DE644075C - Process for the production of Abkoemmlingen of the 1, 2, 3, 4-tetrahydroquinoline series - Google Patents

Process for the production of Abkoemmlingen of the 1, 2, 3, 4-tetrahydroquinoline series

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Publication number
DE644075C
DE644075C DER95177D DER0095177D DE644075C DE 644075 C DE644075 C DE 644075C DE R95177 D DER95177 D DE R95177D DE R0095177 D DER0095177 D DE R0095177D DE 644075 C DE644075 C DE 644075C
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DE
Germany
Prior art keywords
benzoyl
tetrahydroquinoline
abkoemmlingen
production
parts
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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.)
Expired
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DER95177D
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German (de)
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HANS RUPE DR
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HANS RUPE DR
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Quinoline Compounds (AREA)

Description

Es wurde gefunden, daß man zu Abkömmlingen der I, 2, 3, 4-Tetrahydrochinolinreihe gelangen kann, wenn man i-Benzoyl-2-cyan-i, 2-dihydrochinoline reduziert und die dabei entstehenden 2-Benzoylaminomethyli, 2, 3, 4-tetrahydrochinoline gegebenenfalls verseift.It has been found that derivatives of the I, 2, 3, 4-tetrahydroquinoline series are obtained can reach if one i-Benzoyl-2-cyano-i, 2-dihydroquinolines reduced and the resulting 2-benzoylaminomethyli, 2, 3, 4-tetrahydroquinolines optionally saponified.

So erhält man durch Hydrierung von ι -Benzoyl-2-cyan-i, 2-dihydrochinolin der Formel (I)In this way, 2-dihydroquinoline is obtained by hydrogenating ι -Benzoyl-2-cyano-i, 2-dihydroquinoline Formula (I)

CH CCH C

I IlI Il

CH CCH C

^-CH/\^ -CH / \

CHCH

CH-CH-

-CN-CN

CO-C8H3 CO-C 8 H 3

(I)(I)

das 2-Benzoylaminomethyl-i, 2, 3, 4-tetrahydrochynolin der Formel (II)the 2-benzoylaminomethyl-i, 2, 3, 4-tetrahydrochynoline of formula (II)

CHCH

CHCH

I
CHI.
CH

CH.,CH.,

CH-CH2-NH-CO-C6H5 CH-CH 2 -NH-CO-C 6 H 5

(Π)(Π)

Überraschenderweise findet nicht nur eine gleichzeitige Hydrierung des Pyridinkerns und der Cyangruppe statt, sondern es wandert auch die Benzoylgruppe vom Pyridinkern in die Seitenkette.Surprisingly, there is not only a simultaneous hydrogenation of the pyridine nucleus and the cyano group instead, but the benzoyl group also migrates from the pyridine nucleus in the side chain.

Geeignete Ausgangsstoffe sind außer den i-Benzoyl-2-cyandihydrochinolin auch entsprechende im Chinolinkern substituierte Verbindungen. In addition to i-benzoyl-2-cyandihydroquinoline, suitable starting materials are also corresponding ones Compounds substituted in the quinoline nucleus.

Die Reduktion der Ausgangsstoffe wird zweckmäßig mit katalytisch angeregtem Wasserstoff durchgeführt. Dabei erweisen sich unedle Metallkatalysatoren, wie z. B. Nickel und Kobalt, oder deren Gemisch allein oder in Gegenwart von Trägersubstanzen als besonders vorteilhaft. Als Lösungsmittel für die katalytische Reduktion kommen z. B. Essigester oder auch inerte Lösungsmittel, wie Dekahydronaphthalin, in Frage.The reduction of the starting materials is expedient with catalytically activated hydrogen carried out. This turns out to be base metal catalysts, such as. B. Nickel and cobalt, or a mixture thereof, alone or in the presence of carrier substances as special advantageous. As a solvent for the catalytic reduction, for. B. ethyl acetate or inert solvents, such as decahydronaphthalene, can be used.

Die neuen monobenzoylierten Verbindungen lassen sich z. B. durch Behandlung mit Säuren zu den freien Diarainen verseifen. Sowohl die benzoylierten wie auch die entbenzoylierten Basen können in ihre N-Alkylverbindungen übergeführt werden.The new monobenzoylated compounds can be z. B. by treatment with Saponify acids to free diaraines. Both the benzoylated and the debenzoylated Bases can be used in their N-alkyl compounds be transferred.

Aus der Patentschrift 537 187 ist es bekannt, aus ■ 2-Dialkylaminoinethyl-3-chlor-4-anilinochinolinen der FormelFrom patent specification 537 187 it is known from ■ 2-dialkylaminoinethyl-3-chloro-4-anilinoquinolines the formula

NH-CnH-.NH-C n H-.

