JPH1045710A - Production of 3-chloro-1-thiocyanate-2-propene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially and readily obtain the subject compound useful as a synthetic intermediate for agrochemicals in a high yield by using a specific catalyst when 1,3-dichloropropene is reacted with a thiocyanic aid salt in an organic solvent. SOLUTION: 1,3-Dichloropropene is reacted with a thiocyanic acid salt in an organic solvent in the presence of a phase transfer catalyst. A quaternary ammonium salt, a quaternary phosphonium salt, especially tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride, etc., is preferable as the phase transfer catalyst. The phase transfer catalyst is preferably used in an amount of 0.001-0.01mol based on 1mol 1,3- dichloropropene. The organic solvent includes e.g. diisopropyl ether or toluene. 3-Chloro-1-thiocynate-2-propene is useful as a synthetic intermediate for hexahydrotriazine compound useful as an insecticide.

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 agricultural chemicals 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). , He
ft 4, 1980, S, 629).

[0003]

However, the yield of 3-chloro-1-thiocyanato-2-propene in the above method is as low as 47%, and such a method is not an industrially advantageous production method. Thus, the purpose of the present invention is
An object of the present invention is to provide a method for producing 3-chloro-1-thiocyanato-2-propene industrially easily and in a high yield.

[0004]

According to the present invention, the object is to react 1,3-dichloropropene with thiocyanate in an organic solvent in the presence of a phase transfer catalyst. This is achieved by providing a process for producing 3-chloro-1-thiocyanato-2-propene.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The thiocyanate used in the reaction of the present invention includes, for example, alkali metal salts such as sodium thiocyanate and potassium thiocyanate; alkaline earth metal salts such as calcium thiocyanate and magnesium thiocyanate; And ammonium thiocyanate. Among them, it is preferable to use sodium thiocyanate. 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 organic solvent used in the present invention is not particularly limited as long as it does not adversely affect the reaction. For example, hydrocarbons such as benzene, toluene, hexane, heptane and octane; dichloromethane, chloroform, carbon tetrachloride, 1,4 Halogenated hydrocarbons such as 2-dichloroethane and 1,1,2,2-tetrachloroethane; ethers such as diethyl ether, diisopropyl ether, dimethoxyethane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and cyclohexanone; acetonitrile, propionitrile and the like Nitrile; alcohols such as methanol, ethanol, and propanol; and dimethyl sulfoxide. The amount of the organic solvent used is preferably 0.5 to 10 times by weight of the thiocyanate, and
2.0 times by weight is more preferable.

Further, by using an excess of 1,3-dichloropropene as a reaction substrate, the reaction substrate can also serve as a solvent.

The reaction in the present invention is carried out in the presence of a phase transfer catalyst. By using a phase transfer catalyst, 3-chloro-1-thiocyanato-2-propene can be produced in high yield. For example, when dimethyl sulfoxide is used as a solvent, the yield is 47% without using a phase transfer catalyst, whereas the yield is improved to 70% when a phase transfer catalyst is used (see the above-mentioned Journal f. Prakt). . Ch
emie. Band 322, Heft4, 1980, S, 629 and Example 3 described later). In the case of diisopropyl ether,
The reaction hardly proceeds without the use of a phase transfer catalyst, whereas the use of a phase transfer catalyst improves the yield to 82% (see Example 1 and Comparative Example 1 described later).

As the phase transfer catalyst, quaternary ammonium salts, quaternary phosphonium salts, especially tetramethylammonium chloride, tetraethylammonium chloride,
Tetrabutylammonium chloride and benzyltrimethylammonium chloride are preferred. The amount of the phase transfer catalyst to be used is usually in the range of 0.001 to 0.01 mol per 1 mol of 1,3-dichloropropene.

[0010] 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.

[0011] 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.

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).

[0014]

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 In 12 ml of diisopropyl ether, 2.14 g of sodium thiocyanate and 2.66 of 1,3-dichloropropene were used.
g and tetraethylammonium chloride 33mg
And the temperature at which diisopropyl ether refluxes (68
(-70 ° C) for 3 hours. The reaction mixture was cooled to room temperature, and the precipitated salts were filtered. The filtrate was washed with saturated saline 20
Washed with ml, dried over anhydrous sodium sulfate and concentrated under reduced pressure. Next, the concentrate was purified by distillation under reduced pressure,
2.71 g of -chloro-1-thiocyanato-2-propene
I got Yield: 82.7% Purity: 97.9% 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 To 20 ml of toluene was added 2.14 sodium thiocyanate.
g, 2.66 g of 1,3-dichloropropene and 43 mg of tetrabutylammonium chloride were added, and the mixture was heated at a temperature at which toluene refluxed (80 to 85 ° C.) for 5 hours.
The reaction mixture was cooled to room temperature, and 20 ml of water was added to dissolve the salts. The organic layer was separated, washed with 20 ml of saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Next, the concentrate was purified by distillation under reduced pressure,
-Chloro-1-thiocyanato-2-propene 2.59 g
I got Yield: 78.6% Purity: 97.4%

Example 3 In 20 ml of dimethyl sulfoxide, 2.14 g of sodium thiocyanate and 2.66 g of 1,3-dichloropropene were used.
And 43 mg of tetrabutylammonium chloride, and the mixture was reacted at 25 to 30 ° C. for 3 hours. 100 ml of water and 100 ml of isopropyl ether were added to the reaction mixture, and the mixture was stirred and allowed to stand, and the organic layer was separated.
After washing with 0 ml, it was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Next, the product is purified by distillation under reduced pressure.
-Chloro-1-thiocyanato-2-propene 2.41 g
I got Yield: 73.0% Purity: 97.2%

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.

[0019]

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

Claims (1)

[Claims] 1. A reaction between 1,3-dichloropropene and thiocyanate in an organic solvent in the presence of a phase transfer catalyst in 3-chloro-1-thiocyanato-2.
-A process for producing propene.