JP2003160551A - Method for producing cyclopropane carbonitrile - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for economically and safely producing cyclopropane carbonitrile industrially in a high yield. <P>SOLUTION: This method comprises reacting cyclopropane carboaldehyde oxime with an acetic anhydride to obtain a mixed solution containing acetic acid and the cyclopropane carbonitrile, and removing the acetic acid from the mixed solution through azeotropic distillation by using a solvent which azeotropically boils with the acetic acid and has an azeotropic point with the acetic acid, which point is lower than the boiling point of the cyclopropane carbonitrile. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing cyclopropanecarbonitrile. The cyclopropanecarbonitrile obtained by the present invention is useful, for example, as a raw material for aminophenyl ketones, which is a raw material for a sulfamoylurea type herbicide known as a herbicide for paddy rice (see JP-A-7-188132). ).

[0002]

2. Description of the Related Art Conventionally, as a method for producing cyclopropanecarbonitrile, (1) a method of intramolecular cyclization of halobutyronitrile (US Pat. No. 3,853,942)
No. 5, US Pat. No. 5,380,911),
(2) A method in which cyclopropanecarbaldehyde is converted to cyclopropanecarbaldehyde oxime, which is dehydrated with formic acid to produce cyclopropanecarbonitrile, and the resulting reaction mixture is neutralized with an alkali metal compound (special Table 11-510487) is known.

[0003]

However, in the above method (1), expensive bromochloropropane must be used when synthesizing the starting halobutyronitrile, for example, 4-chlorobutyronitrile, Moreover, it is necessary to use a toxic cyanide in the nitration of bromochloropropane. Further, in the above method (2), it is necessary to neutralize the reaction mixture with an alkali metal compound after the dehydration reaction, which causes a problem of treating wastewater containing a large amount of by-produced alkali metal formate salt.

Therefore, an object of the present invention is to provide a method for producing cyclopropanecarbonitrile in good yield, economically, safely and industrially advantageously.

[0005]

That is, the present invention is a method for producing cyclopropanecarbonitrile characterized by reacting cyclopropanecarbaldehyde oxime with acetic anhydride.

In the present invention, cyclopropanecarbaldehyde oxime is reacted with acetic anhydride to obtain a mixed solution containing acetic acid and cyclopropanecarbonitrile, and the mixture is azeotropically distilled with acetic acid and co-evaporated with acetic acid. A method for producing cyclopropanecarbonitrile, characterized in that acetic acid is removed by azeotropic distillation using a solvent having a boiling point lower than that of cyclopropanecarbonitrile.

In a preferred embodiment of the invention, the above azeotropic removal of acetic acid is carried out by azeotropic distillation with acetic acid and the aliphatic or aromatic azeotrope with acetic acid is lower than that of cyclopropanecarbonitrile. With the hydrocarbon of.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclopropanecarbaldehyde oxime used in the present invention is easily produced, for example, by reacting cyclopropanecarbaldehyde with hydroxylamine. In the present invention, the cyclopropanecarbaldehyde oxime produced by the above method may be used as it is as a reaction mixture without purification, or may be purified. When cyclopropanecarbaldehyde oxime is used as the reaction mixture as it is, it is preferable to use a solvent that azeotropes with water, such as toluene, and remove the water from the reaction mixture by azeotropic distillation to use, from the viewpoint of improving the reaction rate. . Although cyclopropanecarbaldehyde oxime has cis and trans isomers, either one of the cis and trans isomers or a mixture of both can be used in the present invention. .

The amount of acetic anhydride used is preferably in the range of 0.5 to 20 times mol, and more preferably in the range of 1 to 5 times mol, of the cyclopropanecarbaldehyde oxime.

The reaction of the present invention can be carried out in the presence or absence of a solvent. Examples of the solvent include hexane, heptane, octane, 2,5-dimethylhexane,
Aliphatic or aromatic hydrocarbons such as cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, styrene, cumene; chlorobenzene, 1,2-
Halogenated hydrocarbons such as dichloropropane, 1,2-dibromopropane, butyl bromide, 1-bromo-3-methylbutane, propyl iodide, isobutyl iodide; diethyl ether, isopropyl ether, t-butyl methyl ether, 1, Ethers such as 4-dioxane; nitroethane, 1-butanol and the like are used. Among these, it is preferable to use aliphatic or aromatic hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene and cumene. When the solvent is used, the amount of the solvent used is preferably 50 times by mass or less, and more preferably 1 to 10 times by mass with respect to the cyclopropanecarbaldehyde oxime. The reaction is carried out in a solution state or a slurry state.

