Patent GB-792486-A (GB)
Title: A process for the production of ª‡-nitrilocarboxylic acid esters
Filed: 1955-12-20
Abstract: a  - Nitrilocarboxylic acid esters are produced by reacting a cyanacetic ester with an organic compound containing a single olefinic double bond and at least four carbon atoms in the molecule, at temperatures between 50 DEG  and 160 DEG  C. and in the presence of an organic peroxide and/or actinic light.  Suitable olefines are the aliphatic olefines such as butene, hexene, heptene, octene, decene, dodecene, hexadecene, and octadecene; cycloaliphatic compounds such as cyclohexene, methylcyclohexene, cyclopentene, cycloheptene, pinene and camphene.  Moreover, the olefines may be substituted by halogen atoms or by nitro, amino, sulphonic, hydroxy, methoxy or carboxyl groups.  Suitable cyanacetic esters are those of methyl, ethyl, propyl or isopropyl alcohols.  Organic peroxides which may be used are diacetyl, dibenzoyl and t-butyl peroxides in amounts between 0.01 and 0.2 mol. per mol. of cyanacetic ester.  The reaction may be effected in inert solvents and in an atmosphere of inert gas, such as carbon dioxide or nitrogen.  When the boiling temperature of the reaction mixture is below the reaction temperature the process may be effected at raised pressure.  The products may be separated by distillation.  The products may be converted into the corresponding a -nitrilocarboxylic acids by careful saponification, or the nitrile group may be converted into an amino, amido, thioamido or carboxylic group.  The products are suitable for the production of lubricants, plasticisers, plastics, textile assistants, washing and wetting agents, insecticides and pharmaceuticals.  In examples: (1) (a) cyanacetic ethyl ester is added with stirring to a mixture of undecylenic acid methyl ester and dibenzoyl peroxide in the presence of gaseous carbon dioxide, the mixture is heated at 110-120 DEG  C. for 2 hours and then 2-nitrilo brassylic acid-1-ethyl-13-methyl ester is separated by distillation; (b) the product so obtained is heated with alcoholic potassium hydroxide for 2 hours at 80 DEG  C. and the salt obtained is acidified with sulphuric acid to give a -nitrilobrassylic acid; (c) operating as in (b) saponification is effected for several hours at 180-200 DEG  C. and the product is undecane-1,1,11-tricarboxylic acid; (d) the product of (a) is heated at 180-200 DEG  C. with hydrochloric acid for 3 hours in a silver autoclave to give brassylic acid; (2) decene is heated with cyanacetic acid ethyl ester and dibenzoyl peroxide and a -cyanododecanoic acid ethyl ester is separated by distillation; the product is saponified with aqueous potassium hydroxide and on acidification gives decylmalonic acid; (3) dodecene is reacted as in (2) to give a -cyanomyristic acid ethyl ester which is hydrolysed and decarboxylated to give myristic acid; (4) butene-(1)-ol-4-acetate is heated with cyanacetic ethyl ester and dibenzoyl peroxide in a current of CO2 and the acetate of a -nitrilo-o -hydroxycaproic acid is separated from the product by distillation; (5) the methyl ester of oleic acid is heated with cyanacetic ethyl ester and dibenzoyl peroxide; (6) cyclohexene is heated with cyanacetic ethyl ester and dibenzoyl peroxide and cyclohexylcyanoacetic acid ethyl ester is separated from the products by distillation; the product is saponified with alcoholic potassium hydroxide and on acidification cyclohexylmalonic acid is precipitated.