Patent GB-787369-A (GB)
Title: Quaternary ammonium salts of benzthiazole azo dyestuffs
IPC: C09B44/20
Filed: 1955-12-14
Abstract: The invention comprises dyestuffs of formula <FORM:0787369/IV (b)/1> where the cation is free of acid dissociating salt forming groups, R1 to R8 are H or substituents which do not dissociate acid in neutral water, R9 and R10 are H or aliphatic, araliphatic, heterocyclic-aliphatics, cycloaliphatic or aromatic substituents, two neighbouring R's may form a ring with the condition that of R1 to R8 at least one R is a substituent or that at least R9 or R10 is a substituent with more than one carbon atom, R11 is an alkyl radicle which may be substituted and X1 is an anion equivalent to the cation. They are made by alkylating the corresponding azo dyestuff at a raised temperature.  R3 is preferably a positive substituent, e.g. an alkyl or ether group, specified being methyl, ethyl, isopropyl, tert.-butyl and -amyl, methoxy, ethoxy, phenoxy, benzyloxy, methyl-and phenyl-mercapto groups and groups forming a ring with a neighbouring substituent such as a dihydroxy- and tetra-methylene group and a dioxine ring. Specified for R11 are methyl, ethyl, propyl, butyl, hydroxyethyl and benzyl radicles.  A neighbouring pair of R1 to R4 may form a fused benzene ring.  The nucleus of the benzthiazole radicle may contain halogen, nitro, acylamino, alkylsulphonyl, carboxylic ester, sulphonamide, phenyl and benzyl groups.  The p-phenylene radicle bound to the azo groups may form part of a fused ring system.  Either of the pairs R5 and R5 and R7 and R8 may form fused benzene rings or hydrogenated isocyclic or heterocyclic rings as e.g. in naphthalene, tetrahydronaphthalene, benzimidazole, benztriazole and indazole residues.  Advantageously, R5 to R8 represent two H atoms in p-position to each other and especially when R5 is a substituent such as an alkyl, alkoxy or acylamino group or a halogen atom.  R5 may also be a nitro or alkylsulphonyl group.  If R5 is an alkyl or an alkoxy group dyestuffs wherein R9 and R10 are H can be obtained directly by coupling otherwise the amino group in the p-position is substituted, preferably organically, by the above indicated substituents, the furyl methyl group being specified. The substituents of the p-amino groups may be further substituted with, e.g., hydroxy-, fluor-, cyan-, alkoxy- and phenoxy-alkyl, alkyl-, halogen- and alkoxy-benzyl and alkyl- and alkoxy-phenyl groups.  Aliphatic substituents of the amino group may form hetero rings including ether atoms or by linking to R6 and R8 as in the piperidino, morpholino, 1,2,3,4-tetrahydroquinoline, lilolidine, julolidine and perimidine compounds.  Advantageously, one of the N-substituents is a cyanethyl, benzyl or phenyl radicle.  Indicated as alkylating agents are esters of strong mineral and sulphonic acids, preferably of lower alcohols. Alkyl chlorides, bromides and iodides, aralkyl halides, e.g. benzyl bromide, benzyl halides nuclear substituted by halogen, alkyl or alkoxy groups, dialkyl sulphates and alkyl-p-toluenesulphonates are mentioned as alkylating agents, other specified anions being metho- and ether-sulphate and bisulphates.  In some cases the dye bases themselves, i.e. X1 is OH, may be obtained. Quaternary ammonium salts of formic, acetic, oxalic, lactic and tartaric acids are mentioned and also double salts with inorganic compounds such as zinc chloride. Advantageously, alkylation is effected in an inert organic solvent, the water-soluble dye salts precipitating out.  Benzene hydrocarbons, halogen- and nitro-benzenes, high boiling aliphatic and alicyclic hydrocarbons and halogen alkanes are classes of solvents mentioned. An excess of alkylating agent may serve as a solvent and also for the subsequent alkylation of any amino groups.  In some cases alkylation may be effected in aqueous or alcoholic solutions.  The salts are stable and may be isolated by any conventional method. They may be modified as by, e.g., acylation.  The starting dyestuffs may be made by diazotizing 2-aminobenzthiazoles and coupling with appropriate p-amino-aryl compounds or by the alkaline condensation of p-nitroso-aminoaryl and 2-aminobenzthiazoles.  The dye salts are basic dyestuffs and dye cotton mordanted with tartar emetic and tannin, silk, leather and fibres of polyacrylonitrile.  Examples are provided of the preparation of the dye salts and their use in dyeing processes the diazo components used being 2-aminobenzthiazole and its 6-methyl, -ethyl, -methoxy, -ethoxy, -carbethoxy, -cyan, -chloro, -methylsulphonyl, -phenyl and -rhodane and 4-methyl, -ethyl, -chloro and -bromo derivatives and 2-amino-(naphtho-11,21,4,5 and 5,4)-thiazoles, the azo components being aniline, N,N - dibenzyl-, -di - b  - hydroxyethyl-, -dimethyl-, -diethyl-, N-methyl - N - b  - hydroxy-and -cyan-ethyl-, N-ethyl-N-benzyl-, 2,5-dimethoxy- and -dihydroxymethyl-, 3-methyl-, -chloro-, -methoxy- and -acetamino-, 2-methoxy-5 - methyl- and -acetamino-, N,N - diethyl - 3 - methyl-, -acetamino, -carbethoxy, -sulphonamido- and sulphonic acid dimethylamide, N-ethyl - N - benzyl - 3 - methoxy- and -bromo-, N,N - di - b  - cyanethyl - 3 - chloro-, N,N - dimethyl - 3 - nitro-, and -2,5 - dimethyl-, N,N-dipropyl - 3 - bromo- and - 2 - ethoxy - 5 - methyl-, N - ethyl - 3 - methyl-, -chloro-, -methoxy-, -ethoxy- and -carbethoxy and -2,5-dimethoxy-, -dichloro- and -dimethyl-, N - methyl - 3 - acetamino-, -2 - methoxy - 5 - methyl- and acetamino-, 2,6 - dimethyl-, N,N - di - n - butyl - 2 - methoxy - 5 - acetamino-, N - methyl - N - b  - cyanoethyl - 3 - methyl- and N,N - diethyl - 2 - methyl - 5 - methylsulphonylanilines, N-methyldiphenylamine, diphenylamine, N - phenylmorpholine, 1,2,3,4 - tetrahydro - 5,6 - benzo - quinoline, 1 - N,N - dimethylamino - naphtha - lene and -2 - methoxy - naphthalene and 1-N-phenylaminonaphthalene, the alkylating-agents being dimethyl and diethyl sulphates, methyl and ethyl p-toluenesulphonate, ethyl and benzyl bromides and methyl, ethyl and butyl iodides, the dyestuffs yielding red and blue slades on the materials mentioned above.