GB435336A - Process for the manufacture of cyclic ketones - Google Patents

Abstract

Cyclic ketones are prepared by condensing compounds having the formula <FORM:0435336/IV/1> in which A and B represent the same or different groups which are derived from carboxylic groups but contain no reactive hydrogen atoms, by means of condensing agents having the formula <FORM:0435336/IV/2> Me X(m - 1) in which R1 and R2 indicate alkyl, aralkyl, aryl or alicyclic radicles, Me and alkali, alkaline earth or earth metal, X a halogen or <FORM:0435336/IV/3> and m the valency of the metal, and saponifiying the products. The carboxylic acid derivatives which may be subjected to the condensation are dicarboxylic esters and dicarboxylic acid amides and imino-esters and amidines in which hydrogen atoms of the amino and imino groups are completely substituted. One of the groups may be a nitrile group. In examples: (1) hexadecane-1 : 6-dicarboxylic acid dimethyl ester dissolved in ethylaniline is run into the reaction product of ethylaniline and sodamide and the ethylanilide of cycloheptadecanone - 1 - carboxylic acid - 2 obtained is boiled with sulphuric acid whereby cycloheptadecanone is produced; hexadecane - 1 : 16 - dicarboxylic acid chloride, prepared from the acid by means of thionylchloride and the corresponding diethylanilide, prepared by reacting the dichloride with diethylaniline may be used instead of the dimethylester; (2) ethereal solutions of cyanheptylic acid diethylamide and lithium diethylamide are run gradually into boiling ether and the resulting a -cyansuberone is saponified to give suberone; cyanheptylic acid diethylamide is obtained from 7-bromheptylic acid by heating with thionylchloride, condensing the resulting acid chloride with diethylamine and treating with potassium cyanide; cyanheptylic acid ethyl ester which may also be used may be prepared from 7-bromheptylic acid by esterifying and reacting with potassium cyanide. Samples have been furnished under Sect. 2(5) of cyclic ketones obtained by saponification of the products derived from: (1) suberic acid dimethylester and sodium ethylaniline; (2) adipic acid dimethylanilide and sodium methylaniline and (3) suberic acid dimethylanilide and potassium methylaniline.