Patent GB-786929-A (GB)
Title: Improvements relating to quaternary ammonium salts of thiazole monazo dyestuffs
IPC: C09B29/033
Filed: 1955-12-14
Abstract: The invention comprises dyestuffs of formula <FORM:0786929/IV (b)/1> where the cation is free of acid dissociating, salt forming groups, R1 is an alkyl radicle which may be substituted, A is an alkene radicle, the two adjacent doubly bound C atoms of which are connected to the N and S atoms of the hetero nucleus, B is the residue of an azo component and X1 is an anion equivalent to the cyclammonium cation.  They may be made by alkylating appropriate dyestuffs.  A is indicated as an ethene, propene, D 1- or D 2-butene or D 3-hexene radicle or a phenyl-, cycloalkyl-, halogen-, alkoxy-, nitro- or acylamino-alkene radicle.  Methyl, ethyl, propyl, butyl, hydroxyethyl and benzyl groups are specified as substituents for the alkyl group of R1.  The azo component may be of the aliphatic, cycloaliphatic, or isocyclic- or heterocyclic-aromatic series, e.g. acyloacetyl compounds, and compounds containing dihydroresorcinol, phenylnaphthyl, pyrrole or pyrazole rings which may contain amino, hydroxy, amido, acylamino, alkyl, aralkyl groups as substituents or may be fused with other rings.  Amino groups in the starting dyestuff may be acylated.  Thus, B may comprise acetoacetyl - phenylamide, hydroxy- and amino- and acylamino-phenyl and -naphthyl, 3-indolyl and 5-hydroxy- and -amino-pyrazole residues.  The starting dyestuffs may be obtained by the usual processes of diazotization and coupling or by the alkaline condensation of p-nitro-phenols or -aminophenyl compounds with 2-aminothiazoles.  Preferred coupling components are isocyclicaromatic amino and hydroxy compounds, especially those coupling in the p-position to these groups.  The isocyclic-aromatic compound may contain fused hetero rings such as 4-aminobenztriazole, aminobenzimidazole or aminoindazole compounds.  The amino group may be primary, secondary or tertiary in character.  The substituents of the amino group may be aliphatic, araliphatic, alicyclic, aromatic or heterocyclic and may be oxalkyl, fluoralkyl, cyanalkyl, alkoxy- and phenoxyalkyl, and alkyl-, alkoxy- and halogen-phenyl and -benzyl residues. Aliphatic substituents of the amino group may form, optionally with an ether oxygen atom or with the aromatic radicle having the amino group, hydrogenated hetero cyclics such as the piperidino, morpholino, 1,2,3,4 - tetrahydroquinolino, lilolidino, julolidino and perimidino compounds.  The preferred p-aminophenyl radicle may contain halogen, alkyl, alkoxy, nitro, acylamino or alkylsulphonyl groups.  Indicated as alkylating agents are esters of strong mineral and organic sulphonic acids, i.e. those of pK at most 4, with preferably low alcohols.  Alkyl chlorides and bromides, aralkyl halides, dialkyl sulphates and alkyl-p-methylbenzene sulphonates may be used.  Other specified anions being metho-and etho-sulphate and bisulphate.  Quaternary ammonium compounds of formic, acetic, oxalic and lactic acid may be obtained and also the dye bases themselves, i.e. X1 is OH.  Further, double salts with inorganic salts, especially those with zinc chloride, may be obtained.  When alkylation is effected in inert organic solvents the dye salts may be precipitated. Solvents mentioned are benzene hydrocarbons, halogen- and nitro-benzenes, cycloaliphatic hydrocarbons and excess of alkylating agent.  An excess of alkylating agent is desirably used, any amino groups being subsequently alkylated if desired. In some cases alkylation may be performed in aqueous or alcoholic solution.  The dye salts may be recovered by salting-out after removal of inert solvent by steam distillation, or they may be isolated by any other conventional method.  The dye salts may be further altered, e.g. acylated.  The dyestuffs are basic and dye cotton mordanted with tartar emetic and tannin, silk, leather and polyacrylonitrile fibres.  Examples are provided illustrating the preparation of the dye salts and their use in dyeing processes the diazo components used being 2-amino-thiazole and its 4-methyl, -acetyl, -methoxy, -n-butyl, -phenyl, 4,5-dimethyl and -diphenyl, 4-methyl-5-ethyl and -(b -oxyethyl), 4-ethyl-5-methyl, 4-carbethoxy-5-methyl and 4-bromo-5-phenyl derivatives; the azo components being 1- and 2-naphthylamine, 1-amino-2-methoxy-, 1-N-phenylamino- and 1-(N,N-dimethyl)aminonaphthalenes, 1,2,3,4 - tetrahydro - 3 - hydroxy-and -5,6-dihydroxy-7,8-benzquinoline, phenol, diphenyl - N - methylamine, 4 - methyl - and -amyl-phenols, 2,5-dimethoxy-aniline, N,N-dimethyl-, -di-(b -oxyethyl)-, -diethyl, -dibenzyl, N-methyl, N,b -oxy- and -cyan-ethyl- and N-ethyl - N - benzyl - anilines, N - methyldiphenylamine, N - phenyl - morpholine, N,N-dimethyl - amino - 3 - nitro -, - methoxy -, methyl- and -carbethoxy-, -2,5-dimethyl- and -dimethoxy- and -2-methoxy-5-methyl-benzenes, N,N - diethylamino - 3 - chloro - benzene, 1 - phenyl - 3 - methyl - 5 - aminopyrazole, pyrrole, indole, 2,5-dimethyl-, 2-methoxy-5-methyl-, 3-chloro- and -methyl- and 2-methoxy-5-acetamino-anilines, N-ethyl-, benzyl- and-phenyl-anilines and 3-methyl- and -chloro-N-ethyl-anilines, and quaternating agents being dimethyl and diethyl sulphate, methyl chloride, methyl and ethyl bromides and iodides, butyl iodide, benzyl bromide and methyl and ethyl p-toluenesulphonates, the dyestuffs yielding blue, orange and red colours on the materials mentioned above.