Patent GB-449241-A (GB)
Title: Improvements in or relating to the manufacture of azo dyestuffs
IPC: C09B44/04
Filed: 1934-09-13
Abstract: Basic azo dyes containing one or more quaternary ammonium groups are made (1) by coupling diazo compounds with aromatic amino compounds having a free p-coupling position to the amino group and containing a quaternary ammonium group attached directly to the nucleus in a position other than the m-position; (2) by coupling diazotized aromatic amines of the benzene series having a free p-position to the amino group and containing a quaternary ammonium group attached directly to the nucleus in o-position to the amino group with coupling components (excluding b -ketocarboxylic acid arylides having a quaternary ammonium group in the arylide residue and oxycarboxylic acid arylides) and (3) by coupling with diazo compounds or diazotizing and coupling with azo components, aromatic amino compounds having a free p-position to the amino group and containing a quaternary ammonium group in a side chain of the general formula O--X--Q where X = a hydrocarbon residue and Q = a quaternary ammonium group.  They may be further diazotized and coupled with azo components (excluding b -ketocarboxylic acid arylides having a quaternary ammonium group in the arylide residue and oxycarboxylic acid arylides). The dyes obtained in some cases may be diazotized and coupled on the fibre or may be coupled on the fibre with diazo compounds. They may also be after-treated with formaldehyde or salts of metals capable of forming complex compounds, e.g. iron, copper, chromium, nickel or cobalt and may be used according to the process described in Specification 427,089.  They also dye on to tannin, antimony salt or katanol mordants and dyeings may also be after treated with tanning materials, katanols &c.  The following dyes are described in examples: (1) aniline --> b -(2-amino-4-methylphenoxy)-ethylmethylpiperidinium methosulphate or -b  (2-amino-4-methylphenoxy) - ethylpyridinium bromide --> b -naphthol (violet on animal and vegetable fibre); (2) p<1>-aminobenzolyl-m-aminophenyltrimethylammonium chloride --> trimethyl-(8-aminonaphthyl-2-)ammonium methosulphate --> a -naphthylamine (blue on cotton); it may be diazotized on the fibre and developed; the middle and end components may be exchanged; using 8-oxyquinoline as end component the dyestuff is capable of forming complex metal compounds; (3) same as (2) using m-phenylenediamine as end component (grey-blue on cotton); the dyeing may be developed with diazotized p-nitroaniline (grey or black), (4) benzidine \sQ trimethyl-(5-aminonaphthyl-2-) ammonium methosulphate (from 5-nitro-2-naphthylamine); when dyed on to the dyestuff benzidine \sQ Cleve's acid or used as an impregnation for dyeing with the latter (c.f. Specification 427,089) a yellowish red fast to washing is obtained; the dyeing may be diazotized and developed with m-phenylene-diamine, b -naphthol or 1-phenyl-3-methyl-5-pyrazolone, (5) b -(1<1>-amino - 2<1> - naphthoxy)-ethylpyridinium bromide --> a -naphthylamine --> trimethyl-(8-aminonaphthyl-2) ammonium methosulphate (blue on cotton) --> (on the fibre) b -naphthol (blue). Samples have been furnished under Sect. 2 (5) of (1) the dyestuff 1-aminobenzene-2-trimethylammonium chloride --> b -naphthol, (2) a dyeing of the dyestuff of example 2 diazotized and developed with m-phenylenediamine, (3) a dyeing on cotton with the dyestuff dianisidine \sQ 1-naphthylamine-7-trimethyl ammonium chloride diazotized and developed with 2 : 3-oxynaphthoic acid anilide. Other components specified are (2-amino-4-methylphenyl)-trimethylammonium chloride, b -(m-aminophenoxy) ethylmethylpiperidinium methosulphate, 2-, 6-, 7-, or 8- quaternary ammonium substituted 1-naphthylamines, (1-amino - 2 - methoxynaphthyl - 7) - trimethylammonium chloride (from 2 : 7-aminonaphthol by exhaustive methylation, nitration and reduction), b -(1-amino-2-naphthoxy)-ethylmethylpiperidinium methosulphate.  b -(1<1>-Amino - 2<1> - naphthoxy) - ethylpyridinium bromide above referred to is obtained from 1 - nitro - 2 - naphthol - b  - bromethylether and pyridine, followed by reduction. Specifications 14494/95, 9343/96, and 4545/98, [all in Class 2], 22069/11, and 8872/12, [both in Class 2 (iii)], 435,249, and 438,025 also are referred to.  The Specification as open to inspection under Sect. 91 comprises broadly the manufacture of basic azo dyes by using as diazo and/or azo components aromatic amino compounds with a quaternary ammonium group and a free p-position to the amino group. The following dyestuff is also described: aminobenzylmethylpiperidinium - methosulphate (from benzyl chloride by nitration, reaction with piperidine, dimethylsulphate and reduction) --> trimethyl-(8-aminonaphthyl 2)-ammonium methosulphate (from 8-nitro-2-naphthylamine by exhaustive methylation and reduction) --> 2 : 3-oxynaphthoic acid anilide (violet on cellulose fibre).  This subject-matter does not appear in the Specification as accepted.