DE1249855B - Process for the manufacture of Inammen - Google Patents
Process for the manufacture of InammenInfo
- Publication number
- DE1249855B DE1249855B DENDAT1249855D DE1249855DA DE1249855B DE 1249855 B DE1249855 B DE 1249855B DE NDAT1249855 D DENDAT1249855 D DE NDAT1249855D DE 1249855D A DE1249855D A DE 1249855DA DE 1249855 B DE1249855 B DE 1249855B
- Authority
- DE
- Germany
- Prior art keywords
- general formula
- bromine
- moisture
- oxygen
- inammen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- -1 cycloaliphatic Chemical group 0.000 claims description 2
- 150000002081 enamines Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ALRXDIKPRCRYAU-UHFFFAOYSA-N 2-methylpropan-2-ol Chemical compound CC(C)(C)O.CC(C)(C)O ALRXDIKPRCRYAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
SCHESSCHES
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. CL: C 07 c /'Int. CL: C 07 c / '
UAX4AXLUAX4AXL
Deutsche Kl.: 12 ο -19/03 German class: 12 ο - 19/03
Nummer: 1 249 855Number: 1 249 855
Aktenzeichen: E 26811IV b/12 οFile number: E 26811IV b / 12 ο
Anmeldetag: 10. April 1964 Filing date: April 10, 1964
Auslegetag: 14. September 1967Opened on September 14, 1967
Die Erfindung hat ein Verfahren zur Herstellung von Inaminen der allgemeinen FormelThe invention has a process for the preparation of ynamines of the general formula
R1C = CNR 1 C = CN
wobei R1 ein Wasserstoffatom, einen aliphatischen, cycloaliphatischen, aromatischen oder den Restwhere R 1 is a hydrogen atom, an aliphatic, cycloaliphatic, aromatic or the remainder
. JXo. JXo
— n:- n:
bedeutet, R2 und R3 sind gleich oder verschieden und bedeuten niedere aliphatische Reste, die auch zu einem Ring geschlossen sein können, der gegebenenfalls ein weiteres Heteroatom enthält zum Gegenstand, das dadurch gekennzeichnet ist, daß man an ein Enamin der allgemeinen Formelmeans R 2 and R 3 are identical or different and mean lower aliphatic radicals, which can also be closed to form a ring which optionally contains a further heteroatom, which is characterized in that an enamine of the general formula is attached
R1CH = CH — N:R 1 CH = CH - N:
bei tiefer Temperatur unter Ausschluß von Feuchtigkeit und Sauerstoff Brom anlagert und anschließend Bromwasserstoff abspaltet. Die Bromanlagerung erfolgt bei tiefen Temperaturen, z. B. bei -8O0C. Um Zersetzungen und die Entstehung unerwünschter Nebenprodukte zu vermeiden, soll man unter Fernhalten von Feuchtigkeit und oxydierenden Stoffen, wie elementarem Sauerstoff oder Luft, arbeiten. Man kann z. B. während der Umsetzung trockenen Stickstoff oder ein anderes Inertgas überleiten. Die Reaktion wird am besten in Gegenwart eines inerten Lösungsmittels durchgeführt.at a low temperature with the exclusion of moisture and oxygen, bromine is deposited and then hydrogen bromide is split off. The bromine deposition takes place at low temperatures, e.g. B. at -8O 0 C. To avoid decomposition and the formation of unwanted by-products, one should work while keeping away from moisture and oxidizing substances such as elemental oxygen or air. You can z. B. pass over dry nitrogen or another inert gas during the reaction. The reaction is best carried out in the presence of an inert solvent.
In der zweiten Stufe des erfindungsgemäßen Verfahrens spaltet man dann in üblicher Weise aus dem Zwischenprodukt Bromwasserstoff ab, wobei die entsprechenden Inamine entstehen. Auch bei dieser Verfahrensstufe soll man Feuchtigkeit und Sauerstoff fernhalten.In the second stage of the process according to the invention, the cleavage is then carried out in the customary manner Intermediate hydrogen bromide from, whereby the corresponding ynamines are formed. Even at this stage of the process one should keep away moisture and oxygen.
