HK1100899A - Utilization of heteroarene carboxamide as dopamine-d3 ligands for the treatment of cns diseases - Google Patents
Utilization of heteroarene carboxamide as dopamine-d3 ligands for the treatment of cns diseases Download PDFInfo
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Description
Dopamine is considered an important central nervous system neurotransmitter. Its action is mediated by dopamine by binding to five different dopamine receptors. These can be classified into D1-like (D1 and D5) and D2-like (D2, D3 and D4) receptors (Neve, K.A. The Dopamine Receptors. Humana Press, 1997). In particular, the subtypes of the D2 family play an important role in the regulation of central nervous processes. While the D2 receptors are predominantly expressed in the basal ganglia and control many neuromotor circuits, there are 151 D3-like receptors in the limbic system, but in the immune system and cognitive systems.
Compounds with arylpiperazine structure have already been described as dopamine receptor-activating ligands (Robarge, M.J.J. Med. Chem. 2001, 44, 3175-3186). Furthermore, benzamides and naphthamides with arylpiperazine partial structure are known to be dopamine receptor ligands (Perrone, R.J. Med. Chem. 1998, 41, 4903-4909; EP 0 779 284 A1). Recently, a phenylpiperazine naphthamide has been described as a selective D3 partialagonist showing promising activity in animal models that could be used for the treatment of cocaine addiction (Pilla, M. et al. 1999, Nature 400, 371-375).
For a few examples, arylpiperazinylamides with oxygen, sulphur or nitrogen heteroaric acid components have been described (ES 2027898; EP 343 961; US 3646047; US 3734915), whereas cyanosubstituted and telluric derivatives and compounds with ferrocenyl partial structure are not known in the literature.
In our structural studies of dopamine receptor ligands, we have discovered new compounds of formula (I) - (IV) which have shown in vitro high affinity and highly selective binding properties to the D3 receptor, which are not yet known, and which could be valuable therapeutics for the treatment of CNS disorders such as schizophrenia, various types of depression, neurodegenerative disorders, sexual dysfunctions, and cocaine, alcohol, opiate and nicotine addiction.
Specific potential uses should also be mentioned: glaucoma, cognitive impairment, restless leg syndrome, hyperactivity disorder (ADHD), hyperprolactinemia, hyperprolactinoma, Parkinson' s-associated movement disorders, treatment of L-DOPA and neuroleptic-induced movement disorders such as akathisia, rigor, dystonia and dyskinesia.
The invention relates to derivatives of 2-hetero-carboxylic amides with arylpiperazinyl partial structure in the form of the free base and their salts as described by the following formulae (I) and (II):
Other
It shall apply in formula (I):
n = 1 - 4 andR = hydrogen, alkyl or halogen and
(a) X = S or O:
(i) if R1 is hydroxy, alkyloxy, alkenyl, alkyl, aryl, acyl, alkoxycarbonyl or cyano, R2 and R3 are independently selected from hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano,
or (b) X = NH:
R1 is selected from hydrogen, hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, trifluoromethyl, acyl, alkoxycarbonyl, halogen and cyano and R2 and R3 are independently selected from hydrogen, hydroxy, alkyloxy, alkyloyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano, provided that the compound is not N-4-4- (((2-methyl) pyetoxyzin-1-yl-2-indolylperabutyl carbamide,
or (c) X = Te:
R1 is selected from hydrogen, hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano and R2 and R3 are independently selected from hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano.
In an embodiment of the invention, the formula (I) applies to:
n=1-4
andX = Te, where R = hydrogen, alkyl or halogen and R1 is replaced by the residues hydrogen, hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano and R2 and R3 are replaced individually or together by the residues hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano,
or X = S or O, where R = hydrogen, alkyl or halogen and R1 is replaced by the hydroxy, alkyloxy, alkenyl, alkynyl, aryl, acyl, alkoxycarbonyl or cyano residues and R2 and R3 are replaced individually or together by the hydrogen residues,Hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano are replaced,
or X = S or O, where R = hydrogen, alkyl or halogen and R1 is replaced by the hydrogen, alkyl, halogen or trifluoromethyl residues and R2 and R3 are replaced individually or together by the hydroxy, alkenyl, alkynyl, aryl, acyl, alkoxycarbonyl or cyano residues,
or X = NH, where R = hydrogen, alkyl or halogen and R1 is replaced by the hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, trifluoromethyl, acyl, alkoxycarbonyl or cyano residues, where the alkyl and alkyloxy must contain at least two carbon atoms and R2 and R3 individually or together by the hydrogen residues,Hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano are replaced and the alkyloxy contains at least two carbon atoms.
In formula (II), the following are represented:
n = 1 - 4 and R1 and R2 individually or together for the residues hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano.
The invention relates in particular to physiologically acceptable salts of the compounds of the invention.
The expert is also aware that optically active compounds can be formed depending on the choice of substituents, in which case both the racemates and the respective pure enantiomeric forms are the subject of the present invention.
The substituents referred to in the specification and the related claims include in particular the groups described below.
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
Err1:Expecting ',' delimiter: line 1 column 43 (char 42)
The preferred structures are compounds of formula (I) where X is represented by NH, S or O.
The compounds of the invention of formula (I) are the following compounds of general formula (Ia) or (Ib):
Other
including:
n=1,4,R = hydrogen, C1-C6-alkyl or halogen,if R1 is a hydroxy, C1-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, if applicable with a methoxy group or halogen substituted phenyl, C1-C6-acyl, C1-C6-alkoxycarbonyl or cyano, R2 and R3 are independently selected from hydrogen, hydroxy, C1-C6-alkyloxy, C1-C6-alkyly, C2-C6-alkyly, C2-C6-alkyly, C2-C6-alkynyl, if R1 is a hydroxy group or halogen substituted phenyl, phenyl, C1-C6-acyl, C1-C6-acyl, C1-C6-cyl, C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C2-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C1-C2-C1-C2-C1-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-C6-
and pharmaceutically acceptable salts thereof, with preference for fluorine, chlorine and bromine as halogen substitutes.
