JPS58174353A - Preparation of mononitrophenyl-beta-hydroxyethyl sulfone - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for synthesizing vinyl sulfone type reactive dye in high purity in high yield, by oxidizing mononitrophenyl-beta-hydroxyethyl sulfide with hydrogen peroxide in the presence of a metal catalyst in a specific solvent. CONSTITUTION:Mononitrophenyl-beta-hydroxyethyl sulfide is oxidized with hydrogen peroxide in the presence of a metal catalyst (e.g., tungsten, molybdenum, etc.) in an aqueous medium containing at least one of nitriles (e.g., acetonitrile, benzonitrile, etc.) at 30-65 deg.C, preferably at 35-55 deg.C, to give the desired substance. The amount of the nitriles is 0.5-10 times as much as that of the raw material sulfide, the amount of the catalyst is 0.1-2wt% based on the raw material, the amount of hydrogen peroxide is 2.1-3.5 times the molar quantity of the raw material, and the amount of water as the reaction medium is 2-10 times as much as that of the raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing mononitrophenyl-β-hydroxyethyl sulfone.

More specifically, the present invention relates to the following formula (I) (Ke°02C2H“0°0”
I) A novel method for producing mononitrophenyl-β-hydroxyethyl sulfone, which is useful as an intermediate for aminophenyl-β-sulfatoethyl sulfone.

Conventionally, aminophenyl-β-sulfatoethylsulfone represented by formula (1) is produced by reacting aniline with acetic anhydride to form acetanilide, and then converting it into sulfonyl chloride in a large excess of chlorosulfonic acid to form acetylaminobenzenesulfonyl chloride. This was reduced with sodium sulfite to give sulfinic acid, and then treated with ethylene oxide or ethylene chlorohydrin to obtain acetylaminophenyl-β-hydroxyethyl sulfone.
It is produced by hydrolyzing it in sulfuric acid and converting it into sulfuric acid ester.

Alternatively, nitrobenzene is converted into sulfonyl chloride in a large excess of chlorenylphone to obtain m-nitrobenzenesulfonyl chloride, which is reduced with sodium sulfite to give the corresponding sulfinic acid, and then treated with ethylene oxide or ethylene chlorohydrin. te m
It is produced by obtaining -nitrophenyl-β-hydroxyethylsulfone, reducing it with iron powder, converting it into m-aminophenyl-β-hydroxyethylsulfone, and then esterifying it with sulfuric acid.

Both of the methods described by Queen Shikaji have various problems listed below in implementing them industrially, and cannot necessarily be said to be industrially advantageous methods.

The sulfonyl chloride formation in the Φ arsulfone is essentially an equilibrium reaction, and an excess of chlorosulfonic acid is required to suppress the by-product of acetylaminobenzenesulfonic acid.

■ Recovery of the above-mentioned excess chlorosulfonic acid is difficult, and ultimately it is necessary to treat it as acidic waste liquid.

■ Acetylaminobenzenesulfonyl chloride is unstable, contributing to lower yields.

■ Reduction to sulfinic acid by sodium sulfite is
The stability of sulfinic acid is low and therefore the reaction yield is low.

■ When aniline is used as a starting material, the acetic acid released by hydrolysis of the acetyl group in the final step reacts with the hydroxyl group, resulting in acetic acid ester as a by-product, resulting in a decrease in purity. The acetic acid produced causes major problems such as corrosion of reaction equipment and water problems.

In view of these circumstances, the present inventors have investigated an industrially advantageous method for producing the compound represented by formula (I), and have investigated mononitrophenyl-β-hydroxyethyl sulfide obtained by oxidizing mononitrophenyl-β-hydroxyethyl sulfide. Aminophenyl-β derived from R from β-hydroxyethyl sulfone, 18
- We have discovered a new manufacturing method that involves converting hydroxyethyl sulfone into a sulfuric acid ester to produce the target compound of formula (1), and we have made the oxidation plant in this new manufacturing method more industrially advantageous. We discussed in detail how to do this.

Conventionally, this oxidation method is carried out in glacial acetic acid using hydrogen peroxide at a relatively high temperature [Proc.

■ndian Acad, 8ci, $3 volume A, 28~!
1G (195B)], a method carried out in an aqueous sodium bicarbonate solution using hydrogen peroxide (Japanese Patent Publication No. 48-24661),
A method using sodium hypochlorite in an aqueous solution of an inorganic compound such as sodium hydroxide, sodium carbonate, or sodium bicarbonate (German Patent No. 944607) is known.

