DE1118784B - Process for the preparation of heterocyclic cyanomethylene compounds - Google Patents
Process for the preparation of heterocyclic cyanomethylene compoundsInfo
- Publication number
- DE1118784B DE1118784B DEF28510A DEF0028510A DE1118784B DE 1118784 B DE1118784 B DE 1118784B DE F28510 A DEF28510 A DE F28510A DE F0028510 A DEF0028510 A DE F0028510A DE 1118784 B DE1118784 B DE 1118784B
- Authority
- DE
- Germany
- Prior art keywords
- benzene
- trimethyl
- heterocyclic
- methylene
- cyanomethylene
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with an alkyl or cycloalkyl radical attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/57—Nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Description
Verfahren zur Herstellung von heterocyclischen Cyanmethylenverbindungen Gegenstand des Patents 1 088 961 ist ein Verfahren zur Herstellung von Cyanmethylenindolinderivaten der allgemeinen Formel in der R ein Wasserstoffatom, einen Alkyl- oder Alkoxyrest und R1, R2 und R3 Alkylgruppen darstellen, das darin besteht, daß man 2-Methylenindoline der allgemeinen Formel mit Cyanhalogeniden, vorzugsweise in Gegenwart organischer Lösungsmittel, umsetzt.Process for the preparation of heterocyclic cyanomethylene compounds The subject of patent 1,088,961 is a process for the preparation of cyanomethylene indoline derivatives of the general formula in which R represents a hydrogen atom, an alkyl or alkoxy radical and R1, R2 and R3 represent alkyl groups, which consists in that 2-methylene indolines of the general formula with cyanide halides, preferably in the presence of organic solvents.
Nach dem Verfahren gemäß (deutsche Auslegeschrift 1110 645) Patentanmeldung F 28509 IV d / 12 p werden bei dieser Umsetzung als säurebindende Mittel andere säurebindende Mittel als die gleichzeitig als Reaktionskomponenten dienenden Indolinverbindungen, wie anorganische Basen und andere organische Basen, verwendet. According to the method according to (German Auslegeschrift 1110 645) patent application F 28509 IV d / 12 p are other acid-binding agents in this reaction acid-binding agents as the indoline compounds which also serve as reaction components, such as inorganic bases and other organic bases.
Es wurde nun gefunden, daß nicht nur die 2-Methylenindoline gemäß dem Verfahren des Patents 1 088 961, sondern ganz allgemein heterocyclische Methylenbasen der allgemeinen Formel in der R4 Alkyl- und Arylgruppen und Z die Er- gänzungsglieder eines heterocyclischen 5- oder - 6gliedrigen Ringsystems bedeuten, oder deren Kernsubstitutionsprodukte sowie quaternäre Ammoniumverbindungen solcher Methylenbasen sich mit Cyanhalogeniden, vorzugsweise in Gegenwart organischer Lösungsmittel und gegebenenfalls unter Zusatz säurebindender Mittel, umsetzen, wodurch man neuartige heterocyclische Cyanmethylenverbindungen erhält.It has now been found that not only the 2-methylene indolines according to the process of patent 1,088,961, but also, in general, heterocyclic methylene bases of the general formula in which R4 is alkyl and aryl groups and Z is the supplementary members of a heterocyclic 5- or 6-membered ring system, or their core substitution products and quaternary ammonium compounds of such methylene bases are reacted with cyano halides, preferably in the presence of organic solvents and optionally with the addition of acid-binding agents, whereby novel heterocyclic cyanomethylene compounds are obtained.
