Patent GB-551160-A (GB)
Title: New anthraquinone derivatives
IPC: C09B1/20
Filed: 1941-07-07
Abstract: 551,160. Dyes. BUCKLEY, G. D., PIGGOTT, H. A., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. July 7, 1941, No. 8549. [Classes 2 (iii) and 15 (ii)] Anthraquinone derivatives containing one or more alkoxyalkoxyalkylamino or alkoxyalkoxyalkoxyalkylamino groups, containing 5 to 10 carbon atoms and in which the terminal alkyl group is unsubstituted attached to the nucleus either directly or through a -CO- grouping are obtained by reaction of a suitable alkoxyalkoxyalkylamine or alkoxyalkoxyalk oxyalkylamine with an anthraquinone derivative carrying in α-positions of the nucleus one or more of the replaceable substituents, hydroxy, alkoxy of not more than 5 carbon atoms, phenoxy, tolyloxy, amino, alkylamino of not more than 5 carbon atoms, chloro, bromo, nitro or sulpho, and/or carrying one or more nuclear -COCl or -COBr groups. The anthraquinone nucleus in the product may carry other substituents, including one or more hydroxyalkylamino groups containing not more than 5 carbon atoms or one or more anilino, toluidino or xylidino groups. When the replaceable substituents are hydroxy, amino or alkylamino groups, the anthraquinone derivative may be caused to react wholly or in part in the form of its leuco compound and the product be subsequently oxidized to the quinonoid form. When the products still carry one or more replaceable substituents, they may be further reacted with ammonia, alkylamines, hydroxyalkylamines containing not more than 5 carbon atoms or arylamines. Nitro groups in the products may be reduced to amino groups. Specified anthraquinone derivatives used as starting materials are the 1-chloro, 4-bromo-1- methylamino, sodium 1-sulphonate, 1:4-dihydroxy, 1:4-di-(methylamino), 1:4-diamino, 1:4:5:8-tetrahydroxy, 1-amino-4-hydroxy, 1:4- dibromo, 4-nitro-1-methoxy, 4-bromo-1-amino- 2-carboxylic acid chloride, 4-nitro-1-amino-2- carboxylic acid chloride (cf. Specification 350,928) and 1-nitro-2-carboxylic acid chloride derivatives. In examples, (1) quinizarin and leuco-quinizarin are heated for 15 hours with #-ammo-#<SP>1</SP>-methoxydiethyl ether in isobutanol under reflux and the product is oxidized by adding a little pyridine and passing air through the boiling solution to obtain 1:4-di-(#<SP>1</SP>- methoxy - # - ethoxyethylamino)-anthraquinone, which dyes cellulose acetate artificial silk a fast bright blue ; similar products are obtained when the amine is replaced by #-amino-#<SP>1</SP>- ethoxydiethyl ether, #-amino-#<SP>1</SP>-butoxydiethyl ether or #-aminoethyl-#-methoxyisopropyl ether ; (2) quinizarin and leuco-quinizarin are heated for 15 hours with diethyleneglycolmethyl-#-aminoethyl ether in isobutanol under reflux, followed by oxidation as in (1) ; the product dyes cellulose acetate artificial silk a bright blue ; (3) 1-chloroanthraquinone is heated for 12 hours with diethyleneglycolmethyl-#-amino ethyl ether or #-aminoethyl- #:#<SP>1</SP>-dimethoxyisopropyl ether in isobutanol under reflux in presence of potassium carbonate and copper acetate ; the products dye cellulose acetate artificial silk a clear yellowish red; (4) 4-bromo-l-methylaminoanthraquinone is heated for 12 hours with diethyleneglycolmethyl-#-aminoethyl ether in nitrobenzene at 135-140C. in presence of potassium carbonate and copper acetate ; the product dyes cellulose acetate artificial silk a reddish blue ; (5) quinizarin and leuco-quinizarin are heated for 12 hours with #-amino-#<SP>1</SP>-methoxydiethyl ether in isobutanol under reflux, followed by oxidation as in (1), to obtain 4-hydroxy-1-#<SP>1</SP>- methoxy - #- ethoxyethylamino - anthraquinone, which dyes cellulose acetate artificial silk a clear