Patent GB-436789-A (GB)
Title: Manufacture of sulphonic acid and carboxylic acid derivatives of 1:1-diaryl-3:3-arylene-5:5-bis-pyrazolones
Filed: 1934-03-12
Abstract: 1 : 1<1> - Diaryl - 3 : 3<1> - arylene - 5 : 5<1> - bis-pyrazolones, substituted with at least one sulphonic or carboxylic group or both in the aryl and (or) the arylene radicles, are prepared by subjecting to ring closure the bis-hydrazones obtained from correspondingly substituted aryl hydrazines and aroylene-bis-acetic esters.  The production of the hydrazone and the ring closure are effected in an aqueous medium, and may be conducted without isolation of the hydrazone; the production of the hydrazone is preferably effected in an acid medium and the ring closure in a neutral or alkaline medium. In the examples, terephthaloyl-bis-acetic ester is condensed (a) with 4<1>-hydroxy-3<1> - carboxy - 4 - sulpho - 1 : 1<1> - diphenyl-sulphone - 2 - hydrazine, yielding a 3 : 3<1>-p - phenylene - 5 : 5<1> - bis - pyrazolone substituted in the 1-position of both pyrazolone rings by the substituted diphenylsulphone residue; (b) with 2-sulphophenylhydrazine, yielding 1 : 1<1> - di - (2<11> - sulphophenyl) - 3 : 3<1>-p - phenylene - 5 : 5<1> - bis - pyrazolone; (c) with 3-sulphophenylhydrazine, 4-sulphophenylhydrazine, 2 - carboxyphenylhydrazine, 2 - chloro - 4 - sulphophenylhydrazine, 2-chloro-5 - sulphophenylhydrazine, 1 - sulpho - 2 - naphthylhydrazine, 3 - carboxy - 2 - hydroxy-5 - sulphophenylhydrazine, 4 - nitro - 2 -sulphophenylhydrazine, and 2 : 5-disulphophenylhydrazine, yielding the corresponding 1 : 1<1>-diaryl - 3 : 3<1> - p - phenylene - 5 : 5<1> - bis-pyrazolones; (2) isophthaloyl - bis - acetic ester is condensed (a) with 4-sulphophenylhydrazine, yielding 1 : 1<1> - di - (4<11> - sulphophenyl) - 3 : 3<1> - m - phenylene - 5 : 5<1> - bis-pyrazolone and (b) with 4-carboxyphenylhydrazine, 2 - methyl - 4 - sulphophenylhydrazine, and 2 - nitro - 4 - sulphophenylhydrazine, yielding the corresponding 1 : 1<1>-diaryl - 3 : 3<1> - m - phenylene - 5 : 5<1> - bis-pyrazolones; (3) naphthoylene - 1 : 4 - bis-acetic ester is condensed with 1-sulpho-2-naphthylhydrazine to yield 1 : 1<1>-di-(2<11>-naphthyl - 1<11> - sulpho) - 3 : 3<1> - (1<111> : 4<111> - naphthylene) - 5 : 5<1> - bis - pyrazolone; (4) naphthoylene : 1 : 5 - bis - acetic ester is condensed with 3 - carboxy - 2 - hydroxy - 5 - sulphophenylhydrazine and 2 - nitro - 4 - sulphophenylhydrazine, yielding the corresponding 1 : 1<1> - diaryl - 3 : 3<1>- (1<111> : 5<111> - naphthylene)-5 : 5<1> - bis - pyrazolones; (5) diphenyloyl-4 : 4<1>-bis-acetic ester is condensed with 2-chloro-4-sulphophenylhydrazine and 2 : 5-disulphophenylhydrazine, yielding the corresponding 1 : 1<1> - diaryl - 3 : 3<1> - (4<111> : 4<1111> - diphenylene) 5 : 5<1> - bis - pyrazolones; (b) chloroterephthaloyl - bis - acetic ester is condensed with 3 - sulphophenylhydrazine, 2 - chloro - 4-sulphophenylhydrazine, and 2-methyl-4 : 5-disulphophenylhydrazine, yielding the corresponding 1 : 1<1> - diaryl - 3 : 3<1> - chloro - p - phenylene - 5 : 5<1> - bis - pyrazolones; (7) nitroterephthaloyl - bis - acetic ester is condensed with 4 - carboxyphenylhydrazine, 1 - sulpho - 2 - naphthylhydrazine, and 4 - nitro-2-sulphophenylhydrazine, yielding the corresponding 1 : 1<1> - diaryl - 3 : 3<1> - nitro - p-phenylene-5 : 5<1>-bis-pyrazolones. The aroylene-bis-acetic esters specified above are obtainable by condensing the corresponding dicarboxylic acid chlorides with two molecular proportions of acetoacetic ester, and treating the aroylene-bis-acetoacetic esters so obtained with alcoholic ammonia, to remove the acetyl groups.  The Specification as open to inspection under Sect. 91 describes the preparation of 1 : 1<1> - di - (4<11> - diphenyl - 4<111> - sulpho) - 3 - 3<1>-(p - phenylene) - 5 : 5<1> - bis - pyrazolone from terephthaloyl-bis-acetic ester and 4<1>-sulpho-4-diphenylhydrazine.  This subject-matter does not appear in the Specification as accepted.