Patent GB-990334-A (GB)
Title: Nitro-p-phenylene diamine derivatives and preparation thereof
IPC: C07C279/26
Filed: 1963-01-25
Abstract: The invention relates to nitro-p-phenylene diamine derivatives of the formula <FORM:0990334/C2/1> in which R is hydrogen or an alkyl or hydroxyalkyl group containing up to 6 carbon atoms and R1 is an imino (=NH) group or oxygen.  The compounds in which R1 is an imino group are obtainable by treating the corresponding nitro-p-phenylene diamines with dicyandiamide in aqueous acidic solution.  The compounds in which R1 is oxygen are obtainable from the compounds in which R1 is an imino group by boiling them with an acid for a time insufficient to effect decomposition of the guanylurea group. Examples are given in which (1) 2-nitro-p-phenylene diamino, treated at 90-95 DEG  C. with dicyandiamide and hydrochloric acid, yields 4 - amino - 3 - nitrophenylbiguanide; the mono- and di-hydrochlorides and the dinitrate of the product are described; (2) under like conditions 4-(b -hydroxyethyl)amino-2 - nitro - 4 - aminobenzene and dicyandiamide yield 4-(b -hydroxyethyl)amino-3-nitrophenylbiguanide; the mono- and dihydrochlorides of the product are described; (3) 1-methylamino - 2 - nitro - 4 - aminobenzene and dicyandiamide yield 4 - methylamino - 3-nitrophenylbiguanide, the mono- and di-hydrochlorides of which are described; (4) the product of Example 1 is boiled for two hours with 20% hydrochloric acid to yield 4-amino-3-nitrophenylguanyl urea, the hydrochloride of which is described; the corresponding 4-methylamino - and 4 - (b  - hydroxyethyl)amino compounds are obtainable similarly.  Other specified products are 4-ethylamino-, 4-propylamino -, 4 - butylamino -, 4 - (31 - hydroxypropyl)amino -, 4 - (21,31 - dihydroxypropyl)-amino - and 4 - (41 - hydroxybutyl)amino - 3-nitrophenylbiguanides The products, particularly the biguanide compounds, are useful for dyeing animal fibres (see Division D1).  2 - Nitro - p - phenylene diamine and its derivatives, for use as starting materials, are obtainable from the corresponding 1-amino-2,4-dinitrobenzenes by catalytic hydrogenation, suitably at 25-70 DEG  C. under a pressure of 2-3 atm. Examples are given of the reduction of N-methyl -, N - ethyl - and N - (b  - hydroxyethyl) - 2,4 - dinitroanilines to the corresponding 2-nitro-4-aminobenzenes.ALSO:The invention relates to nitro-p-phenylene diamine derivatives of the formula <FORM:0990334/C4-C5/1> in which R is hydrogen or an alkyl or hydroxyalkyl group containing up to 6 carbon atoms and R1 is an imino (=NH) group or oxygen. The compounds in which R1 is an imino group are obtainable by treating the corresponding nitro-p-phenylene diamines with dicyandiamide in aqueous acidic solution.  The compounds in which R1 is oxygen are obtainable from the compounds in which R1 is an imino group by boiling them with an acid for a time insufficient to effect decomposition of the guanylurea group. Examples are given in which (1) 2-nitro-p-phenylenediamins, treated at 90-95 DEG  C. with dicyandiamide and hydrochloric acid, yields 4-amino-3-nitrophenyl-biguanide; the mono- and di-hydrochlorides and the dinitrate of the product are described; (2) under like conditions 4-(b -hydroxyethyl) amino - 2 - nitro - 4 - aminobenzene and dicyandiamide yield 4-(b -hydroxyethyl) amino-3-nitrophenylbiguanide; the mono-and di-hydrochlorides of the product are described; (3) 1-methylamino-2-nitro-4-aminobenzene and dicyandiamide yield 4-methylamino-3-nitrophenylbiguanide, the mono- and di-hydrochlorides of which are described; (4) the product of Example 1 is boiled for two hours with 20% hydrochloric acid to yield 4-amino-3-nitrophenylguanyl urea, the hydrochloride of which is described; the corresponding 4-methyl-amino- and 4-(b -hydroxyethyl)amino compounds are obtainable similarly. Other specified products are 4-ethylamino-, 4-propylamino-, 4 - butylamino-, 4 - (31 - hydroxypropyl)amino-, 4 - (21,31 - dihydroxypropyl)amino - and 4 - (41-hydroxybutyl)amino - 3 - nitrophenyl - biguanides. The products, particularly the biguanide compounds, are useful for dyeing animal fibres (see Division D1).ALSO:For dyeing animal fibres, use is made of nitro-p-phenylene diamine derivatives of the formula <FORM:0990334/D1-D2/1> in which R is hydrogen or an alkyl or hydroxyalkyl group containing up to 6 carbon atoms and R1 is an imino (=NH) group or oxygen (see Division C2).  Specified products are 4-amino-3-nitrophenyl-biguanide, 4-(b -hydroxyethyl)amino-3-nitrophenylbiguanide, 4-methylamino-3-nitrophenylbiguanide, 4-amino-3-nitrophenylguinyl urea, the corresponding 4-methylamino-and 4-(b -hydroxyethyl)amino compounds, and 4-ethylamino-, 4-propylamino, 4-butylamino-, 4-(31-hydroxypropyl) amino-4-(21, 31-dihydroxypropyl)-amino-and 4-(41-hydroxybutyl)amino-3-nitro-phenylbiguanides.  The products, particularly the biguanide compounds, are useful for dyeing silk, fur, wool, bristles, feathers and hair, and for this purpose they may be used in association with conventional ingredients, such as alkalizing agents, thickeners, detergents and gums, in aqueous solutions, which may contain an organic solvent. Specified alkalizing agents are ammonia, mono-, di- or tri-ethanolamine, mono- or di-ethyl or propyl amine, propylene diamine, morpholine, calcium or magnesium hydroxide and sodium or potassium hydroxide or carbonate.  A number of suitable detergents, which may be anionic, cationic or non-ionic, are also specified.  Specific compositions useful for dyeing hair are described.