Patent GB-416612-A (GB)
Title: Manufacture of dyestuffs
IPC: C09B1/32
Filed: 1932-02-17
Abstract: Unsulphonated anthraquinone compounds containing as the sole nuclear amino substituents a free amino or aliphatically substituted amino group and in p-position thereto an arylamino group substituted in the aryl group by an aliphatic ether group, are prepared from an anthraquinone compound containing one of the said substituents and in p-position thereto an amino group or a nitro group or other negative atom or group replaceable by amino or substituted amino by the action of ammonia or an amine, (a) when the ether substituted arylamino group is already present, by the action of ammonia or an aliphatic amine or by reduction of the nitro group, or (b) if the free amino or aliphatically substituted amino group is already present, by reaction with a primary arylamine substituted in the nucleus by an aliphatic ether group. Similar unsulphonated anthraquinone compounds containing as the sole nuclear amino substituents a free amino or aliphatically substituted amino group in each of two heteronuclear a -positions and in p-position to each of these groups an arylamino group substituted in the aryl residue by an aliphatic ether group, are prepared from anthraquinone compounds containing in two heteronuclear a -positions either free amino or aliphatically substituted amino groups and in p-position to each of these substituents an amino group or a nitro group or other negative atom or group replaceable by amino or substituted amino by the action of ammonia or an amine, (a) when the two ether substituted arylamino residues are already present by the action of ammonia or an aliphatic amine or by reduction of the nitro group or (b) when the two amino groups or aliphatically substituted amino groups are present, by reaction with a primary arylamine substituted in the nucleus by an aliphatic ether group.  The foregoing compounds are alternatively prepared from anthraquinone compounds containing once or twice in the anthraquinone molecule a free amino group or aliphatically substituted amino group with a hydroxy- or halogen-substituted arylamino group in p-position thereto, by etherifying with an aliphatic radical in the case of a hydroxy group or reaction with an alcoholate in the case of a halogen atom.  Further to the foregoing methods unsulphonated anthraquinone compounds containing as sole nuclear amino substituents once or twice in the anthraquinone molecule an amino group and in p-position thereto an arylamino group substituted in the aryl residue by an aliphatic ether group may be alkylated (including substitution by substituted alkyl) in the nuclear amino group.  Negative substituents replaceable by amino by the action of amines are hydroxy and sulphonic acid groups or chlorine or other halogen atoms, and starting materials specified are 1-amino-4-oxy- or alkoxyanthraquinone, 1-amino-4-nitroanthraquinone, 1-amino-4-bromanthraquinone, diaminoanthrarufin, diaminochrysazin, and 4-amino - 1 . 5 - or 1 . 8 - dichloranthraquinone.  The aliphatic ether residues attached to the arylamino groups are preferably of relatively low mass and attached in o-position to the amino group; substituents such as nitro, halogen, alkyl, acidylamino may also be present in the aryl residues, specified arylamines for reaction purposes being o-anisidine, o-phenetidine, aminohydroquinone - dimethylether, 3 - amino - 4 - methoxytoluene.  Specified aliphatic amines for reaction purposes are methylamine and oxyethylamine. Substituents other than amino may be present in the anthraquinone molecule.  In examples: (1) 1 - amino - 4 - methoxy -, 1 - amino - 4 - chloro -, and 1 - amino - 4 - nitroanthraquinones are condensed with o-anisidine; (2) 4 . 8 - diaminoanthrarufin is condensed with o-anisidine in presence of boric acid; (3) 1-amino-4-(o-anisidino)anthraquinone is heated with ethylenechlorhydrin to give 1 - oxyethylamino - 4 -(o-anisidino) - anthraquinone; (4) 1 - methylamino - 4 - bromanthraquinone is condensed with o-anisidine; (5) 1 - methylamino - 4 - o - oxyphenylaminoanthraquinone is methylated by boiling with p-toluenesulphonic acid methyl ester.  Reference is also made to the manufacture of 1 - amino - 4 - (2<1> . 5<1> - dimethoxyphenylamino) - anthraquinone and 1 - amino - 4 - (2<1> - methoxy - 5<1> - methylphenylamino) - anthraquinone.  The manufacture of 1 - methylamino-4-(4<1> - amino - 2<1> . 5<1> - dimethoxyanilino) - anthraquinone is excluded.  Specification 402,393 is referred to.