JPH1045709A - Method for producing 3-chloro-1-thiocyanato-2-propene - Google Patents

Abstract

(57) [Summary] 3-Chloro-1 useful as an intermediate for agricultural chemicals and the like
A process for industrially advantageously producing thiocyanato-2-propene. SOLUTION: 1,3-Dichloropropene and a thiocyanate are reacted in the presence of an organic solvent having a water solubility and a boiling point of 150 ° C. or less, wherein 3-chloro-1-thiocyanato-2-propene is obtained. Production method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to 3-chloro-1-
The present invention relates to a method for producing thiocyanato-2-propene. 3-Chloro-1-thiocyanato-2 produced according to the present invention
-Propene is useful as a synthetic intermediate for pesticides and the like.

[0002]

2. Description of the Related Art As a method for producing 3-chloro-1-thiocyanato-2-propene, 1,3-dichloropropene is reacted with potassium thiocyanate in dimethyl sulfoxide (Journal f. Prakt. Chemie. Band 322). ,
Heft 4, 1980, S, 629) is known.

[0003]

However, the yield of 3-chloro-1-thiocyanato-2-propene in the above method is as low as 47%. In addition, dimethyl sulfoxide is used as a solvent, but the recovery operation is complicated and is not suitable for industrial use. Therefore, the above-mentioned method cannot be said to be an industrially advantageous method for producing 3-chloro-1-thiocyanato-2-propene. Thus, an object of the present invention is to provide an industrially easy-to-implement and 3-chloro-1-
An object of the present invention is to provide a method for producing thiocyanato-2-propene in high yield.

[0004]

According to the present invention, an object of the present invention is to react 1,3-dichloropropene with a thiocyanate in the presence of a water-soluble organic solvent having a boiling point of 150 ° C. or lower. This is achieved by providing a method for producing 3-chloro-1-thiocyanato-2-propene, which is characterized by the following.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The thiocyanate used in the present invention includes alkali metal salts such as sodium thiocyanate and potassium thiocyanate; alkaline earth metal salts such as calcium thiocyanate and magnesium thiocyanate; ammonium thiocyanate And the like. Among them, sodium thiocyanate is preferred. The use amount of the thiocyanate is preferably in the range of 1.0 to 1.5 mol per 1 mol of 1,3-dichloropropene.

The reaction in the present invention is carried out in the presence of an organic solvent which is water-soluble and has a boiling point of 150 ° C. or lower. With a water-insoluble organic solvent, 3-chloro-1-thiocyanato-2-propene cannot be obtained in high yield (Comparative Example 1 described later).
reference). An organic solvent having a boiling point higher than 150 ° C., for example, dimethyl sulfoxide (boiling point: about 160 ° C.)
Is not suitable for industrial use because the recovery operation is complicated, and the yield of the desired product is as low as 47% (Journal f. P.
rakt. Chemie. Band 322, Heft 4, 1980, S, 629).

As the water-soluble organic solvent having a boiling point of 150 ° C. or less, nitriles such as acetonitrile and propionitrile; alcohols such as methanol, ethanol and propanol; and ketones such as acetone are used. These solvents may be used as a mixture of two or more kinds. More preferably, the boiling point of the solvent is 100 ° C. or lower. The amount of the solvent to be used is preferably 0.5 to 10 times by weight, more preferably 1.0 to 2.0 times by weight, based on the thiocyanate.

[0008] The reaction temperature is preferably in the range of 0 to 150 ° C, more preferably in the range of 20 to 80 ° C. The reaction time is
Although it depends on the reaction conditions, it is usually appropriate for 1 to 4 hours.

The thus obtained 3-chloro-1-
Isolation of thiocyanato-2-propene from reaction mixture
Purification is performed according to a conventional method. For example, after cooling the reaction mixture, the mixture is extracted with an organic solvent such as toluene, diethyl ether, methylene chloride, and ethyl acetate.The extract is washed with saturated saline, dried, concentrated under reduced pressure, and the concentrate is concentrated under reduced pressure. The separation and purification are performed by distillation, chromatography and the like.