Enthalten die erfindungsgemäß zu verwendenden Verbindungen Substituenten, die unter denBedingungen des Verfahrens mit Cyanhalogeniden zu reagieren vermögen, z. B. Aminogruppen oder reaktionsfähige Methylgruppen, so wird dadurch die Hauptreaktion nicht beeinträchtigt. Unabhängig von dieser können in solchen Fällen die entsprechenden Sekundärreaktionen einhergehen. Beispielsweise erhält man so das 1 ,4-Dimethyl-2-cyanmethylen-6-cyanmethyldihydropyridin, indem man 1,4,6-Trimethyl-2-methylendihydropyridin und Chlorcyan in einem indifferenten Lösungsmittel aufeinander einwirken läßt (siehe nachstehendes Beispiel 11). If the compounds to be used according to the invention contain substituents, capable of reacting with cyanide halides under the conditions of the process, z. B. amino groups or reactive methyl groups, it becomes the main reaction not affected. Regardless of this, in such cases the appropriate Secondary reactions go hand in hand. For example, this gives 1,4-dimethyl-2-cyanomethylene-6-cyanmethyldihydropyridine, by adding 1,4,6-trimethyl-2-methylenedihydropyridine and cyanogen chloride in an indifferent Allow solvents to act on each other (see Example 11 below).
Als für das neue Verfahren geeignete heterocyclische Methylenbasen und quaternäre Ammoniumverbindungen solcher Methylenbasen seien z. B. genannt: 1,3 ,3-Trimethyi-5-chlor-2-methylenindolin, 1,3,3-Trimethyl-5-phenyl-2-methylenindolin, 1,3,3-Trimethyl-5-carbmethoxy-2-methylenindolin, 1 ,3,3-Trimethyl-5-carboxy-2-methylenindolin, 1,3, 3-Trimethyl-5-nitro-2-methylenindolin, 1,3,3,5, 6-Pentamethyl-2-methylenindolin, 1 ,3,3,4,5,7-Hexamethyl-2-methylenindolin, 1 ,3,3-Trimethyl-5-dimethylamino-2-methylenindolin, 1 ,3,3-Trimethyl-5-amino-2-methylnindolin, 1 ,3,3-Trimethyl-5-benzoyIamino-2-methylenindolin, 1 ,3,3-Trimethyl-5-acetylamino-2-methylenindolin, 1,3,3 -Trimethyl- 5-arylsulfonylamino-2-methylen indolin, 1 ,3,3Trimethyl-5-methylsulfonyl-2-methylenindolin, 1 ,3,3-Trímethyl-5-methyl-6-methoxy-2-methylenindolin, 1,3,3-Trimethyl-5,7-dimethoxy-2-methylen indolin, 1,3,3-Trimethyl-4, 5-benzo-2-methylenindolin, 1 ,3,3-Trimethyl-6,7-benzo-2-methylenindolin, 1,2,3 ,3-Tetramethyl-5-chlor-indoleniniummethylsulfat, - i ,2,3, 3-Tetramethyl-5, 7-dimethoxy-indoleniniumchlorid, 1 ,4,6-Trimethyl-2-methylendihydropyridin, 1 ,2,4,6-Tetramethyl-pyridinium-methylsulfat, 1 Methyl-2-methylen-dihydrochinolin, 1 -Methyl-6-chlor-2-methylendihydrochinolin, 1 Methyl-5,6-benzo-2-methylendihydrochinolin, 1 ,2-Dimethyl-chinolinium-methylsulfat, 1 ,3-Dimethyl-2-methylendihydrochinoxalin, 1 -Phenyl-3-methyl-2-methylendihydrochinoxalin, 1 -Phenyl-2, 3-dimethyl-chinoxalinium-methylsulfat, 1 ,2-Dimethyl-4-phenyl-chinazolinium-jodid, 2,3-Dimethyl-benzoxazolium-methylsulfat, 2,3 -Dimethyl-5-chlor-benzoxazolium-methylsulfat, 3-Methyl-2-methylenbenzthiazol, 4, 5-Diphenyl-2,3-dimethyl- 1 ,2,4-triazoliumjodid und 4(p-Methoxyphenyl)- 1,3, 5-trimethyl- 1 ,2,4-triazolium-jodid. As suitable heterocyclic methylene bases for the new process and quaternary ammonium compounds of such methylene bases are e.g. B. mentioned: 1.3 , 3-trimethyl-5-chloro-2-methyleneindoline, 