JP3436568B2 - Method for producing thiophene derivative - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to 3, 3,4,4 novel method of manufacturing a tetrachloro-tetrahydrothiophene-1,1-dioxide.

[0002]

2. Description of the Related Art Generally, as a chlorination reaction in which chlorine is allowed to act on an organic compound, a chlorine addition reaction to a carbon-carbon double bond or a chlorine substitution reaction at a carbon-carbon bond is well known. In these reactions, chlorine-containing organic solvents such as carbon tetrachloride, chloroform and dichloromethane are usually used [New Experimental Chemistry Course 14
[II], pp. 335-338, [V] 2639
page〕. In addition, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (I), which is a compound useful as a fungicide, insecticide, and herbicide, has a structural formula

[Chemical 1] In general, butadiene sulfone (II) is chlorinated to give 3,4-dichlorotetrahydrothiophene-1,1-dioxide having adjacent carbon atoms each bonded to a chlorine atom. A method of obtaining (III) and subsequently substituting chlorine for (III) is used.

[Chemical 2]

In the above method, butadiene sulfone (I
The chlorine addition reaction of I) is extremely easy and quantitatively proceeded, so there is no particular problem.
For the chlorine substitution reaction of -dichlorotetrahydrothiophene-1,1-dioxide (III), a method of photochlorination in a carbon tetrachloride solvent (Japanese Patent Laid-Open No. 35-3517) is generally known. Regarding the chlorine substitution reaction of 3,4-dichlorotetrahydrothiophene-1,1-dioxide (III), a method using an organic peroxy compound instead of photochlorination (JP-A-52-102631) or an organic azo system A method using a radical initiator, or a method using light irradiation and an organic radical initiator in combination (JP-A-2-24368).
No. 5) has been proposed, and carbon tetrachloride is used as a solvent in all of these methods.

[0004]

However, the use of carbon tetrachloride used in these chlorination methods is totally prohibited after 1996 (Meeting of the Montreal Protocol in November 1992 / Nikkan Kogyo Shimbun, January 8, 1993). Therefore, a method of chlorinating in good yield without using carbon tetrachloride has been earnestly desired.

[0005]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that a fluorine-containing aromatic
With the system organic solvent, carbon tetrachloride equal to or higher reaction rate chloride, the reaction yield of 3,3,4,4-tetrachloroethene
It was found that rotetrahydrothiophene-1,1-dioxide can be obtained, and the present invention has been completed. That is, the present invention relates to 3,4-dichlorotetrahydrothiof
3,3,4,4-Tetrachlorotetrahydrothiophene , characterized in that the chlorination reaction of chlorine acting on ene- 1,1-dioxide is carried out in a fluorine-containing aromatic organic solvent.
The present invention relates to a method for producing ene-1,1-dioxide . 3,3,4,4-tetrachlorotetrahydrothio according to the invention
Manufacturing method of Fen-1,1-dioxide, et al is suitable for use when performing a chlorine-substitution reaction under light irradiation.
Below, 3,4-dichloro tetrahydrothiophene -1,
Fluorine-containing fragrance while irradiating 1-dioxide and chlorine with light
It reacted with family-based organic solvent, 3,3,4,4 theory to light a process for preparing tetrachloro-tetrahydrothiophene-1,1-dioxide.

The raw material 3,4-dichlorotetrahydrothiophene-1,1-dioxide (III) may be obtained by any method, but in general, butadiene sulfone (II) is chlorinated by a known method. The obtained one is used. The solvent used for this chlorine addition is not particularly limited as long as it does not adversely affect the reaction with chlorine and can dissolve chlorine and the raw materials, and a known inert solvent can be used. Further, by reacting (II) with chlorine in the fluorine-containing aromatic organic solvent of the present invention, (III) can be quantitatively obtained. Thus obtained (III) is It may be used as a raw material as it is, without being separated from the fluorinated aromatic organic solvent. The fluorine-containing aromatic organic solvent used in the present invention may be any solvent as long as it has a boiling point of 50 ° C. or higher and does not react with chlorine during the reaction and can be recovered, (III In the photochlorination reaction from () to (I), a solvent in which chlorine and the raw materials can be dissolved is further used. Such fluorine-containing aromatic organic solvents, full Tsu benzene, trifluoromethyl benzene,
1,3-bis (trifluoromethyl) benzene, 1,4
-Bis (trifluoromethyl) benzene and the like . These may be used alone or in combination, it may be mixed with chlorine-containing organic solvent of dichlorobenzene.
The reaction proceeds even with chlorobenzene, which is a chlorine-containing organic solvent, but the reaction yield is significantly inferior when the reaction time is the same as that of the fluorine-containing aromatic organic solvent. This reaction is carried out while irradiating light, and visible light, near-ultraviolet light, and ultraviolet light are suitable for light irradiation. Near-ultraviolet rays and ultraviolet rays are particularly suitable in terms of irradiation efficiency, and ultraviolet lamps having a wavelength of about 200 to 400 mμ, high-pressure mercury lamps, and low-pressure mercury lamps are preferably used.

