JPS5936908B2 - Synthesis method of bishydroxyethyl sulfone - Google Patents

Description

Detailed Description of the Invention The present invention is characterized in that bishydroxyethyl sulfide or bishydroxyethyl sulfoxide is oxidized using hypochlorite at a pH of 8 to 11 in the reaction system. Concerning the synthesis method of sulfone.

Bishydroxyethyl sulfone is a fiber processing agent, and is particularly useful as an anti-wrinkle agent and an anti-shrink agent for recycled fibers.

Organic peracids, organic peroxides, hydrogen peroxide, nitric acid, and inorganic peracids or their salts are known as oxidizing agents for oxidizing sulfides to sulfones.

When dialkyl sulfide is oxidized with nitric acid, it produces a sulfone, but when bishydroxyethyl sulfide is oxidized with nitric acid, it remains as a sulfoxide and the sulfone is not oxidized. This suggests that the oxidation behavior of bishydroxyethyl sulfide is quite different from that of dialkyl sulfide 1 because it contains hydroxyl groups. As a method for synthesizing bishydroxyethyl sulfone, a method of oxidizing bishydroxyethyl sulfide or bishydroxyethyl sulfoxide with hydrogen peroxide is conventionally known.

However, the method using hydrogen peroxide has drawbacks such as high cost of hydrogen peroxide and difficulty in handling, and there are industrial problems in producing it in large quantities. Therefore, the present inventors investigated various methods for easily oxidizing θ using an inexpensive oxidizing agent.
It has been discovered that bishydroxyethyl sulfone"5 can be produced surprisingly easily and in good yield by oxidizing bishydroxyethyl sulfide or bishydroxyethyl sulfoxide using hypochlorite between 11 and 11, and the present invention I was able to accomplish this.

That is, the present invention involves oxidizing bishydroxyethyl sulfide or bishydroxyethyl sulfoxide in an aqueous solution using hypochlorite while maintaining the pH of the reaction system at 8 to 11. Concerning a method for synthesizing ethyl sulfone.

In carrying out the present invention, the reaction method is to drop an aqueous solution of hypochlorite into an aqueous solution of bishydroxyethyl sulfide or bishydroxyethyl sulfoxide, or conversely, to add bishydrol into an aqueous solution of hypochlorite. Possible methods include dropping an aqueous solution of hydroxyethyl sulfide or bishydroxyethyl sulfoxide, or dropping both at the same time. The reaction is easily initiated without a catalyst and can be carried out at a reaction temperature of σ to 80°C, more preferably 20 to 60°C. In carrying out the present invention, the pH of the reaction system is particularly important; it is greatly influenced by the pH, and if the reaction is carried out in acidic conditions, the liberated hypochlorous acid will decompose, resulting in a decrease in the efficiency of the oxidizing agent. Also, if the alkalinity is strong, side reactions will occur. That is, the bishydroxyethyl sulfone produced becomes 2 under strongly alkaline conditions.
This is not preferable since it then changes to divinyl sulfone, 1.4 thioxane dioxide, hydroxyethyl vinyl sulfone, etc. The preferable pH of the reaction system is 8-11. The control method is to simultaneously introduce an aqueous mineral acid solution such as hydrochloric acid or sulfuric acid into the reaction system together with an aqueous hypochlorite solution, or to add an aqueous hypochlorite solution to a pH of 8 to 11 before the reaction.
Examples include partial neutralization with an aqueous mineral acid solution so that
Examples of the hypochlorite used as an oxidizing agent in the present invention include commercially available sodium hypochlorite, calcium hypochlorite, aqueous solutions thereof, and salami powder, etc.; An aqueous solution containing sodium or calcium hypochlorite obtained from sodium or calcium hydroxide and chlorine can also be used.

Further, the concentration of the hypochlorite aqueous solution used is preferably 5% or more. Example 1 Bishydroxyethyl sulfide 209 and 100 g of water were placed in a 500 d beaker equipped with a thermometer, stirrer, two dropping loads, and a glass electrode connected to the south meter, and the reaction temperature was adjusted to 3σ to 35°C. and maintain the P of the reaction solution.
Sodium hypochlorite 10w while keeping H at 8-9
t% aqueous solution (sodium hydroxide 0.4N aqueous solution) 245
a and 32d of 3N hydrochloric acid were added dropwise over 2 hours.

After the reaction was completed, the value of the reaction solution was 8.5. After the reaction was completed, it was neutralized with hydrochloric acid, a portion of the reaction solution was silylated with bistrimethylsilylacetamide in pyridine, and when analyzed by gas chromatography, the conversion rate of sulfide was 100.
%, the yield of bishydroxyethyl sulfone was 86% based on the charged sulfide. Example 2 The pH was set to 8 to p[]9 in the same manner as in Example 1, except that 22.6 g of bishydroxyethyl sulfoxide, 123 ml of sodium hypochlorite aqueous solution, and 16 ml of 3N hydrochloric acid were used instead of bishydroxyethyl sulfide. When the reaction was carried out while maintaining the temperature, the conversion rate of sulfoxide was 100% and the yield of bishydroxyethyl sulfone was 87%.

