JPH07173129A - Production of 1,4-diaminoanthraquinone-2,3-disulfonic acid - Google Patents

Abstract

PURPOSE:To industrially and advantageously produce 1,4- diaminoanthraquinone-2,3-disulfonic acid or its salt in a high yield without using a quaternary ammonium compound or a quaternary phosphonium compound. CONSTITUTION:A 1,4-diamino-2,3-dihalogenoanthraquinone is reacted with a sulfonating agent in a mixture of a neutral organic polar solvent and water to provide the objective 1,4-diamino-anthraquinone-2,3-disulfonic acid or its salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel process for producing 1,4-diaminoanthraquinone-2,3-disulfonic acid or a salt thereof which is an anthraquinone dye intermediate which is particularly useful in the dye industry.

[0002]

2. Description of the Prior Art 1,4-Diaminoanthraquinone-2,
As a method for producing 3-disulfonic acid, in the presence of a quaternary ammonium compound or a quaternary phosphonium compound,
A method is known in which 1,4-diamino-2,3-dihalogenoanthraquinone is reacted with a sulfonating agent in an aqueous medium (JP-A-59-65067).

[0003]

However, this method involves a complicated operation for recovering a large amount of the quaternary ammonium compound or the quaternary phosphonium compound, so that a simpler method is required. It was being done.

In order to overcome such problems, the present inventors have developed 1,4-diamino-2,3-dihalogenoanthraquinone to 1,4-diaminoanthraquinone-2,3.
As a result of earnest research on a method for obtaining disulfonic acid, 1,4-diaminoanthraquinone was obtained by performing a sulfonation reaction in a specific mixed solvent without using a quaternary ammonium compound or a quaternary phosphonium compound. Two
The present invention has been completed by finding that 3-disulfonic acid can be obtained in high yield.

[0005]

That is, the present invention is as follows.
1,4-diamino-2,3-dihalogenoanthraquinone is reacted with a sulfonating agent in a mixture of a neutral organic polar solvent and water to give 1,4-diaminoanthraquinone-2,
The present invention provides a method for producing 3-disulfonic acid or a salt thereof. This reaction is carried out in a system in which a quaternary ammonium compound or a quaternary phosphonium compound is virtually absent.

The 1,4-diamino-2,3-dihalogenoanthraquinones used in the present invention include 1,4
-Diamino-2,3-dichloroanthraquinone, 1,4
-Diamino-2,3-dibromoanthraquinone and the like. These 1,4-diamino-2,3-dihalogenoanthraquinones may contain 1,4-diamino-2-halogenoanthraquinone.

In the present invention, a mixture of a neutral organic polar solvent and water is used as the solvent. Further, a nonpolar solvent may be added as long as it does not affect the reaction. The mixing ratio of the solvent is usually preferably such that the neutral organic polar solvent is in the range of 20 to 80% by weight, more preferably 40 to 70% by weight, based on the total amount of the solvent. preferable. Such a mixed solvent is usually prepared by
It is used in an amount of 3 to 30 times by weight that of 4-diamino-2,3-dihalogenoanthraquinone, and industrially it is more preferably 3 to 15 times by weight.

Examples of the neutral organic polar solvent include carboxylic acid amides, ureas, sulfoxides, sulfones,
It can be polyethylene glycols, lower alcohols and the like.

The carboxylic acid amides include C _{1 to} C ₃
N, N—C ₁ -C ₃ dialkylamides of carboxylic acids, N
-C ₁ -C ₃ monoalkyl amide, N- unsubstituted amide or amides of cyclic amines, the size of the ring is 5-membered to 7
And the like, such as a a lactam or N-C ₁ ~C ₃ alkyl substituents membered. Further specific carboxylic acid amides include, for example, N, N-dimethylformamide, N,
N-diethylformamide, N, N-dipropylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, N-methylformamide, N-
Ethylformamide, N-propylformamide, N-
Methylacetamide, N-methylpropionamide, formamide, acetamide, propionamide, N-formylmorpholine, N-formylpiperidine, N-acetylmorpholine, N-acetylpiperidine, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, N-
Examples include methyl-2-piperidone, 2-pyrrolidone and 2-piperidone.

