JPS5936982B2 - 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 present invention provides aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β
- An aminoaryl-β-sulfatoethyl sulfone characterized by reacting hydroxyethyl sulfone and sulfuric acid while removing water or water and acetic acid in an apparatus capable of removing volatile components by vaporization or evaporation. It is a manufacturing method. Aminoaryl-β-sulfatoethylsulfone is conventionally produced by hydrolyzing acetylaminoaryl-β-hydroxyethylsulfone in hydrochloric acid or dilute sulfuric acid to isolate it as aminoaryl-β-hydroxyethylsulfone, which is then dried. It can be obtained by subsequent esterification in concentrated sulfuric acid, but this method
-The isolated yield of hydroxyethyl sulfone was low, and the process was complicated due to the necessity of drying, so it could not be said to be industrially advantageous. In addition, special public service
Publication No. 17 describes a method of hydrolyzing and simultaneously converting 4-acetylaminophenyl-β-hydroxyethylsulfone into a sulfuric acid ester using concentrated sulfuric acid or a mixture of concentrated sulfuric acid and an organic solvent. This method actually hydrolyzes 4-acetylaminophenyl-β-hydroxyethylsulfone as described in the Examples, and the resulting 4-aminophenyl-β-hydroxyethylsulfone and 4-amino In order to convert phenyl-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 can be obtained as a large amount of concentrated sulfuric acid solution or oleum solution, and can be used as is or isolated by dilution. However, a large amount of acid must be handled, and the cost of the alkaline agent required to treat excess sulfuric acid and the problem of separation of the resulting sulfate are extremely complicated, which is extremely disadvantageous in industrial production. Furthermore, Japanese Patent Publication No. 45-27096 describes a method for producing aminoaryl-β-sulfatoethylsulfone by hydrolyzing acetylaminoaryl-β-sulfatoethylsulfone in 50% or less sulfuric acid water at 45°C. is listed.

However, this method has the drawback that the reaction requires a long time and also that the yield decreases because hydrolysis of the sulfate ester in the β-sulfatoethyl sulfone group occurs simultaneously with the hydrolysis of the acetylamino group. . Furthermore, conventionally known methods require a large amount of sulfuric acid in order to obtain a sulfuric acid ester 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 times the molar amount of raw material acetylaminophenyl-β-hydroxyethylsulfone. Even in the method disclosed in Japanese Patent Publication No. 45-127096, which uses a relatively small amount, an amount as much as 4.9 times the molar amount is required. The present inventors have improved the various drawbacks of known production methods, produced the desired aminoaryl-β-sulfatoethyl sulfone in high yield with a smaller amount of sulfuric acid than conventional methods, and moreover, it is advantageous for industrial production. As a result of intensive research and study on the manufacturing method, we finally arrived at the method of the present invention.

The most important feature of the method of the present invention is that water present in the reaction system and by-product water and acetic acid are removed from the reaction system by using a device that can remove volatile components by vaporization or evaporation. The purpose is to convert the hydroxyl group in the β-hydroxyethyl sulfone group into a sulfuric acid ester, and as a result, aminoaryl-β-sulfatoethyl You can get sulfone.

That is, as mentioned above, the known method required a large amount of sulfuric acid, but according to the method of the present invention, water or water and acetic acid produced as by-products as the reaction progresses are removed from the reaction system. The sulfuric acid concentration in the reaction system can be maintained at the concentration necessary for the progress of the sulfuric acid esterification reaction, and therefore the sulfuric acid concentration is 1 to 2 times the molar amount close to the theoretically required amount, which was completely unthinkable in conventional methods. The desired aminoaryl-β-sulfatoethyl sulfone can also be obtained in a highly pure state and in a high yield, which is advantageous for industrial production. Further, as mentioned above, the method of the present invention is extremely advantageous from the viewpoint of wastewater treatment, since the amount of sulfuric acid used is small, so there is little contamination of the waste liquid. Next, the present invention will be explained in more detail. In the present invention, aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone refers to benzene-based, naphthalene-based, substituted amino group and β-hydroxyethylsulfonyl group,
Other aromatic compounds may further have various other substituents.

