Patent GB-885815-A (GB)
Title: New water-soluble dyestuffs containing halogen acylamino groups and their manufacture and use
IPC: C09B62/47
Filed: 1958-05-06
Abstract: The invention comprises dyestuffs which contain, in addition to at least one group imparting solubility in water, an a ,b -dihalogenopropionylamino residue bound through its nitrogen atom to which is also bound a hydrogen atom or an aliphatic substituent, preferably an alkyl group.  The group imparting solubility in water may be a sulphonic acid amide group which may be acylated, or a methyl-sulphone group, carboxylic acid group, or sulphonic acid group.  The dyestuffs may contain additional substituents such as halogen atoms, nitro, acylamino, alkyl, or alkoxy groups.  The dyestuffs may be obtained from dyestuff components which already contain the dihalogenated propionylamino residue.  These components may be obtained by acylation of appropriate amino compounds with a halide or anhydride of an a ,b -dihalogeno-propionic acid.  A dyestuff which contains an acylatable amino group may be acylated with an a ,b -dihalogeno-propionic acid halide or anhydride, e.g. the dichloro compound.  The dyestuffs may be of various kinds, e.g. stilbene, azine, dioxazine, xanthone, thioxanthone, nitro, phthalocyanine, anthraquinone, and azo dyestuffs, including metal-free and metalliferous mono- and poly-azo dyes.  Dyes which may be subjected to acylation to produce the characteristic groups include amino-azo dyes which may be obtained by hydrolysis of acylamino-azo dyes, reduction of the nitro groups of nitroazo dyes, or coupling a diazotised aromatic amine with a coupling component containing an acylatable amino group, such as 1-aminophenyl - 5 - pyrazolones, meta - acylamino - aminobenzenes, and aminonaphthol sulphonic acids; amino-anthraquinone dyes such as 1-amino-4-(31 or 41-aminophenylamino)-anthraquinone-2-sulphonic acid, 1-amino-4-(41-aminophenylamino)- anthraquinone-2,31, 6- or -2,31,7-or -2,31,8-trisulphonic acid, 4- or 5- or 8-amino-1-acylaminoanthraquinones (obtainable by acylation of 1-aminoanthraquinones, which contain in the 4- or 5- or 8-position a nitro group, with sulpho or disulpho-benzoic acid halides, followed by reduction of the nitro group); amino-dibenzanthrone sulphonic acids, and aminoisodibenzanthrone sulphonic acids.  Other intermediate dyes may be obtained by reacting 1 mol of a tri- or tetra-sulphonic acid chloride of a coloured anthraquinone derivative or of a phthalocyanine with 1 mol of a diamine, e.g. a diamino-benzene sulphonic acid, and then hydrolysing unreacted sulphonic halide groups and if desired, any acylamino groups.  The acylation with the dihalogeno-propionic halides or anhydrides may be carried out in presence of an acid binding agent such as sodium acetate or carbonate, or sodium hydroxide preferably in an organic solvent or at a relatively low temperature in an aqueous medium.  The dyestuffs of the invention may be used for dyeing or printing fibrous materials of polyhydroxy compounds such as natural or regenerated cellulose, or nitrogenous materials such as leather, silk, and wool, or fibres of polyamides or polyurethanes.  Dyeing may be effected by direct dyeing methods, or by printing or foularding methods, particularly from aqueous alkaline solutions by processes in which the dye is fixed on the material by a heat treatment, if desired, in presence of steam or alkali.  In an example, the dyestuff <FORM:0885815/IV (c)/1> is neutralized with sodium carbonate solution, and after the addition of sodium bicarbonate a solution of a ,b -dichloropropionyl chloride or bromide in toluene is added dropwise at 0-5 DEG C., and the dyestuff which is formed is salted p out.  The production of other mono and disazo dyes by similar treatment is described.  Included in a list of many intermediate dyes are <FORM:0885815/IV (c)/2> and <FORM:0885815/IV (c)/3> An intermediate dyestuff is made by coupling diazotised 5-nitro-2-aminophenol with 2-phenylamino - 8 - hydroxynaphthalene - 31, 6 - di - sulphonic acid and reducing the nitro group in the resultant dyestuff.  This dye is converted into a 1 : 2 chromium complex by treatment with sodium chrome-salicylate and the chromium complex is acylated with a ,b -dichloro-propionyl chloride.  The acylation of cobalt, copper, and chromium complexes of other azo dyes is described.  Other examples describe the acylation with a ,b -dichloropropionyl chloride of such dyestuffs as <FORM:0885815/IV (c)/4> and <FORM:0885815/IV (c)/5> Other examples describe azo dyes in the production of which the a ,b -dihalogeno-propionylamino group is present in either the diazo component or the coupling component or in both prior to the coupling process.  Specification 885,814 is referred to.