Patent GB-926998-A (GB)
Title: New water-soluble azo dyestuffs containing phosphonium groups
Inventor: FISHWICK BRIAN RIBBONS
IPC: C09B69/00
Filed: 1960-04-25
Abstract: Quaternary phosphonium halides for use in the preparation of water soluble azo dyes (see Group IV(c)) are obtained by reacting substituted alkyl halides with tertiary phosphines, the substituted alkyl halides being selected from p-aminophenacyl chloride, p-nitrobenzyl chloride, b -(p-aminophenyl-oxycarbonyl) ethyl chloride, p-nitrophenyl beta-chloroethyl sulphone or sulphoxide, p-aminophenyl b -chloroethyl ether, p-acetamidophenyl b -chloroethyl ketone, N-ethyl-N-b -bromo-ethyl-aniline, N-methyl-N-b -(chloroacetoxy) ethyl-aniline, N - methyl-N-b -chloroethyl-m-chloro-aniline, N - ethyl - N - (g -chloro - b -hydroxypropyl)-1-naphthylamine, N-b  - methoxyethyl-N - g  - chloropropyl - m - toluidine, N:N-bis (b -chloroethyl)-m-toluidine, m - (chloroaceta - mido)N:N-diethylaniline, N-ethyl-N-b -bromo-ethyl-m-toluidine, N - b  - cyanoethyl - N - b 1-chloroethyl-m-toluidine and the tertiary phosphines being selected from phenyl dimethyl-, tri-n-butyl-, triethyl-, triphenyl-, tris-(hydroxymethyl)-, ethyldimethyl-, ethyl diphenyl-and triethylphosphines.  The nitro compounds are reduced to the corresponding amino compounds e.g. by catalytic hydrogenation.ALSO:The invention comprises water-soluble azo dyes which are devoid of sulphonic and carboxylic groups and which contain one or more groups of the formula <FORM:0926998/IV(a)/1> wherein the phosphorus atom is directly attached to a carbon atom of the dye and wherein R1, R2 and R3 are organic radicals, the same or different, each having a carbon atom linked directly to the phosphorus atom and Z is an anion and processes for the preparation thereof wherein (a) a diazotized diazo component is coupled with a coupling component provided that both the said components are devoid of sulphonic and carboxylic acid groups and that one or both of said components contains at least one group of the formula <FORM:0926998/IV(a)/2> directly attached to a carbon atom or (b) a water-insoluble azo dye containing a halogen atom attached to an aliphatic carbon atom is reacted with a tertiary phosphine of the formula P (R1) (R2) (R3) where R1, R2 and R3 have the meanings given above.  Representative of the many diazo components specified are m-amino-phenyl trimethyl-; phenyl dimethyl-p-amino-phenacyl-; triethyl-b -(p-aminophenoxy)ethyl; triallyl-p-aminophenacyl-; 2-thienyl diethyl-p-aminophenacyl-; triethyl-b -(p-aminophenylsulphoxy- and sulphonyl)ethyl-; trimethyl-b -(p-aminophenyl-sulphonamido)ethyl-; tri-n-butyl-b -(p-aminophenylcarbonyloxy)ethyl-; phenyldimethyl p-aminophenyloxycarbonylmethyl-; trimethyl-b -amino-1-naphthylsulphonamido)ethyl-; and (p-aminobenzyl)tri-n-butyl phosphonium chlorides, trimethyl-p-aminophenacylphosphonium bromide and trischloromethyl-p-aminophenacylphosphonium iodide. Representative of the coupling components specified are Y-[N-ethyl-N-(3-methylphenyl)amino] propyldimethyl phenyl-; b -[N-b 1methoxyethyl-N-(3- methylphenyl) amino]ethyl dimethyl-; tri-n-butyl-g -(N-ethyl-N-1-naphthylamino)b -hydroxypropyl;- b -[N ethyl-N-(3-trifluoromethylphenyl)amino) ethyl] tri-n-butyl- and b -(N-cyanoethyl-N-m-tolylamino)ethyl] triethylphosphonium chlorides, N:N-bis-[b -di-n-butylphosphino)ethyl]m - toluidine P:P1-di-n-butochloride and [b -(N-b -cyanoethyl-N-m-tolylamino)ethyl] triethylphosphonium chloride.  Additional coupling component specified include 2-amino- and 2-amino-6-cyano-, nitro, thiocyano and -methylsulphonylbenzythiazole, N:N-diacetoxyethylaniline, phenols, ketomethylene coupling components such as acetoacetanilide and 1-phenyl-3-methyl-pyrazolone and its derivatives.  Representative of the phosphines specified are tris(hydroxyethyl)-; 2-thionyldiethyl-, phenyldiethyl, ethylphenyl-benzyl and triallyl phosphines.  The dyes are particularly suitable for textile materials comprising polymers and copolymers of acrylonitrile and dicyanoethylene.  Examples are furnished.  The preparation of quaternary phosphonium halides for use in the processes is described (see Group IV(b)).