The ureas include, for example, tetramethylurea and 1,3-dimethylimidazolidinone, the sulfoxides include, for example, dimethyl sulfoxide and tetramethylene sulfoxide, and the sulfones include Examples thereof include sulfolane, and examples of polyethylene glycols include PEG200, PEG400, and PEG600. Examples of the lower alcohols include C _{1 to} C ₅ alcohols, cellosolves, propylene glycol monoethers and the like. More specific lower alcohols are, for example, methanol, ethanol, propanol, butanol, isopropanol, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like.

Among the above-mentioned neutral organic polar solvents, preferable ones are N, N-C of C ₁ -C ₃ carboxylic acids.
₁ -C ₃ dialkylamido, C ₁ -C ₃ amide of a carboxylic acid and a saturated cyclic amine ring size is five or six membered lactam ring size is 5-membered or 6-membered or N -C ₁ -C ₃ alkyl substituents, and the like C ₁ -C ₃ alkyl alcohol, mono C ₁ -C ₃ alkyl ethers of ethylene glycol or propylene glycol, among others, N, N- dimethylformamide,
N, N-dimethylacetamide, N-formylmorpholine, N-methyl-2-pyrrolidone, 2-pyrrolidone, ethanol, methanol, methylcellosolve, ethylcellosolve and propylene glycol monomethyl ether are preferably used.

As the sulfonating agent, for example, alkali metal sulfites such as sodium sulfite and potassium sulfite, alkali metal hydrogen sulfites such as sodium hydrogen sulfite and potassium hydrogen sulfite, ammonium sulfite and ammonium hydrogen sulfite are used. . Among them, sodium sulfite, potassium sulfite, sodium hydrogen sulfite and potassium hydrogen sulfite are preferable. These sulfonating agents can be used alone or in combination of two or more kinds. The sulfonating agent is 1,4-
For diamino-2,3-dihalogenoanthraquinone,
It is usually used in the range of 2 to 5 times by mole, preferably in the range of 2.2 to 4 times by mole.

In the present invention, the pH of the reaction system can be changed within a fairly wide range, for example, the reaction can be carried out within a pH range of about 4-11. If the pH is too low, the reaction tends to be slow and sulfonation tends not to occur effectively. On the other hand, if the pH is too high, side reactions such as hydrolysis of raw materials or products are likely to occur, and the yield of the target product tends to decrease.

The pH of the reaction mixture may be controlled if necessary, for example by adding a suitable buffer to the system.
Examples of the buffer include sodium carbonate, sodium phosphate, sodium hydrogen carbonate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate,
Examples include potassium dihydrogen phosphate. The pH of the system may be controlled during the reaction by appropriately supplying an appropriate alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate or the like as an aqueous solution. .

The reaction is usually carried out at a temperature in the range of 80 to 140 ° C., and usually the reaction is completed in 2 to 40 hours. If necessary, a pressure-resistant closed container such as an autoclave may be used.

Thus, 1,4-diaminoanthraquinone-2,3-disulfonic acid or its salt is obtained in the form of a solution. At this time, depending on the type of sulfonating agent used or the pH of the reaction system, the target substance may take the form of a free acid or a salt. Salts may be present in the form of alkali metal salts, especially sodium or potassium salts, and even ammonium salts. Further, this reaction may produce 1,4-diaminoanthraquinone-2,3-disulfonic acid or a salt thereof together with 1,4-diaminoanthraquinone-2-sulfonic acid or a salt thereof. As long as it is used as above, the presence of such a monosulfonic acid or a salt thereof does not matter.

