Patent GB-775829-A (GB)
Title: Improvements in and relating to nitroso derivatives
Inventor: SUREAU ROBERT FREDERIC MICHEL
Filed: 1955-09-15
Abstract: The invention comprises nitroso derivatives of the formula: <FORM:0775829/IV(b)/1> (in which X in one position represents a -CH- or -C-halogen group, and in the other position a nitrogen atom, and Y and Z each represent a hydrogen or halogen atom) and the ferrous complexes of these nitroso derivatives.  The ferrous complexes dye wool, silk, leather, animalized cellulosic fibres, superpolyamides, and superpolyurethanes from a neutral or weakly acid bath.  By reacting the ferrous complexes with amines such as substituted guanidines, cyclohexylamines, or butylamines, products are obtained which are soluble in organic solvents and colour varnishes or printing inks.  The nitrosohydroxyindazoles may be obtained by the action of nitrous acid or hydroxyindazoles, and may be converted to the complexes with ferrous salts.  In examples: (1) 5- or 6-hydroxyindazole is reacted with sodium nitrite and sulphuric or hydrochloric acid to give a precipitate of nitroso derivative which is redissolved by addition of caustic soda solution and reacted with ferrous sulphate; (2) 3-chloro-or bromo-6-hydroxy-indazole is similarly treated to give the nitroso bodies and ferrous complexes thereof; (3) 5-chloro-6-hydroxy-indazole is similarly treated.  In a further example, the ferrous complex of 3-chloro-7-nitroso-6-hydroxyindazole is reacted with di-o-tolyl guanidine or with cyclohexylamine in presence of hydrochloric acid. 3 - Chloro - or bromo - 6 - hydroxy - indazole is obtained from 3-chloro-6-amino-indazole by hydrolysis with sulphuric acid or by diazotization.  3 - Chloro - or bromo - 6 - amino - indazole is obtained by reduction of 3-chloro-6-nitroindazole, which is obtained by the action of calcium hypochlorite or 6-nitro-indazole.  5 - Chloro - 6 - hydroxy - indazole is obtained by hydrolysis of the 6-amino body with sulphuric acid.  5 - Chloro - 6 - amino - indazole is obtained by reduction of 5-chloro-6-nitro-indazole.  5 - Chloro - 6 - nitro - indazole is obtained by the action of sodium nitrite and acetic acid on 5-chloro-4-nitro-2-amino-toluene.ALSO:The invention comprises nitroso derivatives of the formula:-<FORM:0775829/IV(b)/1> (in which X in one position represents a - CH - or - C - halogen group, and in the other position a nitrogen atom, and Y and Z each represent a hydrogen or halogen atom) and the ferrous complexes of these nitroso derivatives.  The ferrous complexes dye wool, silk, leather, animalized cellulosic fibres, superpolyamides, and superpolyurethanes from a neutral or weakly acid bath.  By reacting the ferrous complexes with amines such as substituted guanidines, cyclohexylamines, or butylamines, products are obtained which are soluble in organic solvents and colour varnishes or printing inks. The nitrosohydroxy-indazoles may be obtained by the action of nitrous acid or hydroxy-indazoles, and may be converted to the complexes with ferrous salts.  In examples, (1) 5 - or 6-hydroxy-indazole is reacted with sodium nitrite and sulphuric or hydrochloric acid to give a precipitate of nitroso derivative which is redissolved by addition of caustic soda solution and reacted with ferrous sulphate; (2) 3 - chloro- or bromo - 6 - hydroxy-indazole is similarly treated to give the nitroso and ferrous complexes thereof; (3) 5 - chloro - 6 - hydroxy-indazole is similarly treated.  In a further example, the ferrous complex of 3 - chloro - 7 - nitroso - 6 - hydroxy-indazole is reacted with di- - o - tolylguanidine or with cyclohexylamine in presence of hydrochloric acid.