JPS5936980B2 - Method for producing aminoaryl-β-sulfatoethylsulfone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing aminoaryl-β-sulfatoethyl sulfone, which is important as an intermediate for vinylsulfone-type reactive dyes.

More particularly, the invention relates to aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-
When producing aminoaryl-β-sulfatoethyl sulfone by reacting hydroxyethyl sulfone with sulfuric acid, the reaction is carried out by azeotropic distillation of water or water and acetic acid together with an organic solvent in the presence of an organic solvent at normal pressure or reduced pressure. This is a method for producing aminoaryl-β-sulfatoethyl sulfone, which is characterized in that it is carried out while distilling off.

Conventionally, in order to obtain aminoaryl-β-sulfatoethylsulfone from acetylaminoaryl-β-hydroxyethylsulfone, acetylaminoaryl-β-hydroxyethylsulfone is hydrolyzed in hydrochloric acid or dilute sulfuric acid, and the aminoaryl -β-Hydroxyethylsulfone is isolated, dried, and then esterified in concentrated sulfuric acid. However, this method has disadvantages in that the isolation yield of aminoaryl-β-hydroxyethylsulfone is low and the operation is complicated due to the necessity of drying, so that it cannot be said to be industrially advantageous.

Furthermore, Japanese Patent Publication No. 16617/1983 describes a method of hydrolyzing 4-acetylaminophenyl-β-hydroxyethylsulfone using concentrated sulfuric acid or a mixture of concentrated sulfuric acid and an organic solvent and simultaneously converting it into sulfuric acid ester. There is.

However, this method actually hydrolyzes 4-acetylaminophenyl-β-hydroxyethylsulfone and the resulting 4-aminophenyl-β-hydroxyethylsulfone and 4-hydroxyethylsulfone, as described in the Examples. In order to convert -aminophenyl-β-acetoxyethylsulfone into 4-aminophenyl-β-sulfatoethylsulfone, it is necessary to further add a large amount of oleum to the reaction solution. Therefore, the obtained 4-aminophenyl-β-sulfatoethyl sulfone is obtained as a large amount of concentrated sulfuric acid solution or fuming sulfuric acid solution, and can be used as is or isolated by dilution. However, a large amount of acid must be handled, and the cost of an alkali agent required to treat excess sulfuric acid and the problem of separation of the resulting sulfate are extremely complicated, making the process extremely disadvantageous for industrial production.

Furthermore, the publication also describes the use of an organic solvent during the reaction, but its effect is merely to promote hydrolysis or to facilitate stirring of the reaction solution. Furthermore, in Japanese Patent Publication No. 45-27096, acetylaminoaryl-β-sulfatoethyl sulfone is
A method of hydrolysis in 0% or less sulfuric acid water at 45°C has been described, but this method has the drawback of requiring a long reaction time and simultaneously hydrolyzing the acetylamino group and producing β-sulfatoethyl This method has the disadvantage that the yield decreases due to hydrolysis of the sulfone group.

Furthermore, conventional methods require a large amount of sulfuric acid to obtain an esterified product in good yield.

For example, in Japanese Patent Publication No. 42-16617, the amount of sulfuric acid used is as large as 8.4 to 15.6 moles relative to the raw material acetylaminophenyl-β-hydroxyethylsulfone, and is relatively Even in the method of Japanese Patent Publication No. 45-27096, which uses a small amount, an amount as much as 4.9 moles is required. The present inventors have improved the various drawbacks of known production methods, and have achieved high yields of the desired aminoaryl-β-sulfatoethyl sulfone using a smaller amount of sulfuric acid than conventional methods, while also being advantageous in terms of operation. As a result of intensive study on the manufacturing method, the method of the present invention was arrived at.

The most important feature of the present invention is that a by-product is produced when aminoaryl-β-hydroxyethylsulfone is obtained using aminoaryl-β-hydroxyethylsulfone and sulfuric acid or acetylaminoaryl-β-hydroxyethylsulfone and sulfuric acid. The purpose is to azeotropically distill water or water and acetic acid together with an organic solvent, thereby allowing the water to react with the acetic acid while being distilled off.

