KR840001234B1 - Process for the preparation of 1,4-diamino-2,3-dicyano anthraquinone - Google Patents

Abstract

1, 4-diamino-2, 3-dicyano anthrequinone is prepd. by reacting 1, 4-diamino anthraquinone-2, 3-disulfonic acid (or its salt) with a cyanizing agent in an aq. medium. The reaction condition includes the presence of 2-90 wt. % tetrealkyl ammonium compd. w.r.t. the aq. medium, a temp. of 40-100≰C, and a pH of 8-11. The ammonium compd. is tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride, tetramethyl ammonium methyl sulfate, or tetraethyl ammonium ethyl sulfate.

Description

Method for preparing 1,4-diamino-2,3-dicyanoanthraquinone

The present invention relates to a process for the preparation of anthraquinone dye intermediates, more particularly 1,4-diamino-2,3-dicyanoanthraquinones. A method for producing 1,4-diamino-2,3-dicyano anthraquinone by reacting 1,4-diaminoanthraquinone-2-sulfonic acid and a cyano compound in an aqueous solution is disclosed in Federal Republic of Germany Patent Publication No. 536,998. And British Patent No. 359,850, but this method always yields the desired amount of product as a byproduct, since a certain amount of 1,4-diamino-2-cyanoanthraquinone and 1,4-diaminoanthraquinone are produced. In addition to being as low as 60% and used for dye production, the resulting product must be purified with a reagent such as sulfuric acid.

A method of using an oxidizing agent such as sodium m-nitrobenzenesulfonate as a method of inhibiting the production of these by-products is described in German Patent Application Publication No. 1,108,704 and Soviet Union Patent Publication No. 148,066. According to the present invention, the production of 1,4-diaminoanthraquinone is completely inhibited, and the content of 1,4-diamino-2-cyanoanthraquinone in the reaction product tends to decrease, but the oxidation product resulting from hydrolysis of the target product. Phosphorus secondary by-products and by-products are generated to reduce the purity, so when used for the production of a dye that gives a vivid blue, the purification must be performed, and the yield is low as 70 to 80%.

In addition, a method of obtaining 1,4-diamino-2,3-dicyano anthraquinone by reacting 1,4-diaminoanthraquinone-2,3-disulfonic acid and a cyano compound in an aqueous solution is disclosed in the Federal Republic of Germany. No. 935,669, U.S. Patent Publication No. 3,203,751, and Japanese Patent Application Publication No. 17643/1974, but according to this method 1,4-diamino-2-cyanoanthraquinone- as a by-product. In addition to the production of secondary by-products resulting from 3-sulfonic acid and hydrolysis of the target, yields and purity are highest, as low as about 90% and 86-88%, respectively, since the target is always contaminated with unreacted material. Therefore, if it is to be used for the production of a dye that gives a bright blue color, it must be purified by a suitable method.

The present inventors intensively studied the method for producing 1,4-diamino-2,3-dicyanoanthraquinone, and as a result, the reaction between 1,4-diamino-anthraquinone-2,3-disulfonic acid and a cyanating agent was observed. It has been found that the aforementioned drawbacks can be solved by carrying out the reaction in the presence of a quaternary ammonium compound.

Therefore, the present invention is a 1,4-diamino characterized in that the reaction of 1,4-diaminoanthraquinone-2,3-disulfonic acid or a salt thereof and cyanating agent in an aqueous medium using a quaternary ammonium compound It is to provide a method for producing -2,3-dicyanoanthraquinone.

According to the method of the present invention, when 1,4-diaminoanthraquinone-2,3-disulfonic acid is used as a starting material, 1,4-diamino-2-cyanoane always reaches about 5 to 7% by conventional method. Since the total content of disulfonic acids such as traquinone-3-sulfonic acid and unreacted 1,4-diaminoanthraquinone-2,3-disulfonic acid decreases to 1 to 3% or less, the yield of the target product is remarkably improved.

Further, according to the present invention, almost all of the unreacted organic compounds in the reaction mixture are dissolved in the aqueous medium, so that half of the reaction mixture can be easily obtained with high purity even by simple filtration of the mixture.

The quaternary ammonium compound can be recovered completely from the butyric quaternary ammonium compound itself or its hydroxide form using alkali, and the quaternary ammonium compound itself can be reused as it is, and the hydroxide form can be extracted with an organic solvent. Back extraction by acid can be performed and reused.

The method of the present invention will be described in detail below.

