JPH0229077B2 - 3 * 3 * 4 * 44 TETORAKUROROTETORAHIDOROCHIOFUENN1 * 11JIOKISHIDONOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide has the structural formula It is a compound useful as a fungicide, insecticide, and herbicide. The above compounds are generally butadiene sulfone

It is produced by adding chlorine to [Formula] to obtain 3,4-dichlorotetrahydrothiophene-1,1-dioxide, and then substituting it with chlorine. In the above method, the addition of chlorine to butadiene sulfone is not a particular problem because the reaction proceeds very easily and quantitatively, but 3,4
The chlorine substitution reaction of -dichlorotetrahydrothiophene-1,1-dioxide had problems in terms of reaction rate and reaction rate. That is, a method using photochlorination is generally known for the chlorination reaction of 3,4-dichlorotetrahydrothiophene-1,1-dioxide, but this method requires a long reaction time of 50 to 60 hours. At the same time, the reaction rate was also not satisfactory. Therefore, as a means to solve the above problem, in JP-A-52-102631, 3,4-
A chlorination reaction of dichlorotetrahydrothiophene-1,1-dioxide has been proposed. Although this method improves the reaction rate and reaction rate of the chlorination reaction to some extent and improves the yield of the obtained 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, it is not suitable for industrial use. The current situation is that implementation is still unsatisfactory. In this current situation, the present inventors believe that 3,4-
Research aimed at producing 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide in high yield and in a short time by replacing dichlorotetrahydrothiophene-1,1-dioxide with chlorine. I've been repeating it. As a result, it was found that the above objective could be achieved by reacting 3,4-dichlorotetrahydrothiophene-1,1-dioxide and chlorine in an inert solvent in the presence of a specific radical initiator. This finding led to the completion of the present invention. That is, the present invention is characterized in that 3,4-dichlorotetrahydrothiophene-1,1-dioxide and chlorine are reacted in the presence of an organic azo radical initiator in an inert organic solvent. , 4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. In the present invention, the raw material 3,4-dichlorotetrahydrothiophene-1,1-dioxide may be obtained by any manufacturing method, but
Generally, those obtained by adding chlorine to butadiene sulfone by a known method are used. For example, butadiene sulfone and chlorine are mixed in an inert solvent as described below at a temperature ranging from room temperature to the boiling point of the inert solvent,
By reacting under pressure if necessary, 3,4-dichlorotetrahydrothiophene-
1,1-dioxide can be obtained. Therefore, 3,4-dichlorotetrahydrothiophene-1,1-dioxide obtained by the above method can be used as it is as a raw material in the present invention without being separated from the inert solvent. Further, the inert solvent is not particularly limited as long as it does not adversely affect the reaction with chlorine and can dissolve chlorine and raw materials. For example, carbon tetrachloride, chloroform, carbon disulfide, etc. are generally used, and carbon tetrachloride is particularly suitable because of its excellent stability against reactions. Further, the organic azo radical initiator used in the present invention is not particularly limited, but those having an appropriate half-life at the suitable reaction temperature described below are particularly suitable for industrially implementing the present invention. It is. In general, the half-life is 1 to 100 at 80 to 130℃.
Time, preferably 5 to 20 hours is preferred.
Specifically, 1-tert-butyrazo-1-cyanocyclohexane, 2-tert-butyrazo-2-cyanobutane, 2-tert-butyrazo-2-cyanopropane, etc. may be mentioned, and one or more of these may be used. Preferably, they are used in combination. The amount of the organic azo radical initiator to be used varies depending on its type, reaction temperature, etc., and cannot be absolutely limited, and the optimum amount may be determined by preliminary experiments.
Generally, the amount is 0.5 to 10 mol%, preferably 2 to 5 mol%, based on 3,4-dichlorotetrahydrothiophene-1,1-dioxide. In the present invention, the embodiment in which 3,4-dichlorotetrahydrothiophene-1,1-dioxide and chlorine are reacted in the presence of an organic azo radical initiator in an inert solvent is such that the above components enter the reaction system during the reaction. There is no particular restriction as long as it exists. To illustrate a typical embodiment, an embodiment in which an organic azo radical initiator and chlorine are each continuously or intermittently supplied into an inert solvent in which 3,4-dichlorotetrahydrothiophene-1,1-dioxide is dissolved. In the above embodiment, an embodiment may be mentioned in which the organic azo radical initiator and chlorine are each supplied in a state dissolved in an inert solvent. In particular, the latter embodiment is recommended because the reaction can be easily controlled. In the present invention, the reaction temperature is 3,4-dichlorotetrahydrothiophene-
It is sufficient if the temperature is higher than the dissolution temperature of 1,1-dioxide and higher than the decomposition temperature of the organic azo radical initiator, but if it is too high, the raw materials and products may decompose or the inert solvent may remain in a liquid state. Therefore, high pressure is required, which is impractical. For example, if the inert solvent is carbon tetrachloride, the reaction temperature should be set to 80°C or higher.
