Patent GB-465040-A (GB)
Title: A process for the manufacture and production of compounds of the anthracene series
IPC: C09B5/02
Filed: 1935-10-23
Abstract: Ammonia or a primary amine is reacted with a compound of the general formula <FORM:0465040/IV/1> wherein X is a ring-member in the 1-position of a six-membered ring joined in 1.9-positions containing only carbon and nitrogen, and represents N, NH or N-alkyl, and Y is a hydroxyl or amino group, either in the form of its leuco derivative or in the presence of reducing agents, and the resulting compound if in the leuco-form is, if desired, treated with oxidizing agents.  The process may also be carried out by starting with a mixture of the unreduced compound and its leuco-compound whilst when a reducing agent is present it need not be in amount sufficient to reduce the whole of the initial material.  Suitable reducing agents specified are alkali hydrosulphites preferably in presence of mild alkali, zinc dust, stannous chloride or titanium trichloride, and the final oxidizing agents used may be sodium chlorate, sodium perborate, hydrogen peroxide, iron chloride, aromatic nitro compounds, air, oxygen or oxides of nitrogen.  Suitable starting materials are 4-amino - 1.9 - anthrapyrimidine, 4 - amino-PyC - chlor - 1.9 - anthrapyrimidine, 4-amino-PyC - alkyl - 1.9 - anthrapyrimidines, 4-amino-PyC - aryl - 1.9 - anthrapyrimidines, 4-amino-PyC - amino - 1.9 - anthrapyrimidine, 4-amino-PyC - alkylamino - 1.9 - anthrapyrimidines, 4 - amino - PyC - arylamino - 1.9 - anthrapyrimidines, 4 - amino - PyC - acylaminoanthrapyrimidines, 4 - amino - 2-halogen - 1.9 - anthrapyrimidines, 4 - amino-2 - alkoxy-1.9 - anthrapyrimidines, 4-amino 1.9 - anthrapyrimidine - 2 - sulphonic acids, 4 - oxy - 1.9 - anthrapyrimidines, 4 - amino-1.9 - anthrapyrimidine, 4 - amino - N - alkyl-1.9 - anthrapyrimidones, 4 - oxy - 1.9 - anthra - pyrimidones (prepared from 1 - amino - 4 - oxyanthraquinones with urea), 4 - oxy - N - alkyl-1.9 - anthrapyrimidones (prepared by treating 4 - oxy - 1.9 - anthrapyrimidones with alkylating agents), the corresponding 1 : 9-anthrapyridones, also Py.C.-acyl-1 : .9-anthrapyridones (obtainable from 1-aminoanthraquinones and malonic or acylacetic esters), e.g. 4-amino-PyC - acetyl - 1.9 - anthrapyridone, 4 - amino-PyC - carbalkoxy - 1.9 - anthrapyridones, 4-amino - PyC - benzoyl - 1.9-anthrapyridones and their N-alkyl derivatives, 4-amino-Bz2-alkyl - Bz1 - azabenzanthrones (prepared by condensing 1.4 - diaminoanthraquinone with methylalkyl ketones), 4-amino-Bz2-aryl-Bz1-azabenzanthrones (prepared by condensing 1.4-diaminoanthraquinone with methyl aryl ketones), 4 - amino - Bz2 - halogen - Bz1 - azabenzanthrones (prepared by treating 4-amino - 1.9 - anthrapyridone with phosphorus pentahalides), 4 - amino - Bz2 - amino-(or -alkyl-, -aralkyl-, -cycloalkyl- or -aryl-amino-) Bz1-azabenzanthrones (prepared by treating 4 - amino - Bz2 - halogen - Bz1 - azabenzanthrones with ammonia or amines), 4-amino-Bz2 - Bz3 - tetrahydrobenzene - Bz1 - azabenzanthrones (prepared by treating 1.4-diaminoanthraquinone with cyclohexanone in presence of alkali), the corresponding 4-oxy-Bz1-azabenzanthrones (similarly prepared from 1 - amino - 4 - oxyanthraquinone and methyl alkylketones, methylarylketones or cyclohexanone respectively), 4-amino- or -4-oxy-coeramidenes. The products are suitable for dyeing cellulose esters and ethers, hydrocarbons, fats, oils, waxes and artificial compositions, and in part for dyeing vegetable and animal fibres, e.g. cotton or wool, whilst their sulphonic acids dye wool from acid baths.  The products may also be used for the preparation of other dyes.  In examples: (1) 4-hydroxy-1 : 9 - anthrapyrimidine or its Py.C-alkyl, aralhyl, cycloalkyl, aryl, amino, alkylamino, arylamino, acylamino or halogen derivatives are heated with ammonia in the presence of sodium hydrosulphite and methanol; (2) 4 - amino - 1 : 9 - anthrapyrimidine, or its 2-bromo, 2-methoxy or 2 : 3-dichlor derivative is similarly treated, and the resulting leuco-4-amino-1 : 9-anthrapyrimidine is heated in butanol with n-propylamine or other alkylamines, e.g. methylamine, ethylamine, n-butylamine, amylamines, hexylamines, dodecylamine, stearylamine, monohydroxyethylethylenediamine, ethylenediamine or monophenylethylenediamine; the products may be used in part for dyeing acetate artificial silk and in part for colouring solid and liquid hydrocarbons, oils and waxes; (3) leuco-4-amino-1 : 9-anthrapyrimidine is heated with aniline hydrochloride in the presence of isobutyl alcohol, with access of air, yielding 4-anilido-1 : 9-anthrapyrimidine; the product when sulphonated dyes wool red-yellow shades; the aniline