As quaternary ammonium compounds which can be used in the present invention, lower alkyl quaternary ammonium compounds such as tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium methyl sulfate and tetraethylammonium ethyl sulfate; Higher alkyl quaternary ammonium compounds such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and distearyldimethylammonium chloride; Trialkylbenzylammonium compounds such as trimethylbenzyl ammonium chloride and triethylbenzylammonium chloride; N-alkylpyridinium or N-alkylpicolinium compounds such as N-methylpyridinium chloride, N-ethylpyridinium chloride, N-butylpyridinium chloride, N-laurylpyridinium chloride and N-stearylpyridinium Chloride; Bromide, iodide, sulfate, phosphate and acetate corresponding to the aforementioned chlorides; And mixtures thereof.

Industrially, it is preferable to use trialkylbenzyl ammonium.

The amount of the quaternary ammonium compound depends on the type and starting material of the quaternary ammonium compound, but is generally used in an amount of 2 to 90% by weight based on the total weight of the quaternary ammonium compound and the aqueous medium.

30 to 80% by weight, preferably 40 to 70% by weight relative to the total weight of the quaternary ammonium compound and the aqueous medium when using a lower alkyl quaternary ammonium compound, or quaternary ammonium compounds in the case of higher alkyl quaternary ammonium compounds 10 to 90% by weight, preferably 15 to 80% by weight relative to the total weight of the aqueous medium and 2 to 80% by weight relative to the total weight of the quaternary ammonium compound and the aqueous medium, preferably trialkylbenzylammonium compounds. 2.5 to 70% by weight, in the case of N-alkylpyridinium or N-alkylpicolinium compounds, 2 to 50% by weight, preferably 5 to 40% by weight, based on the total weight of the quaternary ammonium compound and the aqueous medium do.

For example, when using 1,4-diaminoanthraquinone-2,3-disulfonic acid as a starting material, it is 2 to 80% by weight, preferably 2.5 to 50% by weight, based on the total weight of the quaternary ammonium compound and the aqueous medium. Used in% amounts. This amount may be less than the above value when the lipophilic degree of the quaternary ammonium compound used is higher than that of triethylammonium chloride, and more than the above value when the lipophilic correlation is reversed. You may also do it.

Examples of cyanating agents that can be used in the present invention include cyanides of alkali metals or alkaline earth metals and mixtures thereof such as ammonium cyanide or sodium cyanide, potassium cyanide, magnesium cyanide and calcium cyanide. In addition, cyanohydrins, such as acetonecyanohydrin, capable of generating cyano ions in water can also be used. Among these, sodium cyanide and potassium cyanide are particularly preferable.

The cyanating agent is used in an amount of 2.0 to 10 moles per 1 mole of 1,4-diaminoanthraquinone-2,3-disulfonic acid.

The reaction according to the invention is preferably carried out in a pH range of 8 to 11, preferably in a pH range of 8.5 to 10.5. In the case where the reaction is carried out in the range lower than the pH value described above, it is not preferable from the economic point of view because hydrogen is easily generated in the reaction system. On the contrary, in the case where the reaction is performed in the range higher than the pH value mentioned above. It is also undesirable because the hydrolysis of any intermediate and target product is promoted during the reaction.

The pH value of the reaction mixture can be adjusted by adding an appropriate amount of a buffer compound commonly used. In addition, a strong acid or weak acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, diacid, acetic acid or propionic acid, may be added to the reaction mixture during the cyanation reaction operation.

The cyanation operation of the present invention is carried out in an aqueous medium which may contain a water miscible organic solvent when using a lower solubility quaternary ammonium hydrate. Examples of the above organic solvents include ethylene glycol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol, triethylene glycol monoalkyl ether, formamide, methyl formamide, dimethylformamide, N Alkylpyrrolidone, dimethyl sulfoxide, sulfolane, hexamethyl phosphate triamide, methanol, ethanol, propanol, butanol, pyridine, picoline and mixtures thereof.

In the present invention, the reaction temperature is 40 to 100 ° C, preferably 50 to 90 ° C. If the reaction temperature is higher than the above-mentioned range, the reaction tends to proceed quickly, so it is preferable to set the pH value as low as possible to prevent hydrolysis. On the contrary, when the reaction temperature is lower than the aforementioned range, it is preferable to set the pH value as high as possible.

Preferred operation according to the present invention is as follows.

As a starting material, 1,4-diaminoanthraquinone-2,3-disulfonic acid or salts thereof (sodium, potassium, ammonium salt, etc.) is used to dissolve in a mixture of a quaternary ammonium compound and water and, if necessary, The pH may be adjusted to 7.0 using hydroxides, carbonates, bicarbonates or acetates of alkali or alkaline metals, and then a buffer may be added if necessary. Finally, a cyanating agent is added to perform the cyanating operation within the aforementioned pH value and temperature range.

In the above operation, when the effect of the buffer is not satisfactory, the pH value is adjusted within the optimum range by adding a weak acid in the reaction system to neutralize the ions of the glass as the reaction proceeds. If necessary, the cyanating agent may be continuously added dropwise in the reaction system within the aforementioned pH value and temperature range during the reaction.