After the reaction, if it is necessary to isolate the desired product,
A high-purity target product can be obtained by subjecting the mixture after the reaction to usual crystallization means such as acid precipitation and salting-out, and filtering the precipitated crystals. The desired product can be isolated by acid precipitation, usually in the free acid form, while salting out, usually in the salt form. Further, the reaction mixture can be directly used for the next use. The neutral organic polar solvent used in the reaction can be recovered from the mixture after completion of the sulfonation reaction or from the mother liquor after crystallization by means such as distillation. When the reaction mixture is used as it is for the next use, it is not necessary to recover the solvent at this stage, but it is of course possible to recover it at a later stage.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The percentages and parts in the examples are by weight unless otherwise noted.

EXAMPLE 1 43.9 parts of N, N-dimethylformamide were added to a mixture of 91.2 and 91.2.
% Of 1,4-diamino-2,3-dichloroanthraquinone was added and the temperature was raised to 95 ° C. At that temperature, 3 parts of a solution prepared by dissolving 9.5 parts of potassium sulfite in 30 parts of water.
The mixture was added dropwise over 0 minutes and kept warm for 18 hours. Then, after adding 100 parts of water, confirm that the pH is 8 or more,
5 parts of Celite was added and kept warm for another 30 minutes. After hot filtration, wash with warm water to obtain an aqueous solution of 1,4-diaminoanthraquinone-2,3-disulfonic acid dipotassium salt 483.4.
I got a part.

To this aqueous solution was added 111.2 parts of 40% sulfuric acid to carry out acid precipitation. After filtration, wash with 2% sulfuric acid, followed by water, dry and wash with 1,4-diaminoanthraquinone-2,
7.8 parts of 3-disulfonic acid was obtained (yield 94.0%, purity 8
8.9%).

Examples 2 to 9 1,4-diaminoanthraquinone was prepared in the same manner as in Example 1 except that the solvents listed in Table 1 were used instead of the N, N-dimethylformamide. Two
3-disulfonic acid was obtained.

[0022]

[Table 1]

Example 10 To a mixture of 100 parts of propylene glycol monomethyl ether and 100 parts of water was added 20 parts of 1,4-diamino-2,3-dichloroanthraquinone having a purity of 91.7% and 27.8 parts of potassium sulfite. 6 at 125 ° C in autoclave
I kept it warm for an hour. After cooling, it was diluted with 500 parts of water and the pH was adjusted to 1 or less with sulfuric acid. After filtering the reaction solution, the resulting product was washed with diluted sulfuric acid and dried to give 1,4-diaminoanthraquinone-2,3-disulfonic acid 48.3%.
And 1,4-diaminoanthraquinone-2-sulfonic acid 3
26.9 parts of a mixture containing 2.3% was obtained (yield 99.8%).

Example 11 To a mixture of 120 parts of propylene glycol monomethyl ether and 180 parts of water was added 30 parts of 1,4-diamino-2,3-dichloroanthraquinone having a purity of 91.7% and 41.0 parts of potassium sulfite. 6 at 125 ° C in autoclave
I kept it warm for an hour. After cooling, it was diluted with 500 parts of water and the pH was adjusted to 1 or less with sulfuric acid. After filtering the reaction solution, the resulting product was washed with dilute sulfuric acid and dried to give 1,4-diaminoanthraquinone-2,3-disulfonic acid 29.5%.
And 1,4-diaminoanthraquinone-2-sulfonic acid 4
38.5 parts of a mixture containing 5.8% was obtained (yield 94.9%).

Example 12 A mixture of 100 parts of ethanol and 100 parts of water was added with a purity of 9
20% of 1.7% 1,4-diamino-2,3-dichloroanthraquinone and 28.6 parts of potassium sulfite were added, and the mixture was kept at 125 ° C. for 6 hours in an autoclave. After cooling, water 5
It was diluted with 00 parts and the pH was adjusted to 1 or less with sulfuric acid. After filtering the reaction solution, the obtained product was washed with dilute sulfuric acid, dried, and 1,4-diaminoanthraquinone-
Mixture 32.7 containing 64.8% 2,3-disulfonic acid and 5.7% 1,4-diaminoanthraquinone-2-sulfonic acid
Parts were obtained (yield 97.1%).

