JPH01287053A - Production of trans-chrysanthemum-monocarboxylic acids - Google Patents

Abstract

PURPOSE:To efficiently, industrially and advantageously obtain the subject compounds useful as an intermediate for pyrethroid based insecticides by reacting a mercapto compound with cis- or mixed cis/trans-chrysanthemum- monocarboxylic acids in the coexistence of a peroxide or azo compound. CONSTITUTION:An SH compound (preferably aromatic thiols, thiolcarboxylic acids, thiocarboxylic acids or dithio-acids) is reacted with cis- or mixed cis/trans- chrysanthemum-monocarboxylic acids expressed by formula I (X is OH, halogen, 1-20C alkoxy, aralkyloxy or 2,2-dimethyl-8-isobutenylcyclopropanecarboxyl) in the coexistence of a peroxide (preferably diacyl peroxides or peroxy esters) or an azo compound (preferably azonitriles or azo esters) and rearranged to the trans-isomer. Thereby, the trans-chrysanthemum-monocarboxylic acids having higher insecticidal effects than those of the cis-isomer are efficiently obtained by using the readily handleable SH compound normally used as an industrial raw material and stable even to water as the afore-mentioned intermediate.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention relates to a method for producing trans-chrysanthemum acids, and more specifically, the general formula (I) (wherein, X is a hydroxyl group, a halogen atom, or a carbon number of 1 to 20 alkoxy or aralkyloxy groups, or 2,
2-dimethyl-8-isobutenyl cyclopropanecarboxyl group. ) The corresponding trethrin, allethrin, by reacting with an SH compound in the presence of a cis or cis/trans mixed dichroic acid group, a peroxide or an azo compound,
It constitutes the acid component of esters that are well known as pyrethroid insecticides such as phthalthrin, and the chrysanthemum acids represented by the general formula (I) are used as intermediates for these pyrethroid insecticides. Useful.

Chrysanthemum acid has cis and trans geometric isomers, and it is known that the insecticidal effect of the trans ester is stronger than that of the cis ester. Therefore, converting the cis-isomer into a trans-isomer is much more advantageous in terms of insecticidal efficacy than using the cis-isomer or an ester containing a large amount of the cis-isomer.

Conventionally, primary chrysanthemum acid esters among secondary chrysanthemum acids have been industrially produced by a method of reacting 2,6-dimethyl-hexate 2,4-diene with diazoacetic acid ester as shown in the following formula 1. Furthermore, chrysanthemum acid, its halide, its anhydride, etc. are derived from the ester.

However, since the primary chrysanthemum acids obtained by this method are obtained as a mixture of the target product, trans and cis forms, the technology for converting cis or cis/trans mixed primary chrysanthemum acids into the trans form is of great significance. have

Conventionally, a method for converting a cis-m-acid ester into a trans-chrysanthemum acid ester involves adding a lower alkyl primary alkoxy group of an alkali metal to a cis-m-chrysanthemum acid ester in the presence of a lower alcohol at about 150°C. ~200
A method of acting at ℃ (Japanese Patent Publication No. 40-6457),
Alternatively, a method of treatment with a special basic catalyst (Special Publications Showa 5B)
-18495, Japanese Patent Publication No. 58-184968, etc.), and a method of reacting boron trifluoride etherate, iron chloride, aluminium chloride, etc. on cis-chrysanthemum acid ester (Japanese Patent Application Laid-open No. 176980/1982). )It has been known.

In addition, as a method for directly converting cis-chrysanthemum acid into trans-chrysanthemum acid, there is a method of heating cis-chrysanthemum acid at a temperature of 180°C or higher (!! It is said that trans-transformation can be achieved by reacting Tetrahedron Letters with a nitrile complex catalyst of palladium dichloride.
, 22, 885 (1981)), but the former requires heating to a high temperature and has a low 1ζ yield, and the latter requires a relatively large amount of expensive reagents.

The present inventors have made extensive studies to find an excellent method for producing trans-chrysanthemum acids, and as a result, the general formula (I)
To the cis-chrysanthemum acids or mixed cis/trans chrysanthemum acids represented by
It was discovered that the - layer can be smoothly and efficiently converted to the corresponding trans isomer by the action of a compound, and after various studies, the present invention was arrived at.