Another preferred embodiment of the compounds of the invention of formula (I) is the following compounds of general formula (Ic):
Other
including:
n=1-4,R = hydrogen, C1-C6-alkyl or halogen,R1 is selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, where applicable with a methoxy group or halogen substituted phenyl, trifluoromethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl, fluorine, chlorine, bromine and cyano,R2 and R3 are each independently selected from hydrogen, hydroxy, C1-C6-alkynyl, C1-C6-alkynyl, C2-C6-alkoxy, C2-C6-alkynyl, where applicable with a methoxy group or halogen substituted phenyl, cyclocarbonyl, halogen, C1-cyl, C1-cyl, C6-alkynyl, and halogenyl,
and pharmaceutically acceptable salts of this compound, with preference for fluorine, chlorine and bromine as halogen substituents, provided that the compound is not N-4- ((4- ((2-Methoxyphenyl) piperazine-1-yl) butyl-2-indolylcarbamide.
In a further preferred embodiment of the invention, the compounds of general formula (Ic) are:
(a) where R1 is hydroxy, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, trifluoromethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl or cyano substituted with a methoxy group or halogen, as appropriate, R2 and R3 shall be independently selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, methoxy group or halogen substituted with an alkenyl, halogen, thorium phenyl, C1-C6-alkenyl, C1-C6-alkoxycarbonyl and cyano, as appropriate;
and (b) where R1 is hydrogen, C1-C6-alkyl, C1-C6-alkyloxy or halogen, R2 is selected from hydroxy, C2-C6-alkenyl, C2-C6-alkynyl, where appropriate with a methoxy group or halogen substituted phenyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano, and R3 is selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkyloxy, C2-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, where appropriate with a methoxy group or phenyl substituted halogen, halogen, tetrofluorethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano.
In another preferred embodiment of the invention, the compounds of formulae (I), (la), (Ib) and (Ic) are:
The substituent R1 is at position 5 or 6 of the heterocycle and the substituents R2 and R3 are at positions 2 or 3 or 2 or 4 of the phenyl ring, respectively, whereby, if one of the two substituents R2 and R3 is a hydrogen atom, the other substituent is at position 2 of the phenyl ring.
According to a particularly preferred embodiment of the invention, n = 3 in the compounds of the formulas (I), (la), (Ib) and (Ic).
The preferred compound of general formula (II) as defined above is one in which R1 and R2 are independently selected from hydrogen, hydroxy, C1-C6-alkyloxy, C1-C6-alkyl, C2-C6-alkenyl, C2-6 alkynyl, aryl, fluorine, chlorine, bromine, trifluoromethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano.
Concrete compounds of general formula (II) are
(B16): N-4- ((4-)) 2-methoxyphenylpiperazine-1-yl) butyl-2-ferrocenylcarbamide and
The following substances are to be classified as N-methyl-butadiene:
A further aspect of the present invention concerns compounds of general formula (IV):
Other
including:
X = S, NH or O,R is selected from hydrogen, C1-C6-alkyl, fluorine, chlorine and bromine,R1 is selected from hydrogen, C1-C6-alkoxy, C1-C6-alkyl, fluorine, chlorine, bromine, trifluoromethyl and cyano, where R1 is in the 5 or 6 position of the heterocycle,R2 and R3 are independently selected from hydrogen, C1-C6-alkyloxy, C1-C6-alkyl, fluorine, chlorine, bromine and trifluoromethormonyl, where R2 and R3 are in the 2 or 3 positions of the phenyl ring and where, for each substituent phenyl, R2 and R3 are hydrogen atoms, each at the 2 position of the other substituent ring,
and pharmaceutically acceptable salts of this compound,
provided that the compound is not N-4- ((4- ((2-Methoxyphenyl) piperazine-1-yl) butyl-2-indolylcarbamide.
A preferred aspect of the invention is compounds of general formula (IV) as defined above, which are:
If X = NH, then R1 is selected from hydrogen, C1-C3-alkyloxy, C1-C3-alkyl, fluorine, chlorine, bromine and cyano,
and if X = S or O, then R1 is selected from hydrogen, C1-C3-alkyl, fluorine, chlorine, bromine, cyano and trifluoromethyl.
The following compounds are representative of the specific embodiments of the compounds of the invention: ((B18): N-4- ((4- ((2-Methoxyphenyl) -piperazin-1-yl) butyl-5-cyan-2-benzo[b]thiophenylcarbamide ((B19): N-4- ((4-(2,3-Dichlorphenyl) -piperazin-1-yl) butyl-bamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbamethylbameth
and pharmaceutically acceptable salts of these compounds.
In particular, the compounds of the invention of formulae (I), (la), (Ib), (Ic), (II) and (IV), as defined, are suitable for therapeutic use as dopamine D3 ligands.
Err1:Expecting ',' delimiter: line 1 column 55 (char 54)
Err1:Expecting ',' delimiter: line 1 column 125 (char 124)
Err1:Expecting ',' delimiter: line 1 column 132 (char 131)
D3 ligands may have an agonist, antagonist or partial agonist effect on the D3 receptor. The corresponding intrinsic activities of the compounds of the invention can be measured in mitogenesis assays, as described in the literature (Hübner, H. et al. J. Med. Chem. 2000, 43, 4563-4569 and Löber, S. Bioorg. Med. Chem. Lett. 2002, 12.17, 2377-2380). Depending on the pathophysiology of the underlying disease, a more agonist, more antagonistic or a partial agonist activity may be therapeutically desired.
A further subject matter of the invention is therefore a medicinal product containing one or more of the compounds of the general formulae (I), (Ia), (Ib), (Ic), (II) and (IV) or one of the specific compounds as defined above, where appropriate in the form of a pharmaceutically acceptable salt, preferably containing one or more of the compounds of the general formulae (I), (la), (Ib), (Ic) and (IV) or pharmaceutically acceptable salts where X = NH, S or O.
The invention also relates to the use of one or more of the compounds of the general formulae (I), (la), (Ib), (Ic), (II) and (IV) or of one of the specific compounds, where appropriate in the form of a pharmaceutically acceptable salt, for the treatment, including therapy and prophylaxis, of the indications mentioned herein and for the manufacture of a medicinal product for the indications mentioned herein.
