JP2002338542A - Method for producing s-fluoroalkyl= fluoroalkylthiosulfonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an S-fluoroalkyl= fluoroalkylthiosulfonate. SOLUTION: This method for producing the S-fluoroalkyl= fluoroalkylthiosulfonate comprises reacting a fluoroalkylsulfinate with thionyl chloride. Thereby, the S-fluoroalkyl=fluoroalkylthiosulfonate can be obtained from the inexpensive and easily handleable reagents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing S-fluoroalkyl = fluoroalkylthiosulfonate, which is useful as a reagent for producing pesticides and pesticides.

[0002]

2. Description of the Related Art In recent years, a fluoroalkylsulfenyl group, particularly a trifluoromethylsulfenyl group (CF
Compounds having ₃ S) has received attention because of its unique biological activity. In particular, pyrazole derivatives having a trifluoromethylsulfenyl group are useful as insecticides (JP-A-62-228065, JP-A-63-19886).
-3167671, JP-A-3-118369, and JP-A-10-338676).

As a method for producing a heterocyclic compound having a trifluoromethylsulfenyl group, there is known a method in which a trifluoromethylsulfenylating agent such as trifluoromethylsulfenyl chloride is reacted with a heterocyclic compound (Patent No. 2669538). By the way, recently, the present inventors have found that a trifluoromethylsulfenyl group can be introduced into a pyrazole ring by trifluoromethyl = trifluoromethylthiosulfonate (compound 1).

[0004]

Embedded image

As a method for producing Compound 1, a method by disproportionation accompanying hydrolysis of trifluoromethylsulfenyl chloride (RNHaszeldine, JM Kidd, J. Chem. Soc., 2
901 (1955)), the reaction of trifluoromethylsulfinyl chloride with trifluoromethylmercury (DT Sauer, J. et al.
M. Shreeve, Inorganic Chemistry, 10, 358 (1971)),
A method by oxidation of bistrifluoromethyl disulfide (Chem. Ber., 127, 1871 (1994)) and the like are known.

[0006]

However, since the above-mentioned trifluoromethylsulfenyl chloride, trifluoromethylsulfinyl chloride, trifluoromethylmercury and bistrifluoromethyldisulfide are all toxic, the compound is prepared by the above-mentioned known method. 1
Is difficult to produce industrially.

[0007] Accordingly, the present invention provides an S-fluoroalkylsulfenyl group-introducing agent.
An object of the present invention is to provide a method for producing fluoroalkyl = fluoroalkylthiosulfonate from a safe and easily handled raw material.

[0008]

SUMMARY OF THE INVENTION The present inventors obtain fluoroalkyl = fluoroalkylthiosulfonates by reacting thionyl chloride with a fluoroalkylsulfinate such as sodium or potassium trifluoromethylsulfinate. That is, the present invention has been completed.

That is, the present invention provides a fluoroalkyl sulfinic acid salt represented by the general formula (1)

[0010]

Embedded image wherein R-SO ₂ M (1) (wherein, R represents an alkyl group substituted by a fluorine atom, and M represents a cation); Equation (2)

[0011]

Embedded image

(Wherein R has the same meaning as in the general formula (1).) This is a process for producing S-fluoroalkyl = fluoroalkylthiosulfonate represented by the formula: The nomenclature of the compounds used in the present specification is the IUPAC nomenclature rule C-
641.5.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, a fluoroalkylsulfinate is reacted with thionyl chloride. In the present invention, fluoroalkyl means an alkyl group in which one or more fluorine atoms are substituted. The carbon number of the alkyl group is preferably 1 to 4,
Further, the alkyl group may be linear or branched. Specific examples include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, perfluoropropyl, perfluorobutyl and the like, and preferably trifluoromethyl.

M is preferably an alkali metal such as lithium, sodium, potassium, cesium and the like, and particularly preferably sodium or potassium. That is, it is preferable to use sodium trifluoromethylsulfinate or potassium trifluoromethylsulfinate as the fluoroalkylsulfinate.