1,3,3-trimethyl-5-phenyl-2-methyleneindoline, 1,3,3-trimethyl-5-carbmethoxy-2-methyleneindoline, 1,3,3-trimethyl-5-carboxy-2-methyleneindoline, 1,3, 3-trimethyl-5-nitro-2-methyleneindoline, 1,3,3,5,6-pentamethyl-2-methylene indoline, 1,3,4,5,7-hexamethyl-2-methyleneindoline, 1,3,3-trimethyl-5-dimethylamino-2-methyleneindoline, 1,3,3-trimethyl-5-amino-2-methylnindoline, 1,3,3-trimethyl-5-benzoylamino-2-methyleneindoline, 1,3,3-trimethyl-5-acetylamino-2-methylene indoline, 1,3,3-trimethyl-5-arylsulfonylamino-2-methylene indoline, 1,3,3-trimethyl-5-methylsulfonyl-2-methyleneindoline, 1,3,3-trimethyl-5-methyl-6-methoxy-2-methyleneindoline, 1,3,3-trimethyl-5,7-dimethoxy-2-methylene indoline, 1,3,3-trimethyl-4,5-benzo-2-methylene indoline, 1,3-trimethyl-6,7-benzo-2-methyleneindoline, 1,2,3,3-tetramethyl-5-chloro-indoleninium methyl sulfate, - i, 2,3, 3-tetramethyl-5, 7-dimethoxy-indoleninium chloride, 1, 4,6-trimethyl-2-methylenedihydropyridine, 1, 2,4,6-tetramethyl-pyridinium-methylsulfate, 1-methyl-2-methylene-dihydroquinoline, 1 -Methyl-6-chloro-2-methylenedihydroquinoline, 1 methyl-5,6-benzo-2-methylenedihydroquinoline, 1,2-dimethyl-quinolinium-methylsulfate, 1,3-dimethyl-2-methylenedihydroquinoxaline, 1-phenyl-3-methyl-2-methylenedihydroquinoxaline, 1-phenyl-2, 3-dimethyl-quinoxalinium methyl sulfate, 1, 2-dimethyl-4-phenyl-quinazolinium-iodide, 2,3-dimethyl-benzoxazolium-methylsulfate, 2,3-dimethyl-5-chlorobenzoxazolium methyl sulfate, 3-methyl-2-methylenebenzothiazole, 4,5-Diphenyl-2,3-dimethyl-1, 2,4-triazolium iodide and 4 (p-methoxyphenyl) - 1,3, 5-trimethyl-1,2,4-triazolium iodide.
Die verfahrensgemäß erhältlichen heterocyclischen Cyanmethylenverbindungen sind wichtige Zwischenprodukte für Farbstoffsynthesen. The heterocyclic cyanomethylene compounds obtainable according to the process are important intermediates for dye synthesis.
Beispiel 1 Zu einer Lösung von 167 g I,3,3-Trimethyl-5-chlor-2-methylenindolin in 450 ml Benzol wird innerhalb von 300 Minuten bei 65"C eine Lösung von 23 ml Chlorcyan in 400 ml Benzol zugetropft und anschließend noch 100 Minuten bei 65"C gerührt. Nach dem Erkalten wird das ausgeschiedene 1,3,3-Trimethyl-5-chlor-2-methylenindolin-hydrochlorid abgetrenntund das benzolische Filtrat zur Trockne eingeengt. Der feste Rückstand wird aus Methylcyclohexan umkristallisiert. Man erhält das l,3,3-Trimethyl-5-chlor- 2-cyanmethylenindolin in Form gut ausgebildeter, farbloser Kristalle. F. 142 bis 143"C.example 1 A solution of 23 ml of cyanogen chloride in 400 ml of benzene is added dropwise to a solution of 167 g of 1,3,3-trimethyl-5-chloro-2-methyleneindoline in 450 ml of benzene over the course of 300 minutes at 65 ° C. and then for a further 100 minutes stirred at 65 "C. After cooling, the precipitated 1,3,3-trimethyl-5-chloro-2-methyleneindoline hydrochloride is separated off and the benzene filtrate is concentrated to dryness. The solid residue is recrystallized from methylcyclohexane. The 1,3,3-trimethyl-5-chloro-2-cyanomethylene indoline is obtained in the form of well-developed, colorless crystals. F. 142 to 143 "C.
