JPS6361934B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing optically active trans-dairy chrysanthemum acid, and more specifically, to By treating (+)-cis primary chrysanthemum acid represented by the general formula () with a catalyst system in which a nitrile compound is added to a halogenated palladium compound, The present invention relates to a method for producing (+)-trans primary chrysanthemum acid, which comprises converting it to (+)-trans primary chrysanthemum acid represented by (+)-trans primary chrysanthemum acid. Chrysanthemum acid is an important compound that constitutes the acid component of low-toxicity, fast-acting insecticidal esters called pyrethroids, such as pyrethrin, allethrin, and phthalthrin. The carboxylic acid has cis and trans geometric isomers and each of them has (+) and (-) optical isomers, for a total of four isomers. these 4
Among the isomers, pyrethroid esters consisting of the trans isomer exhibit stronger potency than esters consisting of the cis isomer, and furthermore, the (+) isomer exhibits much higher activity than the corresponding (−) isomer. It has been known. By the way, the primary chrysanthemum acid ester contained in naturally occurring pyrethrum is the (+) trans form. (+) Trans-synthetic acid is also useful as a resolving agent for optically active amines. As mentioned above, Daichic acid has its _C1 position and
There are two non-satile carbons at the _C3 position, and a total of four isomers exist. That is, there are four types of isomers: (+)-cis form, (-)-cis form, (+)-trans form, and (-)-trans form, and these are (1R, 3S), respectively.
(1S, 3R) (1R, 3R), (1S, 3S). Conventionally, the following method is known as a method for producing trans primary chrysanthemum acids from cis primary chrysanthemum acids. For example, there are methods in which alkyl esters of cis-dairy chrysanthemum acid are treated with certain basic catalysts (Japanese Patent Publication No. 18495/1983, Japanese Patent Publication No. 18496/1983, etc.), and a method of treating alkyl esters of cis-dairy chrysanthemum acid with A method of heating to a high temperature (Japanese Patent Publication No. 47-26778), a method of thermal isomerization of ethyl cis-dairy chrysanthemum acid (Chemistry & Industry, 1970, 1050), a method of dichlorination into cis-dairy chrysanthemum acid or its ethyl ester Examples include a method in which a palladium nitrile complex catalyst is reacted (Tetrahedron, Letters, 22 , 385 (1981)). However, these methods
Trans isomerization method, in other words, it is a method of converting racemic cis primary chrysanthemum acids to racemic trans isomer, and is a selective stereoconversion from one of the four isomers to another more useful isomer. It does not even include the technical content of For example, the above-mentioned conversion of the cis-synthetic acid alkyl ester to the trans form by the method of treating the cis-synthetic acid alkyl ester with a base catalyst or the method of heating the cis-sulfuric acid chloride to a high temperature is said to be a change in the configuration of the _C1 position. , a method for slightly changing the configuration of the _C3 position is to oxidize the alkenyl group bonded to the _C3 position to convert it into a ketoalcohol group or an aldehyde group, and then to react with a basic reagent. There are only known methods (Special Publications No. 15977, No. 15977, No. 15977, No. 46).
Publication No. 24694). In addition, by reacting a Lewis acid with the acid halide of four isomers of alkenylcyclopropanecarboxylic acid, including daisies chrysanthemum acid, a racemic form, that is, (±)
A method of obtaining unity is also known (Special Publication Act 1973-
(No. 37858, Japanese Unexamined Patent Publication No. 144651/1983) This method is an excellent method in that it can racemize starting from any of the four isomers, and in particular it can racemize the (-)-trans isomer. , (+)-trans isomer is obtained when the (+)-cis isomer is used as the raw material. As described above, several methods are already known for cis, trans isomerization and racemization of primary chrysanthemum acids, but until now, chemical methods have been used to remove the attached functional group with respect to the inhospitable carbon at the _C3 position. By selectively stereoconverting without changing (+)−
Nothing is known about the efficient production of (+)-trans isomers from cis isomers, and it is as if there is no such concept. However, as a result of extensive research into a method for obtaining the (+)-trans form from the (+)-cis form by changing the configuration at the _C3 position ( _C3 epimerization), the present inventors unexpectedly found that ( We have discovered that the objective can be efficiently achieved under mild conditions by treating +)-cis or (+)-cis(+)-trans mixed dichloromethane with a catalyst system in which a nitrile compound is added to a halogenated palladium compound. After further various studies, the present invention was completed. The steric transformation related to the present invention is illustrated as follows. The starting material of the present invention, (+)-cis primary chrysanthemum acid or (+)-cis, (+)-trans mixed primary chrysanthemum acid, is obtained by the optical resolution method of (±)-cis primary chrysanthemum acid (Unexamined Japanese Patent Publication No. 1971-125432), optical resolution method of (±)-cis, trans mixed dichroic acid (Japanese Patent Application Laid-open No. 48-48449), or method of deriving from optically active dihydrochrysansemolactone (Japanese Patent Application Laid-open No. 48-48449) Publication No. 47-30669,
JP-A No. 47-25155). Therefore, by combining the method of the present invention with these techniques, the (+)-trans isomer, which is the component with the highest insecticidal efficacy, can be obtained extremely efficiently. Next, to explain the method of the present invention in more detail, the (+)-cis primary chrysanthemum acid used as a raw material may be the cis-isomer alone or a mixture with the (+)trans-isomer in any proportion, and its optical purity can be determined. There is no problem even if it is only moderate. In this case, considering the nature of the C ₃ epi form, the optical purity of the (+)- form upon trans conversion is almost the same as that of the raw material. By using these optically active cis-dairy chrysanthemum acids as a catalyst with a halogenated palladium compound added with a nitrile compound, _C3 epimerization easily proceeds regardless of external pressure, resulting in the desired (+)- It can be converted to trans-synthetic acid or trans-synthetic acid-enriched. The halogenated palladium compound used in the present invention may be any halogenated palladium compound that can use a nitrile compound as a ligand,
For example, palladium chloride, palladium bromide, etc. are used, and palladium chloride is particularly preferred. The amount used is 1/100 per mole of ester to be treated.
