Patent GB-791932-A (GB)
Title: Quaternary ammonium salts of n-heterocyclic monoazo dyestuffs and their use
IPC: C09B44/10
Filed: 1956-01-27
Abstract: The invention comprises dyestuffs of formula <FORM:0791932/IV (b)/1> the cation part of which is free from sulphonic acid or carboxyl groups, A1 is the residue of an aromatic N-alkyl cyclammonium hetero ring system comprising a single hetero nucleus of five ring members of which at least two are ring N atoms and which is bound to the azo group by a C-atom that forms part of the hetero ring, B is the residue of an azo component and X- is an anion equivalent to the azo dye cation.  They may be made by alkalting the corresponding dyestuff, advantageously in the presence of an inert organic diluent, and with an excess of alkylating agent to ensure cyclammonium salt formation, or from appropriate reactants by diazotization and coupling.  A is advantageously a polyazole ring which may be further condensed, e.g. to contain fused benzene or naphthalene rings. Specified for A are pyrazole, cinnoline, imidazole, triazole, tetrazole, oxidazole, thiadiazole, benzimidazole, naphthimidazole and indazole residues which may be substituted with groups which do not dissociate acid in neutral water such as alkyl, alkoxy, aralkyl, aryl, nitro, acylamino, alkyl-sulphonyl, sulphonamido, carboxylic acid ester and halogen groups.  Indicated for B are residues of acylacetylamino arylamides, naphthols, naphthylamines, phenols, phenylamines and 5 - hydroxy or -amino-pyrazoles and B may also be a 5-hydroxy or -amino-pyrazole, 3-indolyl, 2,4-dihydroxyquinolinyl-(3) and 2,4,6-trihydroxypyrimidyl-(5) residue.  The final products may be alkylated or acylated.  When made by diazotization and coupling processes the coupling components are chiefly isocyclic-aromatic amino and hydroxy compounds, advantageously those coupling p-to the amino or hydroxy group and the isocyclic-aromatic ring may contain fused hetero rings as in 4-aminobenztriazole, -benzimidazole and -aminoindazole.  In the preferred p-aminoaryl-azo dyestuffs the amino group may be primary, secondary or tertiary.  The substituents of the amino group may be aliphatic, araliphatic, alicyclic, aromatic or heterocyclic and further substituted by groups such as hydroxyalkyl, fluoralkyl, cyanalkyl, alkoxy, phenoxy-alkyl and alkyl-, alkoxy- and halogen-phenyl, and -benzyl groups.  Aliphatic substituents of the amino group may form hydrogenated hetero rings optionally together with an ether atom or with the aromatic radicle having the amino group as in the piperidino, morpholino, 1,2,3,4-tetrahydroquinoline, lilolidine, julolidine and perimidine compounds.  The preferred p-aminophenyl radical may be substituted by halogen, alkyl, alkoxy, nitro, acylamino and alkyl sulphonyl groups.  Ethers of strong mineral and organic acids may be used as alkylating agents, many being listed.  The usual halides may also be employed.  The dyestuffs also form salts with weak acids such as acetic, formic, oxalic, lactic and tartaric acids and double salts with inorganic salts such as zinc chloride may be formed, chloro-zircates and -cadmiates also being mentioned.  The dyestuffs dye cellulose, tannin, silk, leather, polyacrylonitrile and polyacrylonitrile fibres.  In examples in which dyestuffs are obtained which dye certain of the above fibres in red, yellow and blue shades the diazo components used are 3-amino-1,2,4-triazole and its 5-methyl and 5-ethyl derivatives, 5-aminotetrazole, 2-aminobenzimidazole, 3-aminoindazole and its 4-methyl, -methoxy and -chloro-derivatives, 2-amino - 5 - methyl - or - phenyl - 1,3,4 - thia- or oxa-diazoles and 2-amino-1,3,4-thiadiazole, the coupling components being N,N-dimethyl-, -diethyl-, -dihydroxyethyl, -dibenzyl-, N-ethyl-N-benzyl-, N-methyl-, N-methyl-N-b -cyanethylaminobenzenes, 1 - N,N - dimethylamino - 3 - methyl-, -methoxy- and -chloro- and 2,5-dimethoxy and 1-N,N-diethylamino-3-methyl-, -2-methoxy-5-methyl- and -3-carbethoxy-benzenes, 1 - amino - 3 - methylbenzene phenol, a - and b -naphthols, phenyl morpholine, 1-phenyl - 3 - methyl - 5 - aminopyrazole and -pyrazolone, 1,2,3,4-tetrahydroquinoline, indole and pyrrole the quaternating agents being dimethyl and diethyl sulphate, methyl p-toluenesulphonate, ethyl bromide and butyl iodide.