That is, in the method of the present invention, water or water and acetic acid produced as by-products as the esterification or esterification and hydrolysis reactions progress are constantly distilled out of the reaction system, so the sulfuric acid concentration in the reaction system is lower than that of sulfuric acid. It is possible to maintain the concentration necessary for the esterification reaction to proceed, and therefore, even if the amount of sulfuric acid is extremely small, which would have been impossible with conventional methods, that is, the amount of sulfuric acid that is at or near the theoretical amount, the target amino acid can be Aryl-β-sulfatoethyl sulfone can be obtained in a highly pure state and in a high yield, which is advantageous for industrial production. Furthermore, in the method of the present invention, since water is distilled off during the reaction, the starting materials aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone and sulfuric acid are in a water-containing state. can be used. This advantage is particularly advantageous when acetylaminoaryl-β-hydroxyethylsulfone is used as the starting material, since hydrolysis of the acetylamino group proceeds rapidly. Furthermore, since an organic solvent coexists, many of the starting materials and by-products that remain as impurities are dissolved in the organic solvent layer and cannot be removed when removing the target aminoaryl-β-sulfatoethyl sulfone. The aminoaryl-β-sulfatoethyl sulfone is obtained in a highly pure state. In addition, the method of the present invention is extremely advantageous from the viewpoint of wastewater treatment, since the amount of sulfuric acid used is small as described above, and therefore there is little contamination of wastewater.

Next, the present invention will be explained in more detail.

Aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β- which is the starting material of the present invention
Hydroxyethyl sulfone can be used either in a wet state or in a dry state.

When using a sulfuric acid containing water, it is necessary to appropriately increase the concentration of sulfuric acid depending on the water content, and in that case, fuming sulfuric acid is used. The sulfuric acid concentration during the reaction is not particularly limited, but is usually 20-100%, preferably 40-98%.
The concentration is adjusted to %. The amount used is 1.0 to 3.0, particularly 1.0, based on the number of moles of aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone used as the starting material.
~2.0 molar amount is preferred. The reaction temperature is 50-20
The temperature is 0°C, preferably 70-180°C. In general, higher temperatures are preferable in order to facilitate the reaction, but excessively high temperatures tend to cause side reactions and reduce the yield. Heat treatment alone is usually sufficient to distill off water or a mixture of water and acetic acid present in the reaction system to the outside of the system, but in some cases nitrogen, air, A method of blowing an inert gas such as carbon dioxide gas may be adopted, or it may be carried out under reduced pressure.

At this time, an inert substance such as diatomaceous earth, activated carbon, silica gel, talc, etc. may be used as appropriate to facilitate stirring, or aminoaryl-β-sulfatoethyl sulfone corresponding to the reaction product may be added. good. The organic solvent used in the present invention must be inert to sulfuric acid and have the property of being azeotropic with water or water and acetic acid at 50 to 200°C.

Examples of commonly used organic solvents include hydrocarbons, halogenated hydrocarbons, nitrated hydrocarbons, ketones, and the like. More specific examples include cyclohexane, heptane, benzene, toluene, xylene, solvent naphtha, trichloroethane, dichloropropane, trichloroethylene, tetrachloroethane, perchloroethylene, chlorobenzene, dichlorobenzene, nitrobenzene, and methyl isobutyl ketone. The amount used is preferably 0.1 to 10 times, particularly 0.1 to 8 times, the weight of the starting material aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone. The method of the present invention can be carried out in a batch-type or continuous-type kneading machine using ordinary cans, tanks, and pots, and can also be carried out in a batch-type or continuous-type kneading machine capable of kneading with strong force. can do.

