Patent GB-421969-A (GB)
Title: Application of dyestuffs of the anthraquinone series
IPC: C09B1/514
Filed: 1933-05-18
Abstract: Fast dyeings on textile materials, particularly animal fibres, are obtained by applying thereto an o-aminophenylthioglycollic acid carrying an anthraquinonyl substituent as defined, and lactamizing the applied compound by treatment with dilute mineral acid at an elevated temperature.  The o - aminophenylthioglycollic acids carrying an anthraquinonyl substituent have the constitution AQ-X-C6H3(NH2)SCHRCO2H where C6H3 is the residue of a phenyl nucleus carrying as substituents amino and thioglycollic acid groups oto each other and an anthraquinonyl radicle AQ, X stands for --NH--, --S--, --NHCO--, --CONH-- or NHSO2 linking AQ to the phenyl residue and R stands for hydrogen, methyl or ethyl; AQ may be furether substituted by bromine, chlorine, hydroxy, alkoxy, alkylamino, acylamino, or arylamino, and the phenyl residue may be further substituted by bromine, chlorine or methyl.  These o-aminophenylthioglycollic acids may be applied with advantage from a bath containing ammonium acetate, ammonium anthranilate, ammonium phosphate, a mixture of ammonium sulphate and ammonia, or anthranilic acid; these substances acidify the bath, presumably by hydrolysis, and in general improve fastness of dyeings to rubbing; a further addition of a mild detergent may also be made. The starting materials are prepared by the processes described in Specifications 394,312, 406,689, 406,733, 412,920 and 413,658 and in the case of the compounds wherein X is represented by --NHSO2-- they are prepared by reacting a halogenanthraquinone with a phenylsulphonamide of the formula <FORM:0421969/IV/1> wherein Y stands for chlorine, bromine, or bromine, or --SCHRCOOH (R having the same meaning as above), and then converting to the aminophenylthioglycollic acid derivative by reduction and, when necessary, reaction with the appropriate thioglycollic acid.  In examples: (1) 2 - aminophenylthioglycollic acid - 4 - (a  - N - anthraquinonyl)-carboxylic acid amide is applied to wool from a bath containing ammonium acetate or ammonium anthranilate at about 80 DEG  C.; the wool is rinsed and entered into a dilute sulphuric acid bath which may also contain cetylpyridinium bromide; heating to about 80 DEG  C. effects lactamization (yellow shades); (2) 1 . 5 - di - (methylaminoanthraquinone - 4 . 8 - di - (4<1> - amino - 3<1> - phenylthioglycollic acid) thioether is applied to wool from a bath containing ammonium acetate and formaldehyde-naphthalene sulphonic acid condensation product at 85--90 DEG  C.; the wool is rinsed and lactamized in dilute sulphuric acid at 80 DEG  C. finally being treated with cetyl sodium sulphate to give blue shades; silk is dyed with this product by applying from a bath containing ammonium acetate at 80 DEG  C. and lactamized as above; (3) 1 . 4 - diaminoanthraquinone - 2 . 3 - di - (3<1> - amino - 4<1> - phenylthioglycollic acid) thioether is applied to wool from a bath containing sodium sulphate at 90--95 DEG  C.; the fibre is rinsed in a bath containing cetyl-sodium sulphate and lactamized in dilute sulphuric acid at 80--85 DEG  C. (blue shades); (4) 1-methylamino-4-(4<1> - amino - 3<1> - phenylthioglycollic acid) aminoanthraquinone is applied to wool from a bath of acetic acid at 90--95 DEG  C. and lactamized in dilute sulphuric acid at 80 DEG  C. (greenish-blue).  A table refers to the following dyes and their lactamized shades:--5 - oxy - 1 . 4 - di - (4<1> - amino - 3<1> - phenylthioglycollic acid) aminoanthraquinone (gree), 1-aminoanthraquinone-2 - (3<1> - amino - 4<1> - phenylthioglycollic acid) carboxylic acid amide - 4 - p - toluenesulphonamide (violet), 1-methylamino-4-(3<1>-amino-4<1>-phenylthioglycollic acid) sulphonamidoanthraquinone (violet), 1-methoxy-5-(3<1>-amino-4<1>-thioglycollicbenzoyl) aminoanthraquinone (yellow), 1 . 4 - di - (3<1> - methyl - 5<1> - amino - 6<1> - phenylthioglycollic)aminoanthraquinone (green), 1-methoxy - 4 - (3<1> - amino - 4<1> - phenylthioethylglycollic acid) - aminoanthraquinone (scarlet), 1 . 4 - di - (4<1> - amino - 3<1> - phenylthioglycollic acid) aminoanthraquinone (green), 1-oxy-4-(4<1>-amino-3<1>-phenylthioglycollic acid) aminoanthraquinone (violet), 1-methylamino-4-(3<1>-amino-4<1>-thioglycollic - benzoyl - ) aminoanthraquinone (bluish-violet), 1-methylamino-4-(3<1>-amino-4<1>-thioethylglycollic-benzoyl -)aminoanthraquinone (reddish-blue), 1 - methylaminoanthraquinone-4 - (4<1> - amino - 3<1> - phenylthioglycollic acid) thioether (violet), 1.4 - dioxyanthraquinone - 2 - (3<1> - amino - 4<1> - phenylthioglycollic acid) thioether (red).  The shades possess good fastness to frothing and alkaline processes.  Specification 377,740 also is referred to.  Reference has been directed by the Comptroller to Specifications 394,312, 406,689, 406,733, 412,920, and 413,658.