JPH0227341B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing anthraquinone intermediates. More specifically, the present invention relates to the general formula () [In the formula, R represents an optionally substituted alkyl group or an optionally substituted cycloalkyl group. ] A compound represented by or a salt thereof in an aqueous medium,
In the presence of a dehydrogenating agent and a quaternary ammonium compound, it is reacted with a cyanating agent to form the general formula () [In the formula, R has the above meaning. ] A method for producing an anthraquinone intermediate, characterized by producing a compound represented by the following. The compound of general formula () is an important intermediate for anthraquinone dyes, and it is known from US Pat. No. 1,938,029 etc. that it can be obtained by reacting an aqueous solution of the compound of general formula () with a cyanide compound. However, these methods produce general formula () and general formula () as by-products. [In the formula, R has the above meaning. ] The compound represented by is always produced at a constant rate, reducing the yield, and it is necessary to add purification using sulfuric acid etc. in the subsequent production of the dye. Also,
The yield is also about 60% at most. As a method of preventing these by-products, West German Patent No. 1108704 and Soviet Patent No. 148066 recommend the combined use of an oxidizing agent, such as sodium m-nitrobenzenesulfonate. However, when applying these methods,
It is true that the compound of general formula () is completely suppressed,
Although the production rate of the compound of general formula () also tends to decrease, oxidation products and secondary hydrolysis products of the main product and by-products are produced, and the apparent appearance of the compound of general formula () is The purity is low compared to the yield of
The yield is about 70-80%, and if subsequent dyes are produced without purification, it will not be possible to obtain clear hues. In cyanating the compound of the general formula () or its salt to obtain the corresponding compound of the general formula (), the present inventors suppressed the above-mentioned impurities, particularly the by-product of the compound corresponding to the general formula (). In addition, the quality is such that no contamination of unreacted substances, secondary oxidation products and hydrolysis products are produced, or even if they are produced, the amount thereof is such that there is no substantial adverse effect on the quality of the dye in the final product. As a result of intensive investigation into a production method with excellent yield, it was discovered that the objective could be achieved by adding a quaternary ammonium compound to the reaction system. By using a quaternary ammonium compound in the reaction in the present invention, the content of the compound of general formula (), which could not be avoided in conventional methods, from about 10 to 20%, can be reduced to 1 to 3% or less. As a result, the yield of the target product can be significantly increased. Furthermore, according to the method of the present invention, in the reaction mixture after the completion of the reaction, most of the organic substances other than the compound of general formula () are dissolved, so the target product with high purity can be easily obtained by simply filtering. . In addition, the quaternary ammonium compound can be extracted from the liquid as it is as a quaternary ammonium compound by using an alkali, or as a quaternary ammonium hydroxide using an organic solvent and then back-extracted with acidic water to eliminate waste. It can be collected and reused. In the present invention, specific examples of the quaternary ammonium compound include the following. Lower alkyl quaternary ammonium compounds such as tetramethylammonium chloride, tetraethylammonium chloride, tetramethylammonium methyl sulfate, tetraethylammonium ethyl sulfate, tetra-n-butylammonium bromide, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethyl Higher alkyl quaternary ammonium compounds such as ammonium chloride Trialkylbenzylammonium compounds such as trimethylbenzylammonium chloride and triethylbenzylammonium chloride N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium chloride, N-laurylpyridinium chloride,
N-alkylpyridinium compounds such as N-stearylpyridinium chloride and N-alkylpicolinium compounds; bromides corresponding to the chlorides of the above compounds;