A suitable amount is about 1/20 to 1/2 mole, preferably about 1/20 to 1/2 mole. The nitrile compound used in the present invention may be any nitrile compound as long as it has the ability to coordinate with the halogenated palladium compound used. Examples of such nitrile compounds include alkyl, aralkyl, and allyl cyanide compounds substituted with nitrile groups such as acetonitrile, propionitrile, butyronitrile, benzonitrile, and benzyl cyanide. The appropriate amount to be used is about 2 moles based on the halogenated palladium compound used, but more may be used. The catalyst used in the present invention is a complex of palladium halide (2) and a nitrile compound as described above, and this complex is easy to manufacture. For example, dichlorobis(benzonitrile)palladium can be obtained in high yield by dissolving palladium chloride in benzonitrile under heating and precipitating it by cooling or adding it to petroleum ether, hexane, etc. (MSKharasch et al., J .Amer Chem.
Soc., 60 , 882 (1938)). Furthermore, when carrying out the reaction, it is preferable to optionally dilute the reaction with a solvent that does not essentially inhibit the reaction. Examples of such solvents include ethers such as dioxane and ethylene glycol dimethyl ether, and halogenated hydrocarbons such as chloroform and dichloroethane. Examples include esters such as ethyl acetate, aromatic hydrocarbons such as benzene and toluene, and acetic acid. Among them, acetic acid ester, dioxane, chloroform, etc. are preferable. The reaction temperature is usually -30°C to 110°C, preferably -
It is advantageous to work in a temperature range of 10°C to 100°C. The time required for the reaction varies depending on the reaction conditions, but usually 1 minute to 20 hours is sufficient. The degree of progress of the reaction can be determined by measuring the optical rotation or by analyzing the diastereoisomer with the optically active alcohol by gas chromatography. Although the method of the present invention can be carried out under reduced pressure or increased pressure, the purpose can be easily achieved under normal pressure. The method of the present invention can be carried out either batchwise or continuously, and the charging method can be either a method in which the raw material ester is put into a reaction vessel together with a catalyst, or a method depending on the progress of the reaction. It is possible to adopt either a method of continuously or intermittently adding the water. After separating and recovering the catalyst from the reaction solution that has completed the reaction as described above, if the reaction solution is fractionally distilled, C ₃
The (+)-trans primary chrysanthemum acid produced by epimization of the position, or trans primary chrysanthemum enriched therein, is obtained. Furthermore, it can be purified by distillation, chromatography, etc., if necessary. The (+)-trans primary chrysanthemum acid thus obtained can be used for various purposes. For example, (+)-trans primary chrysanthemum acid is called a pyrethroid alcohol represented by pyrethrolone and allethrone. Reaction of a group of alcohols can lead to highly potent insecticidal compounds. The method of the invention will now be explained by way of examples. Example 1 (+)-cis form: 98.4%, (-)-cis form: 1.6%
2.0 g of optically active cis-dairy chrysanthemum acid consisting of the following were dissolved in 38.0 g of ethyl acetate, and 1.4 g of dichlorobis(benzonitrile) palladium () prepared from palladium chloride and benzonitrile was added thereto and stirred at 20°C for 3 hours. . After removing the catalyst from the reaction solution,
Add 10% caustic soda aqueous solution to extract and remove neutral substances, add 10% hydrochloric acid to the aqueous layer to acidify, extract with toluene, wash with water, concentrate, and distill to obtain a boiling point of 110-116.
1.42 g of Daishu chrysanthemum acid was obtained at ℃/2 mmHg. As a result of compositional analysis of this product by gas chromatography, (+)-cis form: 7.6%, (-)-cis form: 0.1
%, (+)-trans form: 90.7%, (-)-trans form: 1.6%. Content of (+)- isomer Starting material 98.4% Product 98.3% Example 2 Optically active cis-daisy chrysanthemum acid used in Example 1 2.0
g was dissolved in 38.0 g of dioxane, 0.68 g of dichlorobis(benzonitrile) palladium () used in Example 1 was added, and the mixture was stirred at 50°C for 3 hours. After the reaction, the same procedure as in Example 1 was carried out to obtain 1.50% of chrysanthemum acid.
