Patent GB-951667-A (GB)
Title: New water soluble azo dyestuffs containing quaternary ammonium groups
Inventor: HUNTER JAMES STUART
IPC: C09B44/02
Filed: 1961-04-25
Abstract: p-(b -N-ethyl-phenylaminoethoxy) - phenyl trimethylammonium chloride is obtained by reacting N-ethylaniline with p-nitrophenoxyethyl bromide, catalytically reducing the product with hydrogen, treating the product with dimethyl sulphate and then sodium hydroxide and acidifying the mixture with hydrochloric acid. 3-(41-aminobenzoylamino) phenyl-trimethyl ammonium chloride is obtained by reacting p-nitrobenzoyl chloride with m-aminophenyltrimethyl ammonium bromide, isolating the product as chloride and reducing the nitrogroup catalytically. 3-(31-hydroxy-21-naphthoylamino) phenyl trimethyl ammonium chloride is obtained by condensing m-aminophenyl trimethyl ammonium bromide with 2-hydroxy-3-naphthoyl chloride, isolating the product and treating with hydrochloric acid.  3-(41-aminophenylsulphonylamino) phenyl trimethylammonium chloride is obtained by reacting m-aminophenyl trimethylammonium bromide with p-acetamidobenzene sulphonyl-chloride, hydrolysing the product with hydrochloric acid and isolating the desired chloride.  4-(41-dimethylaminobenzoylamino) phenol is obtained by phosgenating dimethyl aniline and condensing the product with p-aminophenol. N-ethyl-N-p-dimethylaminobenzoyloxyethyl aniline is obtained by condensing the intermediate from the last process with N-ethyl-N-b -hydroxyethylaniline in the presence of pyridine.ALSO:The invention comprises water-soluble dyes of the formula <FORM:0951667/C3/1> wherein D represents the residue of an azo dye devoid of sulphonic and carboxylic groups, A represents an arylene radical, X represents a bivalent non-chromophoric radical which links the arylene radical A to an aromatic ring of the residue D, R, R1 and R11 represent alkyl or substituted alkyl radicals and Z represents an anion and process for the preparation thereof comprising (a) coupling a diazo component with a coupling component, provided that both components are devoid of sulphuric and carboxylic acid groups and one of said components contains, attached to an aromatic ring, a radical of the formula <FORM:0951667/C3/2> or (b) treating a water-insoluble dyestuff of the formula <FORM:0951667/C3/3> with an alkylating agent.  Values specified for X are as follows, the arylene ring being attached to the right-hand side of the divalent radical: -CO-, -SO2-, -OB-, -BO-, -SO2N(Q)-, -COO-, N(Q)B, -N(Q)BO, N(Q)BOCO-, -N(Q)BN(Q)CO-, -N(Q)CO- and <FORM:0951667/C3/4> where Q = hydrogen or a hydrocarbon radical optionally substituted, e.g. methyl, ethyl, b -hydroxyethyl, phenyl, p-tolyl, B = an alkylene radical, e.g. -CH2, -CH2CH2-, -CH2CH2-CH2-, Y = chlorine or bromine, a hydroxyl or amino radical or an organic radical containing O, N or S attached to the triazine ring, e.g. a methoxy, phenoxy, p-tolylthio-, phenylamino or 4-dimethylaminophenylamino radical. A may be o-, m- or p-phenylene or 1 : 4, 1 : 5 or 1 : 7-naphthylene. R, R1 and R11 may be methyl, ethyl or b -hydroxyethyl.  Z may be a chloride, iodide, sulphate, methosulphate, methyl- or p-tolylsulphonate ion. Among the dyes described are 4 - aminophenylmethyl sulphone --> p-(b  - N - ethyl - N - phenylamino - ethoxy) phenyltrimethylammonium chloride, 3 - (41-aminobenzoyloxy) - N : N - diethylaniline --> 1 - phenyl - 3 - methyl - 5 - pyrazolone and 2-chloro - 4 - nitroaniline --> 2 : 4 - di - (41-dimethylaminophenylamino) - 6 - [b  - N - phenylamino - ethylamino] - 1 : 3 : 5 - triazine quaternated with dimethyl sulphate in the presence of magnesium oxide and boiling monochlorbenzene. The dyes are particularly suitable for colouring textile materials of polymers and copolymers of acrylonitrile and dicyanoethylene.