The preferred compounds of the invention which are selective D3 ligands are selected for the manufacture of medicinal products, and highly selective D3 ligands are used.
The compounds of the invention have potential for the treatment or prophylaxis of a number of diseases, in particular those associated with a disturbance of dopamine metabolism or the dopaminergic signalling cascade.
Err1:Expecting ',' delimiter: line 1 column 313 (char 312)
Other examples of treatment or prophylaxis with the compounds of the invention are hyperprolactinemia; hyperprolactinoma; glaucoma; cognitive disorders; restless leg syndrome; hyperactivity syndrome (ADHD); Parkinson's-associated movement disorders, such as rigor, dystonia and dyskinesia; L-dopa-induced disorders, such as anxiety, sleep disturbances, psychosis, dyskinesia and dystonia; idiopathic dystonias, especially Segawa syndrome; neuroleptic-induced (tardive) dyskinesia, dystonia and akisia.
Err1:Expecting ',' delimiter: line 1 column 305 (char 304)
A preferred use is to manufacture a medicinal product for the treatment of dyskinesias and dystonias, which may occur spontaneously in Parkinson's disease but may also be drug-induced.
The medicines may also be used for medication-assisted breast-feeding after pregnancy.
Finally, the medicinal products of the invention may be designed as a combination drug for simultaneous or sequential administration, depending on the disease to be treated.
For example, a sales unit containing a medicinal product containing L-Dopa for the treatment of Parkinson's disease may also include a pharmaceutical composition containing one of the compounds of the invention with, for example, a highly selective, partial agonist profile, where L-Dopa and the compound of the invention may be in the same pharmaceutical formulation, e.g. a combination tablet, or may also be in different application units, e.g. as two separate tablet units.
In a combination preparation, sequential administration may be achieved, for example, by a dosage form, e.g. an oral tablet, having two different layers with differing release profiles for the different pharmaceutically active ingredients.
An embodiment of the invention therefore concerns a medicinal product containing L-Dopa or a neuroleptic and a compound according to the invention to be administered simultaneously or successively to the patient.
Generally, the medicinal products of the invention consist of a pharmaceutical composition containing at least one pharmaceutically acceptable carrier or excipient in addition to the D3 ligands of the invention as described above.
The professional is aware that the pharmaceutical formulation may vary depending on the intended route of application, for example intravenous, intramuscular, intracutaneous, subcutaneous, oral, buccal, sublingual, nasal, transdermal, inhaled, rectal or intraperitoneal.
Err1:Expecting ',' delimiter: line 1 column 447 (char 446)
In a preferred embodiment of the invention, the pharmaceutical formulations containing the compounds of the invention are administered orally and may be, for example, as capsules, tablets, powders, granules, droplets or in liquid form.
The formulation may be rapidly releasing if a rapid onset of action is desired, e. g. oral formulations are described in EP 0 548 356 or EP 1 126 821.
If, on the other hand, prolonged release is desired, a delayed release formulation is recommended.
Alternative pharmaceutical preparations may include, for example, solutions for infusion or injection, oils, suppositories, aerosols, sprays, patches, microcapsules or micro-particles.
Err1:Expecting ',' delimiter: line 1 column 774 (char 773)
In particular, a compound of generic formula (III) can be used to manufacture a drug for the treatment of dopamine-sensitive movement disorders, which may occur spontaneously in the course of Parkinson's disease but may also be drug-induced.
The preferred formulation for the preparation of the medicinal products of the invention is compounds of general formula (III) in which:
R is selected from hydrogen, C1-C6-alkyl, fluorine, chlorine and bromine,R1 is selected from hydrogen, C1-C6-alkoxy, C1-C6-alkyl, fluorine, chlorine, bromine and trifluoromethyl, andR2 and R3 are independently selected from hydrogen, C1-C6-alkyloxy, C1-C6-alkyl, fluorine, chlorine, bromine and trifluoromethyl.
In addition, the use of compounds of formula (III) is preferred, which are:
the substituent R1 is at position 5 or 6 of the heterocycle,the substituents R2 and R3 are at positions 2 or 3 or 2 or 4 of the phenyl ring, respectively, whereby, if one of the two substituents R2 and R3 is a hydrogen atom, the other substituent is at position 2 of the phenyl ring.
A compound of general formula (III) of preference for the manufacture of the medicinal products of the invention, particularly for the treatment of L-dopa-induced dyskinesias, is the following compound:
The following substances are to be classified as N-methyl-butadiene:
The compounds of formulae I to IV were prepared using the methods according to the literature (Glennon, R.A. et al. J. Med. Chem. 1988, 31, 1968-1971).
For this purpose, the acid derivatives of type (A), which were either commercially available or synthesised according to literature requirements, were activated in the form of their carbonic chlorides and converted with the free base of type (B) into the derivatives of formula (I) (including (la), (Ib) and (Ic)), (III) or (IV):
Other
wherein n, R, R1, R2 and R3 are as defined for (I), (III) and (IV) respectively.
Alternatively to the above method of activation of acid derivatives, other reactions can be used, such as the activation of acids by hydroxyabenzotriazole (Kienhöfer, A. Synlett 2001, 1811-1812).
For the production of arylpiperazinylamines of type (B), e.g. commercially available 2-methoxy- or 2,3-dichlorphenylpiperazine can be alkylated with bromobutylphthalamide in xylol, followed by hydrazineolysis of the phthalamide substituted structures to yield the primary amine of type (B), as illustrated by the following sample reaction scheme:
Other
The test mixture is heated at 125°C for 24 hours. After cooling the mixture to 0°C, the filtrate is filtered and the filtrate evaporates. The resulting N-4- (((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((
A solution of 80% hydrazine hydrate (0.45 ml, 2.5 eq) is added to a suspension of N-4-(4-(2,3-dichlorophenyl) piperazine-1-yl) butylphthalamide in 40 ml of ethanol in 5 ml of ethanol. The mixture is heated for 3 hours under return flow, then cooled to RT, the resulting solid is filtered and the ethanol solution is evaporated in a vacuum.
The base 4-(4-(2,3-dichlorophenyl)piperazine-1-yl) butylamine is obtained by flash chromatography with CH2Cl2-MeOH-Me2EtN:90-8-2 with a yield of 900 mg (= 60%).