Iodide sulfate, phosphate, acetate or mixtures thereof Industrially, trialkylbenzylammonium compounds such as trimethylbenzylammonium chloride and triethylbenzylammonium chloride are preferably used. The amount of the quaternary ammonium compound used varies depending on the type of compound used, but for example, in the case of benzyltriethylammonium chloride, it is 2 to 80% by weight, preferably 5 to 60% by weight, based on the aqueous reaction solution or suspension. Weight%. If the quaternary ammonium compound has stronger fresh oil properties than this, the amount added may be even smaller, and conversely, if the fresh oil properties are weaker, the objective can be achieved by using a larger amount than this. In the present invention, the cyanating agent used is, for example, an alkali metal or alkaline earth metal cyanide, such as sodium cyanide, potassium cyanide, ammonium cyanide, magnesium cyanide, calcium cyanide, or a mixture thereof. Among these, sodium cyanide and potassium cyanide are particularly preferably used. Furthermore, cyanohydrins that generate cyanide ions in water, such as acetone cyanohydrin, can also be used. The amount used is 2.0 to 1 molar ratio to the compound of general formula (). In the present invention, dehydrogenating agents include organic nitro compounds such as nitrobenzene, nitrobenzenesulfonic acid, nitrophenol, organic or inorganic peracids such as sodium, potassium, and ammonium such as peracetic acid, persulfuric acid, perboric acid, and perphosphoric acid. Salt or sulfur are used. It is also possible to use atmospheric oxygen. At this time, it is usually preferable to add a catalyst such as ammonium molybdate or ammonium vanadate. The reaction of the present invention is preferably carried out in a range of mm ² 8 to 11, more preferably mm ² 8.5 to 10.5. lower than this
In the case of mm ² range, hydrogen cyanide is released to the outside of the system, which tends to impair the effective use of the cyanating agent. Furthermore, a high mm ² range is not desirable because it promotes higher-order hydrolysis of intermediates and main products during the reaction. The mm ² value of the reaction mixture can be controlled, for example, by adding sufficient amounts of conventional buffer mixtures. In the present invention, the reaction temperature is 50-100°C, preferably 60-100°C. Although the reaction is fast on the high temperature side, it is preferable to set mm ² as low as possible in order to prevent high-order hydrolysis, and conversely, on the low temperature side, it is preferable to set the mm ^{2 as high as possible as long as it does not exceed 11 mm 2} . Specifically, the present invention is carried out, for example, as follows. A compound of general formula () or a salt thereof (such as a sodium or ammonium salt) is dissolved in a mixture of a quaternary ammonium compound and water, and optionally an alkali metal or alkaline earth metal hydroxide, carbonate, heavy mm ² using carbonic acid or acetate
7.0, a dehydrogenating agent is added, optionally a buffering agent is added, and then a cyanating agent is added, preferably in the mm ² range of 8 to 11 mm ² , at 50 to 100 °C,
The cyanation reaction is preferably carried out at a temperature of 60-100°C. In the above reaction, if the buffer is not sufficient, the hydroxide ions liberated as the reaction progresses are neutralized by dropwise addition of a weak acid, and the mm ² is controlled within the optimum pH range. In some cases, the addition of cyanating agents may be
It may also be carried out by continuous dropping within a temperature range of ^mm2 . After the reaction is completed, excess cyanating agent is eliminated with sodium hypochlorite or hydrogen peroxide, and the mixture is filtered to obtain a 2,3-dicyano-anthraquine compound of general formula (). According to the method of the present invention, the purity and yield of the obtained 2,3 dicyanoanthraquinone compound are considerably higher than those using known methods, and the content of the compound of general formula () is also extremely low. Therefore, even if subsequent dyes are produced without purification, dyes with sufficiently vivid hues can be obtained. The present invention will be explained below with reference to Examples. In the text, parts and % mean parts by weight and % by weight unless otherwise specified. Example 1 Benzyltriethylammonium chloride 360
and 840 parts of water, 131.2 parts of 1-amino-4-(2-methoxyethylamino)-anthraquinone-2-sulfonic acid with a purity of 90% was charged with stirring, and then 30 parts of nitrobenzene was charged.
Stir at room temperature until everything is dissolved. ^Then , using 28% sodium hydroxide solution,
After adjusting the temperature to 7.0, 276.9 parts of a 25% aqueous sodium cyanide solution was added dropwise. The mixture was heated to 60-65° C. with thorough stirring and allowed to react until most of the starting material disappeared by chromatography.
During this time, the ^mm2 in the system was 9.5 using a 30% sulfuric acid aqueous solution.
Maintained at ~9.8. Excess sodium cyanide was then decomposed with hypochlorous acid, filtered, washed with warm water, and dried to obtain 105.2 parts of dark blue crystalline powder. 1-amino-4-(2-methoxyethylamino)
When the yield based on -anthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4-(2-methoxyethylamino)-
2,3 dicyanoanthraquinone 92.0% 1-amino-4(2-methoxyethylamino)-2
-Cyanoanthraquinone 1.6% Unreacted raw material 1.2% Example 2 Benzyltriethylammonium chloride 400
91% pure 1-amino-4-cyclohexylaminoanthraquinone in a mixture of 1 part and 800 parts of water.
After charging 138.0 parts of 2-sulfonic acid with stirring, and then charging 42.4 parts of sodium m-nitrobenzesulfonate, a 25% aqueous sodium cyanide solution was added.
283.1 parts were dropped. The mixture was then heated to 80-85° C. with thorough stirring and allowed to react until almost all the starting material disappeared by chromatography. In this relation, mm ² uses 30% phosphoric acid aqueous solution.