That is, the present invention relates to the general formula (I) (wherein, X is a hydroxyl group, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, or an aralkyloxy group, or
2-dimethyl-8-isobutenyl cyclopropanecarboxyl group. ) Industrially excellent trans-chrysanthemum acids, which are produced by reacting an SH compound with a peroxide or an azo compound to convert the cis or cis/trans mixed chrysanthemum acids represented by The present invention provides a method for manufacturing.

Next, the method of the present invention will be explained.

The compounds used as raw materials of the present invention and represented by the general formula CI) include tertiary chrysanthemum acid, tertiary chrysanthemum chloride, methyl tertiary chrysantherate, ethyl tertiary chrysantherate, propyl primary chrysantherate, and tertiary chrysanthemum acid. Examples thereof include butyl acid, cyclohexyl tertiary chrysanthemum acid, cyclohexylmethyl tertiary chrysanthemum acid, benzyl tertiary chrysanthemum acid, and tertiary chrysanthemum acid anhydride.

Further, the cis-chrysanthemum acids may be the cis-isomer alone or a mixture with the trans-isomer in any proportion, but considering the purpose of the present invention, Needless to say, its significance is demonstrated when using .

Further, the SH compound used in the present invention may be one having 18H groups, and thiols, thiocarboxylic acids, dithioacids, etc. are usually used. Specific compounds include:
Aromatic thiols such as thiophenol, 0-lm- and p-thiocresol, ol-lm- and p-methoxybenzenethiol, 1- and 2-naphthalenethiol, dithiocatechol, dithioresorcin, dithiohydroquinone, benzyl mercaptan Aralkylthiols such as methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, dodecanethiol, dithiothritol, Alkylthiols such as dithioerythritol and butanedithiol; thiolcarboxylic acids such as thioglycolic acid, thiosalicylic acid, thiolactic acid, and thiomalic acid; thiocarboxylic acids such as thioacetic acid, thiopropionic acid, thiobutyric acid, and thiobenzoic acid; dithioacetic acid; Examples include dithioacids such as dithiopropionic acid, dithiobutyric acid, and dithiobenzoic acid.

Preferably aromatic thiols, thiol carboxylic acids,
They are thiocarboxylic acids and dithio acids.

The amount of the SH compound used is usually in the range of 1/1000 to 1/4 mole per mole of the chrysanthemum acid to be treated, and usually 1:500 to 1/2 mole for the chrysanthemum anhydride. is within the range of

Examples of azo compounds include azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), i,i'-azobis(cyclohexane-1-carbonitrile), 4°4'-azobis -4-cyanopentanoic acid, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-
Azonitriles such as propyl azoformamide, azo esters such as azobisisobutanol diacetate, methyl azobisisobutyrate, ethyl azobisisobutyrate,
Examples include alkylazos such as azo-t-butane. Preferably, azonitriles and azo esters are used.

The amount used is usually 1/2 per 1 mole of SH compound.
It is in the range of 0 to 5 mol, preferably 1/10 to 2 mol.

Examples of peroxides include hydrogen peroxide, t-butyl hydroperoxide, 1,1°8.8-tetramethylbutyl hydroperoxide, tetrahydrofuran, hydroperoxide produced by the oxidation of ethers such as dioxane, Hydroperoxides such as cumene hydroperoxide and diisopropylbenzene hydroperoxide, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, t-butyl perbenzoate, t-butyl peracetate, diisopropyl peroxydicarbonate, dicyclohexyl Peroxy esters such as peroxydicarbonate, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, dialkyl peroxides such as di-1-butyl peroxide and dicumyl peroxide, peracids such as peracetic acid, etc. can be mentioned. Among these, diacyl peroxides and peroxy esters are preferably used.

The amount of peroxide used is usually 17% per mole of SH compound.
The amount ranges from 20 to 5 mol, preferably from 1/10 to 2 mol.

When carrying out the reaction, it is preferable to use an inert solvent, and examples of such solvents include saturated hydrocarbons, aromatic hydrocarbons, their halides, and ethers.

The reaction temperature ranges from 0°C to the boiling point of the primary chrysanthemum acid (if a solvent is used, the boiling point of the solvent used);
For dilute acids, their halides, and their esters, the temperature is usually 40°C.
-100°C, and in the case of dilute acid anhydride, it is usually 60°C - 140°C.

The time required for the reaction may vary depending on the amounts of the SH compound, peroxide, and azo compound used and the reaction temperature, but usually several minutes to 10 hours is sufficient to achieve the purpose.

