Patent GB-389568-A (GB)
Title: Process for the manufacture and production of intermediates and dyestuffs of the anthraquinone series
IPC: C09B1/16
Filed: 1931-11-25
Abstract: 1-1<1>-Dianthraquinonyls and products derived therefrom.--A product corresponding to the general formula:-- <FORM:0389568/IV/1> wherein Y represents a halogen or the diazo group and X and Z represent hydrogen atoms or both X's and Z's represent double-bonded carbon atoms of the same aromatic compound which may be substituted, is heated with copper or cuprous chloride, and, if desired, the resulting products are subjected to saponification or to saponification and condensation.  The condensation of those products wherein Y is a halogen atom is preferably effected by means of copper in an organic solvent such as halogen-and nitrobenzenes, naphthalene and its alkyl, halogen and nitro derivatives, diphenyls, and paraffin oils.  Those products wherein Y is a diazo group are condensed by means of cuprous chloride in water or a dilute acid such as acetic or sulphuric acid.  The products are 1,1<1>-dianthraquinonyls and may be treated with basic or acid saponifying agents, when the course of the reaction depends on the reacting conditions employed.  Products in which the 2.2<1>-dicarboxylic acid imide ring structures are converted to 2.2<1>-acylamino groups are obtained by saponifying with alkaline agents diluted with water and organic diluents, such as alcohols, at temperatures not above 80 DEG .  The dicarboxylic acid radicles are completely split off by saponifying with substitution products of ammonia, such as hydrazine hydrate and ethylenediamine in organic solvents, particularly those miscible with water, at temperatures not above 50 DEG  C.  By prolonging the action of these reagents, and/or by using higher temperatures, simultaneous saponification and condensation occurs to give flavanthrones. Aqueous dilute alkaline agents may likewise be used for this purpose at temperatures not less than 90 DEG  and as high as 250 DEG  (using pressure); thus 1-10 per cent solutions of caustic alkalis, ammonia, hydrazine hydrate, ethylenediamine, alkali phosphates or alkalineearth metal oxides may be employed.  The use of acid saponifying agents also leads to simultaneous saponification and condensation, either flavanthrones or products in which one amino group appears to be replaced by a hydroxy group, being produced; condensed products of this latter type are generally obtained when sulphuric acid stronger than 90 per cent is used, whereas the weaker acid even employed with higher temperatures yields flavanthrones. These conditions effecting condensation may be applied to the partially or completely saponified products described above to yield flavanthrones, and also the free diamines may be converted by simply heating them above their melting point alone, or in the presence of an organic solvent, or by dissolving them in concentrated sulphuric acid.  The starting materials may be substituted in the anthraquinone nucleus by methyl, ethyl, propyl, butyl, or other alkyl groups, or by hydroxy, alkoxy, aryloxy, acylamino, chlorine, or bromine in the b -position.  They may be prepared by heating 1-halogen-2-aminoanthraquinones with succinic acid anhydride or with aromatic-o-dicarboxylic acid anhydrides or their substitution products, for example those containing methyl, chloro, or nitro groups, preferably in the presence of halides, such as ferric, zinc, or phosphorus halides.  The corresponding diazo compounds are prepared by starting from the 1-nitro-2-aminoanthraquinones and reducing the nitro group after condensation with the acid anhydride, followed by diazotization; alternatively the 1-halogen-2-dicarboxyimino bodies are reacted with a toluenesulphonamide, saponified, and then diazotized.  In examples: (1) 1-chloro-2-aminoanthraquinone is condensed in presence of ferric chloride with succinic anhydride, phthalic anhydride, 3.6-dichlorphthalic anhydride and naphthalene-2.3-dicarboxylic acid anhydride; 1.3-dibrom-2-aminoanthraquinone and 1-chloro-3-methyl-2-aminoanthraquinone are similarly condensed with phthalic anhydride; (2) 1-chloro-2-phthalimidoanthraquinone is heated with copper in naphthalene; the same product is obtained by heating the diazo compound from 1-amino-2-phthalimidoanthraquinone with cuprous chloride in water; (3) 1-chlor-2-phthalimido-3-methylanthraquinone is heated with copper powder in trichlorbenzene; similar treatment is applied to 1-chloro-2-phthalimido-3-methoxyanthraquinone (prepared by treating 2-amino-3-methoxyanthraquinone with sulphuryl chloride and heating the product with phthalic anhydride) and 1.3-dibrom-2-phthalimidoanthraquinone; (4) 1-chloro-2-succinimidoanthraquinone and 1-chloro-2-(2<1>.3<1>-naphthoyleneimino) - anthraquinone are heated with copper powder in naphthalene; (5) the dianthraquinonyl obtained by (2) is converted to a yellow vat dye (flavanthrone) by heating with 10 per cent ammonia at 150-180 DEG , or with hydrazine hydrate in pyridine-water mixture at 95 DEG  while leading in air, or with 5 per cent disodium phosphate or sodium carbonate at 150-170 DEG , or with 1-5 per cent soda at about 160 DEG , or with 85 or 20 per cent sulphuric acid at 120 DEG  C. or 200 DEG  respectively, or with concentrated hydrochloric acid at 200 DEG  C. (in this case the product contains chlorine); if hydrazine hydrate in pyridine is used at about 20 DEG  C. a red intermediate product is obtained which is converted into flavanthrone by solution in concentrated sulphuric acid; by using a dilute aqueousalcoholic soda solution at 50-60 DEG C. a yellow product soluble in alkali solutions is obtained, and this can be converted to flavanthrone by heating in 4 per cent soda at 95-100 DEG  C., or in 5-90 per cent sulphuric acid at 80-150 DEG  C.; if 95 per cent sulphuric acid is used at 95 DEG  C. an orange-yellow product is obtained; (6) the dianthraquinonyl from 1-chlor-2-phthalimido-3-methylanthraquinone is heated with 5 per cent soda at 160 DEG  C. to give an orange vat dye: (7) the dianthraquinonyl from 1.3-dibrom-2-phthalimidoanthraquinone is heated with hydrazine in o-dichlorbenzene at 150 DEG  while leading in air to give an orange-yellow vat-dye; if 95 per cent sulphuric acid at 90-95 DEG  is used instead, and methanol subsequently added, a product in the form of yellow leaflets containing bromine is obtained; (8) the dianthraquinonyl from 1-chlor-2-succinimidoanthraquinone is boiled with 5 per cent caustic soda to give flavanthrone; (9) the dianthraquinonyl from 1-chloro - 2 - (2<1>.3<1>-naphthoyleneimino) - anthraquinone in finely-divided form is heated with 7,5 per cent caustic soda at 95-100 DEG  to give flavanthrone.