I got g. As a result of compositional analysis of this substance by gas chromatography, (+)-cis form: 20.1%,
(-)-cis form: 1.2%, (+)-trans form: 74.3
%, (-)-trans form: 4.4%. Content of (+)- isomer Starting material 98.4% Reactant 94.4% Example 3 2.0 g of the optically active cis-dairy chrysanthemum acid used in Example 1
was dissolved in 38.0 g of isobutyl acetate, 0.46 g of dichlorobis(benzonitrile)palladium () used in Example 1 was added, and the mixture was stirred at 100°C for 3 hours. After the reaction, the same procedure as in Example 1 was carried out to obtain 1.63 g
I got g. As a result of compositional analysis of this substance by gas chromatography, (+)-cis form: 37.0%,
(-)-cis form: 0%, (+)-trans form: 60.6
%, (-)-trans form: 2.4%. Content of (+) substance Starting material 98.4% Reactant 97.6% Example 4 2.0 g of the optically active cis-dairy chrysanthemum acid used in Example 1
was dissolved in 38.0 g of ethyl acetate, 1.40 g of dichlorobis(benzonitrile)palladium () used in Example 1 was added at 0°C, and the mixture was stirred for 3 hours. After the catalyst was deactivated at the same temperature, it was removed from the reaction solution and operated in the same manner as in Example 1 to obtain 1.73 g of daisic chrysanthemum acid. As a result of compositional analysis of this product by gas chromatography, (+)-cis form: 78.0%, (-)-cis form:
1.4%, (+)-trans form: 20.3%, and (-)-trans form: 0.3%. (+)-isomer content Starting material 98.4% Reactant 98.3% Example 5 2.0 g of the optically active cis-dairy chrysanthemum acid used in Example 1
was dissolved in 38.0 g of ethyl acetate, 0.9 g of dichlorobis(acetonitrile) palladium () prepared from palladium chloride and acetonitrile was added at 20°C, and the mixture was stirred for 3 hours. After the reaction, the reaction was carried out in the same manner as in Example 1 to obtain 1.78 g of primary chrysanthemum acid. As a result of compositional analysis of this product by gas chromatography, (+)-cis form: 68.2%, (-)-cis form: 1.0%, (+)-trans form: 30.1%, (-)-trans form: 0.7%. It was hot. Content of (+)- isomer Starting material 98.4% Reactant 98.3% Examples 6 and 7 The following table shows examples in which the reaction was carried out according to Example 1 with different amounts of catalyst.

[Table] * Composition of optically active cis-dairy chrysanthemum acid as a raw material...Same example as Example 1 8, 9, 10, 11 The following table shows examples in which the solvent was changed according to Example 1. It was shown to.

[Table] * Composition of optically active cis-dairy chrysanthemum acid as raw material...Example 1
Same example 12 (+)-cis form: 19.1%, (-)-cis form: 0.6%
(+)-trans form: 77.6%, (-)-trans form:
Dissolve 2.0 g of (+)-enriched chrysanthemum acid consisting of 2.7% in 18.0 g of chloroform, add 1.40 g of dichlorobis(benzonitrile) palladium () prepared from palladium chloride and benzonitrile at 50°C, and stir for 1 hour. did. After the reaction, the same procedure as in Example 1 was carried out to obtain 1.65% of chrysanthemum acid.
I got g. As a result of compositional analysis of this substance by gas chromatography, (+)-cis form: 2.1%,
(-)-cis form: 0%, (+)-trans form: 93.6
%, (-)-trans form: 4.3%. Content of (+) isomer Starting material 96.7% Reactant 95.7% Example 13 (+)-cis isomer: 14.2%, (-)-cis isomer: 1.9%
(+)-trans form: 72.1%, (-)-trans form:
2.0 g of (+)-rich chrysanthemum acid consisting of 11.8% was dissolved in 18.0 g of dioxane, and 0.68 g of dichlorobis(benzonitrile) palladium () used in Example 12 was added at 20°C and stirred for 7 hours. . After the reaction, the same procedure as in Example 1 was carried out to obtain 1.56 g
I got g. As a result of compositional analysis of this substance by gas chromatography, (+)-cis form: 6.2%,
(-)-cis form: 1.1%, (+)-trans form: 79.4
%, (-)-trans form: 13.3%. Content of (+)− substance Starting material 86.4% Product 85.6%

Claims (1)

[Claims] 1 (+)-cis primary chrysanthemum acid or (+)-cis,
(+)-trans Mixed chrysanthemum acid with a complex catalyst of a halogenated palladium compound and a nitrile compound, -
1. A method for producing (+)-trans-daisy chrysanthemum acid, characterized by processing at a temperature in the range of 30°C to 110°C. 2. The method according to claim 1, wherein the treatment is carried out at a temperature range of -10°C to 100°C.