However, each of these methods has the following drawbacks. That is, in the production method in which oxidation is performed using a volume of water peroxide in glacial acetic acid, an acetalized product is produced as a by-product, and as a result, the purity and yield of mononitrophenyl-β-hydroxyethyl sulfone are lowered.

Furthermore, it is extremely difficult to quantitatively recover glacial acetic acid by distillation. Further, the reaction temperature is 70 to 80°C and it takes 10 hours, which is not advantageous for a one-cup production method.

In the method of oxidizing hydrogen peroxide in an aqueous sodium bicarbonate solution, the oxidation reaction did not proceed smoothly due to the unevenness of the anti-nuisance force, and even after 10 hours of incubation, there was a considerable amount of unreacted water. Mononitrophenylene is an intermediate product! -Hydroxyethyls μ fluoride remains. In addition, at reaction temperatures exceeding 46°C,
Self-decomposition of hydrogen peroxide takes precedence over the oxidation reaction, and the yield of the sulfone produced is low. Furthermore, due to the non-uniformity within the system, phenomena such as foaming occur, making it extremely difficult to complete the reaction.

The production method involves oxidation using hypochlorous acid in an aqueous solution of a basic inorganic compound.Because the reaction system is non-uniform, the reaction temperature is 25-80℃, so the oxidation reaction is smooth. Since the reaction does not proceed and a considerable amount of unreacted -bS remains, the purity and yield of the sulfone produced are low. If the reaction temperature is set to 80 to 60°C, the oxidation reaction easily becomes cloudy (L), which is preferable because high melting point substances are produced as by-products.

Furthermore, New Experimental Chemistry Course, Oxidation and Reduction of Cl-2] (Chemical Society of Japan, page 664) shows that phenyl-I-hydroxyethyl sulfide can be oxidized with metal [i] and hydrogen peroxide to give the corresponding sulfone. It is stated that.

However, when the above reaction conditions were applied to the oxidation reaction of mononitrophenyl-β-hydroxyethyl sulfide to sulfone, only the intermediate product sulfoxide was obtained, and no sulfone was produced. It was a very small amount.

Even when the incubation time is further extended, the reaction temperature remains between 68 and 76.
Because of the high temperature (°C), self-decomposition of the peroxide volume took priority and the oxidation reaction could not be completed.

The present inventor C oxidizes mononitrophenyl-β-hydroxyethyl sulfide to produce mononitro, 111::Fe=IL/-β-hydroxyethyl sulfone with high purity and high yield with industrial advantage. As a result of extensive research into the method, it was discovered that the object could be achieved by carrying out oxidation using hydrogen peroxide in the presence of a metal catalyst in a specific reaction medium, and the present invention was completed.

That is, the present invention is characterized in that mononitrophenyl-β-hydroxyethyl sulfide is oxidized using hydrogen peroxide in an aqueous medium containing at least 14 m of a nitrile in the presence of a metal catalyst. - A method for producing β-hydroxyethyl sulfone is provided.

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

Mononitrophenyl-β-hydroxyethyl sulfide used as a starting material in the method of the present invention may be produced by any method, for example, mononitrophenyl-β-hydroxyethyl sulfide, mononitroherobenzene, alcohols, N-alkyl substituted amides, etc. Obtained by reacting with medium mercaptoethanol, 2-. 8-1 is 4-nitrophenyl-β-hydroxyethyl sulfide.

Nitriles used in the method of the present invention are aliphatic and aromatic nitriles, and specifically aliphatic nitriles include acetonitrile, propionitrile, butyronitrile adiponitrile, geltalonitrile and 2-
Methylgeltalonitrile and the like are used, and the aromatic nitriles include benzonitrile and tolnitrile. Of course, mixtures of two or more nitriles can also be used.

Among them, acetonitrile is preferably used. These nitriles can be used in an amount of 0.5 to 10 times the weight of the raw material sulfide. Of course, there is no problem even if it is used ten times or more, but it is inefficient in manufacturing on an industrial scale, and the space-time efficiency becomes poor. A preferable amount is 0.5 to 6 times, and a more preferable amount is 1 to 4 times.

The amount of water used as reaction medium is sufficient to homogenize the added metal catalyst.

As for the amount of the mixed liquid of nitrile and water, the mixing ratio can be changed so that the amount becomes 2 to 10 times, preferably 8 to 8 times the weight of the raw material sulfide.

There is no problem even if the organic solvent used in producing the raw material sulfide is mixed into this reaction medium.

Tungsten, molybdenum, vanadium, titanium and chromium are effective metal catalysts used in the method of the invention.

Among these, tungsten, molybdenum, and vanadium are particularly effective.