The total number of samples of the active substance is calculated by dividing the total number of samples of the active substance by the total number of samples of the active substance.
The solution is dissolved in 4 ml of chloroform and stirred at 0°C to a solution of 0.4 mmol 4-methyl-2-methyl-1-butyl-1-butyl-2-methyl-1-butyl-2-methyl-1-butyl-2-butyl-2-butyl-2-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-butyl-but
The total number of samples of the active substance shall be calculated by dividing the total number of samples of the active substance by the total number of samples of the active substance.
The following substances are to be classified as "metals" in the following headings:
The Commission has also published a report on the implementation of the programme.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and feed additive.
The following shall be added to the list of active substances:
The Commission has also published a report on the implementation of the new rules on the protection of the environment.
The total number of samples of the active substance (s) in the feed additive shall be calculated from the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and the total number of samples of the active substance (s) in the feed additive and feed additive.
The following substances are to be classified as "metals" in the following headings:
The Commission has also adopted a proposal for a directive on the approximation of the laws of the Member States relating to the protection of employees against risks arising from the use of electronic communications networks.
The total number of test concentrations of the active substance in the feed additive shall be calculated from the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the total number of test concentrations of the active substance in the feed additive and the feed additive.
The following shall be added to the list of active substances:
The Commission has also published a report on the implementation of the new rules on the protection of the environment.
The total number of cells in the test tube is calculated by dividing the total number of cells in the test tube by the total number of cells in the test tube by the total number of cells in the test tube.
The following shall be added to the list of active substances:
The Commission has also adopted a proposal for a Regulation on the establishment of a European Works Council.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of the active substance in the feed additive and the total number of the active substance in the feed additive and the feed additive.
The following shall be added to the list of active substances:
The Commission has also adopted a proposal for a Regulation on the establishment of a European Works Council.
0,37 mmol (141 mg) HATU and 0,37 mmol (69 mg) 5-cyano-2-benzo[b]furanylcarboxylic acid (Dann, O. Liebigs Ann. Chem. 1986, 438-455) are dissolved in 1 ml DMF at 0°C and 0,74 mmol (0.13 ml) DIEA is added. Then 0,33 mmol (87 mg) 4-methyphenylpiperazine-1-yl) butylamine is dissolved in DMF and added to the reaction solution at 0°C. After 1 hour, the reaction solution is taken in CH3 and washed with NaHCO3 solution and water. After coating with MgSO4 the solvent is de-hydrated and purified by flash petrochrography (Otheryl-SiO3; 1-ethyl-Ethyl-Ethyl-Ethyl-Ethyl) after 41 mg (28%) cleaning.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and feed additive.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of the active substance in the feed additive and the total number of the active substance in the feed additive and the feed additive.
The total number of samples of the test chemical is calculated by dividing the total number of samples of the test chemical by the total number of samples of the test chemical, and the total number of samples of the test chemical by the total number of samples of the test chemical.
The total number of animals and products treated with the active substance is calculated by dividing the total number of animals and products treated with the active substance by the total number of animals and products treated with the active substance by the total number of animals and products treated with the active substance by the total number of animals and products treated with the active substance by the active substance.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the feed additive and shall be calculated from the total the total number of the total total total total of the active substance in the active substance in the feed additive and shall be calculated from the feed additive and shall be calculated from the total the total the total of the total of the feed additive and shall
The total number of samples of the active substance is calculated by dividing the total number of samples of the active substance by the total number of samples of the active substance.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and feed additive.
The following substances are to be classified as "metals" in the following headings:
The Commission has also adopted a proposal for a Regulation on the establishment of a European Agency for the Management of Operational Cooperation between the European Communities and their Member States.
0,24 mmol (58 mg) HATU, 0,24 mmol HOAt (33 mg) and 0,24 mmol (69 mg) of 5-bromo-2-indol carboxylic acid are dissolved in 5 ml DMF at 0°C and 0,48 mmol (0.094 ml) DIEA is added. Then 0,26 mmol (78 mg) 4-((4-(2,3-dichlorophenylenedipiperazine-1-butylamine) is dissolved in DMF and dripped to the reaction solution at 0°C. After 3 hours, the solution is taken up in CHCl3 and washed with NaHCO3 solution and water. After drying with Mg4 the solvent is evaporated and cleared by flash chromatography (SiO2:MM3:Cl, 98:2) CH: 94 mg.
The total number of samples of the active substance shall be calculated from the total number of samples of the active substance, which is the total number of samples of the active substance, which is the total number of samples of the active substance, which is the total number of samples of the active substance.
The total number of samples of the active substance is calculated by dividing the total number of samples of the active substance by the total number of samples of the active substance.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of samples of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total number of the active substance in the feed additive and shall be calculated from the total the total number of the feed additive and shall be calculated from the total the total the total of the feed additive and shall be calculated from the
The total number of samples of the active substance is calculated by dividing the total number of samples of the active substance by the total number of samples of the active substance.
0,012 mmol (94 mg) HATU and 0,012 mmol (25 mg) 5-Cyano-2-benzo[b]thiophenic acid (Bridges, A. J. Tetr. Lett. 1992, 7499-7502) are dissolved at 0°C in 1 ml DMF and 4 ml CH2Cl2 and 0,024 mmol (0.06 ml) DIEA is added. 0,013 mmol (34 mg) 4-methyphenylpiperazine-1-butylamine is then dissolved in CH2Cl2 and added to the reaction solution at 0°C. After 2 hours, the solution is absorbed in CHCl3 and washed with NaH3CO3L solution and water. After drying with SO4 the solution is purified by flashamp and methanol (SiO2O2), methanol chloride (methyl chloride: 98-22).
The following information is provided for the purpose of the calculation:
The total number of samples of the active substance in the feed additive shall be calculated on the basis of the following formulae:
The following are to be considered as 'reactive substances':
The Commission has also published a report on the implementation of the new rules on the protection of the environment.
The total number of patients treated with this product was approximately 10 in the control group, with a mean of 10 patients treated with this product in the control group, and a mean of 10 patients treated with this product in the control group, with a mean of 10 patients treated with this product in the control group.
