JPH0443905B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the invention] (Industrial application field) This invention provides S-o-halofenyl-N,N obtained by heating a reaction product of O-halofenol and N,N-dialkylcarbamoyl halide.
- O that hydrolyzes dialkylthiocarbamates
- A method for producing halothiophenol. O-halothiophenol is a substance useful as an intermediate raw material for medicines and agricultural chemicals. (Prior art) Conventionally, as a method for producing O-halothiophenol, O-haloaniline is diazotized, and then reacted with potassium ethylxanthate to form O-halophenyl xanthate, which is then hydrolyzed. Methods (Journal of Organic Chemistry 23 ,
1906, 1958) are known. (Problems to be Solved by the Invention) The reactions in this production method are as follows: (1) The diazotization reaction is carried out at a low concentration, so the volumetric efficiency is poor. (2)It is an unstable substance.

[Structure of the invention]

(Means for solving problems) General formula ()

[Formula] (Here, X represents F, Cl, Br, I.) O-halofenol represented by the general formula ()

[Formula] (Here, Y is Cl, Br, I and R are C ₁ to C ₅ alkyl groups.) When reacting N,N-dialkylcarbamoyl halide represented by the general formula ()

[Formula] (wherein, X is F, Cl, Br, I and R are C ₁ ~
Indicates a _C5 alkyl group. ) O-o-
Halophenyl-N,N-dialkylthiocarbamate is produced. This compound is heated at a temperature of 170℃ to 300℃ to give the general formula ()

[Formula] (wherein, X represents F, Cl, Br, I, and a C ₁ to C ₅ alkyl group). By hydrolysis, preferably in the presence of an alkali, the general formula ()

O-halothiophenol represented by the formula: (wherein, X represents F, Cl, Br, or I) can be produced. General formula () which is an intermediate product