After the reaction is completed, the excess cyanating agent is decomposed with hypochlorite or hydrogen peroxide, and then the reaction mixture is filtered and washed to obtain the desired 1,4-diamino-2,3-dicyanoanthraquinone in high yield and High purity can be obtained.

The 1,4-diamino-2,3-dicyanoanthraquinone obtained by the present invention can be used as an intermediate for producing a dye that gives bright blue color without performing any purification operation.

The present invention will be described in more detail with reference to the following Examples, in which all parts and percentages refer to parts by weight and% unless otherwise specified.

Example 1

To a mixture of 360 parts of benzyltriethylammonium chloride and 840 parts of water, 156.5 parts of 1,4-diaminoanthraquinone-2,3-disulfonic acid having a purity of 80.0% were added, followed by stirring at room temperature to dissolve completely.

The pH was then adjusted to 7.0 using an aqueous 28% sodium hydroxide solution, followed by the dropwise addition of 382.1 parts of a 25% aqueous sodium cyanide solution. While stirring sufficiently, the mixture was heated to 70 to 75 ° C. until the starting material was almost completely removed by chromatography. 30% aqueous sulfuric acid solution was used to maintain the pH of the mixture in the range of 9.0 to 9.5.

Subsequently, excess sodium cyanide was decomposed into hypochlorous acid, followed by filtration, warm water washing and drying to obtain 88.7 parts of dark blue crystals.

The result of having measured the yield with respect to 1, 4- diaminoanthraquinone-2, 3- disulfonic acid is described below.

96.0% of 1,4-diamino-2,3-dicyano anthraquinone,

1,4-diamino-2-cyanoanthraquinone-3-sulfonic acid and unreacted starting material 2.0%.

The purity of the target product was 97.0%, which was significantly higher than that of the conventional method.

Example 2

To the mixture of 600 parts of lauryltrimethylammonium chloride and 400 parts of water, 156.5 parts of 1,4-diaminoanthraquinone-2,3-disulfonic acid having a purity of 80.0% were added with stirring. Stirring was continued at room temperature to dissolve completely. Next, after adjusting the pH to 7.0 using sodium carbonate, 305.6 parts of 25% aqueous sodium cyanide solution was added dropwise. While stirring sufficiently, the mixture was heated to 65-70 ° C. until the starting material was almost completely removed by chromatography. 30% aqueous phosphoric acid solution was used during the reaction to maintain the pH of the mixture in the range of 9.0 to 9.5.

After the reaction was completed, excess sodium cyanide was decomposed with hydrogen peroxide, and then filtered, washed with warm water and dried to obtain 89.9 parts of dark blue crystal powder.

The result of having measured the yield with respect to 1, 4- diaminoanthraquinone-2, 3- disulfonic acid is described below.

1,4-diamino-2,3-dicyanoanthraquinone 94.5%.

1,4-diamino-2-cyanoanthraquinone-3-sulfonic acid and 3.0% of unreacted starting material.

The purity of the target product was 95.2%.

Example 3

To the mixture of 60 parts of N-butylpyridinium chloride, 360 parts of pyridine and 780 parts of water, 156.5 parts of 1,4-diaminoanthraquinone-2,3-disulfonic acid having a purity of 80.0% were added with stirring.

Then, the pH was adjusted to 7.0 using an aqueous 28% sodium hydroxide solution, and then 310.0 parts of 25% potassium cyanide was added dropwise. While stirring sufficiently, the mixture was heated to 75 to 80 ° C. until the starting material was almost completely removed by chromatography. During the reaction, the pH of the mixture was maintained within the range of 9.3 to 9.6 using 30% aqueous sulfuric acid solution, and then excess potassium cyanide was decomposed into hypochloric acid. Next, filtration, warm water washing and drying were carried out to obtain 91.5 parts of dark blue crystal powder.

The result of having measured the yield with respect to 1, 4- diaminoanthraquinone-2, 3- disulfonic acid is described below.

1,4-diamino-2,3-dicyanoanthraquinone 94.1%

1,4-Diamino-2-cyanoanthraquinone-3-sulfonic acid and unreacted starting material 2.1%

The purity of the target product was 93.2%.

Example 4

To the mixture of 480 parts of benzyltriethylammonium chloride and 320 parts of water, 156.5 parts of 1,4-diaminoanthraquinone-2,3-disulfonic acid having a purity of 80.0% were added with stirring. Stirring was continued at room temperature to dissolve completely.

