Patent GB-438025-A (GB)
Title: Improvements in or relating to the manufacture of azo dyestuffs
IPC: C09B44/02
Filed: 1934-02-07
Abstract: Water-soluble basic azo dyes are made by coupling a diazo compound with an arylide of an oxycarboxylic acid, the azo component and/or the diazonium compound containing a trialkylammonium or pyridinium group or derivative thereof which is attached to a carbon atom.  They are fast to light and are capable of fixing substantive dyes of an acid character, fast colours being thus obtained when the basic dye contains at least one additional quaternary ammonium group.  They may also act as mordants for non-substantive acid dyes and may be used in conjunction with tanning agents; dyeings with the latter may be after-treated with metal salts and the combinations with acid mordant dyes may be similarly after-treated.  Textiles when dyed with the basic dyes assume a soft feel when treated with solution of soap or similar substances.  In examples: (1) diazotized trimethyl - m - aminophenylammonium methosulphate is coupled with bis-(2<1> : 3<1>-oxynaphthoyl) - benzidide - (orange on cotton); it may be after-dyed with congo red or treated with tanning agents; other diazo components specified are trimethyl - (2 : 4 - dimethyl - 5-aminophenyl) - ammonium - methosulphate, trimethyl - (3 - amino - 4 - methoxyphenyl) - ammonium chloride and trimethyl-(5-amino-1-naphthyl) - ammonium chloride, (2) diazotized trimethyl - (p<1> - aminobenzoyl - m - aminophenyl)-ammonium chloride is coupled with 2 : 3 - oxynaphthoic anilide.  Diazo components also specified are trimethyl-(m- or p-aminophenyl)-ammonium salts and their m<1>- or p<1>-amino benzoyl derivatives, salts of o-, m-or p - aminobenzyl - pyridiniums, trimethyl-(p<1> - aminobenzeneazophenyl) - ammonium salts and aromatic aminotrialkyl ammonium compounds --> m-toluidine, a -naphthylamine or other middle component.  Coupling components specified are arylides from salicylic, p-cresotinic, p-oxybenzoic, 2 : 3-oxynaphthoic, 2 : 3-oxyanthracene carboxylic, 2 : 3- and 3 : 2-oxyphenanthrene carboxylic, 2 : 3-oxycarbazole carboxylic and 8-oxy-quinoline-5-carboxylic acids and aromatic mono or diamines, e.g. aniline and its derivatives, a - or b -naphthylamine, m- or p-phenylene diamine, benzidine and its derivatives, tolidine, dianisidine and p : p<1>-diaminodiphenylamine. Specification 295,032, [Class 2 (iii)], is referred to.  Samples have been furnished under Sect. 2 (5) of the dyestuffs: (1) aminobenzylmethylpiperidinium methosulphate --> trimethyl - (8 - amino-naphthyl - 2) - ammonium methosulphate --> 2 : 3 - oxynaphthoic acid anilide; (2) benzidine \sQ 1-(2<1> : 3<1>-oxynaphthoyl)-amino-3-betainyl chloride - aminobenzene <FORM:0438025/IV/1> (obtained by condensing 2 : 3-oxy-naphthoic acid with m-nitraniline, reducing in pyridine with zinc dust and glacial acetic acid, condensing with chloracetyl chloride and then with trimethylamine).  Trimethyl - (p<1> - aminobenzoyl - m - aminophenyl-) - ammonium chloride is made by condensing m-aminodimethylaniline with p-nitrobenzoylchloride, treating the product with dimethyl sulphate, reducing and salting out. Aminobenzylmethylpiperidinium methosulphate is made by nitration of benzyl chloride, condensing the reaction mixture with piperidine, treating with dimethyl sulphate and reducing.  Trimethyl - (8 - aminonaphthyl - 2) - ammonium methosulphate is obtained from 8-nitro-2-naphthylamine by exhaustive methylation and reduction.  The Specification as open to inspection under Sect. 91 comprises the coupling of an azo component, e.g. an arylide of an oxy- or ketocarboxylic acid with a diazo compound, the azo and/or diazo component containing a quaternary ammonium group.  Of the hydrocarbon groups attached to the quaternary nitrogen one must be of an aromatic or fatty aromatic nature, while the remainder may belong to the aliphatic, alicyclic, aromatic and fatty aromatic series.  The nitrogen atom may also belong to a heterocyclic ring system, e.g. pyridine, quinoline, piperidine and phenazine systems.  Arylides from acetoacetic, benzoylacetic, oxalo acetic, and acetone dicarboxylic acids are specified and also aminophenazonium compounds (safranines). Those dyes containing at least two quaternary ammonium groups are said to be particularly fast.  In examples the following dyes are described: (1) trimethyl - p - aminophenylammonium - methosulphate --> bis - acetoacetic acid tolidide (yellow on cotton and viscose); (2) benzidine \sQ trimethyl-p-acetoacetylaminophenyl ammonium methosulphate; (3) trimethyl - (p<1> - aminobenzoyl - m - aminophenyl) - ammonium chloride --> phenol, b -naphthol or trimethyl-p-acetoacetylaminophenylammonium methosulphate; a middle component, e.g. m-toluidine or a -naphthylamine may be interposed between the diazo and azo component.  This subject-matter does not appear in the Specification as accepted.