Inamine bilden mit Säuren, z. B. mit Salzsäure, Salze, die offensichtlich reaktionsfähige Zwischenprodukte sind und zu einer Reihe wertvoller neuer Verbindungen führen können. Gegenüber vielen ihrer Salze haben die meisten Inamine den Vorteil, daß sie stabiler sind und daher besser gelagert werden können. Verfahren zur Herstellung von InaminenYarnamines form with acids, e.g. B. with hydrochloric acid, salts that are obviously reactive intermediates and can lead to a number of valuable new connections. To many of theirs Most inamines have the advantage of being more stable and therefore easier to store. Process for the preparation of inamines
Anmelder:Applicant:
Union Carbide Corporation,Union Carbide Corporation,
New York, N.Y. (V. St. A.)New York, N.Y. (V. St. A.)
Vertreter:Representative:
Dr. W. Schalk, Dipl.-Ing. P. Wirth,Dr. W. Schalk, Dipl.-Ing. P. Wirth,
Dipl.-Ing. G. E. M. DannenbergDipl.-Ing. G. E. M. Dannenberg
und Dr. V. Schmied-Kowarzik, Patentanwälte,and Dr. V. Schmied-Kowarzik, patent attorneys,
Frankfurt/M., Große Eschenheimer Str. 39Frankfurt / M., Große Eschenheimer Str. 39
Als Erfinder benannt:Named as inventor:
Dr. Heinz G. Viehe, Beersei, Linkebeck (Belgien)Dr. Heinz G. Viehe, Beersei, Linkebeck (Belgium)
Zu 3,5 g (0,02 Mol) Diäthylaminostyrol
(C2H5)2N - CH = CH — C6H5 To 3.5 g (0.02 mol) of diethylaminostyrene
(C 2 H 5 ) 2 N - CH = CH - C 6 H 5
in 70 ml Tetrahydrofuran gibt man bei —8O0C unter einer Stickstoffatmosphäre bei gutem Rühren 1,025 g (0,02 Mol) Brom. Dem Gemisch, aus welchem sich das Salz abscheidet, gibt man nach 5 Minuten 5,92 g (0,04 Mol) t-Butanolat-t-butanol-Komplex als Base zu. Nach dem Erwärmen auf Zimmertemperatur rührt man einige Stunden und destilliert das Umsetzungsgemisch im Vakuum. Hierbei gehen zuerst die flüchtigen Bestandteile (Tetrahydrofuran und t-Butanol) über.in 70 ml of tetrahydrofuran are added at -8O 0 C under a nitrogen atmosphere with good stirring, 1.025 g (0.02 mol) of bromine. After 5 minutes, 5.92 g (0.04 mol) of t-butanolate-t-butanol complex are added as base to the mixture from which the salt is deposited. After warming to room temperature, the mixture is stirred for a few hours and the reaction mixture is distilled in vacuo. The volatile constituents (tetrahydrofuran and t-butanol) are transferred first.
Bei einem Druck von 0,01 Torr wird dann weiter destilliert, wobei ein Produkt erhalten wird, das noch t-Butanol enthält. Durch Trocknen im Vakuum bei Zimmertemperatur während einer Stunde wird auch dieses entfernt.Distillation is then continued at a pressure of 0.01 torr, a product being obtained which is still Contains t-butanol. Drying in vacuo at room temperature for one hour will also this removed.