Examples of the tungsten catalyst include tungstic acid, its alkali metal salts, alkaline earth metal salts, and ammonia salts.

Examples of molybdenum catalysts include molybdic acid, its alkali metal salts, alkaline earth metal salts, and ammonia salts.

Examples of vanadium catalysts include vanadic acid, its alkali metal salts, alkaline earth metal salts, and ammonia salts.

The amount used can vary over a wide range from 0 to 1 O by weight based on the starting sulfide. However, in general, the use of 0.1 to 21 volumes is sufficient.

In an embodiment of the present invention, for example, a metal catalyst is added to the above-mentioned nitrile aqueous solution, the mixture is sufficiently stirred to homogenize it, the raw material sulfide is added, and a predetermined amount of hydrogen peroxide solution is added dropwise at a desired temperature. Keep warm.

The reaction temperature is in the range of 80-65°C, preferably 86-55°C. The time required for dropping the hydrogen peroxide solution in this preferred reaction temperature range is 0.5 to 8 hours.
The reaction is completed by keeping it warm for 1 to 6 hours after the completion of the dropwise addition.

It is not necessarily advantageous to raise the reaction temperature more than necessary because it causes self-decomposition of hydrogen peroxide.

The amount of hydrogen peroxide used is 2.1 to 8.5 times the mole of raw material sulfide. More preferably, it is used in an amount of 2.1 to 8 moles.

According to the method of the invention, mononitrophenyl-! -Hydroxyethyl sulfone can be obtained with high purity and high yield, so it is very advantageously applied industrially.The present invention will be explained in detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, Examples Chubu and Shizu are parts by weight, respectively.
Reward the weight department.

Example 1 0.8 parts of tungstic acid was added to 160 parts of water, and after homogenization, 24011 parts of acetonitrile was added, and then 80 parts of 4-nitrophenyl-β-droxyethyl sulfide was added while stirring.

114 parts of 80% hydrogen peroxide solution (2.5 times the mole) at 40℃
was added dropwise over 1 hour. After finishing dropping, continue at this temperature for 8 hours.
It was kept warm for hours.

1,004 sulfones of interest were produced, and neither the raw material sulfide nor the intermediate product sulfoxide remained.

After removing acetonitrile from the reaction solution under reduced pressure, it was further concentrated, cooled, and then dried.

88 parts of white crystals of 4-nitrophenyl-β-hydroxyethylsulfone were obtained.

The yield was 95 pieces.

Example 2 After 0.2 parts of tungstic acid was added to 120 parts of water and homogenized, 120 m of acetonitrile was added, and 2-nitrophenyl-β-hydroxyethyl sulfide 401S was added while stirring.

At 50°C, 57 parts (2.5 molar ratio) of 80% hydrogen peroxide solution was added dropwise over 1 hour. After the drip route r, the mixture was kept at this temperature for 8 hours.

100 units of the desired sulfone were produced, and neither the raw material sulfide nor the intermediate product sulfoxide remained.

After acetonitrile was distilled off under reduced pressure from the reaction solution, it was further concentrated, cooled, and dried.

White crystals of 2-nitrophenyl-I-hydroxyethylsulfone were obtained at a yield of 954.

Comparative Example 1 (In the absence of acetonitrile) After adding 1.0 part of tungstic acid to 160 parts of water and homogenizing the mixture, 40 parts of 2-nitrophenyl-β-hydroxyethyl sulfide was added without stirring.

At 60°C, 68 parts (8 moles) of 304 hydrogen peroxide solution was added dropwise over 1 hour. After the completion of the dropwise addition, the temperature was further kept at this temperature for 10 hours, but the intermediate product 2-nitrophenyl-β
-Hydroxyethyl sulfoxide is present in 8041A1.
The production of the desired sulfone was approximately 20 times.

Comparative Example 2 (When there is no metal catalyst) In addition to 40 m5 of 2-nitrophenyl-β-hydroxyethyl sulfide and 120 parts of acetonitrile, an additional 80 parts of water was added.
part was added.

At 50°C, 57 parts (2.6 moles) of 804 hydrogen peroxide solution was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was kept at this temperature for another 7 hours, but 80'6Wi4 of the raw material Sulfy F remained, and no production of the desired sulfone was observed.

Claims (1)

[Claims] Mononitrophenyl-β-hydroxyethyl sulfone, characterized in that mononitrophenyl-β-hydroxyethyl sulfide is oxidized using hydrogen peroxide in the presence of a metal catalyst in an aqueous medium containing at least one nitrile. manufacturing method.