Patent GB-753983-A (GB)
Title: Improvements in and relating to aromatic amines sulphonated on their amino groups
Inventor: LANTZ ROBERT LAZARE
IPC: D06P1/12
Filed: 1954-01-11
Abstract: The invention comprises compounds of formula <FORM:0753983/IV(a)/1> wherein X is a hydrogen atom or the -SO3-A group and A is a hydrogen atom or equivalent cation.  They are prepared by sulphonating a benzene derivative substituted by an amino group, by a group convertible into an amino group by reduction or hydrolysis, and by another group which may be either an amino group or a group convertible thereto by reduction or hydrolysis, then converting into an amino group any group so convertible. When two amino groups are present in the starting material, one or both may be sulphonated, depending particularly on the amount of sulphonating agent employed. Sulphonating agents specified are chlorsulphonic acid, sulphur trioxide, oleum, sulphuric acid, sulphamic acid, or combinations of sulphur trioxide with, a tertiary amine such as pyridine, trimethylamine, triethylamine, ethylmorpholine, or dimethylcyclohexylamine, an amide such as dimethyl-formamide, or an ether such as dioxane.  The sulphonation may be carried out in solvents such as nitro- or chloro-hydrocarbons, amides, ethers, tertiary amines and water. Specified groups convertible into an amino group by reduction or hydrolysis are nitro and acylamino.  Reducing agents for the nitro group are alkaline sulphides and polysulphides, hydrosulphites in alkaline medium, neutral sulphites and zinc or iron in slightly acid medium.  The acylamino groups are preferably hydrolysed by caustic alkalies.  The compounds are used as oxidation colouring matters (see Group IV (c)).  In examples (1) 2-nitro-1-amino-4-acetylaminobenzene is sulphonated by a solution of chlorsulphonic acid in pyridine, the sulphonated derivative reduced with iron turnings in the presence of acetic acid, and then hydrolysed with sodium hydroxide solution to give sodium 1 : 2 : 4 - triaminobenzene - N1 - sulphonate; (2) 2 : 4 - dinitro - 1 - aminobenzene is sulphonated and reduced to give the product of (1); (3) 1-amino - 2 : 5 - di - acetylamino - benzene is sulphonated and hydrolysed to give sodium 1 : 2 : 4-triamino - benzen - N2 - sulphonate; (4) 1-nitro - 2 : 5 - diamino - benzene is monosulphonated on the 5-amino group and reduced to give sodium 1 : 2 : 4-triamino-benzene-N4-sulphonate; (5) as in (4) but disulphonating to give sodium 1 : 2 : 4 - triamino - benzene-N1 : N4 - disulphonate; (6) 1 - nitro - 3 : 4 - diamino-benzene treated as in (5) gives sodium 1 : 2 : 4 - triamino - benzene - N1 : N2 - disulphonate; (7) 2 : 4 - diamino - 1 - acetylaminobenzene is disulphonated and hydrolysed to give sodium 1 : 2 : 4-triamino-benzene-N2 : N4-disulphonate; (20) 3 - nitro - 1 : 2 - diamino - benzene is disulphonated and reduced to give sodium 1 : 2 : 3 - triamino - benzene - N2 : N3-disulphonate. Specifications 498,755, [Group IV], and 730,106 are referred to.ALSO:Compounds of formula:-<FORM:0753983/IV(c)/1> wherein X is hydrogen or -SO3-A and A is hydrogen or an equivalent atom (see Group IV(b)) are oxidized on fibres or other objects to give dyeings in brown shades.  The sulphamates, together with an oxidizing agent and catalyst, may be applied to the fibre by dyeing, fulling or printing, and the colour developed in an acid bath or by steaming in neutral or acid vapour. Substances which give acids may be applied to the fibre before steaming.  The sulphamates described above may be admixed with other sulphamates such as those described in Specifications 498,755 [Group IV] and 730,106 or with dihydroxy or amino hydroxy aromatic derivatives such as resorcinol, dihydroxynaphthalenes, and aminophenols.  The compounds may also be used in conjunction with sulphuric esters of leuco derivatives of vat dyestuffs or with mixtures containing a coupling component and a diazoamino compound. The process may be applied to objects or fibres of wool, silk, furs, horse hair, bristles, human hair, natural or regenerated cellulose, cellulose ethers and esters, superpolyamides, superpolyesters and vinyl-chloride polymers.  In examples (8-14, 17 and 18) cotton is printed with mixtures containing sodium 1 : 2 : 4 - triamino - benzene - N1 - or - N2 - or - N4 - sulphonate, or sodium 1 : 2 : 4 -triamino - benzene - N1 : N2 - or N1 : N4 - or - N2 : N4 - disulphonate or a mixture thereof, together with other components selected from sodium - 1 - amino - 4 - phenylamino - benzene - N1 - sulphonate, resorcinol, 1 : 5 - dihydroxynaphthalene, pyrocatechol, sodium chlorate, ammonium chlorate, sodium bichromate, copper sulphate, ammonium vanadate, sodium ferrocyanide, ammonium chloride or ammonium oxalate, thiodiglycol, ammonia, and water and starch or starch-tragacanth thickener; (15) a mixture containing sodium 1 : 2 : 4 - triamino - benzene - N1 - sulphonate and the sulphuric ester of the leuco derivative of dibenz - pyrene - quinone is used to print cotton; (16) a mixture containing sodium 1 : 2 : 4 - triamino - benzene - N1 - sulphonate, a mixture of the diazoamino compound obtained from diazotized 1 - amino - 4 - benzoylamino - 2 : 5 - diethoxybenzene and sarcosine with 1 - amino - 2 - hydroxy - 3 - naphthoyl - benzene, and further components including urea, sodium sulphoricinate, diethylene glycol and soda-lye is used to print cotton; (19) a rabbit skin is dyed in an aqueous solution of sodium 1 : 2 : 4 - triamino - benzene - N1 - sulphonate, hydrogen peroxide and hydrochloric acid.