Patent GB-1205639-A (GB)
Title: Esters of [1-cycloaliphatyloxy- or 1-cycloaliphatylmercaptophenylamino)-1,1-alkylidenej]-malonic acids and process for their manufacture
IPC: C07D215/56
Filed: 1967-09-25
Abstract: 1,205,639. Substituted phenylamines; ethers and thioethers. CIBA Ltd. 25 Sept., 1967 [29 Sept., 1966; 7 April, 1967; 3 July, 1967; 18 Aug., 1967], No. 2190/70. Divided out of 1,205,638. Heading C2C. Novel substituted phenylamines of the general formula wherein R represents a cycloalkyl or cycloalkenyl residue optionally substituted by aliphatic, aromatic or araliphatic hydrocarbon residues or by etherified or esterified hydroxyl groups, A represents a direct bond or a lower alkylene residue, X represents oxygen or sulphur, R 0  represents a carbo-lower alkoxy group, R<SP>0</SP> 1  represents a carbo-lower alkoxy or cyano group, R 2  represents a hydrogen atom or a lower alkyl radical, R 3  represents hydrogen, lower alkyl, lower alkenyl, a free, etherified or esterified hydroxy-lower alkyl group, a free or esterified carboxy-lower alkyl group, an aminolower alkyl group, an aryl-lower alkyl group, or a group of the formula R-A-, and each of the groups Rb and R c  represents hydrogen, lower alkyl, free, etherified or esterified hydroxy or mercapto, trifluoromethyl, nitro, an amino or aryl-lower alkyl (in all cases, " lower " means containing up to 7 carbon atoms), are prepared by the reaction of the compounds of the formulµ in which A 0  is C 1-7  alkyl. 3,4 - Bis - cyclopropylmethoxy - nitrobenzene, 3,4 - bis - cyclobutyl - methoxy - nitrobenzene, 1,2- bis - cyclopropyl - methoxy - benzene, 3 - cyclo - propylmethoxy - 4 - isobutoxynitrobenzene, 4- cyclopropylmethoxy - 2 - trifluoromethylnitro - benzene, 4 - cyclopropylmethoxy - 2 - methylnitrobenzene, 2 - cyclopropylmethoxynitrobenzene, and 4 - cyclopropylmethoxy - 3 - isobutoxynitro - benzene are prepared by reacting the sodium salt of the appropriate phenol with cyclopropylmethyl bromide or chloride or cyclobutylmethyl bromide. 3,4 - Bis - cyclopropylmethoxy - nitrobenzene is prepared by nitrating 1,2-bis-cyclopropylmethoxy-benzene. Ethyl 2 - acetylamino - 5 - cyclopropylmethoxybenzoylacetate is prepared by reacting ethyl 2- amino - 5 - hydroxybenzoylacetate with acetyl chloride in the presence of pyridine, converting the product into its sodium salt with sodium hydride and reacting the sodium salt with cyclopropyl methyl bromide. The sodium salt of pyrocatechol monocyclopropylmethyl ether (obtainable by treating a mixture of pyrocatechol mono- and bis-cyclopropyl ethers with toluene and aqueous sodium hydroxide to precipitate the desired sodium salt) reacts with benzoyl chloride to give 2-cyclopropylmethoxyphenyl benzoate, which is nitrated with fuming nitric acid in acetic acid to give 2-cyclopropylmethoxy - 5 - nitrophenyl benzoate. The latter compound is hydrolysed to give 4-cyclopropylmethoxy - 3 - hydroxynitrobenzene. The sodium salt of catechol reacts with isobutyl bromide to give catechol mono-isobutyl ether, the sodium salt of which reacts with benzoyl chloride to give 2-isobutoxyphenyl benzoate. The latter is nitrated to give 2-isobutoxy-5-nitrophenyl benzoate which is hydrolysed with sodium hydroxide solution to give 3 - hydroxy - 4 - isobutoxynitrobenzene. The potassium salt of catechol reacts with cyclopentyl chloride to give pyrocatechol biscyclopentyl ether, which is nitrated to give 3,4- bis-cyclopentyloxy-nitrobenzene.