Patent GB-551881-A (GB)
Title: Process for the preparation of new anthraquinone derivatives
IPC: C09B1/32
Filed: 1940-12-05
Abstract: 551,881. Dyes. SANDOZ, Ltd. Dec. 5, 1940, No. 17316. Convention date, Dec. 9, 1939. [Classes 2 (iii) and 15 (ii)] Aminoanthraquinone derivatives are obtained by condensing a compound of the general formula where in R represents H or alkyl, X represents H, al kyl, alkoxy, hydroxyalkyl, halogen or SO 3 H and Y represents H, halogen or SO 3 H, with a compound of the general formula wherein Z represents methyl, ethyl, halogen, acylamino, CO.OH or CO.O Alkyl, R 1  represents H, alkyl or hydroxyalkyl and R 2  represents acetyl. The products so obtained may be subjected to sulphonation. Specified first components are the 2-sulphonic acids and 2:5- and 2:8-disulphonic acids of 1-amino-4-halogenanthraquinones, 1-amino-2:4-dibromoanthraquinone, 1-amino - 2 - methyl - 4 - bromoanthraquinone and 1-methylamino-4-bromoanthraquinone, and specified second components are 4 - amino - 2 - acetylaminotoluene, 4 - amino - 2 - (methyl-acetylamino)-toluene (obtainable by reduction of the 4-nitro compound), 4-amino- 1:2-di-(acetylamino)-benzene, 3-amino-6-chloroacetanilide and 4-amino-2-acetylaminobenzoic acid and its methyl ester (obtainable by reduction of the 4-nitro compound). When the first component contains sulphonic acid groups the condensation is advantageously effected in an aqueous medium, with or without the addition of a water-soluble organic solvent, e.g. alcohol, pyridine or phenol, at 60-70‹C. in presence of an acid-binding agent, e.g. sodium carbonate or bicarbonate, and a catalyst, e.g. copper or a copper salt. When the first component is insoluble in water the condensation is advantageously effected in an organic solvent, e.g. alcohol, phenol or nitrobenzene, at 140- 160‹C. in presence of an acid-binding agent, e.g. sodium or potassium acetate, and a similar catalyst. The sulphonated and unsulphonated products are suitable for dyeing animal and cellulose ester fibres respectively in level fast blue shades. In examples, (1) the sodium salt of 1 -amino-4-bromoanthraquinone-2-sulphonic acid is stirred for 2 hours at 65-70‹C. with 4- amino-2-acetylaminotoluene in an aqueous medium containing sodium bicarbonate and copper ; (2) the sodium salt of 1-amino-4- bromoanthraquinone-2-sulphonic acid is stirred for several hours at 70‹C. with 4-amino-2- (methyl-acetylamino)-toluene in an aqueous alcoholic medium ; (3) the sodium salt of 1 - amino - 4 - bromoanthraquinone - 2 - sulphonic acid is stirred for 16 hours at 70‹C. with 3- amino-6-chloro-acetanilide in an aqueous alcoholic medium containing sodium bicarbonate and copper; (4) the sodium salt of 1-amino-4- bromoanthraquinone-2-sulphonic acid is stirred for 5 hours at 65-70‹C. with 4-amino-1:2-di- (acetylamino)-benzene in an aqueous medium containing sodium bicarbonate and copper; (5) the sodium salt of 1-amino-4-bromoanthraquinone-2-sulphonic acid is stirred for 6 hours at 70‹C. with 4-amino-2-acetylaminobenzoic acid methyl ester in an aqueous alcoholic medium containing sodium bicarbonate and copper; (6) 1-amino-2:4-dibromoanthraquinone is stirred for 2 hours at 150‹C. with 4-amino-2- acetylaminotoluene in nitrobenzene containing potassium acetate and copper sulphate and the product is sulphonated by heating for 16 hours in an autoclave at 130‹C. with potassium sulphite in phenol ; (7) the potassium salt of 1-amino-4-bromoanthraquinone-2:5- or 2:8-disulphonic acid is stirred at 70‹C. with 4-amino- 2-acetylaminotoluene at 70‹C. in an aqueous medium containing sodium bicarbonate and copper; (8) 1-methylamino-4-bromoanthraquinone is stirred at 150‹C. with 4-amino-2- acetylaminotoluene in nitrobenzene containing potassium acetate and copper sulphate ; the product may be sulphonated with fuming sulphuric acid. Specifications 302,928, [Class 2 (iii)], 357,380 and 473,884 are referred to. 1-Amino-4-bromoanthraquinone-2:8- disulphonic acid is obtained by bromination of the product of sulphonation of 1-aminoanthraquinone-8- sulphonic acid. The Specification as open to inspection under Sect. 91 comprises also the manufacture of the corresponding dyestuffs in which Z represents alkyl in general, alkoxy, hydroxyalkyl, SO 3 H or alkylsulphone or in which R 2  represents acyl in general or aralkyl. This subject-matter does not appear in the Specification as accepted.