CS218513B1 - Process for preparing 2-aminoantrachinone - Google Patents

Abstract

The invention relates to the production of 2-aminoanthraquinone by ammonolysis of sodium anthraquinone-2-sulfonate, whereby the resulting sulfite anion is removed by oxidation to sulfate with substituted nitrobenzenes containing substituents in position 2 (alkyl to C5, chlorine, -COOX or -SO3X group, where X is an alkali metal cation or ammonium), optionally in positions 3 (-COOX group) and 5 (nitro group, -COOX or -SO3X group, where X has the above meaning).

Description

218313

BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of 2-amino-thionitrile by ammonolysis of anthraquinone sodium 2-sulfonate. In the preparation of 2-amino anthraquinone by ammonium monosodium anionic sodium sulphonate, the sulphite anion formed, which causes the formation of by-products, is removed by oxidation to the sulphate anion. So far, sodium hydrogen carbonate is mainly used for its oxidation. The reaction is carried out at 190 DEG-210 DEG C. in aqueous ammonia at a pressure of 3.8-3 MPa and yields a high yield, up to 90% of theory on sodium anadquinone-2-sulfonate. Also, the quality of the 2-aminoantrachinone obtained is very large and the content of 2-amino anthraquinone in the dried product is up to 98%. A major disadvantage of this process is the fact that sodium hydrogen sulfenate and the resulting sodium arsenate are particularly poisonous. Upon completion of the reaction and the separation of 2-amino anthraquinone, it is unavoidable to remove the above-mentioned arsenic compound from the mother liquors and washings. This operation requires additional production equipment and associated costs to operate it. The solid compounds obtained in the water-insoluble arsenic sulfide or calcium arsenate are undesirable waste from the point of view of ecology. Other oxidizing agents have been retained.

The use of sodium 3-nitrobenzenesulfonate as the oxidizing agent in place of sodium bicarbonate leads to a reduction in the yield of 2-aminoantrachinone by up to 30% of sodium anthraquinone sodium 2-sulfonate. The use of a wide variety of inorganic oxidants is described in the literature, such as copper (II) oxide, copper sulfate, potassium nitrate, potassium chlorate, potassium dichromate, manganese dioxide, which provide a low yield of 2-aminoantrachinone in sodium ammonium isoquinone and is -h poor quality.

The above drawbacks can be avoided by the production of 2-aminoantrachinone by sodium ammonium mono-anthraquinone-2-sulfonate according to

of the present invention. The method consists in that the sulphonate anions formed during the reaction are oxidized by the nitro compounds of the general formula R 1 wherein R 1 = -O 1, 1 - 3 R 2 = -H, -COOX 3 alkyl, -COOX, -SO 3 X

R 5 = -Η, -NO 21, -COOX, -SO 3 X, and X - Na +, K +, Li +, NH 4 +, which are reacted with 0.16 in the reaction mixture; up to 0.8 mole per mole of sodium anthraquinone-2-sulfonate.

In the process of the invention, 2-aminoanthiraquinone can be prepared in high yield and very good quality. The process according to the invention has the disadvantages of the hitherto used sodium bicarbonate technology. Exemplary embodiments

Parts quoted are parts by weight. Example 1

To 330 parts of water and 718 parts of 26% aqueous ammonia solution, 324.7 parts of 77% sodium antrachinone-2-sulfonate are added with stirring. The suspension thus obtained is introduced into an autoclave and 100.0 parts of 52.6% of 2,4-dinitrobenzenesulfonate and 133.3 parts of ammonium chloride are added.

The autoclave contents were heated to 190 ° C with stirring. The contents of the autoclave are kept under stirring for 7 hours at a temperature range of 190 to 200 ° C and a pressure of 4 to 4.8 MPa. After cooling the autoclave contents, at the same time distilling off the ammonia, the water-diluted suspension is further washed with 90 ° C with warm water at 90 ° C to remove impurities.

After drying, 153.7 parts of 95% 2-aminoantrachinone, i.e. 81.2% of theory, were obtained for α-ntra-quinone-2-sulfonate sodium. Example 2

Place in a stirred autoclave. 342.4 parts of 73% sodium anthraquinone-2-sulfonate, 785.0 parts of 28% ammonia water, 111.0 parts of ammonium chloride, 68.5 parts of 2-nitroitaluene and 200.0 parts of water.

