Patent GB-546019-A (GB)
Title: Manufacture of anthraquinone derivatives containing nitrogen
IPC: C09B1/28
Filed: 1940-10-16
Abstract: 546,019. Dyes; dyeing textiles. SOC. OF CHEMICAL INDUSTRY IN BASLE. Oct. 16, 1940, Nos. 15319 and 15320. Convention dates, Oct. 16, 1939 and Sept. 17,1940. [Classes 2 (iii) and 15 (ii)] Aminoanthraquinone derivatives are obtained by reaction of a mono-halogenacetic acid, e.g. mono-chloro- or mono-bromo-acetic acid, with an aminoanthraquinone containing at least 3 amino groups in presence of an indifferent diluent. Specified aminoanthraquinones are 1:4:5 - triamino-, 1 - hydroxy - 4:5:8- triamino- (cf. Specification 353,932) 1:4:5:6- and 1:4:5:8- tetra-amino-anthraquinones and their alkyl and aryl substitution products. Specified diluents are phenols, cresols, glacial acetic acid, solvent naphtha and nitrobenzene. The reaction is advantageously effected in presence of an acid-binding agent, such as an alkali metal acetate or carbonate, an oxide of an alkaline earth metal such as calcium or magnesium, or a tertiary base, the quantity of such agent used being preferably sufficient to bind the hydrohalic acid produced but insufficient to bind also the carboxylic acid. The products are advantageously dried in presence of alkaline buffer substances such as sodium carbonate, borax, disodium phosphate or sodium p-toluenesulphonamide, and in the form of their water-soluble salts dye cellulose ester or ether materials powerful fast blue shades. In examples (1) 1:4:5:8-tetraaminoanthraquinone is heated for 4 hours at 110- 120‹ C. with chloroacetic acid in glacial acetic acid containing potassium acetate and copper acetate ; the product is precipitated from solution in dilute alkali by addition of acid ; (2) 1:1:5:8-tetraaminoanthraquinone is heated for 6 hours at 110-120‹ C. with chloroacetic acid in solvent naphtha containing potassium acetate ; the naphtha is removed by steam distillation and the product isolated as in (1) ; (3) 1:4:5:8-tetraaminoanthraquinone, 1-hydroxy - 4:5:8 - triaminoarithraquinone or its 8-N-methyl-derivative (cf. Specification 353,932) or the 1-N-phenyl- (cf. Specification 344,117) or 1-N-(4<SP>1</SP>-amino)phenyl-derivative of 1:4:5:8- tetraaminoanthraquinone, is heated for ¥ hour at 100‹ C. with chloroacetic acid in crude cresol containing potassium acetate ; the cresol is removed by steam distillation and the product precipitated by acidifying a solution of the residue in aqueous ammonia ; (4) crude 1:4:5:6- tetraaminoanthraquinone is heated for 4 hours at 100-110‹ C. with chloroacetic acid in crude cresol containing potassium acetate and copper acetate and the product is isolated as in (3) ; (5) 1:4:5:8-tetraaminoanthraquinone is heated for 6 hours at 110-115‹ C. with chloroacetic acid in crude cresol containing sodium carbonate and copper acetate and the product is isolated as in (3) ; (6) 1:4:5:8-tetraaminoanthraquinone is heated with chloroacetic acid as in (3) whereupon conc. aqueous ammonia is added, the cresol is removed by steam distillation, more conc. aqueous ammonia is added to the residue, the whole is filtered and the product precipitated by acidifying the filtrate, is washed, dissolved in caustic soda solution with admixture of an alkaline buffer substance as above and the mixture is dried. Examples of the dyeing process are given. The 1-(4<SP>1</SP>-amino)phenyl-derivative of 1:4:5:8- tetraaminoanthraquinone is obtained by reaction of 1:4-diaminobenzene with 1:4:5-triamino- 8-methoxyanthraquinone. 1:4:5:6-Tetraaminoanthraquinone is obtained by hydrolysing the oxalylamino groups in the product of reduction of a nitrated mixture of the dioxalyl derivatives of 1:6- and 1:7-diaminoanthraquinones. The Specification, as open to inspection under Sect. 91, comprises also the production of the corresponding products from aliphatic halogen carboxylic acids in general, other such acids specified being halogenopropionic, halogenohydroxypropionic and halogenobutyric acids and an additional example relates to the reaction of 1:4:5:8-tetraaminoanthraquinone with #-chloropropionic acid in crude cresol containing potassium acetate and copper acetate. This subject-matter does not appear in the Specification as accepted.