-CHO —N<-CH O —N <

,R
R, R
R.

durch Reduktion mit Natrium und Alkohol 2-Dialkylaminomethyltetrahydrochinoline herzustellen. Das vorliegende Verfahren zeigt demgegenüber einen einfachen Weg zur unmittelbaren Herstellung von nicht alkylierteir*; 2-Aminomethyl-i, 2, 3, 4-tetrahydrochinölinen, ausgehend von N-Benzoyl-2-cyan- *· dihydrochinolinen und ist somit von dem bekannten Verfahren ganz wesentlich verschieden. to produce 2-dialkylaminomethyltetrahydroquinolines by reduction with sodium and alcohol. In contrast, the present process shows a simple route for the direct production of non-alkylatedir *; 2-aminomethyl-i, 2, 3, 4-tetrahydroquinolines, starting from N-benzoyl-2-cyano- * · dihydroquinolines and is therefore quite significantly different from the known process.

Gemäß vorliegendem Verfahren werden eine große Reihe neuer Abkömmlinge der i, 2, 3, 4-Tetrahydrochinolinreihe leicht zugänglich. Sie sollen therapeutische Verwendung finden.A large number of new descendants of the i, 2, 3, 4-Tetrahydroquinoline series easily accessible. They should find therapeutic use.

Beispiel 1example 1

Auf 50 Teile N-Benzoyl-2-cyandihydrochinoliij (Formel I), gelöst in 350 Teilen heißem Essigsäureäthylester, läßt man Wasserstoff in Gegenwart von etwa 60 Teilen aktivem, trägerhaltigem Nickelkatalysator unter Druck in der Wärme einwirken. Nach Aufnahme der berechneten Wasserstoffmenge wird vom Katalysator abgetrennt und mit heißem Essigester nach ge waschen. Aus der etwas -eingeengten erkalteten Lösung scheidet sich das 2-Beiizoylaminomethyl-i, 2, 3,4-tetrahydrochinolin (Formel II) vom F. 138 bis 139° aus. Es bildet weiße Nadeln oder Prismen, die sich aus Alkohol Umkristallisieren lassen. Zur Verseifung werden 20 Teile dieser Verbindung in 50 Teilen Alkohol gelöst und während mehreren Stunden mit 200 Teilen konzentrierter Salzsäure gekocht. Nach beendeter Umsetzung verdünnt man mit Wasser und äthert aus. Die wässerige Lösung wird hierauf alkalisch gestellt, ausgeäthert und die Ätherlösung mit Magnesiumsulfat getrocknet. Nach dem Verdampfen des Lösungsmittels erhält man ein Öl vom Kp101700, das sich am Tageslicht langsam bräunt. Die neue Base bildet ein Citrat vom F. 188 bis 1890, ein Diacetat (mit 2 Mol Kristalhvasser) vom F. 49 bis 500 und mit Benzaldehyd eine Benzylidenverbindung vom F. 70 bis 71 °.On 50 parts of N-benzoyl-2-cyandihydrochinoliij (formula I), dissolved in 350 parts of hot ethyl acetate, hydrogen is allowed to act under high pressure in the presence of about 60 parts of active, supported nickel catalyst. After the calculated amount of hydrogen has been taken up, the catalyst is separated off and washed with hot ethyl acetate. The 2-beiizoylaminomethyl-1,2,3,4-tetrahydroquinoline (formula II) with a melting point of 138 ° to 139 ° separates out of the somewhat concentrated, cooled solution. It forms white needles or prisms that can be recrystallized from alcohol. For the saponification, 20 parts of this compound are dissolved in 50 parts of alcohol and boiled with 200 parts of concentrated hydrochloric acid for several hours. After the reaction has ended, it is diluted with water and etherified. The aqueous solution is then made alkaline, extracted with ether and the ether solution is dried with magnesium sulfate. After evaporation of the solvent, an oil with a boiling point of 10 170 0 is obtained , which slowly browns in daylight. The new base forms a citrate, melting at 188-189 0, a diacetate (with 2 moles Kristalhvasser), mp 49-50 0 with benzaldehyde and a benzylidene compound, mp 70-71 °.

Durch Einwirkung von Methylierungs-By exposure to methylation

mitteln auf 2-Aminomethyl-i, 2, 3, 4-tetrahydrochinolin kann man das i-Methyl-2-dimethylaminomethyl-i, 2, 3, 4-tetrahydrochinolin vom Kp11 144 bis 145° (Jodmethylataveraging on 2-aminomethyl-i, 2, 3, 4-tetrahydroquinoline, i-methyl-2-dimethylaminomethyl-i, 2, 3, 4-tetrahydroquinoline with a boiling point of 11 144 to 145 ° (iodomethylate

F. 2050) gewinnen. Durch Methylierung der unverseiften Benzoylverbindung erhält man in ähnlicher Weise das i-Methyl-2-benzoylaminomethyl-1,2,3,4-tetrahydrocliinolmvotnF. 1360, dessen Jodmethylat bei i66° schmilzt undF. 205 0 ) win. Methylation of the unsaponified benzoyl compound gives i-methyl-2-benzoylaminomethyl-1,2,3,4-tetrahydroclinolmvotnF in a similar manner. 136 0 , whose iodine methylate melts at 166 ° and

dessen Verseif ungsprodukt, das I-Methyl-2-aminomethyl-i, 2, 3, 4-tetrahydrochinolin, Öl vom Kp11 154bis 1550 bildet. ',Statt Methylierungsmittel können auch beige andere Alkylierungsmittel angewandt den, wobei entsprechend alkylierte Verentstehen. its saponification product, the I-methyl-2-aminomethyl-i, 2, 3, 4-tetrahydroquinoline, oil with a boiling point of 11 154 to 155 0 forms. 'Instead of methylating agents, other alkylating agents can also be used, with corresponding alkylated compounds being formed.