In the present invention, aminoaryl or acetylaminoaryl-β-hydroxyethylsulfone includes benzene-based, naphthalene-based, and other aromatic compounds,
These can have various substituents. Specifically, the following are examples. 4-(amino or acetylamino)phenyl-β-hydroxyethylsulfone 2-methoxy-5-(amino or acetylamino)phenyl-β-hydroxyethylsulfone 3
-(amino or acetylamino)-4-methoxyphenyl-β-hydroxyethylsulfone 3-aminophenyl-β-hydroxyethylsulfone 4-(amino or acetylamino)-2,5-dimethoxyphenyl-β-hydroxyethylsulfone 5 -(amino or acetylamino)-2,4-dimethoxyphenyl-β-hydroxyethylsulfone 3-chloro-4-(amino or acetylamino)-phenyl-β-hydroxyethylsulfone 3-(amino or acetylamino)- 4-Chlorphenyl-β-hydroxyethylsulfone 2-methyl-5-
(amino or acetylamino)phenyl-β-hydroxyethylsulfone 3-carboxy-4-(amino or acetylamino)phenyl-β-hydroxyethylsulfone 3-hydroxy-4-(amino or acetylamino)phenyl-β-hydroxyethyl Sulfone 3-amino-4-sulfophenyl-β-hydroxyethylsulfone 2-(amino or acetylamino)phenyl-β
-Hydroxyethylsulfone 5-(amino or acetylamino)-1-naphthyl-β-hydroxyethylsulfone 4-(amino or acetylamino)-1-naphthyl-β-hydroxyethylsulfone 5-(amino or acetylamine)-2 -naphthyl-β-hydroxyethylsulfone (amino or acetylamino) -1-
Naphthyl-β-hydroxyethylsulfone 2-(amino or acetylamino)-6-(β-hydroxyethylsulfonino(c)-1-naphthalenesulfonic acid 3-(3)
or 4-aminobenzoyl)aminophenyl-β-hydroxyethylsulfone3-(3 or 4-aminobenzoyl)amino-4-methoxyphenyl-β-hydroxyethylsulfone3-(4-acetylaminophenylsulfonino(c) Aminophenyl-β-hydroxyethylsulfone 3-(4-aminophenylsulfonyl)Aminophenyl-β-hydroxyethylsulfone 4-(4-acetylaminophenoxy)phenyl-β-hydroxyethylsulfone 4-(4-aminophenoxy)phenyl -β-Hydroxyethylsulfone The aminoaryl-β-sulfatoethylsulfone obtained by the method of the present invention is obtained by diluting the reaction mixture in ice water and isolating it from the diluted solution. By neutralizing the diluted solution, it can be used as an intermediate for reactive dyes.

Next, the method of the present invention will be explained in more detail with reference to Examples. Parts and % in the examples represent parts by weight or % by weight, respectively, unless otherwise specified. Example 170% sulfuric acid 29
．． 4 parts (molar ratio 1.05) of 4-acetylaminophenyl-β-hydroxyethylsulfone with stirring.
Add 9.5 parts (purity 98.2%) and heat to 100-105℃
Keep warm for 1 hour.

The resulting mixture was poured into 200 parts of perchloroethylene at 115-120°C over 2 hours while distilling off acetic acid and water, and then kept at 115-120°C for 1 hour to complete the reaction. When the resulting reaction product was analyzed by liquid chromatography, the production rate of 4-aminophenyl-β-sulfatoethyl sulfone was 97%, and in addition, 4-
It contained small amounts of aminophenyl-β-hydroxyethyl sulfone and 4-aminophenyl-β-acetoxyethyl sulfone.

Reference Example 1 The reaction product obtained in Example 1 was poured into ice water, neutralized with sodium carbonate, perchloroethylene was separated, and the product was treated with hydrochloric acid and sodium nitrite in a conventional manner without isolating the product. Perform diazotization of

Thereafter, it is coupled with 38.9 parts (purity 80%) of 1-amino-8-naphthol-3,6-disulfonic acid by a conventional method. By spray-drying the resulting reaction solution, a black dye known as Reactive Black 5 in Color Index was obtained as a highly concentrated product with a low content of inorganic salts. Furthermore, the solution obtained by adding 0.8 parts of diethylene glycol monobutylniter to the reaction solution before spray drying is a concentrated aqueous solution of the dye with a low content of sodium sulfate, and even if left at low temperatures for a long time, crystals will not precipitate. It had excellent storage stability. Furthermore, when cellulose fibers were dyed in a conventional manner using the obtained powdered dye or concentrated dye solution, a strong and deep black dyed product was obtained.

