Patent GB-879073-A (GB)
Title: New heterocyclic azo dyestuffs containing sulphonhalogen-alkylamido groups and their production
Inventor: ROHLAND WERNER
Filed: 1959-06-09
Abstract: The invention comprises dyes of formula:-  <FORM:0879073/IV(c)/1> where A is a naphthol sulphonic acid residue, D is a benzene or naphthalene residue, E a heterocyclic ring containing at least once the group -C=N- and may contain as substituents condensed-on aromatic rings, coloured or uncoloured organic radicals, halogen atoms, primary amino groups and/or hydroxyl groups, G a sulphonic acid halogenalkylamide group attached via S to an aromatic nucleus of the dyestuff and which may be attached to a coloured or uncoloured part of the dye molecule or to the heterocyclic ring, Q a water-solubilizing group, t is 1, y is 1 or 2 and z an integer.  The dyes may be made by (1) coupling a benzene or naphthalene compound containing one or two sulphonhalogenalkylamide groups attached to an aromatic residue with a naphthol sulphonic acid containing the heterocyclic residue, (2) as (1) but the diazo component contains the heterocyclic ring and the azo component the sulphonhalogenalkyamide groups, (3) by condensing an azo dye containing the sulphonhalogenalkylamide group or groups and a primary amino group with an appropriate halo derivative of the heterocyclic compound, (4) by coupling an appropriate diazo component with an azo component containing a heterocyclic ring which is substituted with the sulphonhalogenalkylamide groups, (5) as (4) but the diazo component contains the substituted heterocyclic group, (6) by condensing an azo dye which contains a primary amino group with an appropriate halo compound derived from the heterocyclic compound containing the sulphonhaloalkylamide group or groups, (7) by condensing an azo dye having as substituent a residue of an appropriate haloheterocyclic compound, with an arylsulphonhaloalkylamide containing a primary amino group, (8) by reacting phosgene, thiophosgene or a substance serving as such in a reaction with amino groups, in any sequence on the one hand with an arylsulphonhaloalkylamide containing a primary amino group and on the other hand with a compound containing a primary amino group, of an azo dye containing an appropriate heterocyclic substituent to form an unsymmetrical urea or thiourea, (9) by acylating appropriate heterocyclic azo dyes with arylcarboxylic acid halide sulphonic acid halogenalkylamides and (10) by acylating appropriate heterocyclic azo dyes containing a primary amino group with an arylsulphonic acid halide sulphonic acid halogenalkylamide.  Particularly preferred are dyes of formula:- <FORM:0879073/IV(c)/2> and <FORM:0879073/IV(c)/3> Water-solubilizing groups mentioned are sulphonic, carboxylic and sulphonic acid amide groups.  Indicated as heterocyclic residues are quinolines, quinazolines, pyrimidines, phthalazines and sym triazines.  Coloured radicals indicated include radicals of azo and other dyes. Uncoloured radicals may be attached to the heterocyclic residue via an -NH-, -O-, or -S- bridge and those indicated include residues of aliphatic, araliphatic and aromatic amines, hyroxyl and sulphydryl compounds, aminocarboxylic acids and their amides and esters and aminosulphonic acids and their amides or sulphones.  Indicated arylsulphonhaloalkylamide groups are benzene, diphenyl or naphthalene sulphonic acid chlor- or brom-alkylamides which may contain further substituents in the alkyl group e.g. alkyl, aralkyl, aryl, hydroxyl, alkoxyl, aroxyl, sulphonic acid, sulphonic acid halogenalkylamide, halogen and nitro groups.  The dyes dye or print a variety of textile materials e.g. wool, linear polyamides and native and regenerated cellulose.  Materials containing groups which react with the haloalkylamide groups may be dyed and printed in the presence of acidbinding agents. Examples are provided of the preparation of the dyes and their use in dyeing cellulosic materials.  Red, orange and bluish-red shades are obtained.  Representative of dyes produced are aniline- 4-sulphonic acid beta chlorethylamide --> product of equimols of cyanuric chloride and 1-amino- 8-naphthol-3, 6-disulphonic acid or cyanuric chloride and 1-amino- 8-naphthol-4, 6-disulphonic acid and 1-amino- 4-(4-aminobenzene- 3-sulphonic acid)-aminoanthraquinone- 2-sulphonic acid, aniline-3, 5-disulphonic acid and beta chlorethyl-amide --> product of equimolar quantities of cyanuric chloride, aniline- 2-sulphonic acid and 2-amino-8-naphthol- 6-sulphonic acid, (aniline- 4-sulphonic acid beta-chlorethylamide --> 2-amino- 5-naphthol- 7-sulphonic acid) (2 mols) condensed with cyanuric chloride (1 mol) and the product may be treated with aniline, 1-naphthylamine- 5-sulphonic acid beta chlorethylamide --> product from cyanuric chloride (1 mol), 1-amino- 8-naphthol-3, 6-disulphonic acid (2 mols) and aniline (1 mol), 1-(4-aminobenzoylamino)-benzene- 4-sulphonic acid beta chlorethylamide or 1, 4-diaminobenzene mono-acylated with benzene- 1-sulphonic acid chloride- 4-sulphonic acid-beta chlorethylamide --> product from cyanuric chloride (1 mol), aniline- 2-sulphonic acid (1 mol) and 2-amino- 8-naphthol- 6-sulphonic acid (1 mol), the urea from 1, 4-diaminobenzene- 3-sulphonic acid and the carbamic acid chloride from aniline- 4-sulphonic acid beta chlorethylamide and phosgene --> product of cyanuric chloride (1 mol) and 1-amino- 8-naphthol-3, 6-disulphonic acid, 1, 4-diaminobenzene- 3-sulphonic acid acylated with benzoyl chloride- 3-sulphonic acid beta chlorethylamide --> product of cyanuric chloride (1 mol), 1-amino-5-naphthol- 7-sulphonic (1 mol) and aniline- 4-sulphonic acid (1 mol) and aniline --> product of equimols of cyanuric chloride, 1-amino- 8-naphthol-4, 6-disulphonic acid and aniline- 4-sulphonic acid beta chlorethylamide.  Specifications 209,723, 797,946, 823,098, 830,847, 868,741, 868,742, 876,496 and 877,678 are referred to.