The progress of the reaction can be determined by gas chromatography, etc.
Measuring the geometric isomer ratio (can be determined from this).

<Effects of the Invention> In this way, trans-chrysanthemum acids are produced.According to the present invention, trans-chrysanthemum acids can be efficiently produced, and in addition, they are more common as industrial raw materials and are more resistant to moisture. It also offers advantages such as being able to use SH compounds that are stable and easy to handle.

<Example> The present invention will be explained in further detail with reference to the following example, but the present invention is not limited to these examples in any way.

Example 1 A cis-dilute acid was added to an 80-proof flask. Of, 80℃ after adding 48q of azobisisobutyronitrile and 5f of toluene
A toluene solution of 55 μl of ζthiophenol was added dropwise to the mixture while stirring at the same temperature, and stirring was continued for 1 hour at the same temperature.

After the reaction, dilute hydrochloric acid was added, stirred, and the mixture was separated. The organic layer was extracted twice with a 5F 10% caustic soda aqueous solution, and the resulting aqueous layer was acidified with hydrochloric acid and extracted twice with toluene. After washing the toluene layer with water and drying with sodium sulfate, the solvent was distilled off under reduced pressure, and the residual liquid was distilled to obtain a boiling point of 110-119'C/
A fraction of 0.92f of 2.5+uHf was obtained. This substance was confirmed to be a dilute acid based on its infrared absorption spectrum.

A part of the distillate was analyzed by gas chromatography, and the isomer ratio was determined to be 8.6% of the cis form and 9% of the trans form.
It was 1.5%.

Example 2 85% cis isomer, 66% trans isomer in 8(:)tl flask
The first dilute acid consisting of 96 2. Of1 t-butyl perbenzoate 0.22f,! - After adding 101 toluene, a toluene solution of 0.22 t of thiophenol was added dropwise to the mixture while stirring at 100°C, and stirring was continued at the same temperature for 1 hour.

After the reaction, the same treatment as in Example 1 was carried out to obtain a dilute acid of 1.78%.
I got an F.

When a part of the distillate was analyzed in the same manner as in Example 1, it was found that the cis-isomer content was 7.8% and the trans-isomer content was 7.8%.

Example 8 1.814 dilute acid ethyl ester in a 50-quare T flask
, 80% of azobisisobutyronitrile and 0.0% of thiophenol. 1 1 F toluene solution was added dropwise,
Stirring was continued for 800 minutes at the same temperature.

After the reaction, a 2% aqueous sodium hydroxide solution was added to perform extraction, and the 8AFIA was washed with water. The obtained i-layer was distilled under reduced pressure to a boiling point of 85-88 C/10.
#Hf distillate 1.17F was obtained.

This product was confirmed to be a thin acid edel ester based on the infrared absorption spectrum.

Practical Example 4 35% cis isomer, 66% trans isomer in 50 Ml flask
% ethyl chrysanthemum t. aty, perbenzoic acid t-
After adding 0.12 F of butyl and 62 F of toluene, a toluene solution of 0.11 F of thiophenol was added dropwise to the mixture while stirring at 90° C., and stirring was continued at the same temperature for 1 hour.

After the reaction, post-treatment was carried out in the same manner as in Example 8, and the 1.162-th.
A dilute acid ethyl ester was obtained.

Analysis by gas chromatography revealed that the amount was 8.8% cis-isomer and 91.291% trans-isomer.

Example 5 50 dew! 8. Add cis dilute acid to the flask. After adding 0.29 F of azobisisobutylnitrile, 6 F of toluene, 0.0 F of P-thiocresol was added to this while stirring at 80°C.
An 88F toluene solution was added dropwise, and stirring was continued at the same temperature for 1 hour.

When a part of the reaction solution was sampled and analyzed by gas chromatography, 10.8% of the cis isomer and 8% of the trans isomer were found.
It was 9.2%.

Example 6 50011y of cis-chrysanthemum acid and 481v of azobisisobutyronitrile were dissolved in 5ytl of toluene. While stirring at 80° C., a toluene solution containing 40 Da of 1-butanethiol was added dropwise over 10 minutes, and stirring was continued at the same temperature for 80 minutes.

When a part of the reaction solution was sampled and analyzed by gas chromatography, it was found that the cis isomer was 48.496% and the trans isomer was 51.65%.

