstituted or mono-or polysubstituted: phenyl, furyl or thiophenyl bonded via a saturated, unbranched C1-3-alkyl group and in each case unsubstituted or mono- or polysubstituted.
- Substituted heteroaryl derivatives according to claim 4, whereinR3 denotes phenyl, 4-fluorophenyl, benzyl, butyl or benzothiophenyl.
- Substituted heteroaryl derivatives according to claim 1, whereinB or C represents (CH2)1-4-R21, wherein R21 represents H, OH, SH, COOC1-6-alkyl, COOH, OC(=O)C1-6-alkyl, NH2, NHC(=O)C1-6-alkyl; or C3-8-cycloalkyl, aryl or heteroaryl, in each case unsubstituted or mono- or polysubstituted.
- Substituted heteroaryl derivatives according to claim 6, whereinR21 represents OH, SH, COOCH3, COOH, OC(=O)CH3, NH2, NHC(=O)CH3, NHC(=O)CH2C(CH3)2; or benzimidazole, pyridyl, triazolyl, phenyl, pyrazolyl, tetrazolyl or imidazolyl, in each case unsubstituted or substituted by COOCH3, CH3: or cyclopropyl, cyclohexyl, pyrrolidinyl tetrahydroquinolinyl, pyrrolidinyl, piperidyl, tetrahydroisoquinolinyl, isoindolinyl, piperazinyl, morpholinyl or thiazolinyl, in each case unsubstituted or substituted by =O or CH3.
- Substituted heteroaryl derivatives according to claim 1, whereinR7, R8, R9 and R10 independently of one another represent H; methyl; ethyl; propyl; butyl; pyridyl, O-benzyl, F, Cl, Br, I, CN, CF3, OCF3, OH, OCH3, NH2, COOH, COOCH3, NHCH3 or N(CH3)2 or NO2.
- Substituted heteroaryl derivatives according to claim 8, whereinR7, R8, R9 and R10 independently of one another represent H, F, Cl, NO2, CN, CF3, OCH3, OCF3 or OH.
- Substituted heteroaryl derivatives according to claim 1 from the group(1) 2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethanol, citrate (3) (±) 2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)ethyl acetate hydrochloride(4) (±) 2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-(3-aminopropyl)-1H-indole, citrate(6) (±) 3-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)propan-1-ol hydrochloride(7) (±) 2-(5,6-dichloro-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)ethanol, citrate(8) (±)2-(2-(4-morpholino-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)ethanol, citrate(9) (±)2-(4,6-dichloro-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)ethanol, citrate(10) (±)2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-5-fluoro-1H-indol-3-yl)ethanol, citrate(11) (±)2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-5-(pyridin-3-yl)-1H-indol-3-yl)ethanol, citrate(13) (±)2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-5-nitro-1H-indol-3-yl)ethanol, citrate(14) (±) 2-(2-(4-(benzo[b]thiophen-2-yl)-4-(dimethylamino)cyclohex-1-enyl)-1H-indol-3-yl)ethanol, citrate(15) (±)2-(2-(4-(benzo[b]thiophen-2-yl)-4-(dimethylamino)cyclohex-1-enyl)-5-fluoro-1H-indol-3-yl)ethanol, citrate(16) (±) 2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-methyl-1H-indole, citrate(17) N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(18) N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(19) 2-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)isoindoline-1,3-dione, citrate(20) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)acetamide, citrate(21) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)acetamide, citrate(22) (±)-2-(4-benzyl-4-(dimethylamino)cyclohex-1-enyl)-3-methyl-1H-indole-5-carbonitrile(23) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-methyl-1H-indole-5-carbonitrile(24) (±)-2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-methyl-5-trifluoromethyl-1H-indole(25) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-methyl-5-trifluoromethyl-1H-indole, citrate(26) (±)-2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-methyl-5-fluoro-1H-indole, citrate(27) (±)-2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-methyl-5-fluoro-1H-indole, citrate(28) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-methyl-5-fluoro-1H-indole, citrate(29) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-methyl-5-methoxy-1H-indole, citrate(30) (±)-2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-methyl-1H-indole, citrate(31) (±)-2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-methyl-1H-indole, citrate(32) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-methyl-1H-pyrrolo[2,3-b]pyridine, citrate(33) (±)-2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-cyclopropyl-1H-indole hydrochloride(34) (±)-2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-cyclopropyl-1H-indole(35) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-cyclopropyl-1H-indole(36) (±)-2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-(cyclohexylmethyl)-1H-indole(37) (±)-2-(4-(dimethylamino)-4-benzylcyclohex-1-onyl)-3-benzyl-1H-indole