Example 13 A mixture of 140 parts of ethanol and 60 parts of water was added to a mixture having a purity of 91.7.
% 1,4-diamino-2,3-dichloroanthraquinone and 28.6 parts of potassium sulfite were added, and the mixture was kept at 130 ° C. for 6 hours in an autoclave. After cooling, water 500
It was diluted with 1 part, and the pH was adjusted to 1 or less with sulfuric acid. After filtering the reaction solution, the obtained product was washed with diluted sulfuric acid,
Dried to give 1,4-diaminoanthraquinone-2,3-
25.7 parts of a mixture containing 85.0% of disulfonic acid and 6.0% of 1,4-diaminoanthraquinone-2-sulfonic acid was obtained (yield 100%).

Example 14 A mixture of 140 parts of methanol and 60 parts of water had a purity of 91.7.
% 1,4-diamino-2,3-dichloroanthraquinone (20 parts) and potassium sulfite (28.6 parts) were added, and the mixture was kept at 125 ° C. for 6 hours in an autoclave. After cooling, water 500
It was diluted with 1 part, and the pH was adjusted to 1 or less with sulfuric acid. After filtering the reaction solution, the obtained product was washed with diluted sulfuric acid,
Dried to give 1,4-diaminoanthraquinone-2,3-
28.0 parts of a mixture containing 64.6% disulfonic acid and 14.2% 1,4-diaminoanthraquinone-2-sulfonic acid was obtained (yield 95.0%).

[0028]

According to the present invention, 1,4-diamino-
In one step from 2,3-dihalogenoanthraquinone, 1,
4-Diaminoanthraquinone-2,3-disulfonic acid or a salt thereof is obtained as a high-concentration solution. 1,4-Diaminoanthraquinone-2,3-disulfonic acid or a salt thereof can be easily isolated from this solution, and can be directly reacted without isolation with, for example, an ionic cyanide. It can also be 1,4-diamino-2,3-dicyanoanthraquinone. Also, the present invention does not use such a quaternary ammonium compound or quaternary phosphonium compound, and therefore recovers it, as compared to the conventional method in which a large amount of quaternary ammonium compound or quaternary phosphonium compound is used in the reaction. Its industrial value is very high because it does not require complicated steps.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junji Shiraiwa 3-98 Kasugade, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd. (72) Inventor Hideki Yamakawa 3-chome, Kasugade, Konohana-ku, Osaka No. 1-98 Sumitomo Chemical Co., Ltd. (72) Inventor Kenji Saito 3-1-198 Kasugade, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd.

Claims (5)

[Claims] 1. A 1,4-diamino-2,3-dihalogenoanthraquinone is reacted with a sulfonating agent in a mixture of a neutral organic polar solvent and water.
A process for producing diaminoanthraquinone-2,3-disulfonic acid or a salt thereof. 2. The method according to claim 1, wherein the neutral organic polar solvent is a carboxylic acid amide, a urea, a sulfoxide, a sulfone, a polyethylene glycol or a lower alcohol. Wherein the organic polar solvent neutral, N of C ₁ -C ₃ carboxylic acid, N-C ₁ ~C ₃ dialkylamido, C ₁ -C
_3- Carboxylic acid and amide of saturated cyclic amine having a ring size of 5 or 6 members, ring size of 5 or 6 members
Lactam or its N-C ₁ -C ₃ alkyl substituents are members, C ₁ -C ₃ mono C ₁ alkyl alcohol or ethylene glycol or propylene glycol,
To C ₃ alkyl ether. 4. The neutral organic polar solvent is 20% based on the total amount of the solvent consisting of a mixture of the neutral organic polar solvent and water.
The method according to any one of claims 1 to 3, wherein -80% by weight is present. 5. The method according to claim 1, wherein the sulfonating agent is sodium sulfite, sodium hydrogen sulfite, potassium sulfite or potassium hydrogen sulfite.