DE1181701B - Process for the preparation of basic dibenzo- [a, d] -cyclooctene derivatives and their salts - Google Patents
Process for the preparation of basic dibenzo- [a, d] -cyclooctene derivatives and their saltsInfo
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- DE1181701B DE1181701B DEB66825A DEB0066825A DE1181701B DE 1181701 B DE1181701 B DE 1181701B DE B66825 A DEB66825 A DE B66825A DE B0066825 A DEB0066825 A DE B0066825A DE 1181701 B DE1181701 B DE 1181701B
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- dibenzo
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Description
BUNDESREPUBLIK DEUTSCHLAND Internat. Kl.: C 07 cFEDERAL REPUBLIC OF GERMANY Internat. Class: C 07 c
DEUTSCHESGERMAN
PATENTAMT Deutsche Kl.: 12 ο-25PATENT OFFICE German class: 12 ο-25
AUSLEGESCHRIFTEDITORIAL
BIBLIOTHEKLIBRARY
DES DEUTSCHEM
PATEHTdMTESDES GERMAN
PATEHTdMTES
Nummer: 1181701Number: 1181701
Aktenzeichen: B 66825 IV b / 12 οFile number: B 66825 IV b / 12 ο
Anmeldetag: 14. April 1962Filing date: April 14, 1962
Auslegetag: 19. November 1964Opening day: November 19, 1964
Nach einem älteren Vorschlag werden basische Dibenzo- [a^-cycloocten-Derivate der allgemeinen Formel IAccording to an older proposal, basic dibenzo- [a ^ -cyclooctene derivatives of the general Formula I.
(I)(I)
CH-CH-CH2-ACH-CH-CH 2 -A
in welcher R Wasserstoff oder einen niedrigen Alkylrest und A eine basische Gruppe bedeutet, ihrer Salze und quartären Ammoniumverbindungen hergestellt, indem man 5,6,7,12-Tetrahydro-dibenzo-[a,d]-cycloocten-12-on der Formel IIin which R is hydrogen or a lower alkyl radical and A is a basic group, their salts and quaternary ammonium compounds prepared by adding 5,6,7,12-tetrahydro-dibenzo- [a, d] -cycloocten-12-one of formula II
Verfahren zur Herstellung basischer Dibenzo-[a,d]-cycloocten-Derivate und ihrer SalzeProcess for the preparation of basic dibenzo- [a, d] -cyclooctene derivatives and their salts
Anmelder:Applicant:
C. F. Boehringer & Soehne G. m. b. H.,C. F. Boehringer & Soehne G. m. B. H.,
Mannheim-WaldhofMannheim-Waldhof
Als Erfinder benannt:
Dr.-Ing. Kurt Stach, Mannheim,
Dr. rer. nat. Friedrich Bickelhaupt,
Neckarhausen bei MannheimNamed as inventor:
Dr.-Ing. Kurt Stach, Mannheim,
Dr. rer. nat. Friedrich Bickelhaupt,
Neckarhausen near Mannheim
(II)(II)
(R2 = niedriger Alkylrest) umsetzt und aus den erhaltenen N-Carbalkoxyverbindungen der Formel IV(R2 = lower alkyl radical) and from the resulting N-carbalkoxy compounds of the formula IV
mit Grignardverbindungen der Formelwith Grignard compounds of the formula
HaI-Mg-CH2-CH(R)-CH2-AHal-Mg-CH 2 -CH (R) -CH 2 -A
in welcher R und A die eingangs gegebene Bedeutung besitzen, umsetzt und das Reaktionsprodukt mit Wasserabspaltenden Mitteln behandelt, worauf man die erhaltenen Alkylidenverbindungen (I) gewünschtenfalls in ihre Salze oder quartären Ammoniumverbindungen überführt. Als basische Reste A kommen hierbei vorzugsweise tertiäre Aminogruppen in Frage, z. B. Dialkylaminogruppen oder heterocyclische Reste, wie Piperidino-, Pyrrolidino-, Morpholino- und Piperazinoreste, welche gegebenenfalls auch substituiert sein können.in which R and A have the meaning given at the beginning, and the reaction product with Treated dehydrating agents, whereupon the resulting alkylidene compounds (I), if desired converted into their salts or quaternary ammonium compounds. As basic residues A are preferably tertiary amino groups in question, z. B. dialkylamino groups or heterocyclic Residues such as piperidino, pyrrolidino, morpholino and piperazino radicals, which optionally can also be substituted.
