JPS6150954A - Production of alpha-cyanobenzyl ester compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an agricultural insecticide in high yield in high purity, by adding both a tertiary amine and a phase transfer catalyst to a reaction system of an acid chloride or an acid anhydride, an aldehyde, and an alkali metal cyanide compound. CONSTITUTION:An acid halide shown by the formula I (X is Cl, Br, or group shown by the formula II; R is group shown by the formula III - formula V) or an acid anhydride is reacted with a compound shown by the formula VI and an alkali metal cyanide (e.g., KCN) in a two-phase solvent of an inert organic solvent (e.g., toluene)-water in the presence of both a tertiary amine (e.g., TEA) and a phase transfer catalyst (e.g., tetrabutylammonium halide) to give the aimed compound shown by the formula VII. Addition of the tertiary amine and the phase transfer catalyst to the reaction system makes a reaction rate high, improves extremely purity, and the prepared compound can be used industrially without purifying it. Amounts of the tertiary amine and the phase transfer catalyst are 0.5-6mol%, and 0.01-0.5mol% based on the compound shown by the formula VI, respectively.

Description

Detailed Description of the Invention The present invention is an acid halide or an acid anhydride represented by the formula % (1) (wherein X represents a chlorine atom, a bromine atom, or -6-S-□) A formula characterized by reacting a compound and an alkali metal cyanide in a two-phase bath medium of an inert organic solvent and water in the presence of a tertiary amine and a phase transfer catalyst (in the formula, R has the same meaning as above) ) denoted by α−
This invention relates to a method for producing a cyanobenzyl ester compound.

The method of reacting an acid chloride or acid anhydride with an aldehyde and an alkali metal cyanide in the presence of a phase transfer catalyst in a two-phase system of inert solvent and water to obtain the corresponding ester is well known, and there are various examples. (For example, Japanese Unexamined Patent Publication No. 55-
No. 133349). However, this reaction not only leads to the target product through the route (5) below, but also produces by-products through the routes (B) and (q).

C) (In the formula, R' and R' represent an alkyl, cycloalkyl, or phenyl group that may have a substituent.) Therefore, the final product consists of the above-mentioned by-products and unreacted acid in addition to the desired ester. A mixture of chloride, aldehyde and carboxylic acid was formed, and a highly pure ester could not be obtained. Furthermore, because the product is a viscous oil, common purification methods such as recrystallization or distillation are difficult, and purification by column chromatography is also complicated.

Therefore, there has been a desire for a manufacturing method that can produce products of high purity that can be used industrially without a purification step.

The present inventor further added a catalytic amount of tertiary amine to this reaction system to accelerate the reaction rate and to obtain industrially high-purity α-α without purification steps such as column chromatography.
It has been found that cyanobenzyl ester can be obtained in high yield.

For example, the purity of α-cyanobenzyl ester after liquid separation, drying, and am operation after reacting aldehyde, acid chloride or acid anhydride, and sodium cyanide in a toluene-water two-phase system is If neither the transfer catalyst nor the tertiary amine is added, the reaction will not be completed and the purity after completion will be 9.
It was 1.9%. Further, in the presence of 0.05% mole of tetrabutylammonium bromide (phase transfer catalyst), the reaction proceeded rapidly, but the purity was 92.8%.

However, in the presence of 0.05% mole of tetrabutylammonium bromide and 4% mole of tributylamine (tertiary amine), the reaction proceeded rapidly and the purity was significantly improved to 97.5%. It was found that it can be used industrially without purification.

Examples of the tertiary amine used in the present invention include trialkylamines (triethylamine, tripropylamine, tributylamine, dimethyloctylamine, bicyclotriethylenediamine, etc.), N,N-dialkylaniline (N.

N-dialkylaniline, N,N-diethylaniline, etc.), 2,6-dialkylpyridine (2,6-dimethylpyridine, etc.), or optically active amines (quinine, quinidine, ephedrine, etc.).

Examples of phase transfer catalysts include tetrabutylammonium halides (tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, etc.), benzyltriethylammonium chloride,
Examples include trioctylmethylammonium chloride.

Furthermore, in the present invention, a formula having a quaternary ammonium group and a tertiary amino group in the same molecule (in the formula R, , R2, R
3 and Uma represent an alkyl group, an alkyl-substituted phenyl group, or a phenyl group, Shio represents a halogen ion, and n is 1 to
A compound represented by (representing an integer of 6) can also be used in place of the above-mentioned tertiary amine and phase transfer catalyst.

Examples of the alkali metal cyanide used in the present invention include sodium cyanide and potassium cyanide.

In addition, examples of the inert organic 6 medium include toluene, benzene, xylene, hegetane, cyclohexane, hexane,
Examples include methylene chloride, chloroform, and ethyl acetate.

In the present invention, the amount of the tertiary amine used is preferably 0.5 to 6 mol % based on the compound of formula (2), and the amount of the phase transfer catalyst used is preferably 0.5 to 6 mol % based on the compound of formula (2).
01 SO, 5 moles. In addition, the molar ratio of the tertiary amine to the phase transfer catalyst is preferably 40 to 120 (tertiary amine/phase transfer catalyst).As shown in the figure, since it has two asymmetric carbon atoms, it is a mixture of four optical isomers. However, by high performance liquid chromatography, H-α-cyano-m-
Phexybenzyl(-1-)-2,2-dichloro-1
-(ρ-ethoxyphenyl)cyclopropanecarboxylic acid ester (A form) and (±-α-cyano m-phenoxybenzyl (→-2.2-dichloro#-1-(p-ethoxyphenyl)cyclopropanecarboxylic acid ester) (8 bodies)
The peak of the compound (AB form) of ) and (→-α-cyano m-phenoxybenzyl H-2,2-dichloro-1-(ρ-ethoxyphenyl)cyclopropanecarboxylic acid ester (D
It can be divided into two peaks: the peak of the isocene compound (CD body) and the peak of the isocene compound (CD body). This ester has a diastereomer ratio of CAB form/CD form (less than 2) of 1:1 in the absence of a catalyst as well as in the presence of a phase transfer catalyst such as a 94-grade ammonium salt.
However, trialkylamine was added.

