Patent GB-828353-A (GB)
Title: New stilbene azo dyestuffs
Inventor: ANDREW HERBERT FRANCIS
IPC: C09B62/085
Filed: 1957-02-25
Abstract: The invention comprises dyes which, in the free acid form, are of formula <FORM:0828353/IV(c)/1> where R is a halogen atom, a nitro group, a substituted amino (but not monoalkylamino) group, an acylamino group, a 11, 21, 4,5-naphthatriazolyl group which may be substituted by sulphonic acid, a 4-arylazo-3-substitued-pyrazol-5-on-1-yl group where arylazo may be substituted other than with amino, monoalkylamino or a metallizable system or a group -N = N-B, where B is the residue of a coupling component, X is a direct link or a divalent arylazo group which may be substituted otherwise than with amino, monalkylamino or a metallizable system, Y is H or an alkyl group and Z is a halogen atom, provided that at least one of R or X has at least one azo group.  The dyes are made by reacting a cyanine halide with an appropriate stilbene azo compound.  Reaction is preferably effected at below 10 DEG  C. in water.  Water-soluble organic solvents and acid-binding agents may also be present.  Chlorine and bromine atoms are indicated for R and Z, and Y is specified as methyl, ethyl, butyl, hexyl and octyl.  R is also specified as anilino, p-nitroanilino and dibenzyl-, dimethyl-, benzoyl-and acetyl-amino. Indicated as 3-substituents in the 5-pyrazolones represented by R are methyl, phenyl, carboxy and carbomethoxy.  Indicated as subtituents to be present in any arylazo group which may wholly, or in part, form R and X are chloro, nitro, sulphonic and carboxylic acid, methyl, methoxy and ethoxy, hydroxy, acetyl-, benzoyl-, dimethyl-, diethyl-, dibenzyl-, substituted dibenzyl-amino, anilino, substituted anilino and arylazo groups.  Cyanuric chloride and bromide are specified cyanine halides.  The starting stilbene azo compounds, when X is an arylazo residue, may be made from a 4-aminostilbene-2,21-disulphonic acid, substituted in the 41-position by a group represented by R, e.g. 41-, nitro-, -(5-sulpho-2-naphtho-(11,21,4,5) - triazolyl) -, - acetylamino -, -benzoylamino -, - chloro -, - bromo -, - dimethylamino -, - anilino - and - dibenzylamino - 4-amino - 2,21 - disulphonic acids, by diazotizing and coupling with an aryl- or alkaryl-amine, e.g. aniline and anthranilic acid (as their o -methane-sulphonates), m-toluidine, 2-methoxy-5-methylaniline, o- and m-anisidines, 2,5-dimethoxyaniline, mono-methyl-, -ethyl- and -butylanilines, a  - naphthylamine and 1 - naphthylamine - 6 - and - 7 - sulphonic acids.  4-Substituted - 41 - (411 - aminophenylazo)-stilbene-2,21-disulphonic acids are preferred starting compounds.  They may be made as indicated above or by treating an appropriate 4 - substituted - 41 - nitrostilbene - 2,21 disulphonic acid, e.g. 4,41-dinitrostilbene-2,21disulphonic acid, with a p-phenylene diamine in the presence of an alkali. 1,41-Phenylene diamine 2-sulphonic acid, 2-methyl- and -methoxy-1,4-phenylene diamines and 1,4-phenylene diamine are preferred phenylene diamines, the latter being preferred. Compounds where X is a polyazo compound may be made from those where X is an arylazo group containing an amino group by conventional diazotization and coupling processes.  Where X is a direct link R must have at least one azo group and compounds containing an azo group attached directly to the stilbene residue may be made, e.g. by coupling diazotized 4-nitro-41-aminostilbene - 2,21 - disulphonic acid with an appropriate coupling component and reducing the nitro to an amino group.  When the coupling component contains a diazotizable amino group the product may be diazotized and coupled with a coupling component before reducing the nitro group so that R becomes a polyazo residue.  When amino or monoalkylamino groups are introduced with the coupling components they are acylated, so that they will not react with the cyanuric halide, before the nitro group is reduced.  A great variety of coupling components are specified being chosen from phenols, naphthols, pyrazolones, b -ketoacetoarylides, arylamines, acylaminonaphthols and sulphonic acids derived therefrom.  Starting compounds may also be made by diazotizing a primary aromatic amine, which does not contain an hydroxy, alkoxy or carboxylic acid group o to the amino groups, e.g. aniline-2,5-disulphonic acid, m- and p-nitroaniline, 4-nitroaniline-2-and 3 - nitro - aniline - 4 - sulphonic acids, m-and p - aminoacetanilide, 3 - aminoacetanilide - 4 - and 4 - aminoacetanilide - 3 - sulphonic acids and 4 - amino - 2 - acetoluidide-5-sulphonic acid, and coupling with a 4-amino-41 - (3 - substituted - pyrazol - 5 - on - 1 - yl)-stilbene-disulphonic acid, e.g. 4-amino-41-(3-carboxy - or - methyl - pyrazol - 5 - on - 1 - yl)-stilbene-2,21-disulphonic acids.  Dyes where R is a 4-arylazo-3-substituted pyrazolone group may also be made by treating a cyanuric halide with an appropriate aminostilbenyl-pyrazolone (see Specification 602,170) and coupling with a diazotized aromatic amine. The dyes are preferably isolated at pH 6-8, particularly pH 6.5, e.g. by the use of buffering agent.  The dye paste is preferably dried at below 65 DEG  C.  The dyes, as their alkali metal salts, are preferably used to colour silk, wool, regenerated protein and cellulosic textile materials by treatment with an aqueous solution of the dye in the presence of an alkaline agent vide Specification 797,946.  Silk, wool, regenerated protein, polyamide and modified polyacrylonitrile textile materials may be dyed in conventional fashion from weakly acid or neutral dye baths.  Silk, wool and regenerated protein textile materials may be printed by usual processes.  Orange to yellow shades are obtained.  Dyes made by diazotizing 4 - nitro - 41 - aminostilbene - 2,21 - disulphonic acid, coupling with an aromatic amine, and treating the product with cyanuric chloride are especially valuable for colouring cellulosic textile materials which are to be after-treated, e.g. with a urea-formaldehyde resin.  Numerous examples are provided of the preparation of the dyes from the materials indicated above and their use in dyeing cellulosic materials.  Specification 602,170 also is referred to.