Es wurde nun gefunden, daß sich Verbindungen der obigen Formel I, welche als basischen Rest A eine Monoalkylaminogruppe —NHRi tragen, in besonders vorteilhafter Weise dadurch herstellen lassen, daß man Benzylverbindungen der Formel IIIIt has now been found that compounds of the above formula I, which are the basic radical A carry a monoalkylamino group —NHRi, thereby producing them in a particularly advantageous manner let that one benzyl compounds of the formula III
(IV)(IV)
CH-CH-CH2-N
RCH-CH-CH 2 -N
R.
COOR2
Ri COOR 2
Ri
CH-CH-CH2 CH-CH-CH 2
-N-N
(III) /CH2C6H5 (III) / CH 2 C 6 H 5
die Carbalkoxygruppe in an sich bekannter Weise hydrolytisch abspaltet.the carbalkoxy group is split off hydrolytically in a manner known per se.
Die Umsetzung der Benzylverbindungen III mit den Halogenameisensäureestern (z. B. Chlorameisensäure-äthylester) wird durch Erhitzen in einem inerten Lösungsmittel, ζ. Β. Benzol, bewirkt. Die N-Carbalkoxyverbindungen der Formel IV können ohne besondere Isolierung und Reinigung weiterverarbeitet werden; die hydrolytische Abspaltung der Carbalkoxygruppe wird vorzugsweise mit wäßriger Bromwasserstoffsäure in Eisessig vorgenommen. Die erhaltenen Monoalkylaminoalkylidenverbindungen können gewünschtenfalls in üblicher Weise in ihre Salze übergeführt werden.The reaction of the benzyl compounds III with the haloformic acid esters (e.g. ethyl chloroformate) is made by heating in an inert solvent, ζ. Β. Benzene. the N-carbalkoxy compounds of the formula IV can be further processed without special isolation and purification will; the hydrolytic cleavage of the carbalkoxy group is preferably carried out with aqueous Hydrobromic acid made in glacial acetic acid. The obtained monoalkylaminoalkylidene compounds can, if desired, be converted into their salts in the customary manner.
Die Darstellung der Ausgangsverbindungen III erfolgt in 63%iger Ausbeute durch Umsetzung vonThe preparation of the starting compounds III takes place in 63% yield by reacting
in welcher R die oben angegebene Bedeutung hat und Ri eine niedere Alkylgruppe bedeutet, mit
einem Halogenameisensäureester Hai — COOR2
yf^y
mit Grignardverbindungen der Formelin which R has the meaning given above and Ri is a lower alkyl group, with a haloformic acid ester Hai - COOR 2 yf ^ y
with Grignard compounds of the formula
QMgCHaCHRCH2N(Ri)CH2C6H5 QMgCHaCHRCH 2 N (Ri) CH 2 C 6 H 5
in Tetrahydrofuran und nachfolgende Verkochung des Reaktionsproduktes mit alkoholischer Salzsäure (vgl. Stach und Bickelhaupt, Monatshefte für Chemie, 93 [1962], S. 896). 5,6,7,12-Tetrahydrodibenzo-[a,d]-cycloocten-12-on erhält man durchin tetrahydrofuran and subsequent boiling of the reaction product with alcoholic hydrochloric acid (cf. Stach and Bickelhaupt, monthly journals für Chemie, 93 [1962], p. 896). 5,6,7,12-tetrahydrodibenzo- [a, d] -cycloocten-12-one you get through
409 728/485409 728/485
Cyclisierung der 2-(3-Phenylpropyl)-benzoesäure in 66%iger Ausbeute (s. oben, S. 889).Cyclization of 2- (3-phenylpropyl) -benzoic acid in 66% yield (see above, p. 889).
