Patent GB-939268-A (GB)
Title: Basic dyestuffs
IPC: C09B69/00
Filed: 1960-01-27
Abstract: Aromatic and heterocyclic compounds, free from sulphonic and carboxylic acid groups, and containing at least one group of formula <FORM:0939268/IV(a)/1> where R1 is an alkylene radical and R2 and R3 are alkyl groups which, together with N, may form a heterocyclic radical, and which group is attached to the N atom of a tertiary phenyl amine, are made by oxidising the corresponding amine. Oxidation is preferably effected in an inert solvent or aqueous suspension or solution, at elevated temperatures with an excess of oxidising agent.  Alcohols, ketones, esters and carboxylic acids are indicated as solvents.  Oxidising agents specified include hydrogen peroxide, chromic acid, peracetic acid, perborates, nitric acid, manganese oxides, nitrous oxides, halogens and hypohalogenites. Anodic oxidation may be used.  Representative of amine oxides obtained are those derived from N-ethyl-N-dimethylaminoethylbenzene. 1-(N-ethyl-N-dimethylaminoethyl)-amino-3-bromobenzene and 1-(N-ethyl-N-21-morpholylethyl)-amino-3-methylbenzene.  The amine starting materials are obtained from the corresponding halide on treatment with an appropriate secondary amine.  The products are used in the preparation of azo dyes (see Group IV(c)).ALSO:The invention comprises basic dyes free from carboxylic and sulphonic acid groups which have at least one group of formula <FORM:0939268/IV(a)/1> where R1 is an alkylene radical and R2 and R3 are alkyl radicals which may, together with N, form a heterocyclic ring.  The dyes are made by oxidizing a dye containing an -R1-N(R2)R3 group.  In azo dye preparation the group may be oxidized in either a diazo or coupling component before coupling which is preferably effected in a weakly alkaline to acid medium. Anthraquinone, nitro, phthalocyanine, triphenylmethane, cyanine, perinone, naphthoquinone, oxazine, thiazine, indigo, quinophthalene and azo dyes are mentioned the latter being preferred. The oxidation is preferably effected in an inert solvent or aqueous suspension or solution, at elevated temperatures with an excess of oxidizing agent.  Alcohols, ketones, esters and carboxylic acids are indicated as solvents. Oxidizing agents specified include hydrogen peroxide, chromic acid, peracetic acid, perborate, nitric acid, manganese oxides, nitrous oxides, halogens and hypohalogenites.  Anodic oxidation may be used. The dyes colour polymers containing more than 80% acrylonitrile, e.g. polyacrylonitrile and copolymers with 95% acrylonitrile and 5% vinyl acetate or methyl acrylate or methacrylate. Advantageously the dyes are applied from aqueous, preferably weakly acid, suspension at high temperatures in the presence of dispersing agents.  Wool, cotton and viscose are reserved in blended fabrics.  Synthetic polyamide, cellulose ester, e.g. acetate and triacetate, and terephthalic acid ester fibres are also coloured. Yellow, orange, red, violet and blue shades are obtained.  Examples are provided of the preparation of the dyes and of their use in dyeing polyester and polyacrylonitrile fibres, included amongst the dyes prepared are those of formula <FORM:0939268/IV(a)/2> where R4 is, e.g. 4-nitro-, chloro-, acetyl-, methylsulphonyl-, cyano- and trifluoromethyland 4-nitro-2,6-dichloro-phenyl, thiazolyl-2, benzothiazolyl-2, 6-dimethylaminosulphonylbenzothiazolyl-2 and 5-acetyl-thienyl-2, X is H, Me, Cl, Br, CF3 and acetylamino, y is H, Me and OMe, R5 is Me, Et, propyl, butyl, 21-cyano and acetoxy-ethyl and CH2-CH2-NO-(CH2CH3\t )2 and R6 is CH2CH2-NO(Me)2, CH2CH2NO(Et)2, C2H4NO(C3H7)2 and CH2NO(CH3)2, which when R4 is a thiazolyl, benzothiazolyl, pyridyl, triazolyl, benzimidazolyl, benzoxazolyl, acridyl or isoquinolyl residue may be quaternated to yield N-methyl, ethyl and benzyl salts containing as anions, e.g. Cl, HSO4, H2PO4, ZnCl3, C2H5OSO3, CH3SO3, CH3COO, lactate, oxalate, myristate, oleate, phosphotungstomolybdate and silicomolybdate anions or the anionic form of dyes containing sulphonic and/or carboxylic acid groups or of free dye acids of 2,1- metal complex dyes free from sulphonic and carboxylic acid groups; those of formulae <FORM:0939268/IV(a)/3> where, e.g. alkyl is Me or Et, R10 is -C2H4O2S-, -(CH2)3NHO2S- and -CH2CO-, R11 i H, Cl, Br, CN, CF3, NO2 and CH3SO2, R12 is H, Me, CH3CONH and OEt, R13 is Et and 21-hydroxy and -acetoxy-ethyl, R14 is an R13 and 21-cyano-ethyland n-butyl, R15 is -CH2CO-, -CH2COHN-, -(CH2)2SO2HN- and -(CH2)2OCOHN-, R16 is as R11 and R17 is 21-hydroxy-51-methyl-, 41-hydroxy-, 21-acetylamino-41-hydroxy-, 41-diethylamino-and 41-diethylamino-21-methyl-phenyl and 41-dimethylamino-naphthyl-(11); those of formulae <FORM:0939268/IV(a)/4> those of formula <FORM:0939268/IV(a)/5> where R18 is NH2 or OH, R19 is Cl, CF3, -O(CH2)2NO(C2H5)2 and Br, R20 is H or, together with R19 is =(CO)2=N-CH2CH2-NO-(CH2-CH3) 2, R21 is NH2, NH(CH2)2 NO(C2H5)2 and NHPhSO2NH(C2H4)-NO(C2 H5)2, R22 is H, NO2 or OH, R23 and R24 are H and R25 is H, NO2 or OH; those of formula <FORM:0939268/IV(a)/6> where R26 is -CH2H4-NO-C2H5 2 and CH2C(H) CH3NO(C2H5)2, R27 is H, Me, Et or C2H4 NO(C2H5)2 and R28 is H, Me, OMe and OEt and when R28 is H the ring in which it is substituted may be fully hydrogenated and those of formulae <FORM:0939268/IV(a)/7> <FORM:0939268/IV(a)/8> and <FORM:0939268/IV(a)/9>