Patent GB-954253-A (GB)
Title: N:n - disubstituted - nitro - phenylene - diamines and their use in hair dyeing compositions
IPC: C09B51/00
Filed: 1961-10-06
Abstract: The invention comprises N, N1-disubstituted-nitro-phenylene diamines of formula: <FORM:0954253/C2/1> wherein R is a hydrocarbon group free from olefinic and acetylenic unsaturation and having from 1-8 carbon atoms or a hydroxyalkyl group having from 1-4 carbon atoms and R1 is an alkyl or hydroxyalkyl group having from 1-4 carbon atoms or a polyalkylene glycol group having from 4-9 carbon atoms, provided that at least one of R and R1 is a hydrocarbon group. The compounds are prepared by reacting a 1-secondary amino-2-nitro-4-aminobenzene with an alkylating agent e.g. a dialkyl sulphate, a haloalkanol e.g. 1-hydroxy-2-chloroethane and 1, 2-dihydroxy-3-chloro-propane, or an alkylene oxide e.g. ethylene oxide.  Compounds wherein R is alkyl and R1 is hydroxyalkyl may be prepared by treating a1-alkylamino-2-nitro-4-aminobenzene with tosyl chloride, treating the resultant 4-tosylamino compound with an alkylene chlorhydrin and removing the tosyl group by hydrolysis. The 1-secondary amino-2-nitro-4-amino-benzenes are prepared by a catalytic hydrogenation of the corresponding 2, 4-dinitro-compounds. The compounds are used in hair-dyeing compositions (see Division D1). In examples the following compounds are prepared by the above methods:-1-(21-hydroxyethyl) amino-2-nitro-4-methylaminobenzene, 1-methylamino-2-nitro-4-methylaminobenzene, 1-methylamino-2-nitro-4-(21-hydroxy-ethyl) aminobenzene, 1-methylamino -2-nitro-4-[21-(211-hydroxyethoxy)-ethyl]-amino benzene, 1-phenylamino-2-nitro-4-(21-hydroxy-ethyl)-aminobenzene and 1-cyclohexylamino-2-nitro-4-(21-hydroxyethyl) -aminobenzene. 1-Methylamino-2-nitro-4-aminobenzene is prepared by hydrogenation of 1-methylamino-2, 4-dinitrobenzene in ethanol and hydrochloric acid solution using a platinum on charcoal catalyst; 1-phenylamino-2-nitro-4-aminobenzene and 1-(21-hydroxyethyl) amino-2-nitro-4-aminobenzene are similarly prepared. 1-Methylamino-2-nitro-4-[N-(21-hydroxyethyl)-N-(tosyl) ]-amino-benzene is prepared by reacting 1-methyl-amino-2-nitro-4-aminobenzene with p-toluenesulphonyl chloride to give 1-methylamino-2-nitro-4-tosylamino-benzene which is reacted in aqueous alkaline solution with ethylene chlorhydrin. ALSO:The invention comprises nitro dyes of formula <FORM:0954253/C3/1> wherein R is a hydrocarbon group free from olefinic and acetylenic unsaturation and having from 1-8 carbon atoms or an hydroxyalkyl group having from 1-4 carbon atoms and R1 is an alkyl or hydroxyalkyl group having from 1-4 carbon atoms, or a polyalkylene glycol group having from 4-9 carbon atoms, provided that at least one of R and R1 is a hydrocarbon group. The compounds are prepared by reacting a 1 - secondary amino - 2 - nitro - 4 - aminobenzene with an alkylating agent e.g. a dialkyl sulphate, a haloalkanol e.g. 1-hydroxy-2-chloroethane and 1,2-dihydroxy-3-chloropropane, or an alkylene oxide e.g. ethylene oxide. Compounds wherein R is alkyl and R1 is hydroxyalkyl may be prepared by treating a 1-alkylamino-2-nitro-4-aminobenzene with tosyl chloride, treating the resultant 4-tosylamino compound with an alkylene chlorhydrin and removing the tosyl group by hydrolysis.  The 1 - secondary amino - 2 - nitro - 4 - aminobenzenes are prepared by catalytic hydrogenation of the corresponding 2,4-dinitro compounds. The dyes are used in hair dyeing compositions (see Division D1).  In examples the following dyes and intermediates are prepared by the above methods: - 1-(21-hydroxyethyl) amino - 2 - nitro - 4 - methylaminobenzene, 1 - methylamino - 2 - nitro - 4 - methylamino - benzene, 1 - methylamino - 2 - nitro - 4 - (21 - hydroxyethyl) aminobenzene, 1-methylamino-2-nitro - 4 - [21 - (211) - hydroxyethoxy) - ethyl]-aminobenzene, and 1 - phenylamino - or cyclohexylamino - 2 - nitro - 4 - (21 - hydroxyethyl) - aminobenzene: 1 - methylamino - or phenylamino - or - (21 - hydroxyethyl) amino-2-nitro-4-aminobenzene.ALSO:Hair dyeing compositions comprise a tinctorially effective amount (e.g. 0.05 to 5.0%) of a compound of formula:-  <FORM:0954253/D1-D2/1> wherein R is a hydrocarbon group free from olefinic and acetylenic unsaturation and having from 1-8 carbon atoms or a hydroxyalkyl group having from 1-4 carbon atoms and R1 is an alkyl or hydroxyalkyl group having from 1-4 carbon atoms or a polyalkylene glycol group having from 4-9 carbon atoms, provided that at least one of R and R1 is a hydrocarbon group (see Division C4) distributed in an aqueous medium and preferably with the addition of a base to give a pH of 7-12.  The compositions may also contain solvents such as ethanol, isopropanol and propylene glycol and dispersing agents such as lauryl or myristyl sulphate or sulphonate. Specified bases are ammonium hydroxide, mono-, di- and tri-ethanolamine, mono- and di-ethylamine or -propylamine, propylene diamine, morpholine, calcium and magnesium hydroxides, potassium hydroxide and sodium hydroxide or carbonate or bicarbonate.  The compositions may be formulated as solutions, gels, emulsions or dispersions.  In an example 1-methylamino-2-nitro-4-diethylene-glycolaminobenzene is dissolved in a mixture of isopropanol, water, mono- and tri-ethanolamines, polyacrylic acid and glycerol, the composition heated to 35-37 DEG C. applied to grey hair.  The hair is rinsed and washed after 20 minutes and a blue dyeing is obtained.  By operating in a similar manner with other compounds the following colours are obtained:- 1-methylamino-2-nitro-4- (21-hydroxyethyl) aminobenzene, blue-violet; 1-(21-hydroxyethyl)-amino-2-nitro-4-methylaminobenzene, blue; 1-methylamino-2-nitro-4-methylaminobenzene, reddish purple, 1-phenylamino-2-nitro-4-(21-hydroxyethyl) aminobenzene, violet; 1-cyclohexyl-amino-2-nitro-4-(21-hydroxyethyl) aminobenzene, violet.