When added, the diastereomer ratio was 1.2 Sl, 8 depending on the amount of trialkylamine, and more AB form was produced. This diastereomer causes ebimerization in the container, resulting in a mixture with a diastereomer ratio of 1:1.

is known to exhibit high insecticidal activity and to be useful as an agricultural insecticide (Japanese Patent Publication No. 55-21011).

For example, it is highly effective against leafhoppers, rice weevils, white cabbage butterflies, green peach aphids, armyworms, diamondback moths, black beetles, brown borers, scarab beetles, and soybean sink beetles.

All compounds represented by formula (3) obtained in the present invention are useful as insecticides.

The compound of formula (1), which is the raw material of the present invention, is prepared by a known method using a halogenating agent such as thionyl chloride, trichloride, etc. In the case of an acid anhydride, the compound represented by formula (5) can be obtained by, for example, DC
It can be obtained by heating in an organic solvent in the presence of a dehydrating agent such as C (dicyclohexylcarboxydiimide).

Example 1 ゜m-phenoxybenzaldehyde 20.25P (purity 9
8%, 0.1 mol) and 5 ml of toluene were dissolved in sodium cyanide (5,451 P, 90% pure, 0
．． (103 mol) solution and stirred.

2.2-Dichloro-3-(4-ethoxyphenyl)cyclopropanecarboxylic acid chloride 30.90? (Purity 9
6.91%, 0.102 mol), tetrabutylammonium bromide 16rn9 (0.05 mmol), tributylamine 960d (4 mmol) and toluene 20 ml
A mixed solution was added dropwise over a period of 2 hours at -2°C to 0°C. After stirring for 2 hours at o℃, toluene 15
0mA! Add the toluene layer to 10% caustic soda aqueous solution 5
0++/, 50me of 5% hydrochloric acid, 50ml of saturated saline
Washed with. The toluene layer was dried over anhydrous sodium sulfate, 5J of powdered silica gel was added, filtered and concentrated under reduced pressure to obtain 3-phenoxy-α-cyanobenzyl 2 as a pale yellow oil.
．． 2-dichloro-3-(4-ethoxyphenyl)cyclopropanoic acid ester was obtained. Crude i45.55' (crudeness rate 93.6%), and purity was determined by quantitative determination by high performance liquid chromatography. (Stationary phase Radial Pach
A, Waters 'C-18' mobile phase CH3CN/
l-120=80/20 (V/V), flow rate 2.0 ml
/min), and the purity was 97.5%. Moreover, the ratio of the two diastereomers was 1.37.

Example 2 The amount of tetrabutylammonium bromide and tributyl/L/7 min used was 3.2 mty (0.01 mIJ).
The same procedure as in Example I above was carried out, except that 192# (0.8 mmol) and 192# (0.8 mmol) were used. Rough: 1-46
．． 75' (coarseness rate 96.6%), purity was 96.9%.

Moreover, the ratio of the two diastereomers was 1.3.

Example 3 10.3 mg (0.05 mmol) of 2-(N,N-diethylamino)ethyldiethylbenzylammonium chloride was added in advance to a mixture of aldehyde and sodium cyanide, and tetrabutylammonium bromide and tributylamine were added in advance. The same operation as in the above example was carried out except that neither of the two and - were used.

Roughness: 46.6P (Roughness: 95.8%). Purity is 94.
It was 0%.

Example 4 In place of carboxylic acid chloride, 2,2-dichloro3-(4-x)xyphenyl)cyclopropanoic anhydride 57.155' (stripeness 95%, 0.102 mol) was used. Except for this, the same operation as in Example 1 above was performed. Coarse amount 45. IP (coarseness rate 93.4%) purity is 95
．． It was 3%.

Reference Example 1 The same operation as in Example 1 above was carried out except that neither tetrabutylammonium bromide nor tributylamine was used and the reaction time was 20 hours at room temperature.

Crude amount: 45.4P (crudeness: 93.4%), purity: 91.
It was 9%.

Reference Example 2゜Example 1 above except that tributylamine was not used.
The same operation was performed.

Coarse amount 43.45' (coarse rate 89.8%), purity 92
．． It was 8%.

Reference Example 3 The same operation as in Example 1 above was carried out except that tetrabutylammonium bromide was not used.

Crude amount: 42.7P (crudeness: 88.4%), purity: 93.
It was 0%. Also, the ratio of the two diastereomers is 1.7
It was 5.

Reference example 4゜Example 4 above except that tributylamine was not used.
The same operation was performed.

Roughness: 45.25' (Roughness ratio: 93.5). Purity is 90
．． It was 2%.

Claims (1)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, X represents a chlorine atom, a bromine atom, or ▲ There are mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates. ) and the compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) and the alkali metal cyanide in a two-phase solvent of inert organic solvent and water. α-cyano expressed by the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, R means the same as above.) Method for producing benzyl ester compounds.