Preferably, the temperature is 90°C or higher in order to carry out the reaction quickly. The upper limit of the above reaction temperature is
A temperature of 130°C, preferably 120°C is suitable. Furthermore, at the above reaction temperature, it is less than 100°C until 3,4-dichlorotetrahydrothiophene-1,1-dioxide is chlorinated and almost converted to 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide. The resulting 3,3,4,4-tetrachlorotetrahydrothio This is preferred because the reaction time can be further shortened while maintaining a high yield of phene-1,1-dioxide. That is, in the present invention, the 3,4-
Dichlorotetrahydrothiophene-1,1-dioxide is extremely easy to decompose at temperatures above 100°C, but 3,3,4-trichlorotetrathiophene-1,1-dioxide obtained by replacing it with chlorine has a
It is stable even above ℃, and the reaction is 3, 3,
4-Trichlorotetrahydrothiophene-1,1
The rate-limiting step is the process of converting -dioxide into 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. Therefore,
Until 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide is produced, decomposition of the raw materials can be prevented by carrying out the reaction at the above-mentioned relatively low temperature, and the subsequent reaction can be carried out at a relatively high temperature. By doing this, the rate of the reaction that is the rate-determining step can be accelerated, so the resulting 3,3,
4,4-Tetrachlorotetrahydrothiophene-
It is generally possible to increase the yield of 1,1-dioxide and shorten the reaction time to 1/2 or less compared to organic peroxy compounds, although this varies depending on the conditions. In the present invention, the reaction pressure is determined such that at least a portion of the inert solvent exists in a liquid state at the above-mentioned reaction temperature. For example, in the case of carbon tetrachloride, it is common to employ a pressure in the range of 2 to 5 kg/cm ² G for a reaction temperature in the range of 70° C. to 130° C. In the present invention, the produced 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide can be separated and purified by any known method without particular limitation. For example, a common method is to crystallize in an inert solvent, then separate using a separator such as a centrifuge, and then dry. As understood from the above explanation, according to the method of the present invention, 3,3,4,4-
Tetrachlorotetrachlorotetrahydrothiophene-1,1-dioxide can be obtained in high yield and in a short reaction time. EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 60 g of butadiene sulfone and carbon tetrachloride were placed in a pressurized Nickel reactor with an internal volume of 1 and equipped with a stirrer.
Pour 600ml and add 200ml/chlorine gas at a temperature of 50℃.
It was supplied for 1 hour at min. As a result of gas chromatography analysis, all of the butadiene sulfone was converted to 3,4-dichlorotetrahydrothiophene-1,1-dioxide. Using this 3,4-dichlorotetrahydrothiophene-1,1-dioxide as a raw material,
The chlorine pressure was set at 4 kg/cm ² ·G and the temperature was raised to 95°C. While maintaining this condition, 3.0 g of 1-tert-butyrazo-1-cyanocyclohexane was added to carbon tetrachloride.
20 ml of catalyst adjustment solution dissolved at a rate of 50 ml was added to the reaction apparatus, and chlorine gas was supplied at a rate of 120 ml/min for 2 hours (first stage reaction). Then, raise the temperature to 115℃, add 30ml of catalyst adjustment solution, and add chlorine gas to 80℃.
The reaction was completed by feeding at a rate of ml/min for 4 hours (second stage reaction). According to gas chromatography analysis, at the end of the first stage reaction, the ratio of 3,4-dichloro form, 3,3,4-tri form, and 3,3,4,4-tetra form is 1.2:
It was 88.8:10, but when the reaction was completed it was 0:5:95.
I was getting used to it. A portion of carbon tetrachloride was distilled off from the reaction solution, and then 56.8 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide with a purity of 99 wt% was obtained by crystallization. Example 2 After producing the raw material 3,4-dichlorotetrahydrothiophene-1,1-dioxide in the same manner as in Example 1, the chlorine pressure in the reactor was reduced to 4.
