Patent GB-545251-A (GB)
Title: Manufacture of new anthraquinone derivatives
IPC: C09B1/26
Filed: 1940-09-04
Abstract: 545,251. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. Sept. 4, 1940, Nos. 13845 and 13846. Convention dates, Sept. 12, 1939 and Aug. 16, 1940. Sample furnished. [Classes 2 (iii) and 15 (ii)] Anthraquinone derivatives containing at least two primary amino groups and containing once the grouping -NH-X-O-CO-Y-COOH, in which X represents an alkylene and Y represents an alkylene or arylene residue are obtained by (a) causing a compound of the general formula Hal-X-O-CO-Y-COOH, in 'which Hal represents halogen, to react with a polyaminoanthraquinone, or a leuco compound thereof, (b) causing a compound of the general formula  to react with a polyaminoanthraquinone, or a leuco compound thereof, (c) causing a compound of the general formula H 2 N-X-O-CO-Y-COOH to react with a di-or poly-aminoanthraquinone carrying an exchangeable substituent, or a leuco compound thereof, (d) causing a dibasic carboxylic acid to react with a di- or polyaminoanthraquinone, or a leuco compound thereof, containing a grouping -NH-X-Z, wherein Z represents halogen or OH. The products are suitable for dyeing and printing cellulose ester or other materials. Specified polyamino-anthraquinones for reaction under (a) and (b) above are 1 : 4 : 5 : 8-tetraminoanthraquinone and its isomers, in which one amino group may be substituted by an alkyl or aryl group, e.g. by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, phenyl or substituted phenyl, and triaminoanthraquinones, e.g. 1 :4 :5- or 1 : 4 : 6-triaminoanthraquinones, which may be further substituted as by hydroxy groups. Specified compounds for reaction therewith are the products of reaction of halohydrins, such as 2-chloroethanol or 3-chloro-2-hydroxypropanol, or glycides with di- or poly-carboxylic acids, e.g. maleic, succinic, citric, phthalic, naphthalic or quinolinic acids, or their anhydrides. Specified substituted di- and polyaminoanthraquinones for reaction under (c) above are triaminoanthraquinones, in which one amino group may be alkylated or arylated, substituted by an alkoxy group or by halogen, e.g. chlorine or bromine. Specified compounds for reaction therewith are the esters of aminoethanols or aminopropanols with di- or polycarboxylic acids. In examples, (1) 1 : 4 : 5 : 8- 1 : 4 : 5 : 6- or 1 : 4 : 5 : 7-tetraaminoanthraquinone or 1 : 4 : 5-triaminoanthraquinone or its 8-hydroxy derivative is heated for 2-3 hours with mono-#-choroethyl or mono-γ- chloro-#-hydroxypropyl succinate in cresol at 120‹C. in presence of potassium acetate and, in some cases, copper acetate ; the cresol may be replaced by o-dichlorobenzene, nitrobenzene, dimethylaniline or glacial acetic acid ; (2) 1:4:5:8-tetraaminoanthraquinone is heated for 1¢ hours with mono-#-chloroethyl maleate in cresol and dimethylaniline at 120‹C. in presence of potassium acetate ; (3) 1 : 4 : 5-triamino-8- (4<SP>1</SP>-aminophenyl) aminoanthraquinone is heated for 2-3. hours with mono-γ-chloro-#-hydroxypropyl succinate in nitrobenzene at 140-160‹C. in presence of sodium carbonate (4) 1 : 8- diamino - 4 - hydroxy - 5 - # - hydroxyethylaminoanthraquinone is heated for 20 minutes with succinic anhydride in pyridine at 120‹C ; (5) 1 : 4 : 5 - triamino - 8 - ( y - chloro - # -  hydroxypropyl) aminoanthraquinone is heated for 10 hours with succinic acid in aqueous acetone solution at 120-140‹C. neutralized with caustic soda ; (6) cellulose acetate artificial silk is dyed a fast deep blue by treatment for 1¢ hours in an aqueous liquor at 80‹C. containing Glauber salt and the 1 : 4 : 5-triamin-8-#- hydroxyethylaminoanthraquinone succinic acid ester obtained as in (1) above. Specifications 506,526 and 512,512 are referred to. Mono-#-chloroethyl maleate is obtained by heating maleic anhydride with #-chloroethanol in dimethylaniline at 100‹C. A sample has been furnished under Sect. 2 (5) of the Acts of the dyestuff obtained by condensing 1 : 4 : 5 : 8 : tetraaminoanthraquinone (1 mol.) with the phthalic acid monoester of glycide by heating the reagents together in glacial acetic acid for 10 to 15 hours at 40‹C. The phthalic acid monoester of glycide is obtained by heating phthalic anhydride with glycide in pyridine for ¢ hour at 100‹C. The Specification as open to inspection under Sect. 91 comprises also the manufacture of the corresponding dyestuffs in which X represents an arylene residue. This subject-matter does not appear in the Specification as accepted.