Patent GB-783330-A (GB)
Title: Improvements in preparation of bisamides
IPC: D06M13/402
Filed: 1955-07-21
Abstract: Bisamides of the formula R1-NHCO-CnH2n-CONH-R1, in which R1 is a saturated aliphatic group free of reactive hydrogen, an aralkyl group or a cycloalkyl group, the group R1 having in each case a hydrogen on the carbon attached to the amide nitrogen atom, and n is an integer of from 1 to 3, are prepared by reacting in liquid phase and in the absence of a catalyst a primary amine having the formula R1NH2, water, and a nitrile having the formula Z-CnH2n-CN, Z being -CONH2, -CN, or -COOAlk in which the "Alk" group is (C1-C4) alkyl, and CnH2n including ortho-phenylene when dinitriles are employed as starting materials.  The reaction is preferably carried out at a temperature between 25 DEG  and 150 DEG  C.  Specified amine reactants are methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, amylamine, hexylamine, 2-ethylbutylamine, 2-ethylhexylamine, octylamine, isoctylamine, 2-octylamine, dodecylamine, cetylamine, benzylamine, methylbenzylamine, methoxypropylamine, propoxypropylamine, methoxyethylamine, ethoxyethylamine, ethoxyethoxyethylamine, octoxyethylamine, dodecoxypropylamine, phenoxypropylamine, chlorobenzylamine, cyclopentylamine, cyclohexylamine, methylcyclohexylamine, dimethylaminopropylamine, dimethylaminoethylamine, dibutylaminopropylamine, morpholinopropylamine, piperidinopropylamine, pyrrolidinopropylamine, diethylaminoethylamine, pyrrolidinoethylamine, N : N-dicyclohexylaminopropylamine, N - benzyl - N - methylaminopropylamine and N - n - dodecylN-methylaminopropylamine. Specified nitrile reactants are malonitrile, succinonitrile, phthalonitrile, methylsuccinonitrile, glutaronitrile, methyl, ethyl and butyl cyanoacetates, methyl, ethyl and butyl b -cyanopropionates, methyl and butyl g -cyanobutyrates, methyl b -cyano-n-butyrate, methyl b -cyanoisobutyrate, cyanoacetamide, cyanopropionamide and cyanobutyramide.  Products having tertiary amino substituents may be subsequently quaternized and all the products may be converted to dinitroso compounds by treatment with nitrous fumes.  The examples describe the preparation of N : N1-dimethyl and N : N1-dibenzyl malonamides, N : N1-dimethyl, N : N1-diethyl, N : N1-di - n - butyl, N : N1 - di - 2 - ethylhexyl, N : N1-di - n - octyl, N : N1 - dibenzyl, N : N1 - dicyclohexyl, N : N1 - bis - (g  - dimethylaminopropyl) and N : N1 - bis - (dodecyloxypropyl) succinamides, N : N1 - bis - (2 - dimethylaminoethyl) succinamide and the methiodide thereof, N : N-dimethyl, N : N1-di-n-butyl, N : N1-di-n-octyl and N : N1-dibenzylglutaramides, N : N1-dibenzylphthalamide, N : N1 - dibenzyl - a  - methylsuccinamide, N : N1 - bis - (2 - dimethylaminoethyl)-a -methylsuccinamide and N : N1-bis - (3 - dimethylaminopropyl) - a  - methylsuccinamide; the quaternation of the latter compound with octylbenzyl chloride and dodecenyl chloride is illustrated.  Cyclohexylammonium b  - cyanopropionate is formed as a by-product during the reaction between methyl b -cyanopropionate, cyclohexylamine ethanol and water. Benzylammonium b  - cyanoisobutyrate and benzylammonium b  - cyano - n - butyrate are formed as by-products during the reaction between benzylamine, water and methyl b -cyanoisobutyrate or methyl b -cyano-n-butyrate respectively.