Example 2 In 300 parts of 0-dichlorobenzene, 40 parts of diatomaceous earth and 4-acetylaminophenyl-β were added while stirring.
-49.5 parts of hydroxyethyl sulfone (purity 98.2
%) and 95% sulfuric acid 217. part (molar ratio 1.05).

Then, under reduced pressure (2001 mI! Hg) for 8 hours, 10
The reaction was carried out at 0 to 105°C while water and acetic acid were distilled off. 4-Aminophenyl-β-sulfγ-toethylsulfone was obtained with a production rate of 95%.

Example 3 In Example 2, under reduced pressure (200mlHg) for 8 hours,
Instead of keeping it warm at 100-105℃, it was heated to 10℃ at normal pressure.
Nitrogen gas was blown at 0 to 105° C. for 8 hours.

When the reaction product was analyzed by liquid chromatography, a production rate of 95% was obtained as in Example 2. Example 4 57.5 parts of 2-methoxy-5-acetylaminophenyl-β-hydroxyethyl sulfone (purity 95%) was added to 39.2 parts of 65% sulfuric acid (molar ratio 1.3) with stirring, Insulate at 100-105°C for 2 hours.

The resulting mixture is then poured over 2 hours into 150 parts of toluene to which 40 parts of diatomaceous earth has been kept at 105-110° C. while water and acetic acid are distilled off. After that 105~
The reaction was completed by incubating at 110° C. for 1 hour. Analysis of the reaction product by liquid chromatography revealed that the production rate of 2-methoxy-5-aminophenyl-β-sulfatoethyl sulfone was 95%. Reference Example 2 The reaction product obtained in Example 4 was poured into ice water, neutralized with sodium carbonate, 0-dichlorobenzene and diatomaceous earth were removed, and the product was poured into hydrochloric acid and sodium nitrite without isolating it. Diazotization is carried out using a conventional method.

The mixture was then coupled with 8-acetylamino-1-naphthol-3,5-disulfonic acid at a molar ratio of 1.05 using a conventional method, and the entire product was spray-dried without removing it. A red dye known as Example 3 of Japanese Patent Publication No. 43-24789 could be obtained in good yield. In addition, a solution to which 0.8 parts of diethylene glycol monobutyl ether was added without spray drying was a concentrated aqueous solution with good storage stability and no precipitation of sodium sulfate even when left at low temperatures.

Furthermore, when cellulose fibers were dyed using these dye products in a conventional manner, a strong and deep red dyed product was obtained.

Example 5 56.3 parts of 3-acetylamino-4-methoxyphenyl-β-hydroxyethyl sulfone (purity 97%) was added to 39.2 parts of 60% sulfuric acid (molar ratio 1.2) while stirring and straining.
) and keep warm at 100-105°C for 2 hours.

Next, the resulting mixture was heated under reduced pressure (400 mL Hg) at a temperature of 90 to 95°C, and 200 g of O-dichlorobenzene was added to 10 parts of 3-amino-4-methoxyphenyl-β-sulfatoethylsulfone. was injected into the tank for 2 hours while distilling off acetic acid and water, and then
The reaction was completed by keeping the temperature at 5°C. When the reaction product was analyzed using liquid chromatography, it was found that 3-amino-
4-Methoxyphenyl-β-sulfatoethyl sulfone was obtained at a yield of 90%. Example 6 In 50% sulfuric acid 42.2 parts (molar ratio 1.05), stirred
2-Methyl-4-acetylamino-5-methoxyphenyl-β-hydroxyethylsulfone62.
Add 4 parts (purity 92%) and keep warm at 100-105°C for 1 hour.

Next, the obtained mixture was poured into 120 parts of xylene at a temperature of 115 to 120°C over 2 hours while distilling off the acetic acid and water, and the reaction was completed by keeping the mixture at 105 to 110°C for 2 hours. When the reaction product was analyzed by liquid chromatography, the production rate of 2-methyl-4-amino-5-methoxyphenyl-β-sulfatoethylsulfone was 9.
It was 5%. Example 7 40 parts of diatomaceous earth and 3-
(4-Aminobenzoyl)aminophenyl-β-hydroxyethylsulfone 51.4 parts (purity 95%) and 9
Add 21 parts of 8% sulfuric acid (molar ratio 1.05).