hydrochloride(38) (±)-2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-(cyclohexylmethyl)-1H-indole hydrochloride(39) (±)-2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-benzyl-1H-indole(40) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-(cyclohexylmethyl)-1H-indole hydrochloride(41) (±)-2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-benzyl-1H-indole hydrochloride(42) (±)-2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-propyl-1H-indole(43) (±)-2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-propyl-1H-indole(44) (±)-2-(4-(dimethylamino)-4-phonylcyclohex-1-enyl)-3-propyl-1H-indole(45) (±)2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole(46) (±)2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole(47) (±)2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole(48) (±)-3-(2-(4-benzyl-4-(dimethylamino)cyclohex-1-enyl)-1H-indol-3-yl)propan-1-ol, citrate(49) (±)-3-(2-(4-butyl-4-(dimethylamino)cyclohex-1-enyl)-1H-indol-3-yl)propan-1-ol, citrate(51) (±)2-(2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)ethyl)isoindoline-1,3-dione(52) (±)2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indole(53) (±)2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indole(54) (±)2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indole(55) (±)2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-(2-(piperidin-1-yl)ethyl)-5-fluoro-1H-indole(56) (±)2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-(2-(piperidin-1-yl)ethyl)-5-fluoro-1H-indole(57) (±)2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-(2-(piperidin-1-yl)ethyl)-5-fluoro-1H-indole(58) (±)2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-(2-(piperidin-1-yl)ethyl)-1H-indole, citrate(59) (±)2-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indole(60) (±) 2-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indole(61) (±)2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indole(62) N-(2-(2-(4-butyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)ethyl)-3,3-dimethylbutanamide, citrate(63) (±)N-(2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-3-yl)ethyl)acetamide(64) (±)N-(2-(2-(4-butyl-4-(dimethylamino)cyclohex-1-enyl)-1H-indol-3-yl)ethyl)-3,3-dimethylbutanamide(65) (±)-2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-5-fluoro-6-methoxy-1H-indol-3-yl)ethanol, citrate(66) (±)-2-(2-(4-benzyl-4-(4-methylpiperazin-1-yl)cyclohex-1-enyl)-5-fluoro-1H-indol-3-yl)ethanol(67) (±)-2-(5-fluoro-2-(4-phenyl-4-(pyrrolidin-1-yl)cyclohex-1-enyl)-1H-indol-3-yl)ethanol(68) 2-(4-benzyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indole-5-carbonitrile, citrate(69) 2-(4-benzyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indole-5-carbonitrile, citrate(70) 2-(4-butyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indole-5-carbonitrile, citrate(71) 2-(4-butyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indole-5-carbonitrile, citrate(72) 2-(4-(dimethylamino)-4-phenylcyclohexyl)-3-methyl-1H-indole-5-carbonitrile, citrate(73) 1-benzyl-N,N-dimethyl-4-(3-methyl-5-(trifluoromethyl)-1H-indol-2-yl)cyclohexanamine, citrate(74) 1-benzyl-N,N-dimethyl-4-(3-methyl-5-(trifluoromethyl)-1H-indol-2-yl)cyclohexanamine, citrate(75) 1-butyl-N,N-dimethyl-4-(3-methyl-5-(trifluoromethyl)-1H-indol-2-yl)cyclohexanamine, citrate(76) N,N-dimethyl-4-(3-methyl-5-(trifluoromethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(77) 1-benzyl-4-(5-fluoro-3-methyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(78) 1-benzyl-4-(5-fluoro-3-methyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(79) 1-butyl-4-(5-fluoro-3-methyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine hydrochloride(80) 4-(5-fluoro-3-methyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(81) 4-(5-fluoro-3-methyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(82) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(83) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(84) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(85) 1-benzyl-4-(5-fluoro-3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(86) 1-benzyl-4-(5-fluoro-3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(87) 1-butyl-4-(5-fluoro-3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(88) 1-butyl-4-(5-fluoro-3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(89) 4-(5-fluoro-3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(90) 4-(5-fluoro-3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(91) 1-benzyl-4-(5-fluoro-3-(2-(piperidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(92) 1-benzyl-4-(5-fluoro-3-(2-(piperidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate (2:3)(93) 1-butyl-4-(5-fluoro-3-(2-(piperidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate (4:3)(94) 1-butyl-4-(5-fluoro-3-(2-(piperidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(95) 4-(5-fluoro-3-(2-(piperidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(96) 4-(5-fluoro-3-(2-(piperidin-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(97) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate (2:3)(98) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate(99) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(100) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(101) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(102) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(103) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate(104) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate(105) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate (2:3)(106) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(107) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(108) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate (2:3)(109) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate (4:3)(110) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate (2:3)(111) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate (2:3)(112) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate (4:1)(113) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-benzyl-N,N-dimethylcyclohexanamine, citrate(114) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(115) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(116) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(117) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-5-fluoro-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(118) 2-(4-(dimethylamino)-4-phenylcyclohexyl)-3-methyl-1H-indol-5-ol(119) 2-(4-(dimethylamino)-4-phenylcyclohexyl)-3-methyl-1H-indol-5-ol 120) 1-benzyl-N,N-dimethyl-4-(3-methyl-5-(trifluoromethoxy)-1H-indol-2-yl)cyclohexanamine, citrate(121) 1-butyl-N,N-dimethyl-4-(3-methyl-5-(trifluoromethoxy)-1H-indol-2-yl)cyclohexanamine, citrate(122) 1-butyl-N,N-dimethyl-4-(3-methyl-5-(trifluoromethoxy)-1H-indol-2-yl)cyclohexanamine, citrate(123) N,N-dimethyl-4-(3-methyl-5-(trifluoromethoxy)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(124) N,N-dimethyl-4-(3-methyl-5-(trifluoromethoxy)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(125) 1-butyl-4-(5-methoxy-3-methyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(126) 1-butyl-4-(5-methoxy-3-methyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(127) 4-(5-methoxy-3-methyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(128) 4-(5-methoxy-3-methyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate (4:3)(129) 1-benzyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine, citrate(130) 1-benzyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine, citrate(131) 1-butyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine, citrate(132) 1-butyl-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine, citrate(133) 1-benzyl-4-(3-cyclopropyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(134) 1-benzyl-4-(3-cyclopropyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(135) 1-butyl-4-(3-cyclopropyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine hydrochloride(136) 4-(3-cyclopropyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(137) methyl 2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)acetate, citrate(138) methyl 2-(2-(4-(dimethylamino)4-phenylcyclohexyl)-1H-indol-3-yl)acetate, citrate(139) 1-benzyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(140) 1-benzyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(141) 1-benzyl-4-(3-benzyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(142) 1-benzyl-4-(3-benzyl-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(143) 1-butyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine, citrate(144) 1-butyl-4-(3-(cyclohexylmethyl)-1H-indol-2-yl)-N,N-dimethylcyclohexanamine hydrochloride(145) 4-(3-benzyl-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(146) 4-(3-benzyl-1H-indol-2-yl)-1-butyl-N,N-dimethylcyclohexanamine, citrate(147) 4-(3-(cyclohexylmethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(148) 4-(3-(cyclohexylmethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(149) 4-(3-benzyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(150) 4-(3-benzyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(151) N,N-dimethyl-1-phenyl-4-(3-(pyridin-2-ylmethyl)-1H-indol-2-yl)cyclohexanamine(152) N,N-dimethyl-1-phenyl-4-(3-(pyridin-2-ylmethyl)-1H-indol-2-yl)cyclohexanamine(153) 