Patent GB-419742-A (GB)
Title: The manufacture of neutral, water-soluble complex compounds of trivalent antimony
IPC: C07F9/90
Filed: 1933-05-18
Abstract: Water - soluble organo trivalent - antimony compounds are prepared by reacting in solution an aryl stibine oxide or halide with a benzene derivative containing at least two adjacent hydroxyl groups and at least one acid group, a sufficient quantity of a base being present to render the product neutral.  The reactants need not be present in stoichiometric proportions.  The products possess therapeutic properties.  Examples are given of the interaction of (1) p-acetylaminophenyl stibine chloride with pyrocatechin - 3 : 5 - disulphonic acid and neutralising with diethylaminoethanol, milk of lime, magnesium hydroxide, ammonia or ethanolamine; similar products are obtained using m - chloro - p - acetylaminophenyl stibine chloride, m - p - benzimidazolone stibine chloride, pyrogallol disulphonic acid, gallic acid, pyrocatechin - 3 : 5 - dicarboxylic acid or pyrocatechin - 3 : 5 - diarsonic acid; (2) m-amino - p - carbamidophenyl stibine chloride with pyrocatechin - 3 : 5 - disulphonic acid and neutralizing with caustic soda; (3) 4-hydroxyacetic acid-3-aminophenyl stibine chloride with pyrogallol disulphonic acid and neutralized with diethylamine; benzimidazolone stibine oxide may replace the stibine chloride; (4) benzoxazolone stibine oxide, p-ethyl-acetylaminophenyl stibine oxide, or hydroxyalkylaminophenyl stibine oxide with pyrocatechin-3 : 5- disulphonic acid and neutralizing with caustic soda; (5) p-acetylaminophenyl stibine chloride with calcium-sodium-calcium pyrocatechin - 3 : 5 - disulphonic acid (see U.S.A. Specification 1,879,533) and neutralizing with milk of lime; (6) p-acetylaminophenyl stibine chloride with pyrogallol disulphonic acid and neutralising with caustic soda; (7) chlorobenzoxazolone stibine chloride with pyrogallol disulphonic acid and neutralizing with diethylaminoethanol; similar products are obtained using 4 - acetylamino - 2 - methyl or ethyl - phenyl stibine oxide. Samples have been furnished of (1) the sodium salt of m-bromo-p-acetylaminophenyl stibine oxide - pyrogallol disulphonic acid; (2) the diethylaminoethanol - sodium salt of 4 - acetylamino - 2 - methylphenyl stibine oxide - pyrogallol disulphonic acid; (3) the sodium salt of N-methylbenzimidazolone stibine oxide-pyrogallol disulphonic acid; (4) the sodium salt of p-ethylacetylaminophenyl stibine oxide-pyrocatechin disulphonic acid, and (5) the sodium salt of p-ethyl-carbethoxyaminophenyl stibine oxide - pyrogallol disulphonic acid.  Stibine chlorides.--m - Chloro - p - acetylaminophenyl stibine chloride, m - p - benzimidazolone stibine chloride and chlorobenzoxazolone stibine chloride are prepared by reducing the corresponding stibinic acid with sulphurous acid in the presence of hydrochloric acid.  m - Amino - p - carbamidophenyl stibine chloride is obtained by nitrating p-carbamidophenyl stibine acid and reducing the product with stannous chloride. 4-Hydroxyacetic acid-3-aminophenyl stibine chloride is prepared by reducing with stannous chloride 4-hydroxyacetic acid-3-nitrophenylstibinic acid.  Stibine oxides.--Benzimidazolone stibine oxide, benzoxazolone stibine oxide, p-ethylacetylaminophenyl stibine oxide, hydroxyalkylaminophenyl stibine oxides, m-bromo-p-acetylaminophenyl stibine oxide, N-methylbenzimidazole stibine oxide and p-ethyl-carbethoxyaminophenyl stibine oxide are prepared by reduction of the corresponding stibinic acids, e.g. with sulphurous acid.  Hydroxyalkylaminophenyl stibine oxides are also obtained by treating aminophenyl stibine oxide with an alkylene oxide (see German Specification 413,837).  4 - Acetylamino - 2 - methyl or ethyl-phenyl stibine oxides result from the sulphurous acid reduction of the corresponding stibinic acids (see German Specification 518,208).  Stibinic acids.--Benzoxazolone stibinic acid is prepared by diazotizing aminobenzoxazolone (see German Specification 440,802) and treating the product with antimony oxide ; p-ethylacetylaminophenyl stibinic acid is similarly obtained from aminoethyl acetanilide.  Hydroxyalkylaminophenyl stibinic acids are prepared by treating an aminophenyl stibinic acid with an alkylene oxide (see German Specification 412,171).  4 - Hydroxyacetic acid-3 - nitrophenylstibinic acid is obtained by diazotizing 4 - aminophenoxyacetic acid, acting upon the diazo compound with antimony oxide and nitrating the p-phenoxyacetic acid-stibinic acid obtained. Chlorobenzoxazolone stibinic acid is obtained by reducing nitrochlorobenzoxazolone, diazotizing the product and treating with antimony oxide. m-Bromo-p-acetylaminophenyl stibinic acid is prepared from o-bromo-p-aminoacetanilide by diazotization and treatment with antimony oxide.