Patent GB-461428-A (GB)
Title: Improvements in the manufacture and production of n-substitution products of 1.4-diaminoanthraquinones
IPC: C09B1/51
Filed: 1935-07-09
Abstract: 1.4-N-substituted diaminoanthraquinones and derivatives containing in the other benzene nucleus one or more amino, hydroxyl or alkoxy groups wherein one hydrogen atom in each of the 1- and 4-amino groups is replaced by an alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radicle are prepared by reacting a mixture of a 1.4-dioxyanthraquinone with a 2.3-dihydro-1.4-diaminoanthraquinone, or a 1.4-diaminoanthraquinone with a 2.3-dihydro-1.4-diaminoanthraquinone, or a 1.4-diaminoanthraquinone with a 2.3 - dihydro - 1.4 - dioxyanthraquinone, and at least 2 molecular proportions of a primary amine or a mixture of at least two different primary amines.  The amount of the dihydro compound present may be varied within wide limits but preferably is about 10--30 per cent of the mixture; these dihydro compounds are generally derived by treating the corresponding anthraquinone derivatives with reducing agents (cf. Specifications 15355/08, [Class 2], and 268,891, [Class 2 (iii)]).  The products are suitable for dyeing cellulose esters and ethers, fats, oils, waxes, lacquers, liquid or solid hydrocarbons and artificial compositions.  In examples: (1) 1.4 - dioxyanthraquinone, 2.3-dihydro-1.4-diaminoanthraquinone, and methylamine are reacted in isobutyl alcohol at 60--80 DEG  C.; methylamine may be replaced by ethylamine, normal propylamine, normal butylamine, amylamines, hexylamines, \su-dimethylaminopropylamine, monophenylethylenediamine, monohydroxyethylethylenediamine; the same mixture of anthraquinones may similarly be reacted with ethanolamine, b -oxypropylamine, \su-oxypropylamine, b -oxy-n-butylamine, benzylamine, b -phenylethylamine, o -amino-1-methyl-naphthalene, cyclohexylamine, 1.2.3.4-tetrahydro-2-aminonaphthalene, p-toluidine, aniline, anisidines, aminophenols, naphthylamines, phenylenediamines, aminoquinolines, aminocarbazoles, aminodiphenyleneoxides, or with mixtures of methylamine and n-propylamine, methylamine and ethylamine, methylamine and n-butylamine, ethylamine and n-propylamine, o -propylamine and n-butylamine, methylamine and n-amylamine, methylamine and \su-dimethylaminopropylamine, ethanolamine and p-phenylenediamine, methylamine and benzylamine, ethylamine and b -phenylethylamine, n-propylamine and b -phenylethylamine, n-butylamine and b -phenylethylamine, amylamine and b -phenylethylamine, ethanolamine and b -phenylethylamine, b -oxypropylamine and b -phenylethylamine, methylamine and cyclohexylamine, ethylamine and cyclohexylamine, n-propylamine and cyclohexylamine, n-butylamine and cyclohexylamine, amyl- or hexylamines and cyclohexylamine, ethanolamine and cyclohexylamine, oxypropylamine and cyclohexylamine, monophenylethylenediamine and cyclohexylamine, monoxyethylethylenediamine and cyclohexylamine, ethanolamine and n-butylamine, b -oxypropylamine and ethanolamine, ethanolamine and \su-oxypropylamine, b -oxypropylamine and \su-oxypropylamine, b - or \su-oxypropylamine and butenolamine; (2) 1.4.5.6-tetrahydroxyanthraquinone, 2.3 - dihydro - 1.4-diaminoanthraquinone and ethanolamine are reacted together; the 1.4.5.6-tetroxy derivative may be replaced by 1.4.5.8-tetroxy- or 1.4.5-trioxyanthraquinone and ethanolamine may be replaced by b -oxypropylamine, \su-oxypropylamine, methylamine, butylamine, propylamine; (3) 1.4-diaminoanthraquinone, 2.3-dihydro-1.4-diaminoanthraquinone and n-prepylamine are reacted together; other amines may be used such as methylamine, n-propylamine, ethylamine, ethanolamine, \su-dimethylaminopropylamine, monohydroxyethylethylenediamine, benzylamine, cyclohexylamine, or a mixture of methylamine and n-butylamine may be used; (4) 1.4-diaminoanthraquinone, 2.3-dihydro-1.4-dioxyanthraquinone and normal propylamine are reacted together at 140 DEG  C.; (5) 1.4.5-triaminoanthraquinone, 2.3-dihydro-1.4.5-triaminoanthraquinone, methylamine and ethanolamine are reacted together; 1.4.5.8-tetraminoanthraquinone in presence of its dihydro derivative may similarly be reacted with aliphatic amines or mixtures thereof.  The reaction products are mainly unreduced and only a short treatment with air or other oxidizing agent is necessary to obtain pure products.  The Provisional Specification relates to the condensation of anthraquinones of the general formula <FORM:0461428/IV/1> (wherein the X's are the same or different hydroxy, alkoxy or amino groups) with 2 molecular proportions of a primary amine or at least two molecular proportions of a mixture of at least two different primary amines in the presence of a compound of the formula <FORM:0461428/IV/2> (wherein X is a hydroxy, alkoxy or amino group), or the condensation of a 1.4-diamino-, a 1-amino-4-oxy- or a 1-amino-4-alkoxyanthraquinone with at least 2 molecular proportions of a primary amine or a mixture of at least two different primary amines in the presence of a 2.3-dihydro-1.4-dioxyanthraquinone.