3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)propanoic acid hydrochloride(156) 1-benzyl-N,N-dimethyl-4-(3-propyl-1H-indol-2-yl)cyclohexanamine, citrate(157) 1-butyl-N,N-dimethyl-4-(3-propyl-1H-indol-2-yl)cyclohexanamine hydrochloride(158) 1-butyl-N,N-dimethyl-4-(3-propyl-1H-indol-2-yl)cyclohexanamine, citrate(159) N,N-dimethyl-1-phenyl-4-(3-propyl-1H-indol-2-yl)cyclohexanamine, citrate(160) N,N-dimethyl-1-phenyl-4-(3-propyl-1H-indol-2-yl)cyclohexanamine, citrate(161) 1-benzyl-N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(162) 1-benzyl-N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(163) 1-butyl-N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(164) 1-butyl-N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(165) N,N-dimethyl-1-phenyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate (1:4)(166) N,N-dimethyl-1-phenyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(167) N,N-dimethyl-4-(3-(2-(1-methyl-1H-benzo[d]imidazol-2-yl)ethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(168) N,N-dimethyl-4-(3-(2-(1-methyl-1H-benzo[d]imidazol-2-yl)ethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(169) N,N-dimethyl-1-phenyl-4-(3-(2-(pyridin-2-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(170) N,N-dimethyl-1-phenyl-4-(3-(2-(pyridin-2-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate (2:3)(171) 4-(2-(4-benzyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)butanoic acid hydrochloride(172) 4-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)butanoic acid hydrochloride(173) 4-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)butan-1-ol hydrochloride(174) 4-(2-(4-benzyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)butyl acetate hydrochloride(175) 4-(2-(4-benzyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)butyl acetate hydrochloride(176) 4-(2-(4-butyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)butyl acetate hydrochloride(177) 4-(2-(4-butyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)butyl acetate hydrochloride(178) 4-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)butyl acetate hydrochloride(179) 4-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)butyl acetate hydrochloride(180) 3-(2-(4-benzyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)propan-1-ol, citrate(181) 3-(2-(4-butyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)propan-1-ol hydrochloride(182) 3-(2-(4-butyl-4-(dimethylamino)cyclohexyl)-1H-indol-3-yl)propan-1-ol hydrochloride(183) 3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)propan-1-ol hydrochloride(184) 3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)propan-1-ol hydrochloride(185) 3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)propyl acetate hydrochloride(186) 3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)propyl acetate hydrochloride(187) 1-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)pyrrolidine-2,5-dione(188) 1-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)pyrrolidine-2,5-dione(189) 4-(3-(2-(3,4-dihydroquinolin-1(2H)-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate (4:3)(190) 4-(3-(2-(3,4-dihydroquinolin-1(2H)-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(191) methyl 1-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)-1H-1,2,3-triazole-4-carboxylate, citrate(192) methyl 1-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)-1H-1,2,3-triazole-4-carboxylate, citrate(193) 4-(3-(2-(isoindolin-2-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(194) 4-(3-(2-(isoindolin-2-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(195) 4-(3-(2-(3,4-dihydroisoquinolin-2(1H)-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(196) 4-(3-(2-(3,4-dihydroisoquinolin-2(1H)-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate (2:3)(197) N,N-dimethyl-1-phenyl-4-(3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(198) N,N-dimethyl-1-phenyl-4-(3-(2-(pyrrolidin-1-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(199) N,N-dimethyl-1-phenyl-4-(3-(2-(piperidin-1-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(200) N,N-dimethyl-4-(3-(2-(4-methylpiperazin-1-yl)ethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(201) N,N-dimethyl-4-(3-(2-morpholinoethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(202) N,N-dimethyl-4-(3-(2-morpholinoethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(203) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(204) 4-(3-(2-(1H-benzo[d]imidazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(205) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(206) 