The following is the list of active substances and mixtures:
The Commission has also been consulted on the draft directive on the protection of workers from risks related to exposure to ionising radiation.
Err1:Expecting ',' delimiter: line 1 column 386 (char 385)
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and feed additive.
The following substances are to be classified as "metals" in the following headings:
The Commission has also adopted a proposal for a Regulation on the application of the principle of equal treatment for men and women in matters of employment.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and feed additive.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and feed additive.
The following substances are to be classified as "metals" in the following headings:
The Commission has also adopted a proposal for a Directive on the approximation of the laws of the Member States relating to the labelling of foodstuffs.
The total number of samples of the active substance shall be calculated from the total number of samples of the active substance, which is the total number of samples of the active substance, which is the total number of samples of the active substance, which is the total number of samples of the active substance, which is the total number of samples of the active substance.
The total number of samples of the active substance in the feed additive shall be calculated from the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and the total number of samples of the active substance in the feed additive and feed additive.
The following substances are to be classified as "metals" in the following headings:
The Commission has also adopted a proposal for a Regulation on the application of the principle of equal treatment for men and women in matters of employment.
The biological activities of the compounds of the invention were determined in radio-ligand binding studies. All the radio-ligand experiments were performed according to the methods described by us (Hübner, H. et al. J. Med. Chem. 2000, 43, 756-762). For the measurement of affinities for the D2 family receptors, membrane homogenous Chinese hamster ovarian cells (CHO cells) were used, which were obtained from human D2long- and human D2short- (Hayes, G. et al. Mol. Endocrinol. 1992, 6, 920-926), human D3- (Sokoloff, P. et al. Euribran J. Pharmacol. 1992, 225, 3337) or human D1-CH34 receptors (Sub-type D1-CH1H1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1N1H1H1N1H1N1H1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1HN1
In order to determine the binding strengths of the compounds to the serotonin receptor subtypes 5-HT1A and 5-HT2, cortical membrane preparations of pigs with the radio-ligands [3H]8-OH-DPAT (for 5-HT1A) or [3H]ketanserin (5-HT2) and the compounds were incubated. Evidence of simultaneous binding of the compounds to the serotonergic 5-HT2 receptor and to the adrenergic receptor subtype α1 when labelled with the radio-ligand [3H]ketanserin was confirmed in a parallel experiment with selective blocking of the α1 receptor by prazosin. Some represent Ki values obtained in the presence of 10 μM of prazosin alone that bind to the 5-HT2 receptor. The affinity of the radio-ligand was determined in a separate experiment with the prazosin receptor [3P1].
The results of the receptor binding studies on the dopamine receptor subtypes are summarised in Table 1.
All compounds tested in the binding assay showed good to very good affinities for dopamine receptors with a clear binding preference for the subtypes of the D2 family. Regardless of the partial structure, there is always a clear selectivity for the D3 receptor.
The substitution pattern of the arylpiperazinyl component primarily affects the expression of D3 affinity selectivity with respect to the other receptor subtypes. The 2,3-dichlorophenyl-substituted compounds (examples 2, 6 and 10) show a previously undescribed D3 selectivity with selection coefficients over 1000 with simultaneous subnanomolar affinity. Interestingly, the ferrocenylderivatives of examples 16 and 17 are characterized by high D4 affinity, with example 17 having a very exceptional receptor binding profile with Ki-Words of 0.47 nM for the D3 receptor and 0.63 nM for the D4 receptor.
Studies to determine the intrinsic activity of the sample compounds were performed in a mitogenesis assay based on the literature (Hübner, H. et al. J. Med. Chem. 2000, 43, 4563-4569; Löber, S. Bioorg. Med. Chem. Lett. 2002, 12.17, 2377-2380) and showed partial agonist activity of 49% of the maximum receptor stimulation that can be triggered by the full agonist quinpirol as reference compound, for example, for the D3 receptor. Bindungsdaten und Selektivitätsmuster der Verbindungen von Formel (I) bis (IV) für die Dopamin-Rezeptoren pD1, hD2long, hD2short, hD3 und hD4.4
Bindungsdaten und Selektivitätsmuster der Verbindungen von Formel (I) bis (IV) für die Dopamin-Rezeptoren pD1, hD2long, hD2short, hD3 und hD4.4
| Verbindung | D3-Selektivität | |||||||
| D1 | D2long | D2short | D3 | D4.4 | D2long/D3 | D2short/D3 | D4.4/D3 | |
| 670 | 87 | 52 | 0,23 | 15 | 380 | 230 | 65 | |
| 8800 | 3300 | 2600 | 0,5 | 340 | 6600 | 5200 | 680 | |
| 1100 | 110 | 84 | 1,1 | 30 | 100 | 76 | 27 | |
| 2900 | 320 | 80 | 1,2 | 93 | 270 | 67 | 78 | |
| 590 | 96 | 61 | 0,69 | 17 | 140 | 88 | 25 | |
| 21000 | 10000 | 4800 | 3,4 | 3100 | 2900 | 1400 | 910 | |
| 1400 | 130 | 89 | 4,2 | 57 | 31 | 21 | 14 | |
| 380 | 63 | 39 | 0,72 | 35 | 88 | 54 | 49 | |
| 1400 | 91 | 48 | 0,55 | 150 | 170 | 87 | 270 | |
| 11000 | 3100 | 1600 | 0,56 | 1700 | 5500 | 2900 | 3000 | |
| 920 | 140 | 99 | 0,57 | 24 | 250 | 180 | 44 | |
| 390 | 110 | 44 | 0,24 | 16 | 460 | 180 | 67 | |
| 460 | 160 | 100 | 0,25 | 40 | 640 | 400 | 160 | |
| 4200 | 2300 | 770 | 0,73 | 600 | 3200 | 1100 | 820 | |
| 17000 | 340 | 110 | 0,35 | 630 | 970 | 310 | 1800 | |
| 1500 | 110 | 78 | 6,5 | 0,40 | 17 | 12 | 0,061 | |
| 630 | 31 | 19 | 0,47 | 0,63 | 66 | 40 | 1,3 | |
| 430 | 68 | 39 | 0,46 | 45 | 150 | 85 | 98 | |
| 1700 | 410 | 310 | 0,25 | 650 | 1600 | 1200 | 2600 | |
| 1100 | 210 | 130 | 0,33 | 37 | 640 | 390 | 110 | |
| 1700 | 180 | 60 | 0,26 | 72 | 690 | 230 | 280 | |
| 550 | 49 | 30 | 0,26 | 58 | 190 | 120 | .220 | |
| 4700 | 1700 | 970 | 3,2 | 1700 | 1500 | 300 | 530 | |
| 1200 | 200 | 160 | 0,70 | 40 | 290 | 230 | 57 | |
| 1700 | 140 | 27 | 0,91 | 210 | 150 | 30 | 230 | |
The study of affinities for the serotonin receptor subtypes 5-HT1A and 5-HT2 and for the adrenergic receptor α1 is described in Table 2 and, regardless of the partial structures of the derivatives, a preferential binding to the 5-HT1A subtype compared to 5-HT2 is detected. The compounds in examples 1, 3, 7, 8 and 16 are characterised by high affinity for the α1 receptor with Ki values measured from 8 to 19 nM.