The reaction temperature is preferably in the range of 50 to 120 ° C. from the viewpoint of reaction rate, selectivity and the like, and 80
More preferably, it is in the range of 110 ° C. The reaction time is preferably about 3 to 20 hours.

The cyclopropanecarbonitrile can be separated from the reaction mixture thus obtained by distilling the reaction mixture as it is. However, in one embodiment of the present invention, a solvent that is azeotropic with acetic acid and has a lower azeotropic point with acetic acid than the boiling point of cyclopropanecarbonitrile is added to the above reaction mixture, and acetic acid is added first to the reaction mixture. Is preferably removed by azeotropic distillation and then the residue is distilled. Examples of the solvent which is azeotropic with acetic acid and whose azeotropic point with acetic acid is lower than the boiling point of cyclopropanecarbonitrile include, for example, hexane, heptane, octane, 2,5-dimethylhexane, cyclohexane, methylcyclohexane, toluene, xylene, and ethylbenzene. , Styrene, cumene and other aliphatic or aromatic hydrocarbons; chlorobenzene,
Halogenated hydrocarbons such as 1,2-dichloropropane, 1,2-dibromopropane, butyl bromide, 1-bromo-3-methylbutane, propyl iodide, isobutyl iodide; 1,4-dioxane, nitroethane, 1- Butanol and the like can be mentioned, but from the viewpoint of environment and safety, it is particularly preferable to use an aliphatic or aromatic hydrocarbon such as hexane, heptane, octane, toluene, xylene, ethylbenzene and cumene.

When the reaction of cyclopropanecarbaldehyde oxime and acetic anhydride is carried out in the presence of the above solvent, acetic acid produced can be removed by azeotropic distillation in parallel with the progress of the reaction.

The removal of acetic acid by azeotropic distillation can be carried out under normal pressure, but may be carried out under reduced pressure if necessary. The temperature in the system when it is carried out under reduced pressure varies depending on the pressure, but it is preferably in the range of 40 to 120 ° C.,
More preferably, it is in the range of 110 ° C.

Isolation and purification of cyclopropanecarbonitrile from the residue after removing acetic acid in this way
The organic compound can be isolated / purified by a general method, for example, by distillation under reduced pressure, and the purity can be easily increased.

[0016]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 Synthesis of cyclopropanecarbaldehyde oxime 500 m capacity equipped with stirrer, dropping funnel and thermometer
70.1 g (1.0 mol) of cyclopropanecarbaldehyde was placed in a four-necked flask having a volume of 1 and then 68.1 g of a 50 mass% hydroxylamine aqueous solution was added with stirring.
(1.0 mol) was added dropwise over 3 hours to maintain the temperature of the reaction mixture at 40 ° C. or lower. After the dropping was completed, the reaction mixture was stirred at room temperature for 3 hours. Crystallization of cyclopropanecarbaldehyde oxime was observed in the reaction mixture, so isopropyl ether 1.5 was added to the reaction mixture.
After L was added to dissolve the crystals, the organic layer and the aqueous layer were separated. The organic layer was concentrated under reduced pressure to give cyclopropanecarbaldehyde oxime 80.5 as crystals.
g was obtained (0.945 mol, yield 94.5%).

Example 1 Volume 50 ml equipped with stirrer, dropping funnel and thermometer
In a three-necked flask of 4.25 g (50 m of cyclopropanecarbaldehyde oxime obtained by the method of Reference Example 1).
mol) and 20 ml of toluene, and 5.6 g (55 mmol) of acetic anhydride was added dropwise to this solution over 5 minutes.
The obtained reaction mixture was heated to 105 to 110 ° C. and stirred for 9 hours. When the reaction mixture was analyzed by gas chromatography, it contained 3.18 g (47.5 mol) of cyclopropanecarbonitrile (yield 95%).

Example 2 500 m capacity equipped with stirrer, dropping funnel and thermometer
In a four-necked 1-liter flask, 140 g (2.0 mol) of cyclopropanecarbaldehyde and 140 ml of toluene
Then, 136.2 g (2.05 mol) of a 50 mass% hydroxylamine aqueous solution was added dropwise to this solution over 1 hour and 30 minutes so as to maintain the temperature of the reaction mixture at 20 to 25 ° C. After the dropping was completed, the temperature was raised to 40 ° C. and the mixture was stirred for 2 hours, then, the organic layer and the aqueous layer were separated. 40 g of water layer in toluene
And the extract was combined with the previously separated organic layer and transferred to a 1 L four-necked flask equipped with a stirrer, a dropping funnel and a thermometer. The organic layer was heated to 60 ° C., and 224.6 g (2.20 mol) of acetic anhydride was added dropwise over 50 minutes. After the completion of the dropping, the temperature of the reaction mixture is set to 105 to 11
After heating at 0 ° C for 7 hours, acetic anhydride 22.
5 g (0.22 mol) was added, and at the same temperature, 8
Heated for hours. When 580.5 g of the obtained reaction mixture was analyzed by gas chromatography, it was 125.4 g.
It contained (1.87 mol) of cyclopropanecarbonitrile (yield from cyclopropanecarbaldehyde: 93.5%).

