RU1838293C - Method of purification of 1-nitroanthraquinone synthesized by nitration - Google Patents

Abstract

Usage: in the manufacture of dyes. SUMMARY OF THE INVENTION: Product: 1-nit roanthraquinone containing 98.1% of the main product, 0.3% of anthraquinone and 1.6% of dinitro-anthraquinones. Reagent 1: crude 1-nitroanthraquinone nitration product of anthraquinone. Purification conditions: treatment with an aqueous solution of dimethylformamide containing a mixture of isomers of oxy nitroanthquinone and mineral acid (for example, sulfuric or nitric) at a molar ratio of reagent 1: DMF: H20: oxyantraquinone: acid equal to 1: (5-4) :( 1,3- 1.2) :( 0.4-0.25) :( 0.02-0.005), washing the separated precipitate (eg. Ci-C3 alkanol), spinning and treating dimethyl formamide in the presence of 0.1-10 wt.% Nitride sodium: 2z.p. f-ly. LT,,

Description

The invention relates to the chemistry of nitroaromatic compounds, and in particular to a process for the purification of 1-nitroantraquinone obtained by nitration with acid nitrating agents. Nitroanthraquinone is used for the synthesis of 1-aminoanthraquinone, which is used to make dyes.

The aim of the invention is to increase the yield and quality of 1-nitroanthraquinone in the treatment of paste with high humidity with a high content of impurities.

This goal is achieved by the fact that 1-nitroantraquinone (50 wt.% Moisture) is subjected to dimethylformamide treatment as follows. First, the paste is treated with aqueous dimethylformamide containing nitrooxy anthraquinones and mineral acid with the following ratios of the components of the mixture: 1-nitroantraquinone: dimethylformamide: water: hydroxy nitroantraquinones: mineral acid; (5-4) :( 1,3- 1.2) :( 0.4-0.25): (0.2-0.005). 8 as a mineral acid, sulfuric or nitric acid may be used; The nitroanthrachinoia precipitate is filtered off, washed and sent to treatment with sodium nitrite. The washing of the precipitate can be carried out with either DMF or aliphatic methyl alcohol, ethyl alcohol, isopropyl alcohol).

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Example 1. For the purification of 100 g of a paste of raw 1-nitroantraquinone (1-on), containing 50% moisture and having, in terms of dry matter, the composition: 3.14% anthraquinone; 1.75% 2-on; 6.32% 1,5-di-di; 3.98% of 1,8-din; 12.42% of the sum of 1,6- and 1,7-di-di and 72.4% of 1-one, take 281 g of a mixture containing 250 g of DMF, 20 g of soluble hydroxyquinone-quinones-, 10 g of water and 1 g sulfuric acid. All components are thoroughly mixed at room temperature. In this case, water from paste 1-n passes into the liquid phase, mixing with DMF. As a result, the composition of the liquid phase in terms of dry 1-on: 1-on: DMF: NgO: hydroxy-on: mineral acid - 1: 5: 1.2: 0.4: 0.02. After stirring, they are kept for precipitation a suspension of a fine-crystalline precipitate of a mixture of nitroanthraquin o n ov (10-15 min). The precipitate was then filtered off with suction and washed with isopropyl alcohol until clear drops of filtrate appeared. 225 g of DMF and 0.75 g of sodium nitrite (NaNOa) were added to the resulting paste. The mixture was heated to boiling point (140 ° C) and allowed to stand for 20 minutes. Then the mixture was cooled to room temperature and held for another 30 minutes to isolate crystals. The resulting crystals were filtered off, washed with isopropanol and dried under vacuum. As a result of all operations, 36 g of purification product are obtained, yield 97.5%, containing 98.1% 1-on; 0.3% of anthraquinone and 1.6% of the sum of di-din.