Example 7 82 ml of dilute acid chloride 1.2421 azobisisobutyronitrile consisting of 85% cis isomer and 65% lance isomer was placed in a 50-proof flask. After adding toluene 5F, 80℃
A toluene solution of 0.1 F thiophenol was added dropwise to the mixture while stirring, and stirring was continued for 1 hour at the same temperature.

When a part of the reaction solution was sampled and hydrolyzed and analyzed by gas chromatography, it was found that the cis isomer was 9.2% and the trans isomer was 90.8%.

Example 8 50 g/flask of the same IX-dilute acid used in Example 2 2. oy1 Azobisisobutyronitrile 0.2 t
After adding 10 f of s-benzene, a benzene solution of 0.26 g of 1-thiobenzoic acid was added dropwise to the mixture while stirring at 75°C, and the mixture was stirred at the same temperature for 2 hours.

Post-treatment was carried out in the same manner as in Example 2 to obtain 1.74 F dilute acid. When this product was analyzed by gas chromatography, it was found that the cis form was 7.196% and the trans form was 92.9%.

Example 9 60ml flask 1ζ Same dilute acid as used in Example 2 2. Of, perbenzoic acid t-butyl ester 0.46f,
1Of benzene was added, and while stirring at 75°C, a benzene solution of 0.14 f of thioacetic acid was added dropwise, and stirring was continued at the same temperature for 2 hours.

When a part of the reaction solution was sampled and analyzed by gas chromatography, it was found that 7.8% of the cis-isomer and 9% of the trans-isomer.
It was 2.7%.

Example 10 In a 105O flask, dilute acid methyl ester consisting of 85% cis isomer and 65% trans isomer 2. Of1 Azobisisobutyronitrile 0.18 ? After adding 10 f of benzene, 0.28 g of thiobenzoic acid was added to this while stirring at 75°C.
A benzene solution of f was added dropwise, and stirring was continued for 1 hour at the same temperature.

When a part of the reaction solution was sampled and analyzed by gas chromatography, it was found that 8.6% of the cis isomer and 91% of the trans isomer were detected.
．． It was 4%.

Example 11 5C) The same dilute acid 2. as used in Example 2 was added to the xl flask. Of, thiosalicylic acid 0.28r.

After adding 10 F of benzene, a benzene solution of 0.472 lauroyl peroxide was added dropwise to the mixture while stirring at 60°C, and stirring was continued at the same temperature for 2 hours.

When a part of the reaction solution was sampled and analyzed, it was found that the cis isomer was 6.9% and the trans isomer was 98.1%.

Example 12 50 g/flask of cis dilute acid butyl ester 1. O
After adding y, 2,2'-azobis(2,4-dimethylvaleronitrile) 0.12F and dioxane 5f, 7
A solution of 87 das of P-thiocresol in dioxane was added dropwise to the mixture while stirring at 5°C, and stirring was continued at the same temperature for 2 hours.

When a portion of the reaction solution was sampled and analyzed, it was found to be 9.7% cis-isomer and 90.8% trans-isomer.

Example 18 In a 50 ml flask, 1.0v1 of cis-chrysanthemum acid anhydride, 0.15F of azobisisobutyronitrile, and 102% of toluene.
After adding this, a toluene solution of 117 Da of 1ζP-thiocresol was added dropwise with stirring at 75°C, and at the same temperature 6
Stirring was continued for an hour.

When a part of the reaction solution was sampled and analyzed by gas chromatography after hydrolysis, it was found that the cis isomer was 8.0% and the trans isomer was 92.096%.

Example 14 In a 50-proof flask, cis-thin acid chloride 1, Of, azobisisobutyronitrile 88Mg, dioxane 10t
After adding, a dioxane solution of 0.11 l-thiocresol was added dropwise to this while stirring at 90°C, and 8°C was added at the same temperature.
Stirring was continued for an hour.

When a part of the reaction solution was sampled and hydrolyzed and analyzed by gas chromatography, it was found that the cis isomer was 6.8%;
It was 98.2% trans isomer.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula,
2-dimethyl-3-isobutenyl cyclopropanecarboxyl group. 1. A method for producing trans primary chrysanthemum acids, which is characterized in that cis or cis/trans mixed primary chrysanthemum acids represented by the following formula are reacted with an SH compound in the presence of a peroxide or an azo compound to trans-convert the primary chrysanthemum acids.