[0010] 1,3-Dichloropropene as a raw material is mass-produced as a nematicide and is easily available at low cost.

3-Chloro-1- produced according to the present invention
Thiocyanato-2-propene is rearranged in the presence of a metal salt such as a copper salt, and the obtained 3-chloro-1-isothiocyanato-1-propene is allowed to react with a chlorinating agent to give 2-chloro-5-chlorobenzene. It can be converted to methyl-1,3-thiazole. 2-Chloro-5-chloromethyl-1,3-thiazole is useful, for example, as a synthetic intermediate of a hexahydrotriazine compound useful as an insecticide (see Japanese Patent Publication No. 6-776).

[0012]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and the like, but the present invention is not limited to these Examples.

EXAMPLE 1 2.14 g of sodium thiocyanate was added to acetonitrile 1
The solution was dissolved in 2 ml, and 2.66 g of 1,3-dichloropropene was added to the resulting solution and heated at a temperature at which acetonitrile was refluxed (80 to 82 ° C.) for 3 hours. The reaction mixture was cooled to room temperature, and acetonitrile was distilled off under reduced pressure. Water 2
After adding 0 ml, the mixture was extracted twice with 20 ml of ethyl acetate. The organic layer was washed with 20 ml of a saturated saline solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. next,
The concentrate was purified by distillation under reduced pressure to obtain 2.89 g of 3-chloro-1-thiocyanato-2-propene. Yield 88.4% pure: 98.1% boiling point: 83~88 ℃ / 5mmHg ¹ NMR- spectrum _{(CDCl 3) δ: 6.42 (} d, J = 7.0H
z, (cis)), 6.39 (d, J = 14.0Hz, (trans)), 6.06 (dt, J = 14.
0,7.8Hz, (trans)), 6.04 (dt, J = 7.0,7.0Hz, (cis)), 3.80
(d, J = 7.0Hz, (cis)), 3.59 (d, J = 7.8Hz, (trans))

EXAMPLE 2 2.14 g of sodium thiocyanate was added to 12 m of methanol.
, and 2.66 g of 1,3-dichloropropene is added to the resulting solution.
(66 ° C) for 3 hours. The reaction mixture was cooled to room temperature, and methanol was distilled off under reduced pressure. After adding 20 ml of water, the mixture was extracted twice with 20 ml of ethyl acetate. The organic layer was washed with 20 ml of a saturated saline solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Next, the concentrate was purified by distillation under reduced pressure to give 3-chloro-1-thiocyanato-2.
2.86 g of propene were obtained. Yield: 87.6% Purity: 98.2%

EXAMPLE 3 2.14 g of sodium thiocyanate was added to 12 ml of acetone.
, And 2.66 g of 1,3-dichloropropene is added to the resulting solution, and the temperature at which acetone refluxes (55 to 5).
(8 ° C.) for 5 hours. The reaction mixture was cooled to room temperature, and acetone was distilled off under reduced pressure. After adding 20 ml of water, the mixture was extracted twice with 20 ml of ethyl acetate. The organic layer was washed with 20 ml of a saturated saline solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Next, the concentrate was purified by distillation under reduced pressure to give 3-chloro-1-thiocyanato-2-.
2.72 g of propene were obtained. Yield: 83.1% Purity: 97.9%

Comparative Example 1 2.14 g of sodium thiocyanate and 1,3-dichloropropene in 12 ml of diisopropyl ether
66 g was added, and the mixture was reacted at a temperature at which diisopropyl ether was refluxed (68 to 70 ° C.) for 7 hours. Only the amount was obtained.

[0017]

According to the present invention, 3-chloro-1-thiocyanato-2-propene can be industrially advantageously produced in high yield.

Claims (1)

[Claims] 1. A reaction between 1,3-dichloropropene and a thiocyanate in the presence of a water-soluble organic solvent having a boiling point of 150 ° C. or less, 3-chloro-1-thiocyanato-2-propene. Manufacturing method.