Ausbeute 68,5 g.Yield 68.5g.
Beispiel 2 Zu einem zweiphasigen Gemisch von 9,0 g 1,2,3-Trimethyl-5-phenyl-2-methylenindolin, 15 ml Benzol und 6 ml Wasser werden bei 70"C unter Rühren zunächst im Laufe von 45 Minuten 13 ml einer Lösung von 2,7 g Chlorcyan in 40 ml Benzol getropft. Der Rest dieser Lösung wird gleichzeitig mit 27,8 g 6,30/,der Natronlauge im Laufe von 75 Minuten eingetropft.Example 2 13 ml of a solution of 2.7 g of cyanogen chloride are added dropwise to 40 ml of benzene The remainder of this solution is added dropwise at the same time as 27.8 g of 6.30% of the sodium hydroxide solution over the course of 75 minutes.
Die Benzolschicht wird abgetrennt, das Benzol abgetrieben und der Rückstand aus Methylcyclohexan umkristallisiert. Das 1,3,3-Trimethyl-5-phenyl-2-cyanmethylindolin schmilzt bei 166 bis 168,5°C. Ausbeute 6,1 g (62 0/o der Theorie).The benzene layer is separated off, the benzene is driven off and the Recrystallized residue from methylcyclohexane. 1,3,3-Trimethyl-5-phenyl-2-cyanomethylindoline melts at 166 to 168.5 ° C. Yield 6.1 g (62% of theory).
Beispiel 3 Zu einem zweiphasigen Gemisch von 75,0 g 1,3,3-Trimethyl -5- carbmethoxy - 2 - methylenindolin, 150 ml Benzol, 35,5 g Natriumbicarbonat und 385 ml Wasser wird bei 70"C unter Rühren im Laufe von 210 Minuten eine Lösung von 26,0 g Chlorcyan in 385 mol Benzol zugetropft. Die benzolische Schicht wird dann abgetrennt, zur Trockne eingeengt und der Rückstand aus Methylcyclohexan umkristallisiert.Example 3 A two-phase mixture of 75.0 g of 1,3,3-trimethyl -5-carbmethoxy-2-methylene indoline, 150 ml of benzene, 35.5 g of sodium bicarbonate and 385 ml of water is added at 70 ° C. with stirring over the course of 210 minutes a solution of 26.0 g of cyanogen chloride in 385 mol of benzene is added dropwise, the benzene layer is then separated off and evaporated to dryness and the residue is recrystallized from methylcyclohexane.
Das 1,3,3 -Trimethyl-5-carbmethoxy-2 - cyanmethylenindolin schmilzt bei 170 bis 172"C. Ausbeute 33,4 g.The 1,3,3-trimethyl-5-carbmethoxy-2-cyanomethylene indoline melts at 170 to 172 "C. Yield 33.4 g.
Beispiel 4 Zu einem inhomogenen Gemisch von 16,0 g 1,3,3,4,5 ,7-Hexamethyl-2-methylenindolin, 50 ml Benzol, 8,8 g Natriumbicarbonat und 50 ml Wasser wird unter schwachem Rühren bei 40"C im Laufe von 90 Minuten eine Lösung von 6,4 g Chlorcyan in 100 ml Benzol getropft.Example 4 To an inhomogeneous mixture of 16.0 g of 1,3,3,4,5,7-hexamethyl-2-methyleneindoline, 50 ml of benzene, 8.8 g of sodium bicarbonate and 50 ml of water is added with gentle stirring at 40 ° C. in the course of a solution of 6.4 g of cyanogen chloride in 100 ml of benzene was added dropwise over 90 minutes.
