KR850001780B1 - Process for the preparation of sulfato ethyl sulfon derivatives - Google Patents

Abstract

Compds. of the formula (I) (X1,X2=H, methyl, methoxy, Cl; R1=H, R2=CH2,CH2,OSO3H) are prepd. by esterification and hydrolysis of compds. (II) (R1=COCH3, R2=H) and ethylene chlorohydrine. Thus, 23g 4-MeO-3-acethylaminophenyl sulfinic acid and 11g ClCH2CH2OH were reacted at 65-70≰C, pH8-8.5 to give (II). (I) was dissolved in 45g H2SO4, after maintaining 40-50≰C, 3hr, followed by extraction of 60g ice and 60ml H2O, to give (I). Prepn. of (I) are used in preparing agricultural chemicals, pharmaceutics and dyes.

Description

Method for Preparation of Sulfate Ethyl Sulfone Compound

The present invention relates to a method for preparing a sulfatoethylsulfone compound.

In particular, the present invention relates to a method for preparing an aminosulfate ethylsulfone compound, which is a free acid form of the general formula (I), which is widely used for the preparation of compounds such as pesticides, medicines and salts.

Where X ₁ and X ₂ each represent a hydrogen atom, a methyl group, a methoxy group or a chlorine atom

Currently, an acetylaminosulfonic acid compound is reacted with ethylene oxide under pressure, and the reaction product thereof is esterified and hydrolyzed in concentrated sulfuric acid or fuming sulfuric acid to prepare an aminosulphate ethylsulfone compound. .

Where X ₁ and X ₂ are as defined above.

However, this manufacturing method is difficult to react under inert nitrogen gas in the reactor because (1) ethylene oxide has a high explosion risk in the manufacturing process, and (2) special storage for safe storage and handling of ethylene oxide. It is complicated to have many special devices such as cooling shower-storage and fire and explosion protection device, and (3) expensive autoclave should be installed because it needs to react under high pressure, and (4) pressurized gas -Because of the liquid reaction, it has many disadvantages such as poor yield and difficulty in obtaining high purity products.

An object of the present invention is to use a liquid at room temperature instead of ethylene oxide to solve the above problems of the prior art, by using hydrin as a hydroxyethylating agent with a stable ethylene chromium, to simplify the reaction apparatus, and to handle safely To provide a method for producing a high yield and high purity sulfoethylsulfone compound.

Sulphate ethyl sulfone compound of the following general formula (I) according to the present invention, by adding ethylene chloro hydrin to the aqueous solution of acetylamino sulfinic acid compound of the general formula (II), heated to 65 to 80 ℃, condensation reaction It can be prepared by preparing an acetylamino hydroxyethylsulfone compound of formula (III), then separating and drying it, followed by treatment with concentrated sulfuric acid or fuming sulfuric acid.

Where X ₁ and X ₂ are as defined above.

Examples of the compound of formula (II) used as starting materials in the present invention are as follows.

4-acetylamino naphthalene-1-sulfinic acid,

5-acetylamino naphthalene-1-sulfinic acid,

6-acetylamino naphthalene-2-sulfinic acid,

3-acetylaminophenyl-1-sulfonic acid,

3-acetylaminophenyl-4-methoxy-1-sulfinic acid,

3-acetylaminophenyl-6-methoxy-1-sulfinic acid,

3-acetylaminophenyl-4-methyl-1-sulfinic acid,

3-acetylaminophenyl-6-methyl-1-sulfinic acid,

3-acetylaminophenyl-6-chloro-1-sulfinic acid,

4-acetylaminophenyl-1-sulfinic acid,

4-acetylaminophenyl-3-chloro-sulfonic acid,

4-acetylaminophenyl-3,6-dimethoxy-1-sulfinic acid and

4-acetylaminophenyl-3-methoxy-6-methyl-1-sulfinic acid.

The present invention will be described in more detail with reference to the following Examples.

Example 1

23 g of 4-methoxy-3-acetylaminophenyl sulfinic acid is added to 100 ml of water, neutralized and dissolved in caustic soda, and then 11 g of ethylenechlorohydrin is added.

The reaction mixture is heated to 65-70 ° C., at which time the resulting hydrochloric acid is removed with 10% caustic soda solution and the pH is maintained at 8-8.5.

After the completion of the reaction, the mixture was cooled to 5 ° C. and filtered to dry the cake. As a result, 4-methoxy-3-acetylaminophenyl-β-hydroxyethylsulfone (dry amount 28.7 g, yield 99%) was produced.

The intermediate product was dissolved in 45-50 g of sulfuric acid, maintained at 40-50 ° C. for 3 hours, then discharged in 60 g of ice and 60 ml of water and stirred for 8 hours at 40-50 ° C. to yield 4-meth as the final product. Toxy-3-aminophenyl-β-sulfato ethylsulfone was obtained.

Yield 41 g (wet cake), yield 98%.

[Example 2]

20 g of 4-acetyl aminophenyl sulfinic acid are added to 90 ml of water, neutralized and dissolved in caustic soda, 11.5 g of ethylenechlorohydrin is added, heated to 70 ° C., and the resulting acid is removed with 10% caustic soda solution. To keep the pH between 8 and 8.5. After the completion of the reaction, the mixture was cooled to 5 to 10 ° C., and the cake formed by filtration was dried. As a result, 4-acetylaminophenyl-β-hydroxyethylsulfone was produced (dry amount 26 g, yield 99%).

After the same procedure as in Example 1 to obtain the final product 4-aminophenyl-β-sulfatoethylsulfone 38 (wet cake) (yield 98%).

Example 3-6

As a result of reacting with sulfinic acid as described in Examples 1 and 2, a high purity final product was obtained.

Claims (1)

The acetylamino sulfinic acid compound of the following general formula (II) is reacted with ethylenechlorohydrin (CICH ₂ CH ₂ OH) at a temperature of 65 to 80 ° C. to obtain a hydroxyethylsulfone compound of the general formula (III) Esterification and hydrolysis in sulfuric acid to prepare the sulfatoethylsulfone compound of the following general formula (I);

(In the above formula, X ₁ and X ₂ each represent a hydrogen atom, a methyl group, a methoxy group or a chlorine atom.)