Maintained at 9.0-9.5. Excess sodium cyanide was then decomposed with hydrogen peroxide, filtered, washed with warm water, and dried to obtain 117.6 parts of a dark blue crystalline powder. When the yield based on 1-amino-4-cyclohexylaminoanthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4-cyclohexylamino-2,3
-dicyanoanthraquinone 96.2% 1-amino-4-cyclohexylamino-2-cyanoanthraquinone 2.1% Unreacted raw material 0.9 Example 3 Benzyltriethylammonium chloride 400
92.5% pure 1-
Amino-4-methylamino-anthraquinone-2
- 112.7 parts of sulfonic acid were charged under stirring, followed by 30 parts of nitrobenzene, and the mixture was stirred at room temperature until everything was dissolved. Next, after adjusting mm ² to 7.0 using sodium carbonate, 305.6 parts of a 25% aqueous sodium cyanide solution was added dropwise. The mixture was heated to 80-85° C. with thorough stirring and allowed to react until most of the starting material disappeared by chromatography. During this time, mm ² in the system was maintained at 9.0 to 9.5 using a 30% phosphoric acid aqueous solution. After the reaction was completed, excess sodium cyanide was decomposed with hydrogen peroxide, filtered, washed with warm water, and dried to obtain 93.0 parts of dark blue crystalline powder. When the yield based on 1-amino-4-methylamino-anthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-Amino-4-methylamino-2,3-dicyanoanthraquinone 92.2% 1-amino-4-methylamino-2-cyanoanthraquinone 1.3% Unreacted raw material 1.5% Example 4 Benzyltriethylammonium chloride 420
90.5% pure 1-
135.3 parts of amino-4-(3-methoxypropylamino)anthraquinone-2-sulfonic acid was charged with stirring, followed by 35.0 parts of sodium m-nitrobenzenesulfonate, and the mixture was stirred at room temperature until everything was dissolved. Then, using 28% sodium hydroxide aqueous solution, mm ²
was adjusted to 7.0, and then 310.0 parts of a 25% potassium cyanide aqueous solution was added dropwise. The mixture was heated to 70-75° C. with thorough stirring and allowed to react until most of the starting material disappeared by chromatography. During this time, the ^mm2 in the system was 9.3 to 9.6 using a 30% sulfuric acid aqueous solution.
maintained. After decomposing excess lithium cyanide with hypochlorous acid, the mixture was filtered, washed with warm water, and dried to obtain 107.5 parts of dark blue crystalline powder. When the yield relative to 1-amino-4-(3-methoxypropylamino)-anthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4-(3-methoxypropylamino)
-2,3-dicyanoanthraquinone 91.0% 1-amino-4-(3-methoxypropylamino)
-2-cyanoanthraquinone 2.2% Unreacted raw material 1.4% Example 5 Benzyltriethylammonium chloride 480
146.1 parts of 1-amino-4-(2-methylchlorohexylamino)-anthraquinone-2-sulfonic acid with a purity of 89.0% was charged into a mixture of 1.0 parts and 320 parts of water with stirring, and then 26.0 parts of nitrobenzene was charged. Stir at room temperature until everything is dissolved. Then, using 28% sodium hydroxide aqueous solution, mm ²
was adjusted to 7.0, and then 242.1 parts of a 25% aqueous sodium cyanide solution was added dropwise. The mixture was heated to 75-80° C. with thorough stirring and allowed to react until most of the starting material disappeared by chromatography. During this time, mm ² in the system was filled with 30% sulfuric acid aqueous solution.
Maintained at 9.0-9.5. Excess sodium cyanide was then decomposed with hydrogen peroxide, filtered, washed with warm water, and dried to obtain 118.2 parts of a dark blue crystalline powder. When the yield relative to 1-amino-4-(2-methylcyclohexylamino)-anthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4(2-methylcyclohexylamino)-2,3-dicyanoanthraquinone 91.2% 1-amino-4-(2-methylcyclohexylamino)-2-cyanoanthraquinone 0.8% Unreacted raw material 1.4% Example 6 Benzyl Trimethylammonium chloride 480
1-amino-4-isopropylaminoanthraquinone-2- with a purity of 90.0% in a mixture of
124.4 parts of sulfonic acid was charged with stirring and stirred at room temperature until all was dissolved. Then, using 28% sodium hydroxide aqueous solution, mm ²
was adjusted to 7.0, and then 242.1 parts of a 25% aqueous sodium cyanide solution was added dropwise. The mixture was heated to 65-70° C. with thorough stirring and allowed to react until most of the starting material disappeared by chromatography. During this time, the ^mm2 of the system was 9.4 ~ 9.4 using 30% sulfuric acid aqueous solution.
