Patent GB-1239017-A (GB)
IPC: C07D235/28
Filed: 1968-02-22
Abstract: 1,239,017. Heterocyclic sulphonic acids. GEVAERT-AGFA N.V. 29 Jan., 1969 [22 Feb., 1968], No. 8653/68. Heading C2C. [Also in Division G2] 2 - (3 - Pyridyl) - 5(6) - sulphobenzimidazole, 2 - (4 - pyridyl) - 5(6) - sulphobenzimidazole monohydrate, 2 - (5 - sulpho - 2 - pyridyl) - 5(6)- sulphobenzimidazole dihydrate, N,N-bis (5(6)- sulpho - 2 - benzimidazolylmethyl)- methylamine, 2 - (5(6) - sulpho - 2 - benzamidazolyl) - 3H - imidazo [4,5 - b] pyridine, 2 - (4 - thiazolylmethyl)- 5(6) - sulphobenzimidazole and 3 - (m - sulphophenyl) - 5 - (2 - pyridyl) - pyrazole are prepared by treatment of the corresponding heterocyclic compound or mono-sulphonated derivative thereof with chlorosulphonic acid followed by hydrolysis of the sulphochloride formed. 1,4 - Bis (5(6) - sulpho - 2 - benzimidazolyl)- butane is obtained by sulphonation of the corresponding heterocyclic compound with fuming sulphuric acid. 1,2 - Bis (5 - tetrazolyl) - ethanesulphonic acid sodium salt is prepared by concentrating by evaporation a solution of 1,2-bis (5-tetrazolyl)- ethene in aqueous sodium hydrosulphite. 2 - (5 - Sulpho - 2 - pyridyl) benzimidazole is prepared by heating a mixture of 2-carboxy-5- sulphopyridine and o-phenylenediamine in polyphosphoric acid. 2 - (2 - Pyridyl) - 5(6) - sulphobenzimidazole . 1� hydrate, 2 - (4 - pyridyl) - 5(6)- sulphobenzimidazole . 2/3 phosphoric acid, 2,6-bis- (5(6) - sulpho - 2 - benzimidazolyl) pyridine monohydrate, 2 - [# - (2 - pyridyl) - vinyl] - 5(6) - sulphobenzimidazole hydrochloride monohydrate and 2 - (2 - quinolyl) - 5(6) - sulphobenzimidazole are prepared by heating a mixture of 3,4-diaminobenzosulphonic acid and picolinic acid, isonicotinic acid, 2,6-pyridinedicarboxylic acid, 2- (2-pyridyl) acrylic acid or 2-quinolinecarboxylic acid, respectively, in polyphosphoric acid. 1 - Ethyl - 2 - (2 - pyridyl) - 5 - sulphobenzimidazole and 2 - (2 - pyridyl) - 7 - sulpho - 1H- naphtho[1,2-d]imidazole are prepared by heating 3 - amino - 4 - ethylaminobenzenesulphonic acid and 1,2 - diaminonaphthalene - 6 - sulphonic acid respectively in picolinic acid dissolved in polyphosphoric acid. 1,2 - Bis - (5(6) - sulpho - 2 - benzimidazolyl)- ethane is prepared by refluxing a solution of 3,4- diaminobenzene-sulphonic acid and succinic acid in 6N hydrochloric acid. 1,3-Bis(5(6)- sulpho - 2 - benzimidazolyl) propane is prepared similarly but using glutaric acid instead of succinic acid. 2 - (2 - Pyrrolyl) - 5(6) - sulphobenzimidazole is prepared by refluxing a suspension of 3,4-diaminobenzene-sulphonic acid and 2-pyrrolecarbaldehyde sodium bisulphite addition product in ethanol. 1,2 - Bis - [5 - (3 - sulphopropylthio) - 1H - 1,2,4- triazol - 3 - yl] - ethane disodium salt is prepared by adding propanesultone to a solution of 1,2 - bis - (5 - mercapto - 1H - 1,2,4 - triazol - 3- yl) ethane (prepared as described in Bull. Soc. Chim. Belg. 75, 358 (1966)) and sodium methylate in methanol and refluxing. 1,2-Bis-[5-(1,3- dimethyl - 3 - sulphobutylthio) - 1H - 1,2,4 - triazol-3-yl] ethane disodium salt is prepared by adding 1,1,3 - trimethylpropane-sultone to a solution of 1,2-bis-(5-mercapto-1H-1,2,4-triazol- 3-yl(-ethane and sodium methylate in methanol and refluxing. 3 - (3 - Sulphopropylthio) - 5 - (4 - pyridyl)- 1H-1,2,4-triazole is prepared by adding propanesultone to a solution of 5-(4-pyridyl)-1H- 1,2,4 - triazole - 3 - thiol (prepared as described in Rec. Trav. Chim. Pays-Bas 73 (1954) 113) and sodium methylate in methanol and refluxing. 1,3 - Bis - [5 - (3 - sulphopropylthio) - 1H- 1,2,4 - triazol - 3 - yl] - propane is prepared similarly starting from 1,3-bis-(5-mercapto-lH- 1,2,4-triazol-3-yl)-propane. 2 - (2 - Benzimidazolylmethylthio)- 5(6) - sulphobenzimidazole is prepared by heating with stirring the disodium salt of 2-mercapto-5(6)- sulphobenzimidazole and 2-chloromethylbenzimidazole in dimethylformamide. 2-(2-Pyridylmethylthio) - 5(6) - sulphobenzimidazole is prepared similarly but using 2-chloromethylpyridine instead of the corresponding benzimidazole derivative. The disodium salt of 1,1-bis - [5(6)- sulpho - 2 - benzimidazolylthio] methane is prepared similarly from 2-mercapto-5(6)-sulphobenzimidazole and dibromomethane. 1,3 - Bis - [5 - sulpho - 1,2,4 - triazol - 3 - yl]- propane is prepared by adding dropwise an aqueous solution of potassium permanganate to an aqueous solution of 1,3-bis (5-mercapto-1H- 1,2,4-triazol-3-yl)-propane until the colour did not disappear any more.