Then, the pH was adjusted to 7.0 using an aqueous 28% sodium hydroxide solution, followed by dropwise addition of 25% sodium cyanide and an aqueous solution of 242.1 parts. The mixture was heated to 65-70 ° C. with sufficient stirring until the starting material was almost completely removed by chromatography. 30% aqueous sulfuric acid solution was used to maintain the pH of the mixture in the range of 9.0 to 9.5 during the reaction. Subsequently, excess sodium cyanide was decomposed with hydrogen peroxide, and then filtered, washed with warm water and dried to obtain 90.0 parts of dark blue crystal powder.

1,4-diamino-2,3-dicyanoanthraquinone 96.7%.

1,4-Diamino-2-cyanoanthraquinone-3-sulfonic acid and unreacted starting material 1.7%.

The purity of the target product was 97.3%.

Example 5

To the mixture of 24 parts of benzyltriethylammonium chloride and 776 parts of water, 156.5 parts of 1,4-diaminoanthraquinone-2,3-disulfonic acid having a purity of 80.0% were added with stirring. Stirring was continued at room temperature to dissolve completely.

The pH was then adjusted to 7.0 using an aqueous 28% sodium hydroxide solution, followed by the dropwise addition of 242.1 parts of 25% aqueous sodium cyanide solution. The mixture was heated to 70 to 75 DEG C while stirring with sufficient stirring and at the same time until the starting material was almost completely removed by chromatography. 50% sulfuric acid in the reaction was used to maintain the pH of the mixture in the range of 9.4 to 10.0, and then excess sodium cyanide was decomposed to hydrogen peroxide. Next, filtration, warm water washing and drying were carried out to obtain 90.0 parts of dark blue crystal powder.

The result of having measured the yield with respect to 1, 4- diaminoanthraquinone-2, 3- disulfonic acid is described below.

1,4-diamino-2,3-dicyanoanthraquinone 95.0%

1,4-diamino-2-cyanoanthraquinone-3-sulfonic acid and unreacted starting material 1.7%

The purity of the target product was 92.5%.

Example 6

To the mixture of 600 parts of tetra-n-butyl-ammonium bromide and 600 parts of water, 156.5 parts of 1,4-diaminoanthraquinone-2,3-disulfonic acid having a purity of 80.0% were added. Stirring was continued at room temperature to dissolve completely.

The pH was then adjusted to 7.0 using an aqueous 28% sodium hydroxide solution, followed by the dropwise addition of 242.1 parts of 25% sodium cyanide solution. At the same time, the mixture was heated to 65-70 ° C. until the starting material was almost completely removed by chromatography. 30% aqueous sulfuric acid solution was used to maintain the pH of the mixture in the range of 9.4 to 9.8. The excess sodium cyanide was then decomposed into hydrogen peroxide. Filtration, warm water washing and drying were then carried out to obtain 89.4 parts of dark blue crystal powder.

The results of measuring the yield for 1,4-polyaminoanthraquinone-2,3-disulfonic acid are described below.

1,4-diamino-2,3-dicyanoanthraquinone 96.0%

1,4-diamino-2-cyanoanthraquinone-3-sulfonic acid and unreacted starting material 1.7%

The purity of the target product was 97.3%.

Reference Example 1

(Examples Without Quaternary Ammonium Salts)

156.5 parts of the same 1, 4- diaminoanthraquinone-2, 3- disulfonic acids as used in Example 1 were stirred and added to 1200 parts of water.

Stirring was continued at room temperature to dissolve completely.

The pH was then adjusted to 7.0 using an aqueous solution of 28% sodium hydroxide, followed by the dropwise addition of 25% aqueous sodium cyanide solution. The mixture was heated to 70-75 ° C. until the starting material was almost completely removed by chromatography while stirring sufficiently.

During the reaction, the pH of the mixture was maintained in the range of 9.0 to 9.5 using 30% aqueous sulfuric acid solution, and then excess sodium cyanide was decomposed into hypochloric acid. Filtration, warm water washing and drying were then carried out to obtain 95.3 parts of a dark blue crystal powder.

The results of measuring the yield for 1,4-diaminoanthraquinone-2,3-disulfonic acid are described below.

1,4-diamino-2,3-dicyanoanthraquinone 91.5%

1,4-Diamino-2-cyanoanthraquinone-3-sulfonic acid and unreacted starting material 5.0%

The purity of the target product was 87.0%, and even if the reaction was repeated by changing the reaction conditions, a better quality or purity than the above result could not be obtained.

Claims (1)

1,4-diaminoanthraquinone-2,3-disulfonic acid or salts thereof at a temperature of 40-100 ° C. in the presence of 2-90% by weight of a quaternary ammonium compound based on the total amount of aqueous medium in an aqueous medium and 8 A method for producing 1,4-diamino-2,3-dicyanoanthraquinone, which is reacted with a cyanating agent at a pH of ˜11.