Example 2. For the purification of 100 g of raw paste 1-on, containing 51 g of moisture and having, in terms of dry substance, the composition: 5.67% anthraquinone; 21% of the amount of dinitroan-traquinones; 73% 1-on and 0.2% 2-on, take 215.845 g of a mixture containing 196 g of DMF; 7.35 g of water; 12.25 g of soluble oxynitro-anthraquinones; 0.245 g of nitric acid. All components of the mixture are thoroughly mixed at room temperature. The composition of the liquid phase in relation to the dry substance is as follows: 1-on: DMF: NgO: hydroxy-on: mineral acid 1: 4: 1.2: 0.25: 0.005. The precipitate was isolated by the method described in Example 1, only the washing was carried out with pure DMF.

To the resulting paste (80 g), 240 g of DMF and 0.80 g of NaNOz were added. The mixture was heated to boiling point (153 ° C) and held for 20 minutes. Then, the mixture was cooled and held for another 30 minutes. The precipitated crystals are filtered off, washed with a small amount of DMF and dried under vacuum. 35 g of product are obtained (yield 92.5%) containing 96.5% 1-on; 0.5% anthraquinone; 2.5% of the sum of the di and 0.5% of the 2-on,

Example 3. For the purification of 100 g of a paste of crude 1-nah, containing, in terms of dry substance 3, 67% anthraquinone; 0.98% 2-on; 8.15% 1.5-di; 3.95% 1.8-di: 12.75% of the 1.6- and 1.7-di (the di-24.85%) ; 70.5% of 1-one, as well as containing 50 g of moisture, take 221.19 g of a mixture containing 202.5 g

0 DMF; 3.5 g of water; 14.63 g of soluble oxine and 0.56 g of sulfuric acid. All components of the mixture are thoroughly mixed, while the composition of the liquid phase in relation to dry 1 is next; 1-on: DMF: H20: hydroxy-on

5 ; mineral acid - 1: 4.5-1.3: 0.325: 0.0125. The precipitate is isolated by the method described in Example 1, only the precipitate is washed with ethanol,

225 g of dio methylformamide and 0.75 g of sodium nitrite were added to the resulting paste. The mixture was heated to boiling point (135 ° C) and held for 20 minutes, cooled to room temperature and held for 30 minutes. The obtained crystals are treated analogously to Example 1, using a small amount of ethyl alcohol when washing the crystals on the filter. 34.5 g of a purification product are obtained (yield 94.06%) containing 96.1% .1-on; 0.2% anthraquinone;

0 2.5% of the sum of the di and 0.05% of the 2-on.

Example 4. For the purification of 100 g of paste of crude 1-on containing 50 g of moisture and having, in terms of dry matter, the composition: 4.5% anthraquinone; 1.5% 2-on; 5.5% 1.5-di5 per; 3.5% 1,8-di-di; 13.0% of the sum of 1,6- and 1,7-di-di, take 225.5 g of a mixture containing 200 g of DMF; 10 water; 15 g of soluble oxy-n and 0.5 g of sulfuric acid. All components of the mixture are thoroughly mixed at room temperature. The composition of the liquid phase relative to the dry 1 is as follows: 1-on: DMF: NaO: hydroxy-on: mineral acid 1: 4: 1.2: 0.3 : 0.01. Isolation-precipitation is carried out in a manner

5 specified in example 1, only the precipitate is washed with methyl alcohol.

234 g of DMF and 0.78 g of NaNOa were added to the resulting paste. The mixture is heated to boiling point (132 ° C) and incubated

0 20 min, then cooled to room temperature and incubated for 30 min. The precipitated crystals are filtered off and washed with a small amount of methanol, then dried. sew under vacuum. Obtain 35 g (yield

5 95.08%) of a product containing 97.8 1-on; 0.2% of anthraquinone and 2% of the amount of di-on.