12-(3'-Monomethylamino-propyliden)-5,6,7,12-tetrahydro-dibenzo-[a^j-cycloocten 12- (3'-monomethylamino-propylidene) -5,6,7,12-tetrahydro-dibenzo- [a ^ j-cyclooctene
13 g (0,035MoI) 12-[3'-(N-Benzyl-N-methyl)-aminopropyliden]-5,6,7,12-tetrahydro-dibenzo-[a,d]-cycloocten und 10,8 g (0,105 Mol) Chlorameisensäureäthylester erhitzt man in 60 ml Benzol 6 Stunden zum Sieden und entfernt anschließend im Vakuum auf dem Wasserbad die flüchtigen Anteile. Der so erhaltene Rückstand an rohem 12-[3'-(N-Carbäthoxy-N-methyl)-aminopropyliden]-5,6,7,12-tetrahydrodi- benzo-[a,d]-cycloocten (Ausbeute 10,8 g = 88% der Theorie) wird in 75 ml Eisessig und 75 ml 48%iger Bromwasserstoffsäure 3 Stunden unter Rückflußkühlung erwärmt und im Vakuum der Kolbeninhalt auf ein kleines Volumen eingeengt. Man fügt Wasser und Äther hinzu, trennt die wäßrig-sauren Anteile ab, alkalisiert mit verdünnter Natronlauge und extrahiert mit Äther. Der nach dem Trocknen mit Natriumsulfat und Entfernung des Lösungsmittels verbleibende Eindampfrückstand ergibt bei der Hochvakuumdestillation 5,3 g(= 54,7% der Theorie) 12-(3'-Monomethylamino-propyliden)-5,6,7,12-tetrahydro-dibenzo-[a,d]-cycloocten vom Sdp.0,15 163 bis 1710C; das Hydrochlorid zeigt einen Fp. von 158 bis 160° C (aus Äther—Isopropanol).13 g (0.035MoI) 12- [3 '- (N-Benzyl-N-methyl) -aminopropylidene] -5,6,7,12-tetrahydro-dibenzo- [a, d] -cyclooctene and 10.8 g ( 0.105 mol) of ethyl chloroformate is heated to boiling in 60 ml of benzene for 6 hours and the volatile components are then removed in vacuo on a water bath. The resulting residue of crude 12- [3 '- (N-carbethoxy-N-methyl) aminopropylidene] -5,6,7,12-tetrahydrodibenzo [a, d] cyclooctene (yield 10.8 g = 88% of theory) is refluxed for 3 hours in 75 ml of glacial acetic acid and 75 ml of 48% hydrobromic acid, and the contents of the flask are concentrated to a small volume in vacuo. Water and ether are added, the aqueous acidic components are separated off, made alkaline with dilute sodium hydroxide solution and extracted with ether. The evaporation residue remaining after drying with sodium sulfate and removal of the solvent gives 5.3 g (= 54.7% of theory) of 12- (3'-monomethylamino-propylidene) -5,6,7,12-tetrahydro- dibenzo- [a, d] -cyclooctene from bp 0.15 163 to 171 0 C; the hydrochloride has a melting point of 158 to 160 ° C. (from ether-isopropanol).
Claims (1)
in welcher R Wasserstoff oder einen niedrigen Alkylrest und A eine Monoalkylaminogruppe der FormelR.
in which R is hydrogen or a lower alkyl radical and A is a monoalkylamino group of the formula
/CH2C6H5 (HD
/ CH 2 C 6 H 5
RCH - CH - CH 2 - N
R.
Ri COOR 2
Ri
ihre Salze überführt.in which R, Ri and R 2 have the meaning given above, the carbalkoxy group is hydrolytically split off in a manner known per se, whereupon the monoalkylaminoalkylidene compounds (I) obtained in this way are, if desired
their salts transferred.
»Methoden der organischen Chemie«, 4. Auflage, Bd. 8 (1952), S. 138/139.Considered publications:
"Methods of Organic Chemistry", 4th edition, Vol. 8 (1952), pp. 138/139.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB66825A DE1181701B (en) | 1962-04-14 | 1962-04-14 | Process for the preparation of basic dibenzo- [a, d] -cyclooctene derivatives and their salts |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB66825A DE1181701B (en) | 1962-04-14 | 1962-04-14 | Process for the preparation of basic dibenzo- [a, d] -cyclooctene derivatives and their salts |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1181701B true DE1181701B (en) | 1964-11-19 |
Family
ID=6975285
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DEB66825A Pending DE1181701B (en) | 1962-04-14 | 1962-04-14 | Process for the preparation of basic dibenzo- [a, d] -cyclooctene derivatives and their salts |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1181701B (en) |
-
1962
- 1962-04-14 DE DEB66825A patent/DE1181701B/en active Pending
Non-Patent Citations (1)
Title |
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None * |
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