Nach zweimaliger Destillation des Rückstandes bei einer Badtemperatur von 100 bis 130° C und einem Druck von 0,01 mm Hg erhält man 1,9 g (55% der Theorie) des InaminsAfter two distillation of the residue at a bath temperature of 100 to 130 ° C and one A pressure of 0.01 mm Hg gives 1.9 g (55% of theory) of the ynamine
(C2He)8N-C= C-C6H5 (C 2 He) 8 NC = CC 6 H 5
Die Verbindung ist charakterisiert durch ihr IR-Spektrum mit einem C = C-Stretching bei 4,5 bis 4,6 μ. Das Feldionisations-Massenspektrum zeigt neben dem Inamin des Molgewichts 173 noch Ausgangsenamin des Molgewichts 175 und ein Monobromenamin der Isotopenmolgewichte 253 und 255The compound is characterized by its IR spectrum with a C = C stretching at 4.5 to 4.6 µ. The field ionization mass spectrum shows not only the ynamine of molecular weight 173 but also starting amine of molecular weight 175 and a monobromenamine of isotope molecular weights 253 and 255
709 647/573709 647/573
Claims (1)
K a r r e r, »Lehrbuch der organischen Chemie«Considered publications:
K arrer, "Textbook of Organic Chemistry"
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEE0026811 | 1964-04-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1249855B true DE1249855B (en) | 1967-09-14 |
Family
ID=7072369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1249855D Pending DE1249855B (en) | 1964-04-10 | Process for the manufacture of Inammen |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH430689A (en) |
| DE (1) | DE1249855B (en) |
| GB (1) | GB1092204A (en) |
| NL (1) | NL6504567A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283367A (en) * | 1989-08-30 | 1994-02-01 | Ciba-Geigy Corporation | Substituted 1,4-diamino-2-butene stabilizers |
-
0
- DE DENDAT1249855D patent/DE1249855B/en active Pending
-
1965
- 1965-04-06 CH CH474565A patent/CH430689A/en unknown
- 1965-04-09 GB GB1506865A patent/GB1092204A/en not_active Expired
- 1965-04-09 NL NL6504567A patent/NL6504567A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH430689A (en) | 1967-02-28 |
| GB1092204A (en) | 1967-11-22 |
| NL6504567A (en) | 1965-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1249855B (en) | Process for the manufacture of Inammen | |
| DE1620429A1 (en) | Process for the production of piperidine-N-oxides | |
| DE940981C (en) | Process for the production of vinyl compounds | |
| CH615438A5 (en) | ||
| DE1218453B (en) | Process for the preparation of 5,5'-dialkyl-10,10'-spiro-bis-phenaza compounds | |
| DE2132079A1 (en) | 1,3-diaza-cycloalkenes prepn - by reacting aldehydes with diamines and sulphur | |
| DE2040502C3 (en) | Process for the preparation of cyclic formamidines | |
| DE1174786B (en) | Process for the preparation of azacycloalkene- (2, 3) -2-chloro-1-carboxylic acid chlorides | |
| DE1242214B (en) | Process for the preparation of inamines | |
| DE926549C (en) | Process for the production of chlorine-containing urethanes | |
| DE1914496C3 (en) | Process for the preparation of 1,2,5 thiadiazole derivatives | |
| DE1231714B (en) | Process for the production of bis-2- (1, 3, 2-dioxaborolane), bis-2- (1, 3, 2-dioxaborinane) or bis-2- (1, 3, 2-dioxabenzoborol) | |
| DE1131672B (en) | Process for the preparation of aryl borazoles | |
| DE1163815B (en) | Process for the production of borazoles which are organically substituted on nitrogen | |
| DE1925995A1 (en) | 2-alkyloxymethyl-3-chloro-1,2,4-thiaimidazol-5-ones | |
| DE556733C (en) | Process for the preparation of arsinic acids of the pyridine series substituted on nitrogen | |
| DE1189080B (en) | Process for the preparation of pyrrole derivatives | |
| DE1793319C3 (en) | Process for the preparation of allyl ruthenium tricarbonyl halides | |
| DE1081471B (en) | Process for the preparation of N- [4, 5, 6, 7, 10, 10-hexachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydro-phthalanyl- (1)] - ª ‡ -aminocarboxylic acid esters | |
| DE944729C (en) | Process for the preparation of bacteriostatically active compounds | |
| DE1127899B (en) | Process for the preparation of aliphatic boron heterocycles | |
| DE1192642B (en) | Process for the production of isonitriles | |
| DE1618146A1 (en) | Process for the production of Dithionaxalsäurediamiden | |
| DE1593783A1 (en) | Process for the preparation of 1- (2-nitrilophenoxy) -2-hydroxy-3-isopropylaminopropane and its salts | |
| DE1110636B (en) | Process for the production of cyclopropane hydrocarbons |