[Formula] (wherein, X is F, Cl, Br, I and R are C ₁ ~
Indicates a _C5 alkyl group. ) represented by S-o-
Halophenyl-N,N-dialkylthiocarbamates are novel compounds. (For this compound and its manufacturing method, the present inventors filed an application on September 4, 1980, S-o-halophenyl-N,
(See N-dialkylthiocarbamate and its production method) In the present invention, for example, O-halofphenol and N,
N-dialkylcarbamoyl chloride is reacted with O-o-halophenyl-N,N-dialkylthiocarbamate, which is heated to give S
-o-halophenyl-N,N-dialkylthiocarbamate and further hydrolyzed to produce O-halothiophenol. As the starting material O-halophenol, O-
Fluorophenol, O-chlorophenol, O
-bromophenol, O-iodophenol,
As the N,N-dialkylcarbamoyl halide, N,N-dimethylcarbamoyl chloride,
N,N-dimethylcarbamoyl bromide, N,
N-dimethylcarbamoyl iodide, N,N
-diethylcarbamoyl chloride, N,N-diethylcarbamoyl bromide, N,N-diethylcarbamoyl iodide, N,N-dipropylcarbamoyl chloride, N,N-dipropylcarbamoyl bromide, N,N-dipropylcarbamoyl iodide, Examples include N,N-dibutylcarbamoyl chloride, N,N-dibutylcarbamoyl bromide, and N,N-dibutylcarbamoyl iodide. The O-o-halophenyl-N,N-dialkylthiocarbamate obtained from the above-mentioned raw materials includes O-o-fluorophenyl-N,N-dimethylthiocarbamate, O-o-chlorophenyl-N,N-dimethyl Thiocarbamate, O-o-
Bromophenyl-N,N-dimethylthiocarbamate, O-o-iodophenyl-N,N-dimethylthiocarbamate, O-o-fluorophenyl-N,N-diethylthiocarbamate, O-o-
Chlorophenyl-N,N-diethylthiocarbamate, O-o-bromophenyl-N,N-diethylthiocarbamate, O-o-iodophenyl-
N,N-diethylthiocarbamate, O-o-fluorophenyl-N,N-propylthiocarbamate, O-o-chlorophenyl-N,N-propylthiocarbamate, O-o-bromophenyl-
N,N-propylthiocarbamate, O-o-iodophenyl-N,N-propylthiocarbamate, O-o-fluorophenyl-N,N-di-n
-butylthiocarbamate, O-o-chlorophenyl-N,N-di-n-butylthiocarbamate, O-o-bromophenyl-N,N-di-n-
Examples include butylthiocarbamate, O-o-iodophenyl-N,N-di-n-butylthiocarbamate, and the like. In addition, examples of S-o-halophenyl-N,N-dialkylthiocarbamate include S-o-fluorophenyl-N,N-dimethylthiocarbamate, S-o-chlorophenyl-N,N-dimethylthiocarbamate, and S-o-chlorophenyl-N,N-dimethylthiocarbamate. o-bromophenyl-
N,N-dimethylthiocarbamate, S-o-iodophenyl-N,N-dimethylthiocarbamate, S-o-fluorophenyl-N,N-diethylthiocarbamate, S-o-chlorophenyl-
N,N-diethylthiocarbamate, S-o-bromophenyl-N,N-diethylthiocarbamate, S-o-iodophenyldiethylthiocarbamate, S-o-fluorophenyl-N,N-dibutylthiocarbamate, S -o-chlorophenyl-N,N-dibutylthiocarbamate, S-o
-bromophenyl-N,N-dibutylthiocarbamate, S-o-iodophenyl-N,N-dibutylthiocarbamate, and the like. As a solvent for reacting O-halofenol and N,N-dialkylcarbamoyl halide, water-soluble solvents, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene can be used. Glycol dimethyl ether and the like can be used, but among these solvents, acetone gives good results. Good results are often obtained when the above-mentioned solvents are used in combination with water. The molar ratio when reacting O-halofenol and N,N-dialkylcarbamoyl halide is O
- The amount of N,N-dialkylcarbamoyl halide is approximately equal to 1.0 mole of halophenol, and there is no need to use an excess of one of them. The reaction temperature is preferably from room temperature to about 100°C, and the reaction is often carried out under reflux while maintaining the boiling point of the commonly used solvent. The temperature when heating O-o-halophenyl-N,N-dialkylthiocarbamate is 170°C to 300°C.
Good results can be obtained by heating in the absence of a solvent. When hydrolyzing S-o-halophenyl-N,N-dialkylthiocarbamate, it is desirable to carry out the hydrolysis in the presence of an alkali, but the hydrolysis can be carried out even without the presence of an alkali. Examples of alkalis include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Examples include sodium acetate, but it is economically advantageous to use sodium hydroxide. The amount of alkali used is S-o-halophenyl-
The amount may be at least equimolar to the N,N-dialkylthiocarbamate, but preferably 1.2 to 2.0 times the amount by mole gives good results. As reaction solvents for hydrolysis, in addition to lower alcohols such as methanol, ethanol, isopropanol, and n-butanol, water-soluble acetone, tetrahydrofuran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, and N , N-dimethylformamide, dimethylsulfoxide, sulfolane, etc. can be used. Among these reaction solvents, lower alcohols such as methanol, ethynol, and isopropanol are preferably used. These solvents can be used in combination with water. The reaction temperature during hydrolysis is in the range of 30°C to 100°C, preferably 50°C to 90°C. A detailed explanation will be given below using examples. Example 1 (Synthesis of O-o-chlorophenyl-N,N-dimethylthiocarbamate) 20 g (0.5 mol) of sodium hydroxide and 64.3 g (0.5 mol) of O-chlorophenol were added to a mixture of 320 g of acetone and 45 g of water. and stirred to obtain a homogeneous solution. This solution was cooled to 10°C, N,
N-dimethylthiocarbamoyl chloride 61.8g
(0.5 mol) was added dropwise over 30 minutes. Thereafter, the temperature was gradually raised and the reaction was carried out under reflux at 60°C for 30 minutes, and then the acetone water was distilled off. Add 150g of water to the residue after distilling off the acetone water, extract the reaction product with methylene chloride, distill off the methylene chloride, and then distill to determine the boiling point.
As a fraction of 132℃~135℃/1.5mmHg, O-o-
100.4 g (0.466 mol) of chlorophenyl-N,N-dimethylthiocarbamate was obtained. Yield is 93.2%
It was hot. (Synthesis of S-o-chlorophenyl-N,N-dimethylthiocarbamate) 53.9 g (0.25 mol) of O-chlorophenyl-N,N-dimethylthiocarbamate was added under a nitrogen stream.
After heating at 225℃ for 3 hours to complete the reaction,
Distillation yielded 51.4 g (0.239 mol) of S-o-chlorophenyl-N,N-dimethylthiocarbamate as a fraction with a boiling point of 145° C. to 147° C./1.5 mmHg.
The yield was 95.4%. (Synthesis of O-chlorothiophenol) 21.6 g (0.1 mol) of S-o-chlorophenyl-N,N-dimethylthiocarbamate was dissolved in methanol.
After dissolving in 50 g, 40 g (0.15 mol) of a 15 wt % aqueous sodium hydroxide solution was added, and the mixture was reacted under reflux at 76° C. for 4 hours. After the reaction, methanol water was distilled off, 50 g of water was added to the residue, and after washing with methylene chloride, 18.5 g (0.19 mol) of 50 wt% sulfuric acid was added.
The reaction product was extracted with methylene chloride. Furthermore, methylene chloride is distilled off and the boiling point is 79℃~80℃/
O-chlorothiophenol as a fraction of 10 mmHg
12.5 g (0.086 mol) was obtained. The yield was 86.5%. The yield of O-chlorothiophenol based on O-chlorophenol was 76.9%. Examples 2 to 6 Temperature and time during synthesis of S-o-chlorophenyl-N,N-dimethylthiocarbamate, O-
Alkali when synthesizing chlorothiophenol,
The yields shown in Table 1 were obtained in the same manner as in Example 1, except that the type of solvent and reaction temperature were changed to the conditions shown in Table 1 below.