Reference Example 2 Synthesis of cyclopropanecarbaldehyde oxime 500 m equipped with stirrer, dropping funnel and thermometer
1 in a 4-necked flask with hydroxylamine sulfate 41.
6 g (0.25 mol) and 128 g of water were added, and then 20.9 g (0.50 mol) of sodium hydroxide was added to neutralize. The mixture was stirred at room temperature for 30 minutes, 35 g of toluene was added, and then 35.05 g (0.50 mol) of cyclopropanecarbaldehyde was added to the mixture.
It dripped over minutes. After the dropping is completed, the reaction mixture is stirred at room temperature for 3 hours.
The mixture was stirred for an hour, heated to 50 ° C., and the organic layer and the aqueous layer were separated. When the organic layer was analyzed by gas chromatography, it contained 39.53 g (0.46 mol) of cyclopropanecarbaldehyde oxime (yield 92.
9%). Moreover, 2.97 g (0.035
mol) of cyclopropanecarbaldehyde oxime was contained (yield 7% equivalent: quantified by gas chromatography). After removing water from the above organic layer by azeotropic distillation with toluene, 69.8 g (52.4 mass%) of a toluene solution containing cyclopropanecarbaldehyde oxime was obtained.

Example 3 In a 500 ml four-necked flask equipped with a stirrer, a dropping funnel, a thermometer and a reflux condenser, 69.8 g of a toluene solution of the cyclopropanecarbaldehyde oxime obtained by the method of Reference Example 2 ( 52.4 mass%, 0.43mo
1) was added and heated to 55 ° C. Acetic anhydride 4 in this solution
6.2 g (0.45 mol) was added dropwise over 36 minutes, and then the obtained mixed liquid was heated to 105 to 110 ° C.
Stir for hours. When the obtained reaction mixture was analyzed by gas chromatography, it was found to be 27.53 g (0.41 m
ol) cyclopropanecarbonitrile (yield 95.4%).

Example 4 A 500 ml four-necked flask equipped with a stirrer, a dropping funnel with a volume of 50 ml, a thermometer and a Helipack distillation column (internal diameter 2.4 cm × length 26 cm) was placed in the same manner as in Example 3. 247.8 g of the obtained reaction mixture (containing 57.5 g of cyclopropanecarbonitrile) was added. While maintaining the temperature of the reaction mixture at 110 ° C. or lower, acetic acid was removed from the reaction mixture by azeotropic distillation with toluene under reduced pressure while appropriately adding toluene. The total amount of toluene added was 280 g. By distilling the residue as it is under reduced pressure, 9
Cyclopropanecarbonitrile with a purity of 9% or more 42.
6 g (0.62 mol) was obtained (yield after distillation: 72
%).

[0023]

INDUSTRIAL APPLICABILITY According to the present invention, cyclopropanecarbonitrile can be produced in good yield, economically, safely and industrially advantageously.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masahiro Torihara             2-28 Kurashiki-cho, Nakajo-cho, Kitakanbara-gun, Niigata Prefecture             Inside the ceremony company Kuraray (72) Inventor Yoshin Tamai             2-28 Kurashiki-cho, Nakajo-cho, Kitakanbara-gun, Niigata Prefecture             Inside the ceremony company Kuraray F-term (reference) 4H006 AA02 AC54 AD12 BB11

Claims (3)

[Claims] 1. A method for producing cyclopropanecarbonitrile, which comprises reacting cyclopropanecarbaldehyde oxime with acetic anhydride. 2. A cyclopropanecarbaldehyde oxime is reacted with acetic anhydride to obtain a mixed solution containing acetic acid and cyclopropanecarbonitrile, and the mixture is azeotropic with acetic acid and has an azeotropic point with acetic acid of cyclopropane. A method for producing cyclopropanecarbonitrile, which comprises removing acetic acid by azeotropic distillation using a solvent having a boiling point lower than that of carbonitrile. 3. A solvent which is azeotropic with acetic acid and whose azeotropic point with acetic acid is lower than that of cyclopropanecarbonitrile,
The production method according to claim 2, wherein the production method is an aliphatic or aromatic hydrocarbon.