Specific examples include the following compounds. 4-(amino or acetylamino)phenyl β-hydroxyethylsulfone 2-methoxy-5-(
phenyl-β-hydroxyethylsulfone 3-(amino or acetylamino)
-4-methoxyphenyl-β-hydroxyethylsulfone 3-aminophenyl-β-hydroxyethylsnorrefone 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-chlorophenyl-β-hydroxyethylsulfone 2-methyl-5-(amino or acetylamino)phenyl-β-hydroxyethylsulfone 3-carboxy-4-(amino or acetylamino) amino)phenyl-β-hydroxyethylsulfone 3-hydroxy-4-
(amino or acetylamino)phenyl-β-hydroxyethylsulfone 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 acetylamino)-2-naphthyl-β-hydroxyethylsulfone -1-naphthyl-β-hydroxyethylsulfone 2-(amino or acetylamino)-6
-(β-hydroxyethylsulfonino(c)-1-naphthalenesulfonic acid 3-(3 or 4-aminobenzoyl)aminophenyl -β-hydroxyethylsulfone 3-
(3 or 4-aminobenzoyl)amino-4-methoxyphenyl-β-hydroxyethylsnorrefon 3-(4
-acetylaminophenylsulfonynolyaminophenyl -β-hydroxyethylsulfone 3-(4-aminophenylsulfonyl)aminophenyl -β-hydroxyethylsulfone 4-(4-acetylaminophenoxy)phenyl -β-hydroxyethyl Sulfone 4-(4-aminophenoxy)phenyl-β-hydroxyethyl sulfone These aminoaryl-β-hydroxyethyl sulfones or acetylaminoaryl-β-hydroxyethyl sulfones can be used in either wet or dry form. Generally, 50 to 100% is used.

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 some cases, fuming sulfuric acid may be used. In the present invention, the sulfuric acid concentration is not particularly limited, but is usually 20 to 100%,
Preferably, the concentration is adjusted to 40-100%.

The amount used is 1 to 2 times the molar amount, preferably 1 to 1.5 times the molar number of aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone used, If more than twice the molar amount is used, it becomes difficult to distill off the water. The remaining amount of unreacted aminoaryl-β-hydroxyethyl sulfone tends to increase. The reaction temperature is 50 to 250°C, preferably 80 to 200°C, and is appropriately determined depending on the properties of the starting materials and the equipment used.

Although higher temperatures are preferable in order to facilitate the reaction, excessively high temperatures tend to cause side reactions and deteriorate the product. In addition, when using a device that performs vaporization and evaporation in a short time, it is performed at a relatively high temperature. Removal of water or water and acetic acid present in the reaction system can be performed under normal pressure by heating, but can be easily performed under reduced pressure. At this time, in order to facilitate the distillation of water and acetic acid, an inert substance such as diatomaceous earth, activated clay, activated carbon, silica gel, talc, etc. may be used. As a device capable of removing volatile components by vaporization or evaporation used in the present invention, a batch-type or continuous-type evaporation device, concentration device, or drying device is suitable.

Specific examples include shelf dryers, spray dryers, flash dryers, rotary dryer tunnel and band dryers, drum dryers, cylinder dryers, continuous air dryers, infrared dryers, high frequency Examples include a dryer, a long tube type evaporation concentration tube, a stirring type evaporator, and a rotary type concentrator. In carrying out the present invention, when using aminoaryl-β-sulfate ethyl sulfone, it can be mixed with sulfuric acid and reacted immediately in a drying device, etc. When using ethyl sulfone, it can be reacted in a drying device or the like immediately after being mixed with sulfuric acid, or after being heated once.
The aminoaryl-β-sulfatoethyl sulfone obtained by the method of the present invention can be isolated from the aqueous solution by injecting it into ice water in the state of the reaction product, or by neutralizing the aqueous 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 acid29.
4 parts (1.05 times the molar amount) of 4-acetylaminophenyl-β-hydroxyethyl sulfone with stirring.
Add 5 parts (purity 98.2%) and keep warm at 50-60°C for 2 hours.