Maintained at 9.8. Excess sodium cyanide was then decomposed with hydrogen peroxide solution, filtered, washed with warm water, and dried to obtain 103.6 parts of dark blue crystalline powder. When the yield relative to 1-amino-4-isopropylaminoanthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4-isopropylamino-2,3-
Dicyanoanthraquinone 93.0% 1-amino-4-isopropylamino-2-cyanoanthraquinone 1.8% Unreacted raw material 1.7% Example 7 Lauryltrimethylammonium chloride 600
131.2 parts of 1-amino-4-(2-methoxyethylamino)-anthraquinone-2-sulfonic acid with a purity of 90.0% was added to a mixture of 1.5 parts and 400 parts of water with stirring, and the mixture was stirred at room temperature until the entire solution was dissolved. Then, after adjusting mm ² to 7.0 using sodium carbonate, 25% sodium cyanide aqueous solution 305.6
part was dripped. While stirring thoroughly, heat the mixture to 65~
The mixture was heated to 70° C. and the reaction was allowed to proceed until almost all the starting material disappeared by chromatography. During this time,
The ^mm2 in the system was maintained at 9.5-9.8 using 30% phosphoric acid aqueous solution. After the reaction was completed, excess sodium cyanide was decomposed with hydrogen peroxide, filtered, washed with warm water, and dried to obtain 105.3 parts of dark blue crystalline powder. 1-amino-4-(2-methoxyethylamino)
When the yield based on -anthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4-(2-methoxyethylamino)-
2,3-dicyanoanthraquinone 91.5% 1-amino-4-(2-methoxyethylamino)-
2-Cyanoanthraquinone 1.5% Unreacted raw material 1.5 Example 8 A mixture of 60 parts of N-butylpyridinium chloride, 360 parts of pyridine and 780 parts of water was mixed with 1 with a purity of 91.0%.
138.0 parts of -amino-4-cyclohexylaminoanthraquinone-2-sulfonic acid was charged with stirring,
Then, using 28% sodium hydroxide ^aqueous solution,
After adjusting to 7.0, 25% potassium cyanide aqueous solution
310.0 parts were dropped. The mixture was heated to 70-75° C. with thorough stirring and allowed to react until most of the starting material disappeared by chromatography. During this time, mm ² in the system was maintained at 9.3 to 9.6 using a 30% sulfuric acid aqueous solution. Excess potassium cyanide was then decomposed with hypochlorous acid, filtered, washed with warm water, and dried to obtain 116.3 parts of dark blue crystalline powder. When the yield based on 1-amino-4-cyclohexylamino-anthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4-cyclohexylamino-2,3
-dicyanoanthraquinone 94.1% 1-amino-4-cyclohexylamino-2-cyanoanthraquinone 1.8% Unreacted raw material 0.9% Example 9 Tetra-n-butylammonium bromide
1- of 92.5% purity in a mixture of 600 parts and 600 parts of water.
Amino-4-methylaminoanthraquinone-2-
112.7 parts of sulfonic acid was charged with stirring and stirred at room temperature until all was dissolved. Then, using 28% sodium hydroxide aqueous solution, mm ²
was adjusted to 7.0, and then 242.1 parts of a 25% aqueous sodium cyanide solution was added dropwise. The mixture was heated to 65-70° C. with thorough stirring and allowed to react until most of the starting material disappeared by chromatography. During this time, mm ² in the system was filled with 30% sulfuric acid aqueous solution.
Maintained at 9.5-9.8. Excess sodium cyanide was then decomposed with hydrogen peroxide, filtered, washed with warm water, and dried to obtain 93.6 parts of a dark blue crystalline powder. When the yield relative to 1-amino-4-methylamino-anthraquinone-2-sulfonic acid was determined, the following results were obtained. 1-amino-4-methylamino-2,3-dicyanoanthraquinone 91.8% 1-amino-4-methylamino-2-cyanoanthraquinone 1.2% Unreacted raw material 0.5% Example 10 The corresponding 2,3-dicyanoanthraquinone compound of general formula () was obtained from the sulfonic acid compound of general formula () shown in Table 1. 【table】

Claims (1)

[Claims] 1. General formula [In the formula, R represents an optionally substituted alkyl group or an optionally substituted cycloalkyl group. ] A compound represented by or a salt thereof in an aqueous medium,
By reacting with a cyanating agent in the presence of a dehydrogenating agent and a quaternary ammonium compound, the general formula [In the formula, R has the above meaning. ] A method for producing an anthraquinone intermediate, characterized by producing a compound represented by the following.