Example 3 Sodium hypochlorite aqueous solution 245T used in Example 1
When 497nl of 1N hydrochloric acid was added to I11 to partially neutralize it, the pH was 9.6.

When this aqueous solution was gradually added dropwise to bishydroxyethyl sulfide 209 at a reaction temperature of 30 to 40°C, the conversion of sulfide was 100% and the yield of bishydroxyethyl sulfone was 89 (fl). . Example 4 Attach a thermometer to a 200m1 Erlenmeyer flask, add 109% bishydroxyethyl sulfide and 40f water! and stir with a magnetic stirrer.

The reaction temperature was maintained at 40 to 45° C., and 3N hydrochloric acid and highly refined white powder 209 were added in batches over 2 hours so as to maintain the pH of the reaction solution at 9 to 10 while checking with a universal pH test paper. When the insoluble matter was passed through the mouth and the reaction solution was analyzed, the conversion rate of sulfide was 100%, and the yield of bishydroxyethyl sulfone was 8.
1%, yield of bishydroxyethyl sulfoxide 1.
It was 6%. Example 5 Approximately twice the amount of water was added to the highly refined white flour, stirred well, and insoluble matter was filtered out to obtain a pale yellow aqueous solution containing 1.27 mol/l of calcium hypochlorite.

When reacting in the same manner as in Example 1 except that 130 mt of the above aqueous solution was used instead of the sodium hypochlorite aqueous solution,
Sulfide conversion rate 100%, sulfoxide yield 5
. The yield of sulfone was 78%.

The pH was maintained at 8-10 during the reaction. Example 6 Sodium hydroxide 809 was dissolved in 2507711 water, and chlorine was blown into the solution under cooling to remove the generated sodium chloride to obtain a 20 wt % aqueous solution of sodium hypochlorite.

The reaction was carried out in the same manner as in Example 1 except that 123 ml of this aqueous solution was used. Analysis of the reaction solution revealed that the conversion rate of sulfide was 100% and the yield of sulfone was 80%. During the reaction, the pH of the reaction solution was 8-10. Example 7 123ml of sodium hypochlorite aqueous solution used in Example 1
1 into a 300ml Erlenmeyer flask, add 25ml of 1N hydrochloric acid.
The pH was 9.6 when the mixture was partially neutralized.

The reaction temperature was maintained at 20 to 30°C, and hydroxyethyl sulfide 109 was added dropwise over 20 minutes. Analysis of the reaction solution revealed that the conversion rate of sulfide was 100% and the yield of sulfone was 9.
It was 0 (fl). Reference Example 1 A reaction was carried out in the same manner as in Example 1 while maintaining the pH of the reaction solution at 3 to 4.

As a result of analysis, the conversion rate of sulfide was 100(f) and the yield of sulfone was 63%. Reference Example 2 123d of the aqueous sodium hypochlorite solution used in Example 1 was placed in a 300ml Erlenmeyer flask, and 1N hydrochloric acid was added until the pH reached 4.

Bishydroxyethyl sulfide 109 was added dropwise to this solution over 20 minutes at a reaction temperature of 20 to 30°C. As a result of the analysis,
Sulfide conversion rate 100%, sulfoxide yield 3
1(Ft), the yield of sulfone was 33%. Reference Example 3 P of the sodium hypochlorite aqueous solution used in Example 1
When H was measured, it was 13.2.

Without using hydrochloric acid, 245 ml of this aqueous solution was added to bishydroxyethyl sulfide 209 at a reaction temperature of 30 to 35°C.
The solution was added dropwise over a period of time, and upon completion of the reaction, neutralization and analysis revealed that the conversion rate of sulfide was 100% and the yield of sulfone was 61%. Reference example 4 123ml of sodium hypochlorite aqueous solution used in Example 1
Take 1, in a 300m1 Erlenmeyer flask and add 109
of bishydroxyethyl sulfide at a reaction temperature of 20 to 3
It was added dropwise at 0°C.

During the reaction... was around 13. After the reaction was completed, the mixture was neutralized and analyzed, and the conversion of sulfide was 100%, the yield of sulfoxide was 13%, and the yield of sulfone was 52%. The effects of the present invention are as follows: 1) Bishydroxyethyl sulfide or bishydroxyethyl sulfoxide is easily oxidized in good yield using inexpensive hypochlorite to produce bishydroxyethyl sulfide, which is effective as a fiber processing agent. Can synthesize sulfone.

2) It is easy to handle, non-hazardous, and does not require special reaction equipment.

Claims (1)

[Scope of Claims] 1. Bishydroxyethyl sulfide or bishydroxyethyl sulfoxide is added to the p of the reaction system in an aqueous solution.
A method for synthesizing bishydroxyethyl sulfone, which comprises oxidizing using hypochlorite while keeping H between 8 and 11. 2. The method according to claim 1, in which the hypochlorite is an aqueous sodium hypochlorite solution, an aqueous calcium hypochlorite solution, or salad powder. 3. The method according to claim 1, in which an aqueous solution containing sodium hypochlorite obtained by reacting an aqueous sodium hydroxide solution with chlorine is used as an oxidizing agent. 4. The method according to claim 1, wherein an aqueous solution containing calcium hypochlorite obtained by reacting an aqueous calcium hydroxide solution with chlorine is used as an oxidizing agent.