Structural effects considerations show a significant dependence on the substitution pattern of the arylpiperazinyl partial structure for binding to these receptors. As with dopamine receptors, the 2,3-dichlorophenylresidue derivatives have a significantly reduced binding to the 5-HT and α1 receptors, resulting in an expansion of the selectivity spectrum to the D3 receptor affinity of these compounds. Bindungsdaten der Substanzen von Formel (I) bis (IV) für die Serotonin-Rezeptoren p5-HT1A, p5-HT2 sowie für den adrenergen Rezeptorsubtyp pα1
Bindungsdaten der Substanzen von Formel (I) bis (IV) für die Serotonin-Rezeptoren p5-HT1A, p5-HT2 sowie für den adrenergen Rezeptorsubtyp pα1
| Verbindungen | 5-HT1A | |||
| 41 | 350 | 15 | 6,4 | |
| 360 | 2000 | --- | 370 | |
| 17 | 660 | 14 | 3,3 | |
| 480 | 11000 | --- | 160 | |
| 68 | 140 | --- | 5,3 | |
| 2500 | 540 | --- | 1300 | |
| 37 | 390 | 8,2 | 11 | |
| 69 | 420 | 15 | 3,5 | |
| 130 | 730 | --- | 100 | |
| 610 | 1700 | --- | 220 | |
| 83 | 440 | 24 | 5,9 | |
| 440 | 280 | --- | 6,4 | |
| 47 | 220 | --- | 4,3 | |
| 1600 | 690 | --- | 500 | |
| 390 | 320 | --- | 2000 | |
| 0,60 | 500 | 19 | 30 | |
| 27 | 250 | --- | 73 | |
| 54 | 580 | --- | 2,9 | |
| 190 | 280 | --- | 230 | |
| 71 | 660 | --- | 8,3 | |
| 110 | 290 | --- | 45 | |
| 180 | 760 | --- | 2,5 | |
| 430 | 14000 | --- | 320 | |
| 32 | 420 | 11 | 7,3 | |
| 190 | 220 | --- | 220 | |
Claims (27)
- Compound of general formula (I) Other including: Other- n = 1 - 4 and- R = hydrogen, alkyl or halogen and OtherOther where appropriate, replaced; and pharmaceutically acceptable salts of this compound.(a) X = S or O: Other(i) where R1 is hydroxy, alkyloxy, alkenyl, alkynyl, aryl, acyl, alkoxycarbonyl or cyano, R2 and R3 are independently selected from hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano;(ii) if R1 is hydrogen, alkyl, halogen or trifluoromethyl, R2 is selected from hydroxy, alkenyl, alkynyl, aryl, acyl, alkoxycarbonyl and cyano and R3 is selected from hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano;Other or(b) X = NH: OtherR1 is selected from hydrogen, hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, trifluoromethyl, acyl, alkoxycarbonyl, halogen and cyano and R2 and R3 are independently selected from hydrogen, hydroxy, alkyloxy, alkyloyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano, provided that the compound is not N-4-4- (((2-methyl) pyetoxyzin-1-yl-2-indolylperabutyl carbamide,Other or(c) X = Te: OtherOther wherein the alkyl, alkenyl, alkynyl and aryl groups are independently of each otherR1 is selected from hydrogen, hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano and R2 and R3 are independently selected from hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl and cyano,
- Compound as claimed 1, which includes: Other- n = 1 - 4 and- X = Te, where R = hydrogen, alkyl or halogen and R1 is replaced by the residues hydrogen, hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano and R2 and R3 are replaced individually or together by the residues hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano, or- X = S or O, where R = hydrogen, alkyl or halogen and R1 is replaced by the residues hydroxy, alkylloxy, alkenyl, alkynyl, aryl, acyl, alkoxycarbonyl or cyano and R2 and R3 are replaced individually or together by the residues hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano, or- X = S or O, where R = hydrogen, alkyl or halogen and R1 is replaced by the hydrogen, alkyl, halogen or trifluoromethyl residues and R2 and R3 are replaced individually or together by the hydroxy, alkenyl, alkynyl, aryl, acyl, alkoxycarbonyl or cyano residues, or- X = NH, where R = hydrogen, alkyl or halogen and R1 is replaced by the residues hydroxy, alkyl, alkyloxy, alkenyl, alkynyl, aryl, trifluoromethyl, acyl, alkoxycarbonyl or cyano, whereby the alkyl and alkyloxy must contain at least two carbon atoms and R2 and R3 individually or together are replaced by the residues hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano and the alkyloxy must contain at least two carbon atoms.
- Combination according to claim 1 with the general formula (la) or (1b) Other including: Other- n = 1 to 4- R = hydrogen, C1-C6 alkyl or halogen,- where R1 is hydroxy, C1-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, C1-C6-acyl, C1-C6-alkoxycarbonyl or cyano, where appropriate with a methoxy group or halogen substituted, R2 and R3 are independently selected from hydrogen, hydroxy, C1-C6-alkyloxy, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, where appropriate with a methoxy group or halogen substituted, alkyl, halogen, tetroform phenyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano,- if R1 is hydrogen, C1-C6-alkyl, halogen or trifluoromethyl, R2 is selected from hydroxy, C2-C6-alkenyl, C2-C6-alkynyl, where appropriate with a methoxy group or halogen substituted phenyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano, and R3 is selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, where appropriate with a methoxy group or halogen substituted phenyl, halogen, trifluorethyl, C1-C6-acyl, C1-C1-C6-alkoxycarbonyl and cyano, in which the groups C1-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl are replaced independently, where appropriate,Other and pharmaceutically acceptable salts thereof.
