Patent GB-416611-A (GB)
Title: Manufacture of new colouring matters
IPC: C09B1/514
Filed: 1932-02-17
Abstract: Unsulphonated anthraquinone compounds of the formula <FORM:0416611/IV/1> (other than 1 - amino - 4 - p - tolylamino - 5 - oxyanthraquinone) wherein the anthraquinone nucleus A has, as sole substituents in three a -positions the groups X, Y and Z of which X represents a hydroxy group, Y an arylamino group of the benzene series, and Z a free amino or non-aromatically substituted amino group are prepared from anthraquinones containing X and also Y or Z and in a third a -position an amino group or a nitro group or halogen atom or other negative substituent replaceable by amino or substituted amino by the action of ammonia or an amine, (a) when Y is present by replacing this third substituent by amino or non-aromatically substituted amino by the action of ammonia or a non-aromatic amine, or by reduction in the case of a nitro group, or in the case of a halogen atom by reaction with an acid amide and hydrolysis of the resulting acidylamino compound, or (b) when Z is present replacing this third substituent by reaction with a primary arylamine of the benzene series.  The same compounds are obtained (Z being a non-aromatically substituted amino group) by acylating, aralkylating or alkylating (including substitution by substituted alkyl) the nuclear amino group of those compounds of the above general formula wherein Z is a free amino group.  As replaceable negative substituents there are mentioned sulphonic, hydroxy, alkoxy and aryloxy groups, and starting materials specified are 4-aminochrysazin, 1 . 4 - diamino - 5 - oxyanthraquinone, 5 - amino - 1 . 4 - dioxyanthraquinone, 1 - amino-4 - oxy - 5 - or 8 - sulphoanthraquinone and 1-amino-4-oxy-5- or 8-chloranthraquinone, p-amino- and p-alkylaminochrysazins (prepared by nitrating the boric ester of chrysazin in concentrated sulphuric acid, followed by reduction or reaction with an aliphatic amine) being particularly suitable. When hydroxy groups are to be replaced by amino groups reaction is often more easily effected by reducing the anthraquinone to the leuco form (cf. Specification 310,784, [Class 2 (iii)]). Halogen may be replaced by amino by reaction with an arylsulphonamide or phthalimide followed by hydrolysis.  The phenyl group of the a -phenylamino substituent may be substituted, for example by alkyl, hydroxy, alkoxy, amino or halogen, reference being made in this connection to Specifications 402,391, 402,393, 411,877, and 416,612. Suitable substituents in the case of the non-aromatically substituted amino group are methyl-, ethyl, oxyethyl-, oxypropyl-, g -chloro-b -oxypropyl-, acetyl-, cyclohexyl-, substituted cyclohexyl-, benzyl-, hydrogenized benzyl-, piperidyl-, if desired two such substituents being present; the lower aliphatic residues (acidyl excluded) attached to an amino group yield best results.  In examples: (1) 4-aminochrysazin (prepared by reducing the 4-nitro body with glucose and caustic soda) is condensed with aniline in presence of boric acid to give 1-amino-4-phenylamino-5-oxyanthraquinone; the presence of iron accelerates the reaction; using o-toluidine instead of aniline 1 - amino - 4 - o - tolylamino - 5 - oxyanthraquinone is obtained; (2) leuco - 1 . 4 - diamino - 5 - oxyanthraquinone is condensed with aniline in presence of acetic acid and sodium acetate; (3) 1 - amino - 4 - phenylamino - 5 - oxyanthraquinone is heated with ethylenechlorhydrin in presence of a little magnesia.  British Specification 402,392 and German Specification 201,905 also are referred to.