Patent GB-457386-A (GB)
Title: New anthraquinone dyestuffs and processes for their manufacture
IPC: C09B1/50
Filed: 1935-03-21
Abstract: Anthraquinone dyes are prepared by condensing anthraquinone derivatives of the general formula <FORM:0457386/IV/1> wherein Z stands for a hydroxy, amino, alkylamino or halogen, V for hydroxy or halogen and X for hydrogen, halogen, alkyl, alkoxy or sulphonic acid, with aromatic amines of the general formula <FORM:0457386/IV/2> wherein A represents alkyl, B represents alkyl or chlorine or bromine, and D hydrogen or alkyl, and if desired the products are subjected to sulphonation with sulphuric acid, monohydrate, fuming sulphuric acid or chlorsulphonic acid or by replacement of a b -halogen atom by sulphonic acid by treatment with sulphites. Starting materials on the one hand are 2.6-dimethylaniline, 2.4.6-trimethylaniline, 2.4-dimethyl-6-bromaniline and on the other hand 1-amino-4-bromo-, 1-amino-4-chloro-, 1-amino-2-methyl-4-bromo-, 1-amino-2-sulpho-4-bromo-, 1-methylamino-4-bromo-, 1 - amino - 2 - methoxy - 4 - bromo-, 1-amino-2-4-dibromo- and 1-4-dichlor-anthraquinones.  In examples, (1) 1-methylamino-4-bromanthraquinone is condensed with 2.6-dimethylaniline; the product is used as a dyestuff for lacquers or after sulphonation with oleum, as an acid wool dye; 1-oxy-4-bromanthraquinone is similarly condensed or other o.o<1>-dialkylaromatic amines may be used; (2) 1-amino-2-methyl-4-bromanthraquinone is condensed with 2.4.6-trimethylaniline and the product is sulphonated with oleum: (3) 1.4-dichloranthraquinone is condensed with 2.6-dimethylaniline or 2.4.6-trimethylaniline and the products sulphonated with oleum; (4) 1-amino-2.4-dibromanthraquinone is condensed with 2.6-dimethylaniline and the product treated with potassium sulphite in phenol; (5) 1-amino-4-bromanthraquinone-2-sulphonic acid is condensed with 2.6-dimethylaniline.  The products dye violet to blue shades of good fastness to light, bleaching and milling.  The unsulphonated products are dyes for lacquers such as nitrocellulose lacquers or for cellulose esters or ethers. Samples have been furnished under Sect. 2 (5) of dyes prepared (1) by condensing 1-amino - 4 - bromanthraquinone - 2 - sulphonic acid with 6-ethyl-2.4-dimethylaniline and (2) by condensing 1-amino-2.4-dibromanthraquinone with 6-bromo-2.4-dimethylaniline, followed by treatment of the product with potassium sulphite in phenol.  The Specification as open to inspection under Sect. 91 relates to a manufacture comprising condensing anthraquinone derivatives containing at least one group replaceable by reaction with aromatic amines with amines of the general formula <FORM:0457386/IV/3> wherein positions X and Y are substituted by halogen and/or alkyl and Z stands for hydrogen or alkyl, followed, if desired, by sulphonation by monohydrate, fuming sulphuric acid or chlorsulphonic acid or by replacing a b -halogen atom by means of sulphites, or by condensation with aldehydes, or by treatment with oxidizing agents, or by cyclisation to form anthrapyridones, anthrapyrimidines or anthrapyrimidones.  Additional starting materials specified are 1.5- or 1.8 - dichloranthraquinones, 1.2-dioxyanthraquinone, N-methyl-4-bromanthrapyridone, C-carbethoxy-2-methyl-4-bromanthrapyridone.  By treating the sulphonated or unsulphonated condensation products with aldehydes, di- and tri-aryl-methane derivatives are obtained; by treating them with oxidizing agents such as nitric acid or peroxide of manganese diaryl derivatives are obtained; by subjecting condensation products containing a free amino group to the action of carbonic acid amides or acetoacetic esters or malonic acid anthrapyrimidones or anthrapyridones are obtained.  In addition in examples (a) C-carbethoxy-2-methyl-4-bromanthrapyridone is condensed with 2.4.6-trimethylaniline, and the product sulphonated with oleum; 6-bromo-2.4-dimethylaniline may be used instead of 2.4.6-trimethylaniline; (b) N-methyl-4-bromanthrapyridone is condensed with 2.6-dimethylaniline and the product sulphonated with oleum; (c) the base obtained according to example (1) above is treated with urea in presence of phenol and the anthrapyrimidone obtained is sulphonated; (d) the product of example 5 above is treated in sulphuric acid solution with formaldehyde to give a diphenylmethane derivative or with manganese peroxide to give a diphenyl derivative.  This subject-matter does not appear in the Specification as accepted.