Anschließend wird noch 220 Minuten bei 40° C nachgerührt. Nach dem Abtrennen der Benzolschicht und dem Abdestillieren des Benzols bleibt das rohe 1,3,3,4,5,7 - Hexamethyl - 2 - cyanmethylenindolin in kristalliner Form zurück. F. (nach der Umkristallisation aus Isopropanol) 169 bis 170"C. Ausbeute 16,5 g. The mixture is then stirred at 40 ° C. for a further 220 minutes. After this Separation of the benzene layer and distilling off the benzene remains the crude 1,3,3,4,5,7 - hexamethyl - 2 - cyanomethylene indoline in crystalline form return. F. (after recrystallization from isopropanol) 169 to 170 "C. Yield 16.5 g.
Beispiel 5 Zu einem Gemisch von 37,7 g 1,3,3-Trimethyl-5,7-dimethoxy-2-methylenindolin, 100 ml Benzol, 19,1 g Natriumbicarbonat und 100ml Wasser wird unter Rühren im Laufe von 3 Stunden bei 50"C eine Lösung von 14,0 g Chlorcyan in 200 ml Benzol zugetropft. Anschließend wird noch 1 Stunde bei 500 C nachgerührt. Die Benzolschicht wird abgetrennt und zur Trockne eingeengt. Der Rückstand wird dann mit 15 ml Methylcyclohexan angerührt und abgesaugt.Example 5 A mixture of 37.7 g of 1,3,3-trimethyl-5,7-dimethoxy-2-methyleneindoline, 100 ml of benzene, 19.1 g of sodium bicarbonate and 100 ml of water is added over the course of 3 hours at 50.degree. C. with stirring a solution of 14.0 g of cyanogen chloride in 200 ml of benzene is added dropwise, followed by stirring for a further 1 hour at 500 ° C. The benzene layer is separated off and concentrated to dryness, the residue is then stirred up with 15 ml of methylcyclohexane and filtered off with suction.
Man erhält das 1,3,3-Trimethyl-5,7-dimethoxy-2-cyanmethylenindolin als fast farbloses, feinkristallines Pulver. F. 140 bis 1410C. Ausbeute 22,6 g.The 1,3,3-trimethyl-5,7-dimethoxy-2-cyanomethylene indoline is obtained as an almost colorless, finely crystalline powder. F. 140 to 1410C. Yield 22.6g.
Beispiel 6 Zu einem Gemisch von 40,5 g 1,3,3,5-Tetramethyl-6-methoxy-2-methylenindolin, 100ml Benzol, 22,0 g Natriumbicarbonat und 100 ml Wasser wird bei 40"C unter Rühren im Laufe von 3 Stunden eine Lösung von 16,2 g Chlorcyan in 200 ml Benzol getropft. Nach dem Abklingen der Kohlendioxydentwicklung wird die Benzolschicht abgetrennt, zur Trockne eingeengt und der feste Rückstand aus 180 ml Methylcyclohexan umkristallisiert. Man erhält das 1,3,3,5-Tetramethyl-6-methoxy-2-Cyanmethylenindolin als feinkristallines Pulver. F. 116 bis 117"C. Ausbeute 32,7 g.Example 6 A mixture of 40.5 g of 1,3,3,5-tetramethyl-6-methoxy-2-methylene indoline, 100 ml of benzene, 22.0 g of sodium bicarbonate and 100 ml of water is added at 40 ° C. with stirring over the course of 3 hours a solution of 16.2 g of cyanogen chloride in 200 ml of benzene is added dropwise. After the evolution of carbon dioxide has subsided, the benzene layer is separated off, concentrated to dryness and the solid residue is recrystallized from 180 ml of methylcyclohexane. 6-methoxy-2-cyanomethylene indoline as a finely crystalline powder. F. 116 to 117 "C. Yield 32.7g.
