ESTERS OF alpha-1-AMINO-1,1-ALKYLIDENE MALONIC ACIDS

摘要

1,270,413. Esters of α-(1-phenylamino-1,1- alkylidene) malonic acids. CIBA-GEIGY A.G. 16 June, 1969 [14 June, 1968; 24 Oct., 1968; 18 March, 1969], No. 9653/70. Divided out of 1,270,412. Addition to 1,205,639. Heading C2C. Novel alkylidene malonic acid esters of the formula in which Ph is a 1,2-phenylene residue substituted by a group -X 1 -A-RI and a group -X 2 -RII (in which RI is a cycloaliphatic radical, A is a direct bond or a bivalent aliphatic radical, each of X 1 and X 2 is oxygen or sulphur and RII is a C 8-20 aliphatic group), each of R 0 and R0 1 is carbo-C 1-7 -alkoxy, R 2 is hydrogen or C 1-7 alkyl and R 3 is hydrogen or an optionally substituted aliphatic or cycloaliphatic radical, or the tautomer of such a compound in which R 3 is hydrogen, are prepared by condensing an aniline containing the appropriate -X 1 -A-RI or -X 2 -RII substituents with a di-C 1-7 alkyl ester of an α-(1-C 1-7 alkoxy-1,1-alkylidene) malonic acid. Preferred compounds are dimethyl and diethyl esters of phenylaminomethylene-malonic acid in which the phenyl group is substituted by a cyclopropylmethoxy group and a decyloxy, dodecyloxy, octyloxy or tetradecyloxy group. The substituted aniline reactants are obtained by reduction of the co-responding nitro compounds. 4-Cyclopropylmethoxy - 3 - decyloxynitrobenzene is obtained by reacting cyclopropylmethyl bromide with pyrocatechol to yield pyrocatechol monocyclopropylmethyl ether which is condensed with benzoyl chloride to obtain 2- cyclopropylmethoxy-phenylbenzoate which is nitrated to 2 - cyclopropylmethoxy - 5 - nitrophenyl benzoate which on hydrolysis yields 4- ayclopropylmethoxy - 3 - hydroxy - nitrobenzene, reaction with decyl bromide providing the required ether. 3 - Cyclopropylmethoxy - 4- decyloxynitrobenzene is obtained by reacting pyrocatechol with decyl bromide, esterifying the resultant pyrocatechol monodecyl ether with benzoyl chloride to obtain 2-decyloxyphenyl benzoate which is nitrated, hydrolysing the 2- decyloxy - 5 - nitrophenyl benzoate obtained to 4 - decyloxy - 3 - hydroxy - nitrobenzene and reacting this with cyclopropylmethyl bromide to obtain the diether. 4-Cyclopropylmethoxy-3- dodecyloxy - nitrobenzene, 4 - cyclopropylmethoxy - 3 - octyloxynitrobenzene, and 2 - cyclopropylmethoxy-3-decyloxynitrobenzene are prepared by similar methods.