Patent GB-560817-A (GB)
Title: Anthraquinone dyestuffs
IPC: C09B1/32
Filed: 1942-07-15
Abstract: Aminoanthraquinone derivatives, giving on cellulose acetate fibres dyeings which are fast to gas fumes, are obtained by condensing a halogen-, nitro-, hydroxy- or amino-substituted anthraquinone or its leuco compound with m-aminobenzyl alcohol or a nuclearly-substituted derivative thereof.  In examples: (1) 1-methylamino-4-bromoanthraquinone is heated for 8 hours with m-aminobenzyl alcohol in etheylene glycol monoethyl ether at 137 DEG C. containing anhydrous potassium acetate and copper acetate to obtain 1-methylamino-4-(m-methylolanilino)-anthraquinone, which from a soapy aqueous dispersion dyes cellulose acetate fibres bluish green; (2) 1-amino-2 : 4-dibromoanthraquinone is heated for 12 hours with m-aminobenzyl alcohol is ethylene glycol monoethyl ether at 128 DEG  C. containing potassium acetate, potassium carbonate and copper acetate to obtain 1 - amino - 2 - bromo - 4 - (m-methylolanilino)-anthraquinone, which dyes cellulose acetate fibres blue; (3) to (5), a mixture of quinizarin and leuco-quinizarin is heated for 12 hours with (3) m-aminobenzyl alcohol; (4) 4-methoxy-3-methylol-aniline, (5) 2-methyl-5-methylol-aniline, in denatured alcohol at 78 DEG  C. containing boric acid to obtain (3)-1-hydroxy - 4 - (m - methylolanilino) - anthraquinone, (4) 1 - hydroxy - 4 - (41 - methoxy - 31 - methylolanilino) - anthraquinone, (5) 1-hydroxy - 4 - (21 - methyl - 51 - methylolanilino)-anthraquinone; (6) and (7) a mixture of quinizarin and leuco-quinizarin is heated for 8 hours with (6) m-aminobenzyl alcohol, (7) 4-methoxy-3-methylolaniline, in ethylene glycol monomethyl ether at 90-95 DEG  C. containing boric acid to obtain 1 : 4-di-(31-methylol anilino)-anthraquinone and its di-(41-methoxy) derivative respectively which dye cellulose acetate fibres greenish blue; (8) a mixture of 1 - hydroxy - 4 - anilino - anthraquinone and leuco-quinizarin is heated under reflux for 12 hours with m-aminobenzyl alcohol in ethyl alcohol containing boric acid to obtain 1-anilino-4 - (m - methylolanilino) - anthraquinone, which dyes cellulose acetate fibres greenish blue; (9) a mixture of 1 : 4 : 5 : 8-tetrahydroxy-anthraquinone and its leuco compound is similarly treated to obtain 1 : 4-di-(m-methylol-anilino)-5 : 8-dihydroxy-anthraquinone, which dyes cellulose acetate fibres greenish blue; (10) a mixture of 1 : 4 : 5 : 8-tetrahydroxy-anthraquinone and its leuco compound is heated under reflux for 15-30 minutes with aniline in ethyl alcohol containing boric acid and the resulting 1-anilino-4 : 5 : 8-trihydroxyanthraquinone is heated under reflux for 4 hours with m-aminobenzyl alcohol in ethyl alcohol to obtain 1 - anilino - 4 - (m - methylolanilino)-5 : 8-dihydroxy-anthraquinone, which dyes cellulose acetate fibres greenish blue; (11) leuco-1 : 4 : 5-trihydroxyanthraquinone is heated for 12 hours with m-aminobenzyl alcohol in ethylene glycol monoethyl ether at 90-95 DEG  C. to obtain a leuco - dihydroxy - (m - methylolanilino)-anthraquinone, which is then oxidised with nitrobenzene containing piperidine; the product dyes cellulose acetate fibres reddish blue; (12) 1 : 4 : 5 : 8-tetrahydroxyanthraquinone is heated for 3 hours with m-aminobenzyl alcohol in pyridine at 90-95 DEG  C. and air is blown into a suspension of the leuco-1 : 5 : 8-trihydroxy-4-(m - methylolanilino) - anthraquinone; the product dyes cellulose acetate fibres a pure blue; (13) 1-chloroanthraquinone is heated for 12 hours with m-aminobenzyl alcohol in ethylene glycol monoethyl ether at 137 DEG C. containing anhydrous potassium acetate and copper acetate to obtain 1-(m-methylolanilino)-anthraquinone, which dyes cellulose acetate fibres pink; the anilino nucleus may carry additional substituents, e.g. alkyl, alkoxy, hydroxy or thioalkoxy groups. 4-Methoxy-3-methylolaniline is obtained by hydrolysis and reduction of the product of the action of formaldehyde and hydrogen chloride on 4-nitroanisole.