In this reaction, the mode of reacting (III) with chlorine in a fluorine-containing aromatic organic solvent while irradiating with light is not particularly limited as long as the above components are present in the reaction system during the reaction. . For example, while the light irradiated to the fluorine-containing aromatic organic solvent continuously or intermittently supplying embodiments of chlorine with irradiation, chlorine dissolved in the fluorinated aromatic organic solvent prepared by dissolving (III) The aspect etc. which supply (III) continuously or intermittently are mentioned. The latter embodiment, which allows easy control of the reaction, is preferably used.
The reaction temperature is (II) with respect to the fluorine-containing aromatic organic solvent.
It may be higher than the melting temperature of I), but if it is too high, decomposition of raw materials and products will occur, which is not practical. The reaction temperature is usually preferably 50 to 110 ° C, more preferably 60 to 110 ° C.
It is 80 ° C. The reaction can be carried out under normal pressure. A known method can be used without particular limitation for the separation and purification of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (I) produced in this reaction. For example, a method in which crystallization is performed in a fluorine-containing aromatic organic solvent, followed by separation by a separator such as centrifugation and drying is common. In this case, since the solubility of (I) in the fluorine-containing aromatic organic solvent is low, it is not necessary to distill off the solvent after the reaction as compared with the case of using conventional carbon tetrachloride, and for example, nitrogen substitution is performed to dissolve the solvent. After removing the hydrochloric acid, it can be easily crystallized by cooling at about 5 ° C.

[0008]

The production method of the present invention, 3,4-dichloroethylene
Chlorination of lorotetrahydrothiophene-1,1-dioxide can be performed in high yield in a short time .

[0009]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The high-pressure mercury lamp described in the examples is a 100 W mercury lamp manufactured by Ushio, and the wavelength is 250 to 450 mμ. Example 1 In a 1 L Kolben equipped with a stirrer, which was replaced with nitrogen gas,
70 g of 4-dichlorotetrahydrothiophene-1,1-dioxide (III) and trifluoromethylbenzene 50
Chlorine gas was continuously blown at a rate of 5 to 10 liters per hour while irradiating a high pressure mercury lamp at a reaction temperature of about 80 ° C. for about 6 hours. Hydrochloric acid gas by-produced during the reaction was removed by introducing nitrogen gas into Kolben. After completion of the reaction, the dissolved hydrochloric acid was removed by nitrogen substitution, and the mixture was cooled to about 5 ° C. to precipitate 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (I). This was filtered through a nutsche filter, washed with 200 ml of trifluoromethylbenzene and then dried to give 68.0 g.
(I) was obtained (yield 71.2%).

Example 2 60 g of butadiene sulfone (II) and 400 ml of trifluoromethylbenzene were placed in a 1 L Kolben equipped with a stirrer, which had been replaced with nitrogen gas, and the reaction temperature was about 20 ° C. for about 4 hours.
Chlorine gas was continuously blown in at a rate of 5 to 10 liters per hour. Next, without isolating (III), the reaction solution of trifluoromethylbenzene was used as it was at a reaction temperature of about 80 ° C.
Chlorine gas was continuously blown in at a rate of 5 to 10 liters per hour while irradiating the high pressure mercury lamp for a period of time. Hydrochloric acid gas by-produced during the reaction was removed by introducing nitrogen gas into Kolben. After completion of the reaction, the dissolved hydrochloric acid was removed by nitrogen substitution, and the mixture was cooled to about 5 ° C. to precipitate (I). This is filtered through a nutsche, and trifluoromethylbenzene 2
After washing with 00 ml, it was dried to 68.7 g (yield 48.6).
%) (I) was obtained.