The reaction between the fluoroalkylsulfinate and thionyl chloride can be carried out without solvent.
It is preferable to carry out in the presence of a solvent. As the solvent, those which are inert to fluoroalkylsulfinates and thionyl chloride can be used. For example, aromatic hydrocarbon solvents such as toluene and benzene, aliphatic hydrocarbon solvents such as hexane and heptane, halogenated hydrocarbon solvents such as dichloromethyl and chloroform, ether solvents such as tetrahydrofuran and diethyl ether, and fatty acids such as ethyl acetate Ester solvents, ketone solvents such as acetone, and polar aprotic solvents such as dimethylformamide and dimethylsulfoxide can be used. Of these, aromatic hydrocarbon solvents are preferred, and toluene is particularly preferred.

As a method of reacting a fluoroalkylsulfinate with thionyl chloride, a method of adding thionyl chloride to fluoromethylsulfinate, a method of adding fluoroalkylsulfinic acid to thionyl chloride,
And a method of simultaneously adding a fluoroalkylsulfinate and thionyl chloride to the reaction vessel,
It is preferable to dissolve or suspend the fluoroalkyl sulfinic acid salt in the above-mentioned solvent, and to add thionyl chloride to the solution. Thionyl chloride is generally used in an amount of 0.5 equivalent to 2 moles, preferably 0.8 mole to 1 mole, based on the fluoroalkyl sulfinic acid salt.

The reaction is carried out at a temperature between -100 ° C and 100 ° C, preferably between 0 ° C and 50 ° C. The reaction time is 10
Minutes to 24 hours, preferably 1 hour to 5 hours. The produced S-fluoroalkyl = fluoroalkylthiosulfonate can be isolated from the reaction mixture by distillation, but can also be used for the sulfenylation reaction as it is without isolation and purification.

According to the present invention, S-fluoroalkyl = fluoroalkylthiosulfonate includes S-trifluoromethyl = trifluoromethylthiosulfonate,
S-difluoromethyl = difluoromethylthiosulfonate, S-fluoromethyl = fluoromethylthiosulfonate, S-pentafluoroethyl = pentafluoroethylthiosulfonate, S-perfluoropropyl = perfluoropropylthiosulfonate, S-perfluoro Butyl = perfluorobutylthiosulfonate and the like can be produced.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 A suspension obtained by suspending 29.27 g (0.17 mol) of potassium trifluoromethylsulfinate in 30 ml of toluene was kept at 5 ° C., and 16.9 g (0.14 mol) of thionyl chloride was added thereto. It was dropped. After stirring at room temperature for 1 hour, normal pressure distillation was performed to obtain 5 g of S-trifluoromethyl trifluoromethylthiosulfonate having a boiling point of 32-34 ° C. GC-MS analysis (ionization mode EI ⁺ ) m / z Relative intensity 47.95 4.1 62.97 5.6 63.95 3.1 69.01 100 81.97 14.4 100.91 3.6 132.89 3.1 164.82 5.0 233.80 0.6 (M ⁺ ) ¹⁹ F-NMR Literature 76.8 ppm, 36.3 ppm (Inorganic Chemistry 1
2,8, p1896 (1973)) Actual measured values 76.4 ppm, 36.0 ppm (Reference Example) A solution of 0.23 g of S-trifluoromethyl trifluoromethylthiosulfonate obtained in Example 1 in 2 ml of toluene was added to 1- (2 , 6-Dichloro-4-trifluoromethylphenyl) -5-aminopyrazole-3-
0.001 mol of carbonitrile and 0.26 g of p-toluenesulfonic acid dimethylamine salt (0.0015 mol
l) and reacted at room temperature overnight. The conversion was 96%, the reaction yield (quantified by high performance liquid chromatography) was 76%, and the isolation yield was 60%. Dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfenyl-5-aminopyrazole-3
-Carbonitrile was obtained.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Kazuya Okano 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Pref.

Claims (3)

[Claims] 1. A fluoroalkyl sulfinic acid salt represented by the general formula (1): R-SO ₂ M (1) (wherein R represents an alkyl group substituted by a fluorine atom; Represents a cation.) A method for producing S-fluoroalkyl = fluoroalkylthiosulfonate represented by the general formula (2), wherein thionyl chloride is allowed to act on the cation. Embedded image (In the formula, R has the same meaning as in the general formula (1).) 2. The method for producing S-trifluoromethyl trifluoromethylthiosulfonate according to claim 1, wherein R is an alkyl group having 1 to 4 carbon atoms substituted by a fluorine atom. . 3. A process for producing S-trifluoromethyl trifluoromethylthiosulfonate, which comprises reacting thionyl chloride with sodium trifluoromethylsulfinate or potassium trifluoromethylsulfinate.