Beispiel 7 Zu einem Gemisch von 17,9 g 1,3,3-Trimethyl-5-dimethylamino-2-methylenindolin, 50 ml Benzol, 9,1 g Natriumbicarbonat und 50 ml Wasser wird im Laufe von 70 Minuten bei 25 bis 30"C unter Rühren eine Lösung von 6,7 g Chlorcyan in 100 ml Benzol getropft.Example 7 A mixture of 17.9 g of 1,3,3-trimethyl-5-dimethylamino-2-methyleneindoline, 50 ml of benzene, 9.1 g of sodium bicarbonate and 50 ml of water is added over the course of 70 minutes at 25 to 30 ° C Stirring a solution of 6.7 g of cyanogen chloride in 100 ml of benzene was added dropwise.
Nach dem Abklingen der Kohlendioxydentwicklung wird die Benzolschicht abgetrennt, das Benzol abgetrieben und der Rückstand aus 175 ml Methylcyclohexan unter Zusatz von wenig Aktivkohle umkristallisiert. Man erhält das 1,3,3-Trimethyl-5-dimethylamino-2-cyanmethylenindolin in Form schwachgraugefärbter Kristalle. F. 145 bis 146"C. Ausbeute 10,1 g.After the evolution of carbon dioxide has subsided, the benzene layer becomes separated off, driven off the benzene and the residue from 175 ml of methylcyclohexane recrystallized with the addition of a little activated carbon. The 1,3,3-trimethyl-5-dimethylamino-2-cyanomethylene indoline is obtained in the form of pale gray colored crystals. M.p. 145 to 146 "C. Yield 10.1 g.
Beispiel 8 Zu einem inhomogenen Gemisch von 40,2 g 1,3,3-Trimethyl-2-methylen-4, 5-benzoindolin, 100 ml Benzol, 21,2 g Natriumbicarbonat und 100 ml Wasser wird unter schwachem Rühren bei 40"C im Laufe von 4 Stunden eine Lösung von 15,5 g Chlorcyan in 200 ml Benzol getropft. Anschließend wird noch 3 Stunden bei 40"C nachgerührt. Die Benzolschicht wird abgetrennt und zur Trockne eingeengt. Der zurückbleibende Kristallbrei wird aus Isopropanol umkristallisiert. Man erhält fast farblose Kristalle von 1,3,3- Trimethyl - 2 - cyanmethylen - 4,5 - benzoindolin.Example 8 To an inhomogeneous mixture of 40.2 g of 1,3,3-trimethyl-2-methylene-4, 5-benzoindoline, 100 ml of benzene, 21.2 g of sodium bicarbonate and 100 ml of water is added with gentle stirring at 40 ° C. in the course A solution of 15.5 g of cyanogen chloride in 200 ml of benzene is added dropwise over a period of 4 hours. The mixture is then stirred at 40 ° C. for a further 3 hours. The benzene layer is separated and evaporated to dryness. The remaining crystal slurry is recrystallized from isopropanol. Almost colorless crystals of 1,3,3-trimethyl-2-cyanomethylene-4,5-benzoindoline are obtained.