Kg/cm ² ·G and the temperature was 95°C. A catalyst adjustment solution prepared by dissolving 3.0 g of 1-tert-butylazo-1-cyanocyclohexane in 60 ml of carbon tetrachloride is supplied to the above reactor in 20 ml portions each at 3 hours and 6 hours after the start of the substitution reaction, and Gas was continuously supplied at 60 ml/min and the reaction was carried out at a constant temperature for 9 hours. In gas chromatography analysis, 3,4-dichloro form, 3,3,4-tri form, 3,3,4,4-
The ratio of tetra-isomers was 0:11:89. A portion of carbon tetrachloride was distilled off from the reaction solution, and then 54.0 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide with a purity of 95 wt% was obtained by crystallization. Example 3 After obtaining the raw material 3,4-dichlorotetrahydrothiophene-1,1-dioxide in the same manner as in Example 1, the chlorine pressure in the reactor was increased to 4 kg/cm ² G.
Then, the temperature was raised to 90°C. 2-tert-butylazo-2-cyanobutane was added to the above reactor under these conditions.
20 ml of a catalyst preparation solution in which 3.0 g of carbon tetrachloride was dissolved in 60 ml of carbon tetrachloride was added, and chlorine gas was supplied at 140 ml/min for 1 hour and 55 minutes (first stage reaction). after that,
The temperature was raised to 110°C, 20 ml of catalyst adjustment liquid was further added, and chlorine gas was supplied at 60 ml/min for 5 hours to complete the reaction (second stage reaction). In the second stage reaction, an additional 20 ml of the catalyst adjustment liquid was supplied 2 hours and 30 minutes after the start of blowing chlorine gas at 64 ml/min. After the reaction was completed, gas chromatography analysis revealed that 3,4-dichloro form, 3,3,4-tri form,
The ratio of 3,3,4,4-tetra was 0:9:91. A portion of carbon tetrachloride was distilled off from the reaction solution, and then 57.1 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide with a purity of 99 wt% was obtained by crystallization. Comparative Example 1 After obtaining 3,4-dichlorotetrahydrothiophene-1,1-dioxide in exactly the same manner as in Example 1, the chlorine pressure in the reactor was set to 4 Kg/cm ² ·G and the temperature was set to 90°C. I made it. The reaction was carried out in exactly the same manner as in Example 2, except that benzoyl peroxide was used as a catalyst. As a result, gas chromatography analysis of the reaction product revealed that the 3,4-dichloro form, 3,
The ratio of 3,4-trichloro and 3,3,4,4-tetrachloro was 0:22:78. After the reaction was completed, benzoyl peroxide was further added and chlorination was continued for 9 hours under the above pressure and temperature.
The production rate remained almost unchanged. After partially distilling off carbon tetrachloride from the reaction solution, the purity is determined by crystallization.
48.8 g of 95 wt% 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide was obtained. Example 4 The catalyst was changed to 2-tert-butylazo-2-cyanopropane, and the reaction temperature in the second stage reaction was 105°C.
The reaction was carried out in exactly the same manner as in Example 3, except that the reaction was changed to . As a result, the ratio of 3,4-dichlor, 3,3,4-trichlor, and 3,3,4,4-tetrachlor in the reaction product by gas chromatography was 0:13:87. Next, after distilling off a portion of carbon tetrachloride from the reaction solution, the purity is determined by crystallization.
52 g of 95 wt% 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide was obtained.

Claims (1)

[Claims] 1 3,4-dichlorotetrahydrothiophene-
3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, which is obtained by reacting 1,1-dioxide and chlorine in an inert solvent in the presence of an organic azo radical initiator. manufacturing method. 2. The organic azo radical initiator is at least one member selected from the group consisting of 1-tert-butyrazo-1-cyanocyclohexane, 2-tert-butyrazo-2-cyanobutane, and 2-tert-butyrazo-2-cyanopropane. A method according to claim 1. 3. The method according to claim 1, wherein the inert solvent is carbon tetrachloride. 4 3,4-dichlorotetrahydrothiophene-
After performing a reaction between 1,1-dioxide and chlorine at a temperature below 100°C to produce 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide,
The method according to claim 1, wherein the reaction with chlorine is carried out at a temperature of 100 to 130°C.