The resulting mixture is placed in an evaporating dish and kept warm for 8 hours in a hot air circulation dryer (manufactured by Nishiyama Seisakusho) at 110 to 115°C.
During this time water and acetic acid are distilled off. When the obtained reaction product was analyzed by liquid chromatography, the production rate of 4-aminophenyl-β-sulfatoethylsulfone was 98.5%, and 4-aminophenyl-β-hydroxyethylsulfone and 4-aminophenyl-β-hydroxyethylsulfone were also found. 4-aminophenyl-β-
Contained a small amount of acetoxyethyl sulfone. Reference example
1 The reaction mixture obtained in Example 1 was placed in ice water, and 38.9 parts (purity 80%) of 38.9 parts (purity 80%) It is coupled with 1-amino-8-naphthol-3,6-disulfonic acid in a conventional manner.

By spray drying this reaction solution, a black dye known as Reactive Black 5 by Color Index was obtained as a highly concentrated product with a low inorganic salt content. In addition, the solution obtained by adding 0.8 parts of diethylene glycol monobutyl ether to the reaction solution before spray drying without separating the sodium sulfate is a concentrated aqueous solution of the dye with a low content of sodium sulfate, and is kept for a long time at low temperature. Even when left to stand, there was no precipitation of crystals and the product had excellent storage stability. Furthermore, the obtained dye had excellent solubility and exhibited good fastness when cellulose fibers were dyed black by a conventional reactive dye dyeing method using an alkali.

Example 2 2-methoxy-5-acetylaminophenyl-β- was stirred in 33.2 parts (1.1 times the molar amount) of 65% hydrochloric acid.
Add 56.3 parts of hydroxyethyl sulfone (purity 97%) and keep warm at 100-105°C for 2 hours.

Next, the obtained mixture is thoroughly mixed with 40 parts of diatomaceous earth, and kept at a temperature of 80 to 85 for 6 hours using a rotary vacuum evaporator (manufactured by Tokyo Rikakiki) to distill off water and acetic acid. Analysis of the reaction product by liquid chromatography revealed that it was 2-methoxy-5-aminophenyl-β-
The production rate of sulfatoethyl sulfone was 97%. Reference Example 2 The reaction product obtained in Example 2 was placed in ice water, neutralized with sodium carbonate, and diatomaceous earth was removed to isolate the product. Diazotization was carried out in a conventional manner using hydrochloric acid and sodium nitrite.

Thereafter, 1.05 times the molar amount of 8-acetylamino-1-
By coupling with naphthol-3,5-disulfonic acid in a conventional manner and spray-drying the entire amount without taking out the product, the red dye known in Example 3 of Japanese Patent Publication No. 43-24789 can be produced in a good yield. I was able to get it. Further, a solution to which 0.8 parts of diethylene glycol monobutyl ether was added without spray drying could be used as a concentrated aqueous liquid with good storage stability and no precipitation of sodium sulfate even when left at low temperatures. Furthermore, the obtained dye had excellent solubility, and cellulose fibers were dyed in a bright red color using a conventional reactive dye dyeing method using an alkali, and had good fastness.

Example 3 281.5 parts of 3-acetylamino-4-methoxyphenyl-β-hydroxyethyl sulfone (purity 97%) was added to 196 parts of 60% sulfuric acid (1.2 times the molar amount) with stirring. Incubate at ~105°C for 2 hours.

The resulting mixture was then heated to an inlet temperature of 200°C and an outlet temperature of 7.
Spray dry using a spray dryer at 0°C. The volatile components water and acetic acid were removed to obtain a powdery reaction product. When this reaction product was analyzed by liquid chromatography, it was found that 3-amino-4-methoxyphenyl-β
-Sulfate ethyl sulfone was obtained with a production rate of 95%.
Example 4 292.9 parts of 2-methyl-4-acetylamino-5-methoxyphenyl-β-hydroxyethyl sulfone (purity 98%) in 140 parts (1.0 times the molar amount) of 70% sulfuric acid with stirring Add and keep warm at 100-105°C for 2 hours.