F. 168 bis 169"C. Ausbeute 25,6 g.M.p. 168 to 169 "C. Yield 25.6g.
Beispiel 9 Zu einem Gemisch von 26,8 g l-Phenyl-3-methyl-2-methylendihydrochinoxalin, 75ml Benzol, 13,5 g Natriumbicarbonat und 50 ml Benzol wird bei 40"C im Laufe von 60 Minuten unter Rühren eine Lösung von 9,9 g Chlorcyan in 80 ml Benzol getropft. Anschließend wird noch 60 Minuten bei 40"C nachgerührt. Die Benzolschicht wird dann abgetrennt und zur Trockne eingeengt. Die zurückbleibende dunkle, feste Masse wird unter Zusatz von Aktivkohle aus Isopropanol umkristallisiert. Das l-Phenyl-3-methyl-2-cyanmethylendihydrochinoxalin wird in Form gelber Kristalle erhalten. F. 227 bis 228"C. Ausbeute 10,4 g.Example 9 To a mixture of 26.8 g of 1-phenyl-3-methyl-2-methylenedihydroquinoxaline, 75 ml of benzene, 13.5 g of sodium bicarbonate and 50 ml of benzene, a solution of 9.9 g of cyanogen chloride are added dropwise to 80 ml of benzene. The mixture is then stirred at 40 ° C. for a further 60 minutes. The benzene layer is then separated and concentrated to dryness. The remaining dark, solid mass is recrystallized from isopropanol with the addition of activated charcoal. The 1-phenyl-3-methyl-2-cyanomethylene dihydroquinoxaline is obtained in the form of yellow crystals. M.p. 227 to 228 "C. Yield 10.4 g.
Beispiel 10 Zu einem Gemisch von 107,5 g l-Methyl-chinaldinium-methylsulfat, 200 ml Wasser und 350 ml Benzol wird im Laufe von 135 Minuten bei 35 bis 40"C unter Rühren gleichzeitig eine Lösung von 27,1 g Chlorcyan in 300 ml Benzol und 335 g 10,50/ige Natronlauge getropft. Anschließend wird 60 Minuten bei 30"C nachgerührt. Die Benzolschicht wird abgetrennt und zur Trockne eingeengt. Das zurückbleibende rohe Nitril erstarrt beim Anreiben mit der gleichen Menge Methylcyclohexan kristallin.Example 10 A solution of 27.1 g of cyanogen chloride in 300 ml of benzene is added to a mixture of 107.5 g of 1-methylquinaldinium methyl sulfate, 200 ml of water and 350 ml of benzene over the course of 135 minutes at 35 to 40 ° C. while stirring and 335 g of 10.50% sodium hydroxide solution are added dropwise. The mixture is then stirred at 30 ° C. for 60 minutes. The benzene layer is separated and evaporated to dryness. The remaining crude nitrile solidifies in crystalline form when rubbed with the same amount of methylcyclohexane.
Die Kristalle werden abgetrennt, gewaschen und getrocknet. Ausbeute 34,1 g. The crystals are separated off, washed and dried. yield 34.1 g.
Zur weiteren Reinigung wird das Produkt unter Zusatz von Aktivkohle aus viel Methylcyclohexan umkristallisiert. Man erhält das l-Methyl-2-cyanmethylen-1,2-dihydrochinolin in Form gelber Nadeln. For further purification, the product is added with activated carbon recrystallized from a lot of methylcyclohexane. 1-methyl-2-cyanomethylene-1,2-dihydroquinoline is obtained in the form of yellow needles.
F. 118°C.118 ° C.
Beispiel 11 Zu einer Lösung von 5 g 1 ,4,6-Trimethyl-2-methylen dihydropyridin in 400 ml Benzol wird im Laufe von 60 Minuten bei Zimmertemperatur unter Rühren eine Lösung von 4,9 g Chlorcyan in 100 ml Benzol getropft.Example 11 To a solution of 5 g of 1,4,6-trimethyl-2-methylene dihydropyridine in 400 ml of benzene, a solution of 4.9 g of cyanogen chloride in 100 ml of benzene is added dropwise over the course of 60 minutes at room temperature.