The contents of the autoclave are heated to 188-192 [deg.] C. and maintained at this temperature for 14 hours at a pressure of 4.6-5 MPa. The reaction mass is distilled off during the aftercooling and after dilution with 800 parts of water. toluidine. After filtration and washing, 16.5 parts of 99% 2-amino-anthraquinone are obtained, corresponding to 90.8% of sodium anthraquinone sodium 2-sulfonate. Subsequently, after separation, 27 parts of 2-toluidine and 10 parts of 2-nitrotoluene are obtained. Example 2 To 785 parts of a 28% aqueous ammonia solution, 342 parts of 73% sodium anthraquinone-2-sulfonate were added with stirring. The obtained suspension is introduced into the dp autoclave. Then he adds

Claims (1)

2 18 5 13 s β suspension prepared from 200 parts of water, 106.9 parts of 69% 2-nitrobenzenesulfonium chloride saponified sodium 2-nitrobenzenesulfonate 26.7 parts of sodium hydroxide which forms a solution in 40 parts of water. After addition of 111 parts of ammonium chloride, the contents of the autoclave are maintained at 180 DEG C. for 2 hours and then at 190 DEG C. and 4.8 to 4 bar for 13 hours. After cooling the contents of the autoclave while distilling off the ammonia, 500 parts of the boiling water of the diluted suspension is filtered at 90 ° C and washed with 90 ° C with hot water to wash off the impurities. After drying, 169.5 parts of 2-amino anthraquinone are obtained at 97.8%, corresponding to 92.3% of theory for anthraquinone sodium 2-sulfonate. EXAMPLE 4 353.1 parts of 70.8% anthraquinone-2-sulfonate sodium, 572.0 parts of 35% aqueous ammonia, 111.0 parts of ammonium chloride, 170.92 parts of 54.2% 2-nitrotoluene were introduced into a stirred autoclave. 4-sulfonate and 270.0 parts water. The contents of the autoclave were kept under stirring at 180 DEG C. for two hours and at 16 DEG C. at 190 DEG C. and at a pressure of 4.3 MPa. After isolation and drying, 162 parts of 98% 2-aminoantrachinone are obtained, i.e. 88.3% of sodium anthraquinone sodium 2-sulfonate. EXAMPLE 5 411 parts of 73% sodium anthraquinone-2-sulfoate, 718 parts of 30% ammonia water, SUBSTITUTE FOR Preparation of 2-aminoanthraquinone by sodium amnolysis of anthracene-2-sulphonate, designated in that the sulphite ions formed during the reaction are oxidized by the nitro compounds of the formula 133 parts ammonium chloride and 373 parts 32% 3-nitro-1,2-phthalic acid. The contents of the autoclave are kept under stirring at 180 ° C for 3 hours, then at a temperature of 190 to 195 ° C for 12.5 hours at a pressure of 4-5 MPa and finally at 195 to 200 ° C for 2 hours. After isolation, 187 parts of 96% 2-amino-anthraquinone, i.e. 83.2% of theory, are obtained on sodium anthraquinone non-2-sulphonate. EXAMPLE 6 353.1 parts of 70.8% anthraquinone-2-sulfonate, 572.0 parts of 35% aqueous ammonia, 111.0 parts of ammonium chloride, 70.0 parts of 3-nitro-1,4-phthalic acid are introduced into a stirred autoclave. 98% and 295.0 parts of water. The contents of the autoclave are kept under stirring at 190 ° C for 17 hours. After isolation, 164 parts of 96% 2-amino anthraquinone, i.e. 87.5% of theory, were obtained for sodium anthraquinone-2-sulfonate. EXAMPLE 7 411 parts of 73% sodium anthraquinone-2-sulfonate, 718 parts of 30% ammonia water, 40.5 parts of 2i, 4-dinitrochlorobenzene, 133 parts of ammonium chloride and 200 parts of water are introduced into a stirred autoclave. The contents of the autoclave are kept under stirring at 190 ° C for 16 hours and a pressure of 4.0 to 4.8 MPa. After isolation and drying, 198 parts of 98% 2-amino anthraquinone, i.e. 89.9% of theory, are obtained with Naantrachinone-2-Sodium Sulfonate. Wherein R 1 = -Cl, alkyl C 1 -C 8, -COOX, SO 3 X, R 2 = -H, -COOX R 3 = -Η, -NO 2, -COOX, -SO 5X, and X- = Na +, K +, Li +, NH 4 + which are introduced into the reaction mixture at a rate of 0.16 to 0.8 mole per mole of sodium antinquinone-2-sulphonate.