The resulting mixture was then heated at 30 c/min! Width of n movement 10C! It was continuously placed in a thin layer on an IL Teflon plate and passed through a ventilated vessel at a temperature of 100 to 105°C. During this time water and acetic acid were continuously removed. When the flaky reaction product continuously produced from the outlet of the vessel was analyzed by liquid chromatography, 95% of 2-methyl-4-amino-5-methoxyphenyl-β-sulfatoethyl sulfone was found.
% production rate.

Example 5 29.4 parts of 100% sulfuric acid (1.5 times the molar amount) and 41.9 parts of 3-aminophenyl-β-hydroxyethyl sulfone (
96% purity) and 40 parts of diatomaceous earth are thoroughly mixed.

This is kept warm for 8 hours in a hot air circulation dryer (manufactured by Yasuda Seiki Seisakusho) at 120 to 125°C. When the obtained reaction product was analyzed by liquid chromatography, the production rate of 3-aminophenyl-β-sulfatoethyl sulfone was 9.
Obtained at 5%. Example 6 7-acetylamino-1-naphthyl-β-hydroxyethylsulfone 6 in 65.3 parts of 60% sulfuric acid with stirring
Add 2.1 parts (purity 95%) and keep warm at 100-105°C for 2 hours.

The resulting mixture is placed in an evaporating dish and kept at 90-95°C in a vacuum dryer for 8 hours. During this time water and acetic acid are removed. When the obtained reaction product was analyzed by liquid chromatography, 7-amino-1-naphthyl-β-sulfatoethyl sulfone was obtained with a production rate of 96%. Example 7
~13 When the reaction was carried out in the same manner as in Example 5 except that 3-aminophenyl-β-hydroxyethylsulfone was changed as shown in the following table and the amount of sulfuric acid and reaction temperature were changed, the following results were obtained.

Example 1 23.3 parts of 45% oleum (1.2 times the molar amount)
While stirring, 72.2 parts of 3-acetylamino-4-methoxyphenyl-β-hydroxyethylsulfone (purity 75.6%) was added to the wet cake while externally cooling at 30-40°C, and then 100-105 Keep warm at ℃ for 2 hours.

The resulting mixture was then thoroughly mixed with 40 parts of diatomaceous earth,
This is kept warm for 8 hours in a natural convection electric constant temperature dryer (manufactured by Mitamura Riken Kogyo Co., Ltd.) at 110 to 115 soil C. When the obtained reaction product was analyzed by liquid talomatography, 3-amino-4-methoxyphenyl-β-sulfatoethyl sulfone was obtained with a production rate of 97%. Example 15 2475 parts of 4-acetylaminophenyl-β-hydroxyethyl sulfone (purity 98.2%) was added to 1470 parts (1.05 times the molar amount) of 70% sulfuric acid with stirring,
Insulate at 100-105°C for 1 hour.

The resulting mixture was flashed at 190-195°C.
Water and acetic acid are distilled off using a long evaporative concentration tube.
When the obtained reaction product was analyzed by liquid chromatography, 4-aminophenyl-β-sulfatoethyl sulfone was obtained with a production rate of 98%. Reference Example 3 The reaction product obtained in Example 15 was placed in ice water and diazotized using a conventional method with hydrochloric acid and sodium nitrite.
．． The mixture is coupled with 0.5 times the molar amount of 3-sulfo-J-methyl-acetylaminonaphthol using a conventional method, and the entire amount is spray-dried without taking it out.

C. I. A red-orange dye known as Reactive Orange 16 could be obtained in good yield.

In addition, a solution obtained by adding 4.0 parts of diethylene glycol monobutyl ether to the reaction solution before spray drying has a low sodium sulfate content and can be used as a concentrated aqueous solution with good storage stability without precipitation of crystals even when left at low temperatures. Ta.

Claims (1)

[Claims] 1. Aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone and sulfuric acid are mixed with water or water and acetic acid in an apparatus capable of removing volatile components by vaporization or evaporation. A method for producing aminoaryl-β-sulfatoethyl sulfone, which comprises reacting while removing the aminoaryl-β-sulfatoethyl sulfone. 2. The manufacturing method according to claim 1, wherein the amount of sulfuric acid used is 1 to 2 times the molar amount of aminoaryl-β-hydroxyethylsulfone or acetylaminoaryl-β-hydroxyethylsulfone.