JP2000264884A - Production of 3-cyanotetrahydrofuran - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for readily producing 3-cyanotetrahydrofuran useful as an intermediate for a medicine, an agrochemical or the like, and an electrolyte for a nonaqueous electrolyte secondary battery in high selectivity by reacting ethylene oxide with acrylonitrile in the presence of a catalyst. SOLUTION: Ethylene oxide is reacted with acrylonitrile in the prepence of a catalyst to provide the objective compound. The catalyst is preferably an iodine compound and/or crown ethers (e.g. 12-crown-4-ether). The iodine compound is a metal iodide (e.g. an alkali metal iodide), an ammonium iodide (e.g. tetrapentylammonium iodide), a phosphonium iodide (e.g. tetrabutylphosphonium iodide) and hydrogen iodide. The catalyst can be used singly or in combination. The reaction can be carried out by using a solvent (e.g. tetrahydrofuran). The reaction temperature is preferably 100-180 deg.C, and the reaction time is preferably 1 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel process for producing 3-cyanotetrahydrofuran. 3-Cyanotetrahydrofuran is useful as an intermediate for pharmaceuticals, agricultural chemicals and the like, and is also useful as an electrolyte for non-aqueous electrolyte secondary batteries.

[0002]

2. Description of the Related Art 3-Cyanotetrahydrofuran is a known substance, and its production method is described in the literature. However, only one such method is known. The method is a method in which tetrahydrofuran and chlorocyan are irradiated with ultraviolet rays in the presence of sodium bicarbonate (German Patent 1234).
No. 227, Chem. Ber. 96 (9), 2319
(1963)).

[0003]

However, this method has a very low conversion, the main product is 2-cyanotetrahydrofuran, and the target 3-substituted product is only 1/10 of the 2-substituted product. The lack of this is specified in the literature.

As described above, the method for producing 3-cyanotetrahydrofuran is a reaction having a very low selectivity for a target substance. In addition, an industrially unsuitable manufacturing method called ultraviolet irradiation is used.

An object of the present invention is to provide a method for producing 3-cyanotetrahydrofuran easily and with high selectivity.

[Means for Solving the Problems]

The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that industrially inexpensive and widely used ethylene oxide and acrylonitrile with high selectivity to 3-
The present inventors have found that it is possible to produce a substituted product, and have completed the present invention.

That is, the present invention is characterized by reacting ethylene oxide with acrylonitrile in the presence of a catalyst.

Embedded image This is a method for producing 3-cyanotetrahydrofuran represented by the following formula:

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Ethylene oxide and acrylonitrile used as raw materials of the present invention are commercially available and can be easily obtained. Typical examples of the catalyst used in the present invention include iodine compounds and crown ethers. The iodine compound used here is a metal iodide, an ammonium iodide, a phosphonium iodide, or hydrogen iodide.

Examples of the metal iodide include alkali metal iodide, zinc iodide, magnesium iodide, potassium iodide and the like. Examples of ammonium iodide salts include tetrapentylammonium iodide, tetrahexylammonium iodide, tetraoctylammonium iodide and the like. Examples of the phosphonium iodide salt include tetrabutylphosphonium iodide, triphenyl (methyl) phosphonium iodide, and triphenyl (hexyl) phosphonium iodide. Examples of crown ethers include 12-crown-
4-ether, 15-crown-5-ether, 18-
Crown-6-ether and the like.

The above mentioned catalysts may be used alone or in combination. Typical examples of the combination include a crown ether and an iodide salt, an iodide salt and an ammonium iodide salt, and an iodide salt and a phosphonium iodide salt.

The reaction is usually carried out without a solvent, but a solvent may be used. Solvents used include tetrahydrofuran, dioxane, dichloromethane, dichloroethane, acetone, methyl ethyl ketone, acetonitrile,
N, N-dimethylformamide, 1,3-dimethyl-2
-Imidazolidinone, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol,
Ethylene glycol and the like. These solvents can be used as a mixture in any ratio.

The reaction temperature is usually preferably 10 ° C. or higher, particularly preferably 100 to 180 ° C. The reaction time is generally between 0.1 and 24 hours, but is preferably 1 hour.

The reaction can be carried out at normal pressure or under pressure.

[0014]

The contents of the present invention will be specifically described below with reference to examples and comparative examples. The analysis conditions by gas chromatography are as follows. Filler DB-WAX detection method FID

Example 1 0.19 g of 18-crown-6-ether, 0.12 g of potassium iodide and 0.23 g of zinc iodide were dissolved in 20 g of acrylonitrile. The reaction solution was heated to 130 ° C. in a 70 ml autoclave made of SUS, and 5 g of ethylene oxide was added.
And stirred for 1 hour. After cooling, the reaction mixture was analyzed by gas chromatography to find that the selectivity for 3-cyanotetrahydrofuran was 100%.

Example 2 In 20 g of acrylonitrile, 0.43 g of tetra-n-octylammonium iodide and 0.23 g of zinc iodide were dissolved. The reaction solution was heated to 130 ° C. in a SUS 70 ml autoclave, charged with 5 g of ethylene oxide, and stirred for 1 hour. After cooling, the reaction mixture was analyzed by gas chromatography to find that the selectivity for 3-cyanotetrahydrofuran was 100%.

Example 3 In 20 g of acrylonitrile, 0.31 g of methyltriphenylphosphonium iodide and 0.23 g of zinc iodide were dissolved. The reaction solution was placed in a SUS 70 ml autoclave for 1 hour.
The temperature was raised to 30 ° C., and 5 g of ethylene oxide was charged and stirred for 1 hour. After cooling, the reaction mixture was analyzed by gas chromatography to find that the selectivity for 3-cyanotetrahydrofuran was 1
00%.

Comparative Example 1 Acrylonitrile (20 g) was heated to 130 ° C. in a SUS 70 ml autoclave, charged with 5 g of ethylene oxide, and stirred for 1 hour. After cooling, the reaction solution was analyzed by gas chromatography. As a result, a trace amount of a polymer was formed, and 3-cyanotetrahydrofuran was not contained.

Comparative Example 2 1.14 g of copper (I) chloride was dissolved in 20 g of acrylonitrile. The reaction solution was heated to 130 ° C. in a SUS 70 ml autoclave, charged with 5 g of ethylene oxide, and stirred for 1 hour. After cooling, the reaction solution was analyzed by gas chromatography. As a result, a trace amount of a polymer was formed, and 3-cyanotetrahydrofuran was not contained.

[0020]

As described above, according to the method of the present invention, 3-cyanotetrahydrofuran, which is useful as an intermediate for pharmaceuticals and agricultural chemicals, can be produced from a very inexpensive raw material. Moreover, a 3-position-substituted product can be selectively obtained, which is particularly excellent as a production method.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kyokichi Watanabe 1-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. F-term (reference) 4C037 DA13 4H039 CA42 CH40

Claims (2)

[Claims] 1. A compound of the formula (1) wherein ethylene oxide and acrylonitrile are reacted in the presence of a catalyst. A method for producing 3-cyanotetrahydrofuran represented by the formula: 2. The method according to claim 1, wherein the catalyst is an iodine compound and / or crown ethers.