JPS5828263B2 - 3 3-dimethyl-2-(2 2-dihalovinyl) cyclopropane carbonate ester - Google Patents

Description

Detailed Description of the Invention The present invention is a group represented by the general formula (wherein R is a group represented by the general formula, and Y is 10- or CH=C
H-, R1 is a hydrogen atom, a phenoxy group or a benzyl group, and X is the same or different halogen.

) The present invention relates to a method for producing 3,3-dimethyl-2-(2,2 dihalobinyl)cyclopropanecarboxylic acid ester.

More specifically, the present invention relates to the general formula [In the above general formula, be.

] γ or general formula halocarboxylic acid ester, R and X are the same as above. young [In the above general formula, R is the same as above.

] to the γ-unsaturated carboxylic acid ester represented by the general formula (In the formula, X is the same or different...logen.

) The γ-no-locarponic acid ester represented by the general formula (II), which is formed by adding a carbon tetrahalide represented by the formula (II) under radical reaction conditions, is treated with a base, 3 represented by (I)
- It relates to a method for producing 3-dimethyl-2-(2,2-dihalobinyl)cyclopropanecarboxylic acid ester.

3,3-dimethy/L/- represented by the above general formula (I)
2-(2,2-dihalobinyl)cyclopropanecarboxylic acid ester is a compound that has attracted attention for its usefulness as an insecticide.
,, Nature, 246.169 (1973) Conventionally, as a method for producing this 3,3-dimethyl-2-(2,2-dihalobinyl)cyclopropanecarboxylic acid ester, 3,3-dimethyl-2(2, A method has been proposed in which a lower alkyl ester of cyclopropanecarboxylic acid (2-dihalobinyl) is hydrolyzed, then converted into an acid halide, and then reacted with a desired alcohol.

[Refer to JP-A-4947531] However, in this conventional method, lower alkyl ester of 3,3-dimethyl-2-(2,2-dihalovinyl)cyclopropanecarboxylic acid must be first synthesized as a raw material, and The disadvantage is that the reaction steps are long, such as via an acid/ride, and moreover, an equivalent amount or more of a base such as an amine is required for esterification.

Alternatively, after hydrolyzing ethyl 3,3-dimethyl-2-(2,2-dibromvinyl)cyclopropanecarboxylate, it is dehydrated and condensed with 5-benzyl-3-furylmethyl alcohol using dicyclohexylcarbodiimide. A CD that also suggests ways to do this.

Brown et alj, Agr, Food
Chem, 21°767 (1973)].

However, this method also requires expensive reagents for esterification and is difficult to employ industrially.

As a result of intensive studies aimed at solving these drawbacks of conventional methods, the present inventors have discovered a novel compound, 3,3-dimethyl-4halo-5-trihalomethylyethyloxychloride, represented by the general formula (n). It is possible to synthesize 3,3-dimethyl-2(2,2-dihalobinyl)cyclopropanecarboxylic acid ester represented by general formula (I), which is attracting attention for its usefulness as an insecticide, from grass acid ester in one step. We have now completed an industrially advantageous method for producing the cyclopropane carboxylic acid ester.

The γ-unsaturated carboxylic acid ester represented by the general formula (■') used as a raw material in the method of the present invention is, for example, γ
- Can be easily produced in one step from lower alkyl esters of unsaturated carboxylic acids (see reference side below).

Examples of the other starting material, carbon tetrachloride, include carbon tetrachloride, carbon tetrabromide, carbon trichloride bromide, carbon dichloride dibromide, and carbon trifluoride iodide. I can do it.

These carbon tetrahalides are compounds used as industrial raw materials and are easily available.

γ-... represented by the general formula (n) in the present invention
It is essential that the step of forming the locarboxylic acid ester be carried out under radical reaction conditions.

Radical reaction conditions are those that can be achieved by the presence of a radical reaction initiator or by irradiation with light.

Examples of radical reaction initiators include azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), acetyl peroxide, di-t-butyl peroxide, t-butyl peracetate, t-butyl perbenzoate, and peroxide. t-butyl phthalate,
Examples include 1-butyl hydroperoxide, combinations of transition metal compounds and amines, transition metal compounds and phosphite esters, and catalysts with halogen abstraction ability such as transition metal carbonyl compounds.

It is sufficient to use a so-called contact amount of these radical reaction initiators.

In the reaction, equimolar amounts of the starting compounds are used, and no solvent is particularly required, but if desired, a solvent that does not directly participate in the reaction,
For example, alcohols such as carbon disulfide N-N-dimethylformamide, acetonitrile, ethanol, propatool, etc., or hydrocarbon solvents such as benzene may be used.

In addition, when a liquid substance such as carbon tetrachloride is used as a rogogenating agent, a large amount of the liquid substance itself can be used to carry out the reaction.

When using light as a radical reaction initiation method, it is preferable to carry out the reaction at room temperature and 100°C, and when using other radical initiators, it is preferable to carry out the reaction at 70°C to 150°C.