4-(3-(2-(1H-imidazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(207) 4-(3-(2-(1H-1,2,4-triazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(208) 4-(3-(2-(1H-1,2,4-triazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(209) N,N-dimethyl-1-phenyl-4-(3-(2-(thiazolidin-3-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(210) N,N-dimethyl-1-phenyl-4-(3-(2-(thiazolidin-3-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(211) N,N-dimethyl-4-(3-(2-(5-methyl-2H-tetrazol-2-yl)ethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(212) N,N-dimethyl-4-(3-(2-(5-methyl-2H-tetrazol-2-yl)ethyl)-1H-indol-2-yl)-1 phenylcyclohexanamine, citrate(213) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(214) 4-(3-(2-(1H-pyrazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(215) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(216) 4-(3-(2-(1H-1,2,3-triazol-1-yl)ethyl)-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(217) N,N-dimethyl-4-(3-(2-(5-methyl-1H-tetrazol-1-yl)ethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(218) N,N-dimethyl-4-(3-(2-(5-methyl-1H-tetrazol-1-yl)ethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(219) 2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethanol(220) 2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl acetate(221) N,N-dimethyl-4-(3-methyl-1H-pyrrolo[3,2-c]pyridin-2-yl)-1-phenylcyclohexanamine, citrate(222) N,N-dimethyl-4-(3-methyl-1H-pyrrolo[3,2-c]pyridin-2-yl)-1-phenylcyclohexanamine, citrate(223) N,N-dimethyl-4-(3-methyl-1H-pyrrolo[2,3-b]pyridin-2-yl)-1-phenylcyclohexanamine, citrate(224) N,N-dimethyl-4-(3-methyl-1H-pyrrolo[2,3-b]pyridin-2-yl)-1-phenylcyclohexanamine, citrate(225) N,N-dimethyl-4-(3-methylbenzofuran-2-yl)-1-phenylcyclohexanamine, citrate(226) N,N-dimethyl-4-(3-methylbenzofuran-2-yl)-1-phenylcyclohexanamine, citrate(227) 4-(1H-indol-3-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(228) (±)-3-(4-(dimethylamino)-4-benzylcyclohex-1-enyl)-1H-pyrrolo[2,3-b]pyridine(229) (±)-3-(4-(dimethylamino)-4-butylcyclohex-1-enyl)-1H-pyrrolo[2,3-b]pyridine(230) (±)-3-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-pyrrolo[2,3-b]pyridine, citrate(231) (±)-4-(1H-indol-3-yl)-N,N-dimethyl-1-phenylcyclohex-3-enamine, citrate(232) (±)-4-(1H-indol-3-yl)-N,N-dimethyl-1-phenylcyclohex-3-enamine(233) (±)-2-(3-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)benzo[b]thiophen-2-yl)ethanol hydrochloride(234) (±)-2-(3-(4-(dimethylamino)-4-(pyridin-2-yl)cyclohex-1-enyl)benzo[b]thiophen-2-yl)ethanol hydrochloride(235) 4-(1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(236) 4-(1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine, citrate(237) 1-benzyl-N,N-dimethyl-4-(1H-pyrrolo[2,3-b]pyridin-3-yl)cyclohexanamine hydrochloride(238) 1-butyl-N,N-dimethyl-4-(1H-pyrrolo[2,3-b]pyridin-3-yl)cyclohexanamine hydrochloride(239) (±)-4-(benzofuran-2-yl)-1-benzyl-N,N-dimethylcyclohex-3-enamine hydrochloride(240) (±)-N,N-dimethyl-4-(3-methylbenzofuran-2-yl)-1-phenylcyclohex-3-enamine, citrate(241) (±)-2-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)benzofuran-3-yl)ethanethiol, citrate(242) (±)-N,N-dimethyl-4-(3-methylbenzo[b]thiophen-2-yl)-1-phenylcyclohex-3-enamine, citrate(243) N,N-dimethyl-4-(3-methylbenzo[b]thiophen-2-yl)-1-phenylcyclohexanamine, citrate(244) N,N-dimethyl-1-phenyl-4-(1H-pyrrolo[2,3-b]pyridin-3-yl)cyclohexanamine, citrate(246) 1-(dimethylamino)-3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-3-methyl-1H-indol-1-yl)propan-2-ol(247) N,N-dimethyl-4-(3-methyl-1-(oxiran-2-ylmethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine(248) 4-(1,3-dimethyl-1H-indol-2-yl)-N,N-dimethyl-1-phenylcyclohexanamine(249) 2-(4-butyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indol-5-ol, citrate(250) 2-(4-butyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indol-5-ol, citrate(251) (±)-2-(4-(dimethylamino)-4-(thiophen-2-yl)-cyclohex-1-enyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole(252) (±)-2-(4-(dimethylamino)-4-(3-fluorophenyl)-cyclohex-1-enyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole(253) (±)-2-(4-butyl-4-(pyrrolidin-1-yl)cyclohex-1-enyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole(254) (±)-2-(4-(methylamino)-4-phenylcyclohex-1-enyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole(255) (±)-2-(4-(dimethylamino)-4-(thiophen-2-yl)-cyclohex-1-enyl)-3-methyl-1H-indole, citrate(256) N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)-1-(thiophen-2-yl)cyclohexanamine, citrate(257) N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)-1-(thiophen-2-yl)cyclohexanamine, citrate(258) 2-(4-butyl-4-(pyrrolidin-1-yl)cyclohex-1-enyl)-3-methyl-1H-indole(259) N-methyl-4-(3-methyl-1H-indol-2-yl)-1-phenylcyclohexanamine