violet; (6) sodium anthraquinone-1- sulphonate is heated for 6 hours with diethyleneglycol-methyl-#-aminoethyl ether in water under. pressure at 160C. to obtain a product as in (3) ; (7) 1-nitroanthraquinone-2- carboxylic acid chloride is heated for 2 hours with #-amino-#<SP>1</SP>-methoxydiethyl ether in isopropanol at 90C. to obtain the 2-carboxylic acid #<SP>1</SP>-methoxy-#-ethoxyethylamide of 1-#<SP>1</SP>- methoxy - # - ethoxyethylamino-anthraquinone, which dyes cellulose acetate artificial silk a fast bright red ; (8) leuco-1:4:5:8-tetrahydroxyanthraquinone is heated for 12 hours with #-amino-#<SP>1</SP>-methoxydiethyl ether in isobutanol under. reflux in presence of boric acid, followed by oxidation as in (1) ; the product dyes cellulose acetate artificial silk a brilliant blue-green ; (9) 1-nitroanthraquinone-2-carboxylic acid chloride is stirred for 6 hours with #-amino #<SP>1</SP> methoxydiethyl ether in cold aqueous solution and the resulting 1-nitroanthraquinone-2-#<SP>1</SP>- methoxy-#-ethoxyethylamide is heated for 6 hours with methylamine or ammonia in ethanol at 60C.; the products dye cellulose acetate artificial silk fast bright red and brilliant orange shades respectively; (10) 4-nitro-1-aminoanthraquinone-2-carboxylic acid chloride is stirred for 6 hours with #-amino-#<SP>1</SP>-methoxydiethyl ether in cold aqueous solution and the resulting 4 -nitro -1 - aminoanthraquinone-2 - carboxylic acid #<SP>1</SP>-methoxy-#-ethoxyethylamide is reduced with sodium sulphide to the 1:4- diamino compound, which dyes cellulose acetate artificial silk a fast bright blue-violet ; (11) leuco-1:4-di-(methylamino) or leuco-1:4- diamino-anthraquinone is heated for 6 hours with #-amino-#<SP>1</SP>-methoxydiethyl ether in isobutanol under reflux, followed by oxidation as in (1) to obtain a product as in (1) ; (12) 4-nitro- 1-methoxyanthraquinone is heated for 18 hours with #-amino-#<SP>1</SP>-methoxydiethyl ether in ethyleneglycol monoethyl ether at 80C. to obtain 4-nitro-1-#<SP>1</SP>-methoxy-#-ethoxyethylaminoanthraquinone which is reduced with sodium sulphide to the 4-amino compound. which dyes cellulose acetate artificial silk a bright violet : (13) 4-bromo-1-aminoanthraquinone-2-carboxvlic acid chloride (cf. Specification 492,291) is stirred for 6 hours with #-amino- #<SP>1</SP>-methoxydiethyl ether in cold aqueous solution and the resulting #<SP>1</SP>-methoxy-#-ethoxyethylamide of 4-bromo-1-aminoanthraquinone- 2-carboxylic acid is heated for 16 hours with aniline at 120-125C. in presence of potassium acetate and copper acetate to obtain the 4- anilino compound, which dyes cellulose acetate artificial silk a fast blue ; (14) the aniline in (13) is replaced by p-anisidine to obtain the corresponding 4-p-anisidino compound, which dyes cellulose acetate artificial silk a bright greenish blue. 1-Nitroanthraquinone-2-carboxylic acid chloride is obtained by reaction of 1-nitroanthraquinone- 2-carboxylic acid with thionyl chloride in nitrobenzene. 4-Nitro-1-methoxyanthraquinone is obtained by nitration of 1-methoxyanthraquinone. #-amino- #<SP>1</SP>-alkoxydiethyl ethers are obtained by heating the corresponding #-chloro-#<SP>1</SP>- alkoxydiethyl ethers with aqueous ammonia to 100C. #-aminoethyl-#-rnethoxyisopropyl ether is obtained by catalytic hydrogenation of the nitrile resulting from the action of cuprous cyanide on the product of interaction of methyl #-hydroxypropyl ether with formaldehyde and hydrochloric acid. #-aminoethyl-#:#<SP>1</SP>-dialkoxyisopropyl ethers are obtained similarly from glycerol-1:3-dialkyl ethers. Diethylene glycol-methyl-#-aminoethyl ether is obtained by the action of ammonia on the condensation product from ethylene glycol monomethyl ether and #:#<SP>1</SP>-dichlorodiethyl ether.