DE933028C - Process for the preparation of diarylacetonitriles substituted on the central carbon atom - Google Patents

Process for the preparation of diarylacetonitriles substituted on the central carbon atom

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Publication number
DE933028C
DE933028C DEF8725A DEF0008725A DE933028C DE 933028 C DE933028 C DE 933028C DE F8725 A DEF8725 A DE F8725A DE F0008725 A DEF0008725 A DE F0008725A DE 933028 C DE933028 C DE 933028C
Authority
DE
Germany
Prior art keywords
diarylacetonitriles
preparation
carbon atom
substituted
central carbon
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.)
Expired
Application number
DEF8725A
Other languages
German (de)
Inventor
Josef Dr Kaupp
Friedrich Dr Nolte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to DEF8725A priority Critical patent/DE933028C/en
Application granted granted Critical
Publication of DE933028C publication Critical patent/DE933028C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles

Description

Verfahren zur Herstellung von am zentralen Kohlenstoffatom substituierten Diarylacetonitrilen Zusatz zum Patent 894394 Nach dem Verfahren des Patents 894394 können unter anderem substituierte Diarylacetonitrile der allgemeinen Formel in welcher R und R1 Arylgruppen und R2 den Rest eines veresterbaren, nicht basischen Alkohols bedeuten, erhalten werden.Process for the preparation of diarylacetonitriles substituted on the central carbon atom Addition to patent 894394 According to the process of patent 894394, substituted diarylacetonitriles of the general formula in which R and R1 signify aryl groups and R2 signify the remainder of an esterifiable, non-basic alcohol, are obtained.

In Weiterentwicklung dieses Verfahrens wurde gefunden, daß solche Ester in besserer Ausbeute ch aus den entsprechenden, ebenfalls nach dem vorstehend genannten Verfahren des deutschen Patents 894 394 zugänglichen Dinitrilen hergestellt werden können, wenn man diese in Gegenwart eines Alkohols mit Halogenwasserstoff, zweckmäßig mit gasförmigem Chlorwasserstoff, behandelt. Bei der Aufarbeitung im wäßrigen Medium wird der dem angewandten Alkohol entsprechende Ester in sehr guter Ausbeute erhalten. Die Umsetzung erfolgt nach dem allgemeinen Formelschema: R Verseifung ~ R Verseifung C-CN ~~~~~~~~~ C-CN R1 1 Veresterung R1 l CH,-CH,-CN CH2-CH-COOR2 Überraschenderweise bleibt bei dieser Reaktion die am quaternären C-Atom befindliche C N-Gruppe vollkommen unberührt.In a further development of this process, it was found that such esters can be produced in better yield ch from the corresponding dinitriles, also accessible by the above-mentioned process of German patent 894 394, if they are mixed in the presence of an alcohol with hydrogen halide, advantageously with gaseous hydrogen chloride, treated. When working up in an aqueous medium, the ester corresponding to the alcohol used is obtained in very good yield. The implementation takes place according to the general formula scheme: R saponification ~ R Saponification C-CN ~~~~~~~~~ C-CN R1 1 esterification R1 l CH, -CH, -CN CH2-CH-COOR2 Surprisingly, the C N group on the quaternary carbon atom remains completely unaffected in this reaction.

Gegenüber dem in Compt. rend. Acad. sci., Band zu 3, 1941, Seite I82 bis I 84 beschriebenen Verf ahren zur Herstellung des 4, 4-Diphenyl-4-cyanbuttersäureäthylesters aus Diphenylacetonitril und co-Brompropionsäureäthylester (Ausbeute 60 bis 65 O/o) in Gegenwart von Natriumäthylat besitzt das vorliegende Verfahren den Vorteil der größeren Wirtschaftlichkeit, da trotz der Notwendigkeit von zwei Reaktionsstufen eine bedeutend höhere Ausbeute (etwa goO/o) erzielt wird. Auch ist das Arbeiten mit Natriumäthylat und damit mit metallischem Natrium im technischen Maßstab umständlich und gefährlich. Compared to that in Compt. rend. Acad. sci., Volume 3, 1941, p I82 to I84 described processes for the preparation of the 4, 4-diphenyl-4-cyanobutyric acid ethyl ester from diphenylacetonitrile and ethyl co-bromopropionate (yield 60 to 65%) in the presence of sodium ethylate, the present process has the advantage of greater economic efficiency, because despite the need for two reaction stages a significantly higher yield (about goO / o) is achieved. Also is working with sodium ethylate and thus with metallic sodium on an industrial scale cumbersome and dangerous.