hydrobromide(260) N-methyl-4-(3-methyl-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(261) 1-(3-fluorophenyl)-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine, citrate(262) 1-(3-fluorophenyl)-N,N-dimethyl-4-(3-methyl-1H-indol-2-yl)cyclohexanamine, citrate(263) (±)-2-(4-(dimethylamino)-4-(3-fluorophenyl)-cyclohex-1-enyl)-3-methyl-1H-indole(264) 2-(4-benzyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indol-5-ol, citrate(265) 2-(4-benzyl-4-(dimethylamino)cyclohexyl)-3-methyl-1H-indol-5-ol, citrate(266) 2-(4-butyl-4-(pyrrolidin-1-yl)cyclohexyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole, citrate(267) 2-(4-butyl-4-(pyrrolidin-1-yl)cyclohexyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole, citrate(268) 2-(4-(azetidin-1-yl)-4-phenylcyclohexyl)-3-methyl-1H-indole, citrate(269) 2-(4-(azetidin-1-yl)-4-phenylcyclohexyl)-3-methyl-1H-indole, citrate(270) 2-4-(azetidin-1-yl)-4-phenylcyclohexyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole hydrochloride(271) 2-(4-(azetidin-1-yl)-4-phenylcyclohexyl)-3-(2-(pyridin-4-yl)ethyl)-1H-indole hydrochloride(272) 2-(4-butyl-4-(pyrrolidin-1-yl)cyclohexyl)-3-methyl-1H-indole, citrate(273) 3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-pyrrolo[2,3-b]pyridin-3-yl)propan-1-ol, citrate(274) 1-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-3-methyl-1H-indol-1-yl)-3-(methylamino)propan-2-ol, citrate(275) 1-benzyl-3-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)urea, citrate(276) 1-benzyl-3-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)urea, citrate(277) 1-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)-3-phenylurea, citrate(278) 1-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)-3-phenylurea, citrate(279) 1-cyclopentyl-3-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)urea, citrate(280) 1-cyclopentyl-3-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)urea, citrate(281) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)-cyclopentanesulfonamide, citrate(282) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)cyclopentanesulfonamide, citrate(283) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3 yl)ethyl)benzenesulfonamide, citrate(284) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)thiophene-2-sulfonamide, citrate(285) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)thiophene-2-sulfonamide, citrate(286) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)nicotinamide, citrate(287) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)nicotinamide, citrate(288) N-(2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethyl)benzamide, citrate(289) 1-(3-fluorophenyl)-N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine(290) 1-(3-fluorophenyl)-N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(291) N-methyl-1-phenyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(292) N-methyl-1-phenyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)cyclohexanamine, citrate(293) 2-(4-butyl-4-(pyrrolidin-1-yl)cyclohexyl)-3-methyl-1H-indole, citrate(294) N,N-dimethyl-1-phenyl-4-(1-(phenylsulfonyl)-1H-indol-2-yl)cyclohexanamine(295) N,N-dimethyl-1-phenyl-4-(1-(phenylsulfonyl)-1H-indol-2-yl)cyclohexanamine(296) N,N-dimethyl-4-(3-methyl-1-(oxiran-2-ylmethyl)-1H-indol-2-yl)-1-phenylcyclohex-3-enamine(297) N,N-dimethyl-4-(3-methyl-1-(oxiran-2-ylmethyl)-1H-indol-2-yl)-1-phenylcyclohexanamine, citrate(298) 1-(dimethylamino)-3-(2-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-3-methyl-1H-indol-1-yl)propan-2-ol, citrate(299) 1-(dimethylamino)-3-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-3-methyl-1H-indol-1-yl)propan-2-ol, citrate(300) 2-(3-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-1H-indol-1-yl)ethanol hydrochloride(301) (±) 3-(4-(dimethylamino)-4-phenylcyclohex-1-enyl)-(1-(phenylsulfonyl)-1H-indole) hydrochloride(302) 1-benzyl-N,N-dimethyl-4-(1-methyl-1H-indol-2-yl)cyclohex-3-enamine; hydrochloride(303) N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)-1-(thiophen-2-yl)cyclohexanamine hydrochloride(304) N,N-dimethyl-4-(3-(2-(pyridin-4-yl)ethyl)-1H-indol-2-yl)-1-(thiophen-2-yl)cyclohexanamine hydrochloride(305) N-methyl-4-(3-methyl-1H-indol-2-yl)-1-(4-methylthiazol-2-yl)cyclohexanamine(306) N-methyl-4-(3-methyl-1H-indol-2-yl)-1-(4-methylthiazol-2-yl)cyclohexanamine(307) 2-(2-(4-(dimethylamino)-4-phenylcyclohexyl)-1H-indol-3-yl)ethanol in the form of the racemate; of the enantiomers, diastereomers, mixtures of the enantiomers or diastereomers or of an individual enantiomer or diastereomer; of the bases and/or salts of physiologically acceptable acids.