Example 3 The same operation as in Example 1 was carried out except that 30 g of (III) and 250 ml of 1,4-bis (trifluoromethyl) benzene were used, and 33.5 g (yield 81.8%). (I) was obtained. Example 4 The same operation as in Example 1 was carried out except that 20 g of (III) and 200 ml of 1,3-bis (trifluoromethyl) benzene were used, and 21.0 g (yield 77.7%) of (I ) Got .

Comparative Example 1 In a 1 L Kolben equipped with a stirrer, which was replaced with nitrogen gas (II
28 g of I) and 250 ml of carbon tetrachloride were added, and the reaction temperature was 6
Chlorine gas was continuously blown at a rate of 5 to 10 liters per hour while irradiating the high pressure mercury lamp at about 5 ° C. for about 6 hours. Hydrochloric acid gas by-produced during the reaction was removed by introducing nitrogen gas into Kolben. After the reaction was completed, the dissolved hydrochloric acid was removed by nitrogen substitution, and the mixture was cooled to about 5 ° C (I).
Was deposited. This is filtered with Nutsche and carbon tetrachloride 1
After washing with 00 ml, it was dried to 29.5 g (yield 77.4).
%) (I) was obtained.

Comparative Example 2 In a 1 L Kolben equipped with a stirrer, which was replaced with nitrogen gas, (I
20 g of I) and 250 ml of carbon tetrachloride were added, the reaction temperature was kept at around 20 ° C. while cooling, and about 5 hours / hour for 5 hours.
Chlorine gas was continuously blown at a rate of 1 liter. Hydrochloric acid gas produced as a by-product during the reaction was removed by introducing nitrogen gas into Kolben. Next, without isolating (III), chlorine gas is continuously blown at a rate of 5 to 10 liters per hour while irradiating a high-pressure mercury lamp at a reaction temperature of about 80 ° C. for about 6 hours in a reaction solution of carbon tetrachloride. It is. Hydrochloric acid gas by-produced during the reaction was removed by introducing nitrogen gas into Kolben. After completion of the reaction, the dissolved hydrochloric acid was removed by nitrogen substitution, and the mixture was cooled to about 5 ° C. to precipitate (I). This was filtered through a nutsche filter, washed with 100 ml of carbon tetrachloride and dried to obtain 24.0 g (yield 55.0%) of (I).

Comparative Example 3 The procedure of Comparative Example 1 was repeated except that 20 g of (III) and 200 ml of O-dichlorobenzene were used, and 4.1 g
(I) was obtained (yield 15.1%). Comparative Example 4 The same operation as in Comparative Example 2 was carried out except that 40 g of (II) and 400 ml of chlorobenzene were used, and 19.4 g (yield 1
(9.2%) of (I) was obtained. Comparative Example 5 The same operation as in Comparative Example 1 was carried out except that 30 g of (III) and 200 ml of toluene were used, but (I) was not obtained at all. Comparative Example 6 The same operation as in Comparative Example 1 was carried out except that 30 g of (III) and 200 ml of p-xylene were used, but (I) was not obtained at all. Comparative Example 7 The same operation as in Comparative Example 1 was carried out except that 30 g of (III) and 200 ml of acetic acid were used, but (I) was not obtained at all.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 4-20506 (JP, A) JP 4-20508 (JP, A) JP 52-10263 (JP, A) JP 6- 56729 (JP, A) JP 6-340562 (JP, A) JP 6-239928 (JP, A) JP 52-9656 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 333/48 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. 3,4-Dichlorotetrahydrothiophene
Characterized by chlorinating -1,1-dioxide with chlorine in a fluorine-containing aromatic organic solvent
3,3,4,4-tetrachlorotetrahydrothiophene
Method for producing -1,1-dioxide . 2. The method according to claim 1, wherein the reaction is performed under light irradiation.
3,3,4,4-tetrachlorotetrahydrothiophene
Method for producing -1,1-dioxide .