hydrochloride may be replaced by the salts of other aromatic amines, e.g. toluidines, anisidines, aminohydroxybenzenes, phenylenediamines, aminonaphthalenes, aminodiphenyls, aminocarbazoles, aminodiphenylene oxides, aminoquinolines, or aminoisquinolines; (4) leuco-4-amino-1 : 9-anthrapyrimidine is heated with hydrazine hydrate, phenylhydrazine or naphthylhydrazine in the presence of methanol; the products may be oxidized to 4-hydrazino-, phenylhydrazino- or naphthylhydrazino - 1 : 9 - anthrapyrimidine; (5) a mixture of leuco - 4 - amino - 1 : 9 - anthrapyrimidine and 4-hydroxy-1 : 9-anthrapyrimidine is heated with cyclohexylamine in the presence of isobutyl alcohol to produce 4-cyclohexylamino-1 : 9-anthrapyrimidine; the product dyes acetate artificial silk yellow shades; the cyclohexylamine may be replaced by 1 : 2 : 3 : 4-tetrahydro-2-aminonaphthalene, the product when sulphonated dyeing wool yellow shades; (6) 4-amino-1 : 9-anthrapyrimidine is heated with ethanolamine in the presence of sodium hydrosulphite, methanol and water, and the product is heated with nitrobenzene and a little piperidine to yield 4-hydroxyethylamino-1 : 9-anthrapyrimidine; the product yields yellow dyeings on acetate artificial silk and on wool, and reddish yellow dyeings on tannin-mordanted cotton; the ethanolamine may be replaced by 1 : 2- or 1 : 3-propanolamine; (7) 4-hydroxy - 1 : 9 - anthrapyrimidine and benzylamine similarly yield 4-benzylamino-1 : 9 - anthrapyrimidine; benzylamine may be replaced by other aralkylamines, e.g. b -phenylethylamine or o -aminomethylnaphthalene; (8) 4-hydroxy- or 4-amino- Bz.2-methyl-Bz.1-azabenzanthrone is treated with ethanolamine as in (6) to produce leuco-4-hydroxyethylamino-Bz.2-methyl-Bz.1-azabenzanthrone, which may be oxidized with nitrobenzene; the product dyes acetate artificial silk yellow shades; the ethanolamine may be replaced by other hydroxyalkylamines, alkylamines, aralkylamines or cycloalkylamines; (9) 4-amino- or 4-hydroxy-N-methyl-1 : 9-anthrapyrimidone, 4-amino- or 4-hydroxy-1 : 9-anthrapyrimidone or -anthrapyridone, 4-amino-or 4 - hydroxy - N - methylanthrapyridone, 4-amino- or 4-hydroxy-Py.C-acyl-1 : 9-anthrapyridone or 4-amino- or 4-hydroxy-Py.C-acyl-N-methyl-1 : 9-anthrapyridone is similarly treated; arylamines may also be used as the second reaction component; (10) 4-amino-N-methyl-1 : 9-anthrapyrimidone is heated with aqueous ammonia in the presence of sodium hydrosulphite and methanol, the resulting leuco - 4 - amino - N - methyl - 1 : 9 - anthrapyrimidone is heated with n-butylamine and methanol, and the product is dried in air and thus oxidized to 4-n-butylamino-N-methyl-1 : 9-anthrapyrimidone; other alkylamines, or aralkylamines, cycloalkylamines or arylamines may be similarly employed; (11) 4-hydroxy-1 : 9-anthrapyrimidone is reduced with tin and hydrochloric acid in the presence of glacial acetic acid, the leuco-compound is heated with aqueous methylamine in the presence of methanol, and air is led through the mixture after adding copper acetate and pyridine; the resulting 4-methylamino-1 : 9-anthrapyrimidine dyes acetate artificial silk yellow shades; Py.C-substituted anthrapyrimidines, and other alkylamines, aralkylamines, or cycloalkylamines may be similarly employed; (12) 4-hydroxymethylcoeramidonine (obtainable by heating 1-p-tolylamino-4-hydroxyanthraquinone with sulphuric acid) is heated with n-butylamine in the presence of sodium hydrosulphite, methanol and water, and the product is oxidized as in (11) to 4-n-butylaminomethylcoeramidonine.  Specification 407,363 is referred to.  The Provisional Specification comprises the treatment of compounds of the formula given above in which the ring of which X is a member is any ring joined in the 1 : 9-position, and in which Y may be additionally an alkyl-, aralkyl-, cycloalkyl-, aryl- or acyl-amino group.  Additional starting materials specified are: 4-acylamino- 1 : 9-anthrapyrimidines (e.g. 4-acetyl- or benzoylamino-1 : 9-anthrapyrimidine, 4-p-chloro-benzoylamino - Py.C - methyl - 1 : 9 - anthra - pyrimidine, 4 - (2<1> : 5<1> - dichlorbenzoylamino)-Py.C - phenyl - 1 : 9 - anthrapyrimidine, 4 - p - toluylamino - Py.C - anthraquinonyl-1 : 9 - anthrapyrimidine and 4 - benzoylamino-Py.C - benzoylamino - 1 : 9 - anthrapyrimidine), 4 - alkylamino-, 4 - aralkylamino-, 4 - cycloalkylamino- and 4 - arylamino - 1 : 9 - anthrapyrimidines, 4 - amino - 1 : 9 - anthrapyrimidines containing a heterocyclic radicle in the amino group, and 4-acylamino-1 : 9-anthrapyrimidones (e.g. 4-benzoylamino-, 4-anthraquinonylamino - N - methyl-, 4 - acetylamino-, 4-alkylamino-, 4-aralkylamino-, 4-cycloalkylamino and 4-arylamino-1 : 9-anthrapyrimidones.