Patent GB-571663-A (GB)
Title: New anthraquinone derivatives
IPC: C09B1/20
Filed: 1943-06-17
Abstract: Anthraquinone derivatives are obtained by acylating a polyalkylene glycol monoalkyl ether of the general formula R-(OR1)n-OH, wherein R represents an unsubstituted alkyl residue, R1 represents an alkylene residue, n represents 1, 2 or 3 and the total number of carbon atoms is less than 16, with an anthraquinone-2-carboxylic acid halide, substituted in 1-position by an amino, alkylamino or nitro group or by halogen and substituted, if desired, in 4-position by a hydroxyl, nitro or acylamino group or by halogen.  A nitro group or halogen atom in 1-position may be replaced by an amino, alkylamino or acylamino group and a nitro group or halogen atom in 4-position may be replaced by an amino, arylamino or acylamino group subsequently to the acylation.  Certain of the products are dyestuffs for cellulose acetate artificial silk.  Examples relate to the acylation of (1) ethylene glycol monomethyl ether with 1 - aminoanthraquinone - 2 - carboxylic acid chloride; (2) diethylene glycol monomethyl or monobutyl ether or dipropylene glycol monomethyl ether with 1-aminoanthraquinone-2-carboxylic acid chloride; (3) triethylene glycol monomethyl ether with 1-aminoanthraquinone-2-carboxylic acid chloride; (4) diethylene glycol monomethyl ether with 1-methylaminoanthraquinone - 2 - carboxylic acid chloride; (5) 4 - bromo-1-aminoanthraquinone-2-carboxylic acid chloride with diethylene glycol monomethyl ether and condensation of the product with either (a) aniline in presence of potassium acetate and copper acetate at 115 DEG  C., or (b) p-toluenesulphonamide in presence of potassium acetate and copper acetate in boiling butanol, followed by hydrolysis with sulphuric acid; (6) diethylene glycol monomethyl ether with 1-amino-4-hydroxyanthraquinone-2-carboxylic acid chloride; (7) diethylene glycol monomethyl ether with 1-chloroanthraquinone-2-carboxylic acid chloride and condensation of the product with (a) ammonia in aqueous alcohol at 80 DEG  C. containing copper bronze and copper acetate, or (b) p-toluenesulphonamide in presence of potassium acetate, copper bronze and copper acetate in boiling butanol, followed by hydrolysis with sulphuric acid, or (c) methylamine in aqueous alcohol at 60 DEG  C. containing copper bronze and copper acetate; (8) diethylene glycol monomethyl ether with 1-nitroanthraquinone-2-carboxylic acid chloride and (a) reduction of the nitro group to amino with sodium hydrosulphite, or (b) treatment with methylamine in aqueous alcohol containing copper bronze and copper acetate to replace the nitro group by methylamino; (9) diethylene glycol monomethyl ether with 4-nitro-1-aminoanthraquinone-2-carboxylic acid chloride and reduction of the nitro group to amino with sodium hydrosulphite; (10) triethylene glycol monomethyl ether with 1-chloroanthraquinone-2-carboxylic acid chloride and (a) condensation as in 5 (b) with p-toluenesulphonamide, followed by hydrolysis with sulphuric acid or (b) treatment with ammonia in aqueous alcohol containing copper bronze and copper acetate; (11) triethylene glycol monomethyl ether with 1 - nitroanthraquinone - 2 - carboxylic acid chloride, followed by reduction of the nitro group to amino with sodium hydrosulphite.  Di- and tri-ethylene glycol monoethyl and monobutyl ethers are obtained by reaction of ethylene oxide in presence of sodium with ethyl and butyl alcohols respectively.  Di-, tri- and tetra-propylene glycol monomethyl and monoethyl ethers are obtained by reaction of propylene oxide in presence of sodium with methyl and ethyl alcohols respectively. 1-Amino-4-hydroxyanthraquinone-2-carboxylic acid chloride is obtained by treating with thionyl chloride in nitrobenzene at 100 DEG  C. the product of the action of boric and sulphuric acids on 1-amino-4-bromoanthraquinone-2-carboxylic acid.