- Process for the preparation of substituted heteroaryl derivatives of the formula lc wherein ketones of the general formula B are reacted with heteroaromatics of the general formula A in organic solvents or solvent mixtures, for example ethyl acetate, chloroform, methylene chloride (MC), dichloroethane (DCE), diethyl ether (Et2O), acetonitrile (MeCN) or nitromethane, with the addition of an organic or inorganic acid, for example HCl, HBr, trifluoromethanesulfonic acid, methanesulfonic acid, acetic acid, trifluoroacetic acid, or without a solvent in an organic or inorganic acid or acid mixtures at temperatures of between 0 °C and 150 °C, optionally using microwave irradiation, and then reacted with the addition of an organic or inorganic reducing agent, e.g. triethylsilane or tin powder, at temperatures of between 0 °C and 150 °C, optionally using microwave irradiation.
- Process for the preparation of substituted heteroaryl derivatives of the general formula Id or Ie wherein heteroaromatics of the general formula A or A' are reacted with cyclohexanones of the general formula B in organic solvents or solvent mixtures, for example chloroform, methylene chloride (DCM), dichloroethane (DCE), diethyl ether (Et2O), acetonitrile (MeCN) or nitromethane, with the addition of an organic or inorganic acid, for example HCl, HBr, trifluoromethanesulfonic acid, methanesulfonic acid, acetic acid, trifluoroacetic acid, at temperatures of between 0 °C and 150 °C, optionally using microwave irradiation or heteroaromatics of the general formula A or A' are reacted with cyclohexanones of the general formula B with the addition of a base, for example, KOH or NaOH, in an organic solvent, for example methanol, at temperatures of between 20 and 100 °C.
- Process for the preparation of substituted heteroaryl derivatives of the general formulae lc or If by reduction of the compounds Id or le by means of hydrogen in the form of HBr/glacial acetic acid/Sn or HCl/Sn (nascent hydrogen) or H2 in the presence of a metal catalyst, such as e.g. palladium on charcoal, platinum on charcoal, platinum oxide, Raney nickel, rhodium or ruthernium complexes, in a suitable solvent or solvent mixture, for example methanol, ethanol, acetone, ethyl acetate, HBr or acetic acid, at temperatures of between 0 °C and 150 °C.
- Medicament containing at least one substituted heteroaryl derivative according to one of claims 1 to 10, optionally in the form of its racemate, of the pure stereoisomers, in particular enantiomers and diastereomers, in any desired mixture ratio: in the form of its acids or of its bases or in the form of its salts, in particular the physiologically acceptable salts or salts of physiologically acceptable acids or cations; or in the form of its solvates, in particular the hydrates, and optionally containing suitable additives and/or auxiliary substances and/or optionally further active compounds.
- A substituted heteroaryl derivative according to one of claims 1 to 10, optionally in the form of its racemate, of the pure stereoisomers, in particular enantiomers and diastereomers, in any desired mixture ratio; in the form of its acids or of its bases or in the form of its salts, in particular the physiologically acceptable salts or salts of physiologically acceptable acids or cations; or in the form of its solvates, in particular the hydrates; for use for treatment of pain, in particular acute, neuropathic, chronic pain or inflammation pain.