Beispiel 2 g Example 2 g

50 Teile N-Benzoyl-2-cyan-6-methoxydihydrochinolin (F. 94 bis 950, dargestellt durch Einwirkung von Benzoykhlorid auf 6-Methoxychinolin und Kaliumcyanid in Gegenwart von Wasser) werden in 300 Teilen Essigester gelöst und durch Reduktion nach der im Beispiel ι beschriebenen Weise das 2-Benzoylaminomethyl-6-methoxy-i, 2, 3, 4-tetrahydrochinolin vom F. 131 bis 1320 gewonnen. Durch Verseifen mit alkoholischer Salzsäure erhält man die freie Base vom Kp12 190 bis 1930·50 parts of N-benzoyl-2-cyano-6-methoxydihydroquinoline (F. 94 to 95 0 , represented by the action of benzoyl chloride on 6-methoxyquinoline and potassium cyanide in the presence of water) are dissolved in 300 parts of ethyl acetate and by reduction according to the example ι manner described the 2-benzoylaminomethyl-6-methoxy-i, 2, 3, 4-tetrahydroquinoline from F. 131 to 132 0 obtained. Saponification with alcoholic hydrochloric acid gives the free base with a boiling point of 12 190 to 193 0

Die Reduktion verläuft in ähnlicher Weise auch mit andersartig substituierten Verbindungen, wie z. B. mit N-Benzoyl-2-cyan-8-alkoxydihydrochinolinen, mit N-Benzoyl-2-cyandihydrochinaldin usw.The reduction proceeds in a similar way with other types of substituted compounds, such as B. with N-benzoyl-2-cyano-8-alkoxydihydroquinolines, with N-benzoyl-2-cyandihydrochinaldine etc.

Beispiel 3Example 3

Auf 15 Teile N-Benzoyl-2-cyandihydrochinolin läßt man in Essigesterlösung Wasserstoff in Gegenwart von Palladiumschwarz unter Druck in der Wärme einwirken und erhält nach dem Aufarbeiten das bereits im Beispiel 1 beschriebene 2-Benzoylaminomethyli, 2. 3, 4-tetrahydrochinolin.To 15 parts of N-benzoyl-2-cyandihydroquinoline hydrogen is allowed to act in ethyl acetate solution in the presence of palladium black under high pressure and is obtained after working up the 2-Benzoylaminomethyli already described in Example 1, 2. 3, 4-tetrahydroquinoline.

Beispiel 4Example 4

25 Teile N-Benzoyl-2-cyandihydrochinolin reduziert man in alkoholischer Lösung in Gegenwart von Nickelkatalysator unter Druck in der Wärme. Die nach dem Aufarbeiten gewonnene Verbindung ist identisch mit der nach Beispiel 1 erhältlichen.25 parts of N-benzoyl-2-cyandihydroquinoline is reduced in alcoholic solution in the presence of a nickel catalyst under pressure in the warmth. The compound obtained after working up is identical to that according to Example 1 available.

Claims (2)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung von Abkömmlingen der i, 2, 3, 4-Tetrahydrochinolinreihe, dadurch gekennzeichnet, daß man i-Benzoyl-2-cyan-i, 2-dihydrochinoline reduziert und die dabei entstehenden 2-Benzoylaminomethyl-i, 2, 3, 4-tetrahydrochinoline gegebenenfalls verseift.1. A process for the preparation of derivatives of the i, 2, 3, 4-tetrahydroquinoline series, characterized in that i-Benzoyl-2-cyano-1,2-dihydroquinolines reduced and the resulting 2-benzoylaminomethyl-i, 2, 3, 4-tetrahydroquinolines saponified if necessary. 2. Ausführungsform des Verfahrens nach Anspruch 1, dadurch gekennzeichnet, daß man die Reduktion mit Wasserstoff in Gegenwart unedler Metallkatalysatoren, wie z. B. Nickel oder Kobalt, ausführt.2. Embodiment of the method according to claim 1, characterized in that that the reduction with hydrogen in the presence of base metal catalysts, such as. B. nickel or cobalt executes.
DER95177D 1935-12-21 1936-01-11 Process for the production of Abkoemmlingen of the 1, 2, 3, 4-tetrahydroquinoline series Expired DE644075C (en)

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Application Number Priority Date Filing Date Title
CH644075X 1935-12-21

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DE644075C true DE644075C (en) 1937-04-23

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