Patent GB-460440-A (GB)
Title: Improvements in the manufacture of amino compounds of the anthraquinone series
IPC: C09B1/20
Filed: 1935-07-25
Abstract: Amino or aliphatically substituted amino derivatives of anthraquinone are prepared by subjecting an anthraquinone containing in the 1- and 4-positions hydroxy, amino or substituted amino groups to the action of ammonia or an aliphatic amine in presence of a compound of a heavy metal or of a metal capable of forming a complex nitrogenous compound with a nitrogenous base.  By these means the substituent hydroxy groups may be replaced by amino groups, the amino groups by aliphatically substituted amino groups, and the substituted amino groups differing therefrom.  Suitable metals, used in the form of their oxides, hydroxides or salts, include bismuth, cadmium, cobalt, copper, gold, iron, lead, magnesium, manganese, mercury, nickel, palladium, platinum, silver, thallium, tin, vanadium and zinc; the proportion may vary from 0,1--5,0 per cent of metal on the weight of anthraquinone compound.  Suitable starting materials comprise on the one hand 1.4.5-trioxy-anthraquinone, 1.4.5.8-tetroxyanthraquinone, 1 - amino - 4.5.8 - trioxyanthraquinone, 1.4-diaminoanthraquinone, 1.5-diamino-4.8-dioxy-anthraquinone, 1.8-diamino-4.5-dioxyanthraquinone, 1-oxy-4-aminoanthraquinone, 1-oxy-4-methylaminoanthraquinone and 1 - oxy - 4 - phenylaminoanthraquinone; and on the other hand monomethylamine, monoethylamine, ethylenediamine, a .b -diaminopropane, unsymmetrical diethylethylenediamine, oxyalkylamines such as b -oxyethylamine, b .\su-dioxy-propylamine, cyclohexylamine, methyl- or alkyl-cyclohexylamine, benzylamine, p-sulphobenzylamine; amines containing up to 7 or 8 carbon atoms are of value in producing cellulose acetate dyes.  An inorganic alkali such as an alkali metal carbonate or hydroxide may be advantageously added to the reaction mixture which may take place in presence of a diluent such as alcohol; boric acid may also be present, especially if an aqueous diluent is present.  In examples: (1) quinizarin, manganese sulphate, sodium carbonate and aqueous methylamine are heated in alcohol in an autoclave at 120 DEG  C. for 4 hours to give 1-methylamino-4-oxyanthraquinone; (2) quinizarin, copper sulphate, sodium carbonate, and aqueous methylamine are heated in alcohol in an autoclave at 140 DEG  C. for ten hours to give 1.4-di-(methylamino)-anthraquinone; (3) 1.4.5-trioxyanthraquinone, manganese chloride, sodium carbonate and ethanolamine are heated in alcohol in an autoclave at 140 DEG  C. for 16 hours to give 1.4-di-(oxyethylamino) - 5 - oxyanthraquinone; (4) quinizarin, manganese chloride, sodium carbonate, and aqueous ammonia are heated together in alcohol in an autoclave at 110 DEG  C. for 12 hours to give 1-amino-4-oxyanthraquinone; (5) quinizarin, platinic chloride, sodium carbonate and aqueous methylamine are heated together in alcohol in an autoclave at 120 DEG  C. for 6 hours to give 1-oxy-4-methylaminoanthraquinone.  Reference is also made to the production of 1.4-diethanolamino-5.8-dioxyanthraquinone from 1.4.5.8-tetroxyanthraquinone or 1-amino-4.5.8-trioxyanthraquinone and mono-ethanolamine.  Two samples have been furnished under Sect. 2 (5) of 1.4-di-(oxyethylamino)-anthraquinone prepared by (a) heating 1.4-diaminoanthraquinone with manganese chloride in ethanolamine under reflux for 4 hours, and (b) by heating 1.4-di-(methylamino)-anthraquinone and copper sulphate in ethanolamine under reflux for 2 hours.