In the second step of the present invention, it is essential to treat the r-halocarboxylic acid ester represented by the general formula (II) with a base.

Examples of the base include sodium hydroxide, potassium hydroxide, alkali metal alkoxides, alkali metal hydrides, and alkali metal amides, but alkali metal alkoxides are preferably used because of their high reaction efficiency.

The amount of the base used is 1.5 molar equivalents or more, preferably 2 to 5 molar equivalents, based on the raw material.

The reaction is preferably carried out in a solvent, and examples of the solvent include alcohols such as t-amyl alcohol and t-butanol, ethers such as ether and tetrahydrofuran, benzene,
Examples include hydrocarbons such as toluene, N.N-dimethylformamide, and the like.

The reaction temperature is preferably room temperature or the reflux temperature of the solvent from the viewpoint of ease of operation.

The present invention will be explained in more detail below using Examples and Reference Examples.

Example 1 245 μm of m-phenoxybenzyl ester of 3,3-dimethyl-4-pentenoic acid was dissolved in 5 ml of carbon tetrachloride,
The mixture was placed in a pressure-resistant tube, 2 μm of benzoyl peroxide was added thereto, the atmosphere was replaced with argon, the tube was tightly stoppered, and the mixture was heated to 140°C.

After 5 hours, 2 parts of benzoyl peroxide was added and the mixture was kept at 140°C for an additional 5 hours.

After this, add 2■ benzoyl peroxide twice every 5 hours,
After heating at 140°C for a total of 20 hours, the mixture was cooled, washed with water, aqueous sodium bicarbonate, and water, and then dried over anhydrous magnesium sulfate.

After distilling off the solvent, it was purified by silica gel column chromatography (benzene) to obtain pure 3,3-dimethyl-4-
m-phenoxybenzyl ester of chloro-5 trichloromethylvaleric acid was obtained as 3001T9.

Yield 82% Nuclear magnetic resonance spectrum of product (CCI4, δ) 7.3
5-7.05 (m14H), 7.05-6.75 (
m, 5H), 4.96 (s, 2H), 4.30
(d, d, IH), 3.30-2.80 (m, 2
H), 2.57 (d, LH), 2.26 (a.

IH), 1.15 (s, 3H), 1.07 (s.

3H) Example 2 200 μm of m-phenoxybenzyl ester of 3,3-dimethyl-4-chloro-5-trichloromethylvaleric acid was dissolved in 1 ml of anhydrous tetrahydrofuran, and the solution was suspended with 124 μm of sodium butoxide under water cooling. The mixture was added dropwise to 5rI'Ll of anhydrous tetrahydrofuran.

1! After a period of f, the mixture was returned to room temperature, stirred for an additional hour, and then neutralized with an anhydrous ether solution of hydrogen chloride.

The mixture was poured into ice water, extracted with ether, and dried over anhydrous magnesium sulfate.

After evaporating the solvent, it was purified by silica gel column chromatography (benzene) to obtain pure 3,3-dimethyl-2-(2,2-
m-phenoxybenzyl ester of cyclopropanecarboxylic acid (dichlorovinyl) in 126 ml.

Yield 75%.

Nuclear magnetic resonance absorption spectrum (CCI δ) of the product7.
50-6.80 (m, 9H), 6.25 (bd), 5
．． 60 (d, IH), 5.05 (s, 2H), 2.40
~1.40 (m, 2H), 1.40~1.05 (
m, 6H) Example 3 5-benzyl-3-furylmethyl ester of 3,3-dimethyl-4-bromo-5-toIJ from methylvaleric acid 5
85 mg was dissolved in 3 liters of anhydrous t-butanol.

This solution was mixed with anhydrous t-chloride in which 70 m9 of metallic sodium was dissolved.
The mixture was added dropwise to 40 ml of butanol, and the mixture was further stirred at room temperature for 3 hours.

Thereafter, the mixture was neutralized with an ether solution of hydrogen chloride, poured into ice water, and extracted with ether.

By distilling off the solvent, 3,3-dimethyl-2-(
5-benzyl-3furylmethyl ester of 2,2-dibromvinyl)cyclopropanecarboxylic acid 154TnJi
I got /.

Yield 35%.

This product was recrystallized from n-hexane to obtain a pure trans isomer having a melting point of 65°C.

Nuclear magnetic resonance absorption spectrum of product (CDC13, δ)
7.07 (m, 6H), 6.01 (d, IH), 5
．． 89 (s, IH), 4.81 (s, 2H)
, 3.85 (s, 2H), 2.12 (ml 1H)
, 1.57 (dl 1H), 1.20 (s, 3H)
, 1.12 (s13H) Reference example 1 ethyl 3,3-dimethyl-4-pentenoate 3741nI
? 400 m9 of m-phenoxybenzyl alcohol was placed in a reaction flask, dissolved in 10 ml of dry toluene, and 16 ml of sodium ethoxide was added. A Dean-Stark reactor was attached and the mixture was heated under vigorous reflux for 24 hours.

