Patent GB-318491-A (GB)
Title: Manufacture of organic arsenic and antimony compounds
IPC: C07F9/00
Filed: 1929-08-30
Abstract: 318,491. I. G. Farbenindnstrie Akt.- Ges. Sept. 3, 1928, [Convention date]. Organic arsenic and antimony compounds are prepared by (1) introducing an hydroxy-acyl residue into an aromatic amino-substituted arsenic or antimony compound, or (2) introducing an arsenic acid or stibinic acid residue with an hydroxy-acylamino compound of the benzene series, followed if desired by conversion of the product into an arsenoxide or stibinoxide, or into a symmetrical or unsymmetrical arseno- or stibino-benzene, or with an arsenostibincbenzene. According to the examples, (1) 2-methoxy-5- glycollylaminophenylarsinic acid is prepared by introducing arsenic into 2-methoxy-5-nitraniline by Bart's method, reducing the nitro group and heating with glycollic acid; the product may be reduced by known methods into the corresponding arsenoxide and arsenobenzene: (2) m-aminophenylstibinic acid is heated with glycollic acid and the product reduced with sodium hydrosulphite; the resulting stibinobenzene may be converted into the corresponding stibinic acid by oxidation with hydrogen peroxide in ammoniacal solution; (3) p-glycollylaminophenylarsinic acid results when the p-arsanilic acid is heated with glycollic acid; the reduction with sodium hydrosulphite of a mixture of the said arsinic acid with 3-amino-4-hydroxyphenylarsinic acid yields 4- glycollyamino-3<1>-amino-4<1>- hydroxyarsenobenzene; (4) 5-amino-2-glycollyl-anisol, obtained by interaction of 5-nitro-2-amino-anisol with glycollic acid and reduction of the product, is diazotized and treated with antimony trioxide in the presence of glycerine and copper powder; the ammonium salt of the 3-methoxy-4-glycollylaminophenylstibinic acid so obtained is reduced with sodium hydrosulphite in the presence of 3- amino-4-hydroxyphenylarsinic acid and forms 3- amino-4-hydroxy- 3<1> -methoxy- 4<1> -glycollylaminoarsenostibinobenzene. The Specification as open to inspection under Sect. 91 (3) (a) includes also the following examples, (1) p-nitraniline is heated with glycollic acid, the nitro group of the resulting p-glycollylaminonitrobenzene is reduced to the amino group by treatment with hydrogen under pressure in the presence of nickel, and the amino group is then transformed into either the arsinic acid or stibinic acid group by diazotization and treatment with arsenious acid or antimony trioxide, giving p-glycollylaminophenylarsinic or stibinic acid respectively ; (2) marsanilic acid is heated with glycollic acid to form m-glycollylaminophenylarsinic acid; (3) 2-glycollylamino-4-aminophenol, prepared by inter. action of 2-amino-4-nitrophenol with glycollic acid followed by catalytic reduction with hydrogen under pressure, is diazotized and treated with arsenious acid or antimony trioxide, yielding 3- glycollylamino-4-hydroxyphenyl-arsinic acid or - stibinic acid; the arsenic acid can also be prepared by heating 3-amino-4-hydroxyphenyl with glycollic acid; (4) 3-lactylamino-4-hydroxyphenylarsinic acid is obtained from 2-amino-4-nitrophenol by heating with lactic acid, reducing with hydrohulphite to the amino body, and treating the diazotized product with arsenious acid; (5) the amino group of 3-chloro-4-glycollylaminoaniline, prepared by chlorinating p-nitroglycollic acid anilide and catalytically reducing the product, is replaced by the arsinic or stibinic acid group by diazotization and treatment with arsenious acid or antimony trioxide; (6) interaction of 3-amino-4-chlorophenylarsinic acid, 2- methyl-5-aminophenylarsinic acid, or 2-chloro-4- aminophenyl arsinic acid with glycollic acid forms the corresponding glycollylamino compound; (7) p : p<1>-diglycollylaminoarsenobenzene is prepared by hydrosulphite reduction of p-glycollylaminophenylarsinic acid ; similar reduction of 4-glycollylamino-3-methoxyphenylstibinic acid gives 3: 3<1>- methoxy 4: 4<1>-diglycollylaminostibinobenzene; (8) 4 : 3<1> - diglycollylamino - 4<1> - hydroxyarsenobenzene is obtained by reduction with hydrosulphite of p-glycollylaminophenylarsinic acid and 3-glycollylamino-4-hydroxyphenylarsinic acid; (9) 4-hydroxy - 3 - glycollylaminophenylarsenoxide is formed by the reduction of the corresponding arsinic acid with hydriodic and sulphurous acids. In the case of arsinic and stibinic acids, they may be converted into water-soluble salts by treatment with an alkali, ammonia, or an organic base such as ethanolamine, piperidine and diethylamine. This subject-matter does not appear in the Specification as accepted.