- Compound according to claim 1 with general formula (Ic) including: Other- n = 1 to 4- R = hydrogen, C1-C6 alkyl or halogen,- R1 is selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, trifluoromethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl, fluorine, chlorine, bromine and cyano, where appropriate, substituted with a methoxy group or halogen,- R2 and R3 are independently selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, halogen, trifluoromethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano, where appropriate, with a methoxy group or halogen substituted, in which the groups C1-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl are replaced independently, where appropriate,Other and pharmaceutically acceptable salts of this compound, provided that the compound is not N-4- ((4-)) 2-Methoxyphenyl) piperazine-1-yl) butyl-2-indolylcarbamide.
- Compound as claimed by claim 4, where applicable Other(a) where R1 is hydroxy, C2-C6-alkenyl, C2-C6-alkynyl, phenyl, trifluoromethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl or cyano substituted with a methoxy group or halogen, as appropriate, R2 and R3 shall be independently selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, methoxy group or halogen substituted with an alkenyl, halogen, thorium phenyl, C1-C6-alkenyl, C1-C6-alkoxycarbonyl and cyano, as appropriate; and(b) where R1 is hydrogen, C1-C6-alkyl, C1-C6-alkyloxy or halogen, R2 is selected from hydroxy, C2-C6-alkenyl, C2-C6-alkynyl, where appropriate with a methoxy group or halogen substituted phenyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano, and R3 is selected from hydrogen, hydroxy, C1-C6-alkyl, C1-C6-alkyloxy, C2-C6-alkyloxy, C2-C6-alkenyl, C2-C6-alkynyl, where appropriate with a mxy group or halogen substituted phenyl, halogen, tetrahydrocaryphyl, C1-C6-acyl, C1-coxycarbonyl and cyano; in which the groups C1-C6-alkyl, C2-C6-alkenyl and C2-C6-alkynyl are replaced independently, where appropriate,Other and pharmaceutically acceptable salts of this compound.
- a connection according to one of the preceding claims, with: Other- the substituent R1 is at position 5 or 6 of the heterocycle, and- the substituents R2 and R3 are in positions 2 and 3 respectively or in positions 2 and 4 respectively of the phenyl ring, whereas, if one of the two substituents R2 and R3 is a hydrogen atom, the other substituent is in position 2 of the phenyl ring.
- connection according to one of the previous claims, where n = 3.
- Compound with general formula (IV) Other including: Other- X = S, NH or O,- R is selected from hydrogen, C1-C6 alkyl, fluorine, chlorine and bromine,- R1 is selected from hydrogen, C1-C6-alkoxy, C1-C6-alkyl, fluorine, chlorine, bromine, trifluoromethyl and cyano, with R1 in the 5 or 6 position of the heterocycle,- R2 and R3 are independently selected from hydrogen, C1-C6-alkyloxy, C1-C6-alkyl, fluorine, chlorine, bromine and trifluoromethyl, where R2 and R3 are at positions 2 and 3 respectively or at positions 2 and 4 respectively of the phenyl ring, and where, in the case where one of the two substituents R2 and R3 is a hydrogen atom, the other substituent is at position 2 of the phenyl ring, in which the C1-C6-alkyl groups are independently substituted, if necessary,Other and pharmaceutically acceptable salts of this compound, provided that the compound is not N-4- ((4- ((2-Methoxyphenyl) piperazine-1-yl) butyl-2-indolylcarbamide.
- The compound as claimed in claim 8, which is: Other- if X = NH, then R1 is selected from hydrogen, C1-C3 alkyloxy, C1-C3 alkyl, fluorine, chlorine, bromine and cyano, and- if X = S or O, then R1 is selected from hydrogen, C1-C3 alkyl, fluorine, chlorine, bromine, cyano and trifluoromethyl.
- Compound according to one of the above claims, selected from: OtherN-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-5-cyan-2-benzo[b]thiophenylcarbamide, containing by weight:N-4-(4-(2,3-dichlorophenyl)piperazine-1-yl)butyl-5-cyan-2-benzo[b]thiophenyl carbamide, whether or not chemically defined,N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-6-cyan-2-benzo[b]thiophenylcarbamide, containing by weight:N-4-(4-(2,3-dichlorophenyl)piperazine-1-yl)butyl-6-cyan-2-benzo[b]thiophenyl carbamide, whether or not chemically defined,N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-2-benzo[b]thiophenylcarbamide, whether or not chemically defined,N-4-(4-(2,3-dichlorophenyl)piperazine-1-yl)butyl-2-benzo[b]thiophenylcarbamide, whether or not chemically defined,N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-5-brom-2-benzo[b]thiophenylcarbamide, whether or not chemically defined,N-4-(4-(2,3-Dichlorhenyl)piperazine-1-yl)butyl-5-bromo-2-benzo[b]thiophenylcarbamide, whether or not chemically defined,N-4- ((4- ((2,3-Dichlorophenyl) piperazine-1-yl) butyl-2-indolyl carbamide, containing by weight:N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-5-cyan-2-indolylcarbamide, with a purity by weight of not more than 0,5%N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-5-bromo-2-indoylcarbamide, whether or not chemically defined,N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-6-cyan-2-indolylcarbamide, with a purity by weight of not more than 0,5%N-4-(4-(2,3-dichlorophenyl)piperazine-1-yl)butyl-5-bromo-2-indoleylcarbamide, whether or not containing by weight more than 0,5% of nitrogen,N-4- ((4- ((2,3-Dichlorophenyl)piperazine-1-yl) butyl-6-cyan-2-indolecarbamide, whether or not chemically defined,N-4- ((4- ((2,3-Dichlorophenyl)piperazine-1-yl) butyl-5-cyan-2-indolecarbamide, whether or not chemically defined,N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-5-cyan-2-benzo[b]furanylcarbamide, with a purity by weight of not more than 0,5%N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-2-benzo[b]furanylcarbamide, whether or not chemically defined,N-4- ((4-(2,3-dichlorophenyl)piperazine-1-yl) butyl-2-benzo[b]furanylcarbamide, whether or not chemically defined,N-4- ((4- ((2-Methoxyphenyl)piperazine-1-yl) butyl-5-bromo-benzo[b]furanylcarbamide, with a purity by weight of not more than 0,5%N-4-(4-(2,3-dichlorophenyl)piperazine-1-yl)butyl-5-bromo-2-benzo[b]furanylcarbamide, whether or not containing by weight:N-4- ((4- ((2-Methoxyphenyl) piperazine-1-yl) butyl-2-benzo[b]tellurophenyl carbamide andN-4- ((4- ((2,3-Dichlorophenyl) piperazine-1-yl) butyl-2-benzo[b]tellurophenyl carbamideOther and their pharmaceutically acceptable salts.