Thereafter, the mixture was neutralized with an ether solution of hydrogen chloride, poured into water, extracted with ether, and dried.

After distilling off the solvent, reduce the boiling point to 155-158°C by distillation under reduced pressure.
m-phenoxybenzyl ester of 3,3-dimethyl-4-pentenoic acid with 0.3 miHg 520m9
I got it.

Yield 70%.

Nuclear magnetic resonance absorption spectrum of product (CC14, δ)7
．． 32-7.08 (m, 4H), 7.05-6.70
(m15H), 5.76 (d, d, IH), 4
．． 92 (S, 2H), 4.96-4.70 (m.

2H), 2.22 (3, 2H), 1.08 (s, 6H) Reference Example 2 Except for using Reference Example 1, 810 μm of benzyl alcohol was used instead of m-phenoxybenzyl alcohol, and the reaction scale was tripled. Perform the same operation to obtain a boiling point of 92~
1.01 of benzyl 3,3-dimethyl-4-ntenoate with a temperature of 98° C./0.1 mmHg was obtained.

Yield 65%.

Nuclear magnetic resonance absorption spectrum of product (CC14, δ)7
．． 29 (b, s, 5H), 5.84 (d, d, 1)
(), 5.10-4.70 (m14H), 2.22 (
s12H), 1.06 (516H) Example 4 Benzyl 3,3-dimethyl-4-pentenoate 4361n
9 and 618 m9 of carbon tetrachloride were mixed and placed in a pressure tube.

Then, a solution of 440 ml of N-N-dimethylformamide, 38 ml of hexagonal salt of ferric chloride, and 41 ml of n-butylamine was added.

After replacing the inside of the tube with argon, the tube was tightly stoppered and heated to 120° C. for 8 hours.

After cooling, 50 ml of ether was added and washed with water, followed by washing with dilute hydrochloric acid, water, then aqueous sodium bicarbonate, and finally washing with water and drying.

After evaporating the solvent, it was purified by silica gel column chromatography (benzene) to obtain pure 3,3-dimethyl-4-chloro-5-
Benzyl trichloromethylvalerate 4707Q was obtained.

Yield 63% Nuclear magnetic resonance spectrum (CCI δ) of product 7.22
(b, s, 5H), 4.98 (s, 2H), 4.
31 (d, dllH), 3.32-2.80 (m.

2H), 2.58 (d, IH), 2.28 (d.

IH, ), 1.17 (s, 3H), 1.08 (s, 3H
) Example 5 335.7 ml of benzyl 3,3-dimethyl-4-chloro-5-trichloromethylvalerate was dissolved in 2 ml of anhydrous tetrahydrofuran.

This solution was added dropwise to 8 ml of anhydrous tetrahydrofuran in which 192 m9 of sodium t-butoxide was suspended while cooling with water.

After 2 hours, the temperature was returned to room temperature, and stirring was continued for an additional 30 minutes.

After neutralizing with a dry ether solution of hydrogen chloride while cooling with ice, the mixture was poured into ice water and extracted with ether.

It was washed with a sodium bicarbonate solution and a saline solution, and then dried.

After distilling off the solvent, the boiling point is 114-11 by distillation under reduced pressure.
3,3-dimethyl-2 with 10,13 Hg at 8°C
2101n9 of benzyl (2,2-dichlorovinyl)cyclopropanecarboxylate was obtained.

Yield 78%.

Nuclear magnetic resonance absorption spectrum (CCI4, δ) of the product 7
．． 22 (bs, 5H), 6.18-5.50 (d.

IH), 5.01 (S, 2H), 2.40-1.5
0 (m, 2H), 1.42-1.05 (m16H)
.

Claims (1)

[Scope of Claims] 1. 3,3-dimethyl-2-(2,2 dihalovinyl)cyclopropanecarboxylic acid represented by the general formula, which is characterized by treating a γ-halocarboxylic acid ester represented by the general formula with a base. Method for producing acid ester [
In the above general formula, R is a group represented by the general formula, where Y is 10- or CH=CH-, R1 is a hydrogen atom, phenoxy or benzyl group, and X is the same or different halogen It is. ]. 2 General formula C to the γ-unsaturated carboxylic acid ester represented by the general formula
3,3-dimethyl represented by the general formula, which is obtained by treating a γ-halocarboxylic acid ester represented by the general formula, which is formed by adding a carbon tetrahalide represented by X4 under radical reaction conditions, with a base. ~Production method of 2-(2,2 dihalobinyl)cyclopropanecarboxylic acid ester [
In the above general formula, R is a group represented by the general formula, where Y is or CH=CH-, R1 is a hydrogen atom, a phenoxy group or a benzyl group, and X is the same or different... It is. ].