Next, the mixture was reacted at 105 to 120° C. for 4 hours while water was distilled off. 3-(4-Aminobenzoyl)aminophenyl-β-sulfatoethyl sulfone was obtained at a yield of 95%.

Example 8 Add 4 parts of diatomaceous earth to 300 parts of 0-dichlorobenzene while stirring.
0 parts, 50.3 parts of a wet cake of 3-aminophenyl-β-hydroxyethylsulfone (purity 80%) and 24.8 parts of 95% sulfuric acid (molar ratio 1.2) are added.

Next, the mixture was reacted at 160 to 165° C. for 5 hours while water was distilled off. 3-Aminophenyl-β-sulfatoethyl sulfone was obtained with a yield of 97%.

Examples 9 to 15 The production rate when 29.4 parts of 70% sulfuric acid (molar ratio 1.05) of Example 1 was changed as shown in the table below, and the type of organic catalyst, reaction temperature, and amount of diatomaceous earth were changed. Shown in the table below.

Example 16 266.5 parts of 7-amino-1-naphthyl t-β-hydroxyethylsulfone (purity 95%), 9
120 parts of 8% sulfuric acid (molar ratio 1.2) and 133 parts of O-dichlorobenzene are added.

The reaction was then kept at a temperature of 100 to 105° C. under reduced pressure (15011 Hg) for 5 hours while distilling off the produced water to complete the reaction. When the obtained reaction product was analyzed by liquid chromatography, 7-amino-1-naphthyl-β-sulfatoethyl sulfone was obtained with a production rate of 93%. Example 17 247.5 parts of 4-acetylamino-β-hydroxyethyl sulfone (purity 98.2%) was added to a two-shaft, double-arm type 21-D1 (manufactured by Inoue Seisakusho) that was rotating at 60 revolutions per minute. Add 300 parts of diatomaceous earth.

Next, 105 parts of 9.8% sulfuric acid (molar ratio 1.05) was added to this.
Add. While adding 250 parts of xylene dropwise under reduced pressure (500 nHg), the mixture was kept at 120 to 125° C. for 6 hours while acetic acid and water were distilled off to complete the reaction. When the obtained reaction product was analyzed by liquid chromatography, 4-amino-β-sulfatoethyl sulfone was obtained with a production rate of 95%. Reference Example 3 The reaction product obtained in Example 17 is placed in ice water, residual xylene and diatomaceous earth are removed, and diazotization is carried out in a conventional manner using hydrochloric acid and sodium nitrite.

The C.I. I. An orange dye known as Reactive Orange 16 could be obtained in good yield. In addition, a solution prepared by adding 4.0 parts of diethylene glycol monobutyl ether to the reaction solution before spray drying has a low sodium sulfate content and does not precipitate crystals even when left under low water, resulting in good storage stability. It is a concentrated aqueous solution.

Furthermore, when cellulose fibers were dyed using these dye products in a conventional manner, a strong and deep red-orange dyed product was obtained.

Example 18 3-acetylamino-4-methoxyphenyl-β- was added to 23.3 parts of 5% oleum (molar ratio 1.2) with stirring.
Hydroxyethyl sulfone wet cake 7 2.2
(purity 75.6%) is added while cooling to 20-30°C, and then kept at 100-105°C for 2 hours.

The resulting mixture was then heated under reduced pressure (500 uHg) with a polarity of 1
The temperature is maintained at 00 to 105°C.

40 parts of diatomaceous earth was added. The reaction mixture was poured into 200 parts of -dichlorobenzene over 2 hours while distilling off acetic acid and water, and then kept at 100-105°C for 2 hours to complete the reaction.

Claims (1)

[Claims] 1. When reacting aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone with sulfuric acid to produce aminoaryl-β-sulfatoethylsulfone, the reaction is carried out at normal pressure or in the presence of an organic solvent. 1. A method for producing aminoaryl-β-sulfatoethyl sulfone, which is carried out under reduced pressure while water or water and acetic acid are distilled off together with an organic solvent by azeotropic distillation.