- Compound of general formula (II) Other wherein n = 1 - 4 and R1 and R2 stand individually or together for the residues hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano.
- Compound as claimed 11, wherein R1 and R2 are independently selected from hydrogen, hydroxy, C1-C6-alkyloxy, C1-C6-alkyl, C2-C6-alkenyl, C2-6-alkynyl, aryl, fluorine, chlorine, bromine, trifluoromethyl, C1-C6-acyl, C1-C6-alkoxycarbonyl and cyano, wherein the groups C1-C6-alkyl, C2-C6-alkyl, C2-C6-alkynyl and aryl are independently additionally substituted, if necessary.
- Compound according to claim 12, selected from: OtherN-4- ((4- ((2-Methoxyphenyl) piperazine-1-yl) butyl-2-ferrocenyl carbamide andThe term 'biocidal compounds' includes compounds which are chemically defined as:
- A medicinal product containing one or more of the compounds referred to in one of the foregoing claims.
- Medicinal products as claimed 14, containing additional L-Dopa for concomitant or sequential administration to patients.
- Use of a compound according to any of claims 1 to 13 to manufacture a medicinal product for the treatment or prophylaxis of cocaine, alcohol, opiate and nicotine addiction; neurodegenerative disorders, in particular Parkinson's disease; sexual dysfunction; depression or schizophrenia.
- Use of a compound according to any of claims 1 to 13 to manufacture a medicinal product for the treatment or prophylaxis of hyperprolactinaemia, hyperprolactinoma, glaucoma, cognitive impairment, restless leg syndrome, hyperactivity syndrome (ADHD), Parkinson' s-associated movement disorders, L-dopa-induced disorders, Segawa syndrome, tardive movement disorders and medication-assisted lactation after pregnancy.
- Use according to claim 17, where the product is intended for the treatment or prophylaxis of Segawa syndrome, spontaneous Parkinson' s-associated dyskinesia or dystonia, or tardive or L-dopa-induced dyskinesia or dystonia.
- Use of a compound of general formula (III) Other including: n = 1 - 4 and X = S, O or NH, where R = hydrogen, alkyl or halogen and R1 is replaced by the residues hydrogen, alkyl, halogen, trifluoromethyl and R2 and R3 are replaced individually or together by the residues hydrogen, hydroxy, alkyloxy, alkyl, alkenyl, alkynyl, aryl, halogen, trifluoromethyl, acyl, alkoxycarbonyl or cyano, to develop a medicinal product for the treatment or prophylaxis of cocaine, alcohol, opiate and nicotine addiction; neurodegenerative disorders, in particular Parkinson's disease; or sexual dysfunction.
- Use of a compound as claimed 19 to manufacture a medicinal product for the treatment or prophylaxis of depression or schizophrenia.
- Use of a compound as claimed in claim 19 to manufacture a medicinal product for the treatment or prophylaxis of hyperprolactinaemia, hyperprolactinoma, glaucoma, cognitive impairment, restless leg syndrome, hyperactivity syndrome (ADHD), Parkinson's-associated movement disorders, L-dopa-induced disorders, Segawa syndrome, tardive dyskinesia or medication-assisted lactation after pregnancy.
- Use according to claim 21, where the product is intended for the treatment or prophylaxis of Segawa syndrome, spontaneous Parkinson' s-associated dyskinesia or dystonia, or tardive or L-dopa-induced dyskinesia or dystonia.
- Use according to any of claims 19 to 22 where: Other- R is selected from hydrogen, C1-C6 alkyl, fluorine, chlorine and bromine,- R1 is selected from hydrogen, C1-C6-alkoxy, C1-C6-alkyl, fluorine, chlorine, bromine and trifluoromethyl, and- R2 and R3 are independently selected from hydrogen, C1-C6-alkyloxy, C1-C6-alkyl, fluorine, chlorine, bromine and trifluoromethyl,Other where the C1 to C6 alkyl groups are independently substituted, if necessary, in addition.
- Use according to any of claims 19 to 23, with the following: Other- the substituent R1 is in the 5 or 6 position of the heterocycle,- the substituents R2 and R3 are in positions 2 and 3 respectively or in positions 2 and 4 respectively of the phenyl ring, whereas, if one of the two substituents R2 and R3 is a hydrogen atom, the other substituent is in position 2 of the phenyl ring.
- Use according to one of claims 19 to 24, where the compound is N-4- ((4- ((2-Methoxyphenyl) piperazine-1-yl) butyl-2-indolylcarbamide.
- Processes to produce a compound of general formula (I), (III) or (IV) as defined above, involving the conversion of a compound of general formula (A) into an activated form, in particular in the form of carbonic acid halides: Other with a compound of the general formula (B): wherein n, R, R1, R2 and R3 are as defined for the general formulae (I), (III) and (IV).
- Method for the preparation of a compound of general formula (II) as defined above, consisting of the conversion of ferroacetic acid in its activated form to a compound of general formula (B'): Other wherein n, R1 and R2 are as defined in formula (II).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10230062 | 2002-07-04 | ||
| DE10232020 | 2002-07-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| HK1100899A true HK1100899A (en) | 2007-10-05 |
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