Anschließend wird noch 30 Minuten nachgerührt, filtriert und das Filtrat zur Trockne eingeengt. Der zurückbleibende feste Rückstand wird aus Isopropanol unter Zusatz von Aktivkohle umkristallisiert. Man erhält das 1 ,4-DimethyI-2-Cyanmethylen-6-cyanmethyldihydropyridin in Form fast farbloser Kristalle vom Schmelzpunkt 196 bis 197"C. Ausbeute 1,3 g.The mixture is then stirred for a further 30 minutes, filtered and the filtrate concentrated to dryness. The remaining solid residue is made from isopropanol recrystallized with the addition of activated charcoal. 1,4-Dimethyl-2-cyanomethylene-6-cyanmethyldihydropyridine is obtained in the form of almost colorless crystals with a melting point of 196 to 197 "C. Yield 1.3 g.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF28510A DE1118784B (en) | 1959-05-25 | 1959-05-25 | Process for the preparation of heterocyclic cyanomethylene compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF28510A DE1118784B (en) | 1959-05-25 | 1959-05-25 | Process for the preparation of heterocyclic cyanomethylene compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1118784B true DE1118784B (en) | 1961-12-07 |
Family
ID=7092909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF28510A Pending DE1118784B (en) | 1959-05-25 | 1959-05-25 | Process for the preparation of heterocyclic cyanomethylene compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1118784B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7091234B2 (en) * | 1999-05-04 | 2006-08-15 | Wyeth | Thio-oxindole derivatives |
-
1959
- 1959-05-25 DE DEF28510A patent/DE1118784B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7091234B2 (en) * | 1999-05-04 | 2006-08-15 | Wyeth | Thio-oxindole derivatives |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0010063A2 (en) | Process for the preparation of furanyl-benzazoles | |
| DE2147023A1 (en) | PROCESS FOR PRODUCING 1HTETRAZOLE COMPOUNDS | |
| DE1159462B (en) | Process for the preparation of s-triazine derivatives | |
| DE1118784B (en) | Process for the preparation of heterocyclic cyanomethylene compounds | |
| DE4131584A1 (en) | IMIDAZOLYLMETHYL-PYRIDINE, THEIR PRODUCTION AND USE AS A PHARMACEUTICAL | |
| DE1470070B1 (en) | Process for the preparation of benzimidazole derivatives | |
| DE2124907A1 (en) | 3 Amino 1,2,4 oxadiazoles, process for their preparation and medicinal preparations | |
| DE1095806B (en) | Process for the preparation of derivatives of N-fluorosulfonylcarbamic acid | |
| DE1153375B (en) | Process for the preparation of benzoxazine- (1, 3) -dione- (2, 4) | |
| DE1545842C3 (en) | Process for the preparation of N-substituted 3-halobenzisothiazolium halides | |
| DE2755749A1 (en) | 4,5-DISUBSTITUTED IMIDAZOLE-2-THIONE AND ITS SALTS AND METHOD FOR THE PRODUCTION THEREOF | |
| DE1010531B (en) | Process for the production of dioxane compounds | |
| DE1645938A1 (en) | Process for the preparation of 6-aminopenicillanic acid esters | |
| DE1670224A1 (en) | Process for the preparation of triazolo-tetrazolo-pyridazine derivatives | |
| DE914973C (en) | Process for the preparation of substituted threo-configured ª ‡ -halogen-ª ‰ -oxy-acylamino-ethanes | |
| DE1445800C (en) | Process for the preparation of diben zoazepines | |
| DE1570034A1 (en) | Process for the production of nicotinic acid amides | |
| EP0513534B1 (en) | Cyclic acylphosphinic acid derivatives and process for their preparation | |
| AT215996B (en) | Process for the preparation of new pyridine derivatives | |
| DE1100030B (en) | Process for the preparation of heterocyclic compounds | |
| DE2137649B2 (en) | ||
| DE1149356B (en) | Process for the preparation of N-substituted thiosaeuramides | |
| DE1545658B2 (en) | Process for the preparation of 3,5-disubstituted 1,2,4-oxadiazole derivatives | |
| DE1063173B (en) | Process for the preparation of quaternary ammonium alkyl derivatives of alpha-carboline-beta-carboline or 3, 4, 5, 6-tetrahydro-beta-carboline | |
| CH341816A (en) | Process for the preparation of benzoic acid sulfonamides |