Example 5 (comparative). To clean 100 g of raw 1-paste, containing 50% moisture and having, in terms of dry matter, the composition: 3.8 anthraquinone;

2.0% 2-na; 6.5% 1,5-di-nv; 3.8% 1,8-di-di; 13.1% of the sum of 1,6- and 1.7-di-di and 70.8% of 1-one, take 290.5 g of a mixture containing 250 g of DMF; 25 g of water; 15 g of soluble oxy-n and 0.5 g of sulfuric acid. All components are thoroughly mixed at room temperature. The composition of the liquid phase in terms of dry 1 is as follows: 1-on: DMF: H20: hydroxy-on: mineral acid 1: 5: 1.5: 0.3: 0.01. The precipitate was isolated as in Example 1.

To the resulting paste, 240 g of DMF, 0.8 g of NaN02 were added and the mixture was heated to boiling point (14 ° C) to give a 20-minute exposure. Then the mixture is cooled to room temperature and incubated for 30 minutes. The obtained crystals are treated analogously to Example 1. 35 g of a precipitate are obtained (yield 91.9%) containing 93% 1-; 2% A; 0.2% of 2-on and 4.5% m of the amount of di-on.

Example 6 (comparative). For cleaning, take 100 g of paste containing 50 g of water and 30 g of dry matter composition: 3.14% A; 22.7% of the sum of the di-on and 72.4% of the 1-on. Proceed further analogously to example 1, only instead of 250 g of DMF take 350 g of DMF. As a result of the primary treatment of raw 1-on, the liquid phase has the following composition: 1-on: DMF: H20: hydroxy-on: mineral acid 1: 7-1., 2: 0.4: 0.02. Further, the processing of 1-on paste with DMF and NaNOa at an elevated temperature is carried out analogously to Example 1. The result is 27 g (yield 73.6%) of a precipitate containing 98.8% 1-one; traces of anthraquinones and about 1% of the sum of dinitroantraquinones.

PRI me R 7 (comparative). For cleaning, take 100 g of paste containing 50% water and 50 g of dry matter composition: 3.14% A; 22.7% of the sum of the di-on and 72.4% of the 1-on. Then, as indicated in Example 1, they only use DMF containing 40 g of soluble oxy nitroanthraquinones per 250 g of DMF. As a result, after mixing the components during the initial processing of the paste at room temperature, the liquid phase has the composition: 1-on: DMF: H20: hydroxy- on: mineral acid 1: 5: 1.2: 0.80: 0.2. Subsequently, the treatment is carried out in DMF with NaN02 at an elevated temperature, as in Example 1, and 35 g of a precipitate are obtained (yield 89.92%) containing 93% 1-one; 0.3% A and 6% of the sum of the Dee.

Example 8 (comparative). For cleaning, take 100 g of paste containing 50 g of water and 50 g of dry matter composition: 72.4%, 1-on; 3.14% A and 22.7% of the sum of di-Din. They do the same as in example 1, only use 250 g of pure, not containing oxy nitroantrahi-k. . dimethylformamide, 10 g of water and 1 g of sulfuric acid. The ratio of the components of the liquid phase after mixing during the initial treatment of raw 1-on at room temperature 1-on: 5 DMF: H2O: mineral acid 1: 5:: 1.2: 0.02. The processing of the paste obtained as a result of the previous treatment is carried out analogously to example 1. The result is 28 g of precipitate (yield 10 75.1%) containing 97.1% of 1-one, 0.2 anthraquinone and 3% of the sum of dinitroantraquinones . Example 9 (comparative). For cleaning, 100 g of paste containing 50 g of water and 50 g of dry matter of the composition similar to Example 15 are taken. Processing at room temperature is carried out in the manner described in Example 1, only 100 g is taken instead of 250 g of DMF. As a result, when primary processing of raw 1-on liquid phase has the composition: 1-on: DMF:: hydroxy-on: mineral acid 1; 2: 1.2: 0.4: 0.02. Further processing was carried out analogously to Example 1 and 36 g of a precipitate (yield 91.3%) containing 92% 1-one were obtained; 2.5%

5 and 6% of the sum of dee.