- A substituted heteroaryl derivative according to one of claims 1 to 10 for use for treatment of anxiety states, of stress and syndromes associated with stress, depression, epilepsy, Alzheimer's disease, senile dementia, catalepsy, general cognitive dysfunctions, learning and memory disorders (as a nootropic), withdrawal symptoms, alcohol and/or drug and/or medicament abuse and/or dependency, sexual dysfunctions, cardiovascular diseases, hypotension, hypertension, tinnitus, pruritus, migraine, impaired hearing, lack of intestinal motility, impaired food intake, anorexia, obesity, locomotor disorders, diarrhoea, cachexia, urinary incontinence or as a muscle relaxant, anticonvulsive or anaesthetic or for co-administration in treatment with an opioid analgesic or with an anaesthetic, for diuresis or antinatriuresis, anxiolysis, for modulation of motor activity, for modulation of neurotransmitter secretion and treatment of neurodegenerative diseases associated therewith, for treatment of withdrawal symptoms and/or for reduction of the addiction potential of opioids.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006033109.5 | 2006-07-18 | ||
| DE102006033109A DE102006033109A1 (en) | 2006-07-18 | 2006-07-18 | Substituted heteroaryl derivatives |
| PCT/EP2007/006325 WO2008009415A2 (en) | 2006-07-18 | 2007-07-17 | 4-heteroaryl-substituted 1-aminocyclohexane-1- and cyclohexene-1-derivatives having effects on the opiod receptor system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1126479A1 HK1126479A1 (en) | 2009-09-04 |
| HK1126479B true HK1126479B (en) | 2013-04-05 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2044016B1 (en) | 4-heteroaryl-substituted 1-aminocyclohexane-1-and cyclohexene-1-derivatives having effects on the opiod receptor system | |
| EP3752510B1 (en) | Macrocycles as modulators of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions thereof, their use in the treatment of cycstic fibrosis, and process for making them | |
| EP2262807B1 (en) | Novel tyrosine kinase inhibitors | |
| EP2917214B1 (en) | Substituted pyrimidinyl and pyridinyl-pyrrolopyridinones, process for their preparation and their use as kinase inhibitors | |
| EP2518067B1 (en) | Derivatives of n-[(1h-pyrazol-1-yl)aryl]-1h-indole or 1h- indazole-3-carboxamide and their therapeutic uses as p2y12 antagonists | |
| EP3002285B1 (en) | Tetrahydrocarboline derivative | |
| EP1832590B1 (en) | Heterotricyclic compounds as CRF receptor antagonists | |
| EP3027602B1 (en) | Novel derivatives of indole and pyrrole, method for the production thereof and pharmaceutical compositions containing same | |
| EP2295437A1 (en) | Diazabicyclic central nervous system active agents | |
| JP2010527340A (en) | 3,3-spiroindolinone derivatives | |
| CN101296926A (en) | Aspartyl protease inhibitors | |
| JP2021534106A (en) | Substituted thienopyrol as a PAD4 inhibitor | |
| EP0204349A2 (en) | Heteroaromatic amine derivatives, medicaments containing them and process for their preparation | |
| EA019030B1 (en) | Indole carboxamides as ikk2 receptor inhibitors | |
| TW202140477A (en) | Heterocyclic pad4 inhibitors | |
| EP1301516B1 (en) | Modulators of protein tyrosine phosphatases (ptpases) | |
| EP1831197A2 (en) | Substituted oxindole derivatives, medicaments containing said derivatives and use thereof | |
| JP2008524213A (en) | Novel pyrazole derivatives and their use as modulators of nicotinic acetylcholine receptors | |
| EP1930320A1 (en) | Novel fused pyrrole derivative | |
| HK1126479B (en) | 4-heteroaryl-substituted 1-aminocyclohexane-1- and cyclohexene-1-derivatives having effects on the opiod receptor system | |
| CN119768169A (en) | Substituted fused bicyclic compounds and related methods of treatment | |
| CN101454317A (en) | Imidazole derivatives as nitric oxide synthase dimerisation inhibitor | |
| EP2254864B1 (en) | Substituted 4-aminocyclohexane derivatives for the treatment of pain | |
| HK40042698A (en) | Macrocycles as modulators of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions thereof, their use in the treatment of cycstic fibrosis, and process for making them | |
| HK40042698B (en) | Macrocycles as modulators of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions thereof, their use in the treatment of cycstic fibrosis, and process for making them |