[Table] Examples 7 to 11 O-halofenol, N,N- shown in Table-2
The same procedure as in Example 1 was performed except that dialkylthiocarbamoyl chloride was used to obtain the results shown in Table 2.

【table】

〔Effect of the invention〕

By carrying out the present invention, O-halothiophenol can be produced from O-halophenol and N,N-dialkylcarbamoyl halide,
It is possible to provide an industrially advantageous production method because raw materials are easily available, volumetric efficiency is better than in conventional techniques, and there is no risk of producing unstable or toxic substances.

Claims (1)

[Claims] 1 O-halofenol represented by the general formula () [formula] (wherein, X represents F, Cl, Br, I), and general formula () [formula] (wherein , Y is Cl, Br, and I and R are C ₁ to C ₅ alkyl groups. F, Cl, Br, I and R are C ₁ -
Indicates a _C5 alkyl group. ) O-o-
Halophenyl-N,N-dialkylthiocarbamate is prepared and heated to give the general formula () [Formula] (where X is F, Cl, Br, I and R are C ₁ -
Indicates a _C5 alkyl group. ) represented by S-o-
O-halothiophenol represented by the general formula () [Formula] (wherein, Production method. 2. The method according to claim 1, wherein in the general formulas [Formula] [Formula] [Formula] [Formula] and [Formula], X is Cl, Y is Cl, and R is CH ₃ . 3. The method according to claim 1, wherein acetone is used as a reaction solvent when O-halofenol and N,N-dialkylcarbamoyl halide are reacted to produce O-o-halofenyl-N,N-dialkylthiocarbamate. Method. 4 A patent in which the heating temperature when heating O-o-halophenyl-N,N-dialkylthiocarbamate to form S-o-halophenyl-N,N-dialkylthiocarbamate is in the range of 170°C to 300°C The method according to claim 1. 5. The method according to claim 1, wherein the O-o-halophenyl-N,N-dialkylthiocarbamate is heated to form the S-o-halophenyl-N,N-dialkylthiocarbamate without a solvent. 6. The method according to claim 1, wherein an alkali is present when hydrolyzing the S-o-halophenyl-N,N-dialkylthiocarbamate. 7. The method according to claim 6, wherein the alkali is sodium hydroxide. 8. The method according to claim 1, wherein a lower alcohol is used as a reaction solvent when hydrolyzing S-o-halophenyl-N,N-dialkylthiocarbamate. 9. The method according to claim 8, wherein the lower alcohol is methanol.