Example 10 (comparative), For processing take 100 g of paste of crude 1-on, containing 50 g of water and 50 g of dry matter of a composition similar to example 1. For

For the initial treatment, 271 g of anhydrous DMF, 20 g of soluble oxy nitroantraquinones and 1 g of sulfuric acid are taken. The ratio of the components of the liquid phase in this case is 1-on: DMF: oxy-on

5: mineral acid 1: 5: 0.4: 0.02. Further processing is carried out by ana. logical example 1 and get 20 g of sediment (yield 53.7) containing 97.3% 1-on; 0.1% A and 2.5% of the sum of Dee.

0 Example 11 (comparative). For processing, 100 g of paste of crude 1-one containing 50 g of water and 50 g of dry matter, similar in composition to Example 1, 280 g of a mixture containing 250 g of DMF are taken; 20 g of soluble oxy-on and 10 g of water. Subsequently, they proceed analogously to Example 1, but mineral acid is not added. In this case, the ratio of the components of the liquid phase during the initial treatment corresponds to 1: DMF: PrO: oxy 1: 5: 1.2: 0.4. Subsequent treatment at elevated temperature in DMF with NaN02 is similar to Example 1. The result is 36.5 g (97.7% yield) of product containing

5 96.9% 1-on; 0.5% A; 0.5% of 2-on and 1, y% of the sum of the di-on.

PRI me R (comparative m prototype),

For S .--; - 100 g pzsta raw 1-on, soder; kzgo 50 g and 50 g.: Ear--

residual substances: 72.4% 1-on; 3.14% anthraquinone; 1.75% 2-on; 6.32% 1,5-di-ne; 3.98% of 1,8-di-di; 12.42% of the sum of 1,6 and 1,7-di (the total of the di is 22.72%). Then proceed similarly to the method described in the prototype, namely: azeotropic distillation from DMF, a mixture of nitroantraquinones is dried. As a result, the water content of the paste is adjusted to 20%. The amount of DMF per 50 g of the dry mixture was 50 g (1: 1). To the resulting mixture nitroantrachino-. 7.5 g of triethanolamine and 0.5 g of NaN02 are added to the crude, water and DMF. The mixture is heated to 110 ° C and stirred at this temperature for 3 hours, then cooled to 20 ° C, the filtrate is suctioned off under vacuum, and the crystals are washed on the filter successively with a small amount of DMF and methanol, then dried. Obtain 21.25 g of product (yield 55.9%) containing 4.5% anthraquinone and 95.24% 1-on.

Thus, the proposed method for the purification of raw 1-on allows to increase the yield of pure 1-on up to 97.5 wt.% (Prototype 55.9%) and improve the quality of the product: 1-on content up to 98.1% (by prototype 95.2%), the content of anthraquinone up to 0.2% (rio prototype 4.5%). In addition, this purification method allows purification to be carried out immediately after separation of the nitration products from the nitration mixture and water washing. Thus, there is no need to neutralize and pre-dry before cleaning.

Claims (3)

1. The method of purification of 1-nitroanthraquinone obtained by nitration of anthraquinone, comprising treating with a solution of dimethylformamide in the presence of 0.1-10 wt.% Sodium nitrite at elevated temperature, characterized in that the crude 1-nitroantraquinone is pretreated with an aqueous solution of dimethylformamide containing a mixture of oxy nitroanthraquinone isomers and mineral acid in a mass ratio of 1-nitroanthraquinone: dimethylformamide: water: hydroxyanthraquinone: mineral acid, equal to 1: 5-4: 1.3-1.2: 0.4-0.25: 0.02-0.005, and the separated precipitate is washed, squeezed and sent for treatment with sodium nitrite. 2. The method according to claim 1, characterized in that sulfuric or nitric acid is used as the mineral acid. 3. The method according to PP. 1 and 2, cast. especially that the washing of the separated precipitate is carried out with Ci-C3 alkanol.