Patent GB-787299-A (GB)
Title: Improvements relating to anthraquinone dyestuffs and their use
IPC: C09B1/32
Filed: 1955-12-30
Abstract: 6-Alkyl-1-aminobenzene aryl ethers and thioethers are made by condensing 6-alkyl-1-nitrohalogen benzene compounds with alkali metal phenolates or naphtholates, or alkali metal thiophenolates or thionaphtholates, followed by reduction of the nitro group. Products specified are 1-amino-2,6-dimethyl-benzenes having in 3- or 4-position one of the following substituents:-phenoxy, phenylthio, 21- or 31-, or 41 - methylphenoxy -, 41 - methylphenylthio, 41-chlorophenylthio-, 21- or 31- or 41-chlorophenoxy-, 4-tert.-butylphenoxy, 41-tert.-amylphenoxy, 41-benzylphenoxy, 41-phenylphenoxy, 41-phenoxyphenoxy, 41-butyl- or phenylsulphonylphenoxy, 41-acetyl- or benzoyl-phenoxy, and also 6-methyl-1-aminobenzenes and 4,6 - dimethyl - 1 - aminobenzenes having said substituents in 2-position, and also 6-methyl- and 4,6-dimethyl-1-amino-2-(11- or 21-naphthyloxy) benzenes, and 2,6-dimethyl-1-amino-4-(11- or 21-naphthyloxy) benzenes.ALSO:The invention comprises a process of making acid wool dyes by reacting anthraquinone derivatives having two substituents which can be exchanged for amino groups by reaction with amines in 1- and 4-positions and which may be further substituted, with 6-alkyl-1-aminobenzene aryl ethers or thioethers substituted in 2-position by an alkyl, ether, or thioether group, and which may contain further alkyl substituents, to form the corresponding 1,4-bis-phenylamino-anthraquinone compounds, sulphonating these dye bases to introduce not more than two sulphonic groups, and converting the sulphonic acids to water-soluble salts.  The invention also comprises dyes of the formula <FORM:0787299/IV (b)/1> wherein of X1 and X2, one X represents phenyloxy, phenylthio, or naphthyloxy, the other X is hydrogen or alkyl, Y is alkyl, Z1 and Z2 each represent hydrogen or halogen, and X1 is always other than hydrogen. Anthraquinone starting materials specified are 1,4-dihalogen-, 1-halogen-4 - nitro-, 1 - halogen - 4 - hydroxy-, 1 - alkoxy-4 - halogen-, 1 - hydroxy - 4 - nitro-, and 1,4-dihydroxy-anthraquinones, and these may contain, e.g. in 6 and 7 positions, fluorine, chlorine, bromine, arylthio-, and alkyl sulphonyl groups.  The condensation may be carried out by heating the components as a melt, in the presence of low fatty acids, high-boiling alcohols, acid-binding agents, copper catalysts, and boron stabilizers.  Sulphonation may be effected with sulphuric acid, oleum, chlorosulphonic acid, or sulphur trioxide as its addition compound with pyridine or dioxane.  The products dye wool and other natural or synthetic polypeptide fibres, e.g. silk, lanital, nylon, polyurethanes, reddish-blue shades.  In examples: (1) quinizarin, alone or mixed with leuco-quinizarin, is condensed with 4-amino-3,5-dimethyl-1-phenoxy-benzene, 4 - amino - 3,5 - dimethyl - 1 - (11-or 21 - naphthyloxy) - benzene, 4 - amino - 3,5 - dimethyl - 41 - chloro- or bromo - diphenyl ether, 4 - amino - 3,5 - dimethyl - 1 - (41 - benzoylphenoxy or phenylsulphonylphenoxy) - benzene, 4 - amino - 3,41,5 - trimethyl diphenyl sulphide, 4 - amino - 3,5 - dimethyl diphenyl sulphide, 4 - amino - 3,5 - dimethyl - 41 - n - butyl diphenyl sulphide, 4 - amino - 3,5 - dimethyl-41-chloro - diphenyl sulphide, 3 - methyl - 2 - amino - 1 - phenoxybenzene, 2 - amino - 3,41,5 - trimethyl - 1 - phenoxybenzene, and 3 - amino-2,4 - dimethyl - 1 - phenoxy - benzene.  Also in examples: (2) 1,4 - dichlor- or 1 - chlor - 4 - nitro-, or 1 - methoxy - 4 - chlor - anthraquinone is condensed with 4-amino-3,41,5-trimethyl-diphenyl ether, 4 - amino - 3,5 - dimethyl - 1 - (41 - benzylphenoxy) - benzene, and 4 - amino-3,5 - dimethyl - 1 - (41 - phenoxyphenoxy) - benzene; (3) a mixture of 6-chloroquinizarin and its leuco body is condensed with 4-amino-3,21,5-trimethyldiphenyl ether; (4) a mixture of 6,7-dichloroquinizarin and its leuco body is condensed with 4-amino-3,31,5-trimethyl diphenyl ether.  In each case the products are sulphonated.  Alternative reactants are specified, and a dyeing example is given.