Beispiel 4, 4-Diphenyl-4-cyanbuttersäuremethylester. Example 4, 4-diphenyl-4-cyanobutyric acid methyl ester.

IOQO Gewichtsteile a, a-Diphenylglutarsäurenitril werden in 4000 Raumteilen Methanol gelöst und unter Einleiten von Chlorwasserstoffgas 4 Stunden am RückfluBkühler erhitzt. Das Reaktionsgemisch wird mit Wasser verdünnt, ausgeäthert und der Atherextrakt destilliert. Man erhält das obengenannte Produkt in einer Ausbeute von go bis 92 ovo der Theorie, Kr. 12 = 204 bis 2050; F. = 39,60. IOQO parts by weight of a, a-diphenylglutaric acid nitrile are in 4000 Dissolved parts of the volume of methanol and the introduction of hydrogen chloride gas for 4 hours heated on the reflux condenser. The reaction mixture is diluted with water and extracted with ether and the ether extract is distilled. The above product is obtained in one yield from go to 92 ovo of theory, Kr. 12 = 204 to 2050; F. = 39.60.

Analog diesen Angaben wurden unter Verwen- -dung der entsprechenden Alkqhole die folgenden Ester erhalten: 4, 4-Diphenyl-4-cyanbuttersäurebutylester, Kp. 0,9 = 220 bis 2220; F =43,80; Ausbeute = 85 bis goO/o. Analogous to this information, using the appropriate Alkqhole obtained the following esters: 4, 4-Diphenyl-4-cyanobutyric acid butyl ester, Bp 0.9 = 220 to 2220; F = 43.80; Yield = 85 to goO / o.

4, 4-Diphenyl-4-cyanbuttersäurebenzylester, F. = 64,80; Ausbeute = 80 bis 85°/o. Benzyl 4,4-diphenyl-4-cyanobutyrate, m.p. = 64.80; yield = 80 to 85 per cent.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von am zentralen Kohlenstoffatom substituierten Diarylacetonitrilen der allgemeinen Formel in welcher R und Rt Arylgruppen und R2 den Rest eines veresterbaren, nicht basischen Alkohols bedeuten, nach Patent 894 394, dadurch gekennzeichnet, daß man a, a-Diarylglutarsäurenitrile in Gegenwart eines entsprechenden Alkohols bei erhöhter Temperatur, mit vorzugsweise gasförmigem Halogenwasserstoff, zweckmäßig mit Chlorwasserstoffgas, behandelt und das Reaktionsprodukt in wäßrigem Medium in bekannter Weise aufarbeitet.PATENT CLAIM: Process for the preparation of diarylacetonitriles of the general formula substituted on the central carbon atom in which R and Rt are aryl groups and R2 is the residue of an esterifiable, non-basic alcohol, according to Patent 894 394, characterized in that a, a-diarylglutaric acid nitriles in the presence of a corresponding alcohol at elevated temperature, preferably with gaseous hydrogen halide, advantageously with hydrogen chloride gas , treated and the reaction product worked up in an aqueous medium in a known manner.
DEF8725A 1952-04-03 1952-04-03 Process for the preparation of diarylacetonitriles substituted on the central carbon atom Expired DE933028C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEF8725A DE933028C (en) 1952-04-03 1952-04-03 Process for the preparation of diarylacetonitriles substituted on the central carbon atom

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF8725A DE933028C (en) 1952-04-03 1952-04-03 Process for the preparation of diarylacetonitriles substituted on the central carbon atom

Publications (1)

Publication Number Publication Date
DE933028C true DE933028C (en) 1955-09-15

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Application Number Title Priority Date Filing Date
DEF8725A Expired DE933028C (en) 1952-04-03 1952-04-03 Process for the preparation of diarylacetonitriles substituted on the central carbon atom

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Country Link
DE (1) DE933028C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005003094A1 (en) * 2003-07-03 2005-01-13 Poseidon Pharmaceuticals A/S Diarylmethyl derivatives as potassium channel modulators

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005003094A1 (en) * 2003-07-03 2005-01-13 Poseidon Pharmaceuticals A/S Diarylmethyl derivatives as potassium channel modulators

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