JPH0135819B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () The present invention relates to a novel substituted benzyl ester represented by: and an insecticide containing the same as an active ingredient. However, in the above general formula (), R is the following general formula () or general formula ()

【formula】

[Formula] Represents a group represented by the following. In the group represented by general formula (), R ¹ is

[Formula] Group or

[Formula] represents a group. Here, X and X' are the same or different and each represents a halogen atom such as a fluorine atom, chlorine atom, or bromine atom; Y and Y' are the same or different and each represents a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; It represents a halogen atom or a methyl group; Z represents a hydrogen atom or a halogen atom such as a chlorine atom or a bromine atom. In addition, in the group represented by the general formula (), Q is a fluorine atom, a chlorine atom,
Represents a halogen atom such as a bromine atom. From the viewpoint of insecticidal activity exhibited by the substituted benzyl ester represented by the general formula (), the nitro group of the substituent is preferably located at the meta or para position, and the group represented by the general formula () or the general formula () Among these, groups represented by the following general formula ()' are particularly preferred. [In the formula, X has the same meaning as in the general formula (). ] Conventionally, 4-cyanobenzyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate, 4-trifluoromethylbenzyl 2,2-dimethyl-3-(2-methyl-1- Chrysanthemum carboxylic acid benzyl esters such as propenyl) cyclopropanecarboxylate, 2,6-dichloro-4-nitrobenzyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate have insecticidal activity. However, the insecticidal activity of these chrysanthemum carboxylic acid benzyl esters is not satisfactory, and their residual efficacy is low. Also 4-nitrobenzyl (10)
-trans-2,2-dimethyl-3-(2,2-
It has been reported that the American cockroach hydrolytically metabolizes substituted benzyl chrysanthemum esters such as (dichlorvinyl) cyclopropane carboxylate (see Abstracts of the 5th Annual Conference of the Japanese Society of Pesticides, No. 115); however, these substituted benzyl chrysanthemum esters has low insecticidal activity. The present inventors have conducted intensive research to create an excellent pyrethroid compound with higher insecticidal activity than these conventional chrysanthemum acid esters, and as a result, the general formula ()
The substituted benzyl ester shown in (1) has significantly higher and faster insecticidal efficacy than conventional chrysanthemum acid esters, and (2) is resistant to organophosphorus insecticides and/or carbide insecticides. (3) It is highly effective against pests that have
On the other hand, they found that it does not have environmental persistence like organic chlorine insecticides, and (4) has extremely low toxicity to humans and animals, leading to the completion of the present invention. Substituted benzyl esters represented by the general formula () can cause damage to paddy rice, field crops, cotton, fruit trees, forests, etc., such as leafhoppers, planthoppers, black beetles, stink bugs, aphids, green caterpillars, fall armyworms, mealybugs, cutworms,
It not only exhibits excellent insecticidal efficacy against agricultural, horticultural and forest pests such as scale insects, leafhoppers, spider mites, silver beetles, white beetles, gypsy moths, and bark beetles, but also against black weevils,
It also has a strong insecticidal effect against grain storage pests such as the snail moth, as well as sanitary pests such as flies, mosquitoes, and cockroaches. Representative substituted benzyl esters represented by the general formula () of the present invention are listed below. Note that these esters include geometric isomers based on the three-dimensional structure of the acid moiety and alcohol moiety, and optical isomers based on the asymmetric carbon atom.

【table】

[Table] Substituted benzyl esters represented by the general formula () are represented by the general formula () A substituted benzyl alcohol or a reactive derivative thereof represented by the general formula () RCOOH...() [wherein R has the same meaning as in the general formula (). ] It can be easily produced by reacting with the carboxylic acid shown in the following formula or a reactive derivative thereof. Here, examples of reactive derivatives of substituted benzyl alcohol include halides and arylsulfonates. Reactive derivatives of carboxylic acids include lower alkyl esters, acid halides, acid anhydrides, alkali metal salts, silver salts, or salts of organic tertiary bases. Below, the above-mentioned typical manufacturing method will be specifically explained. (Production method a) Method by reaction of alcohol and carboxylic acid halide Substituted benzyl alcohol represented by the general formula () and the general formula R COX'' [wherein R has the same meaning as in the general formula (), ″ represents a halogen atom. The carboxylic acid halide represented by ] is preferably a carboxylic acid chloride and a benzene,
By reacting the substituted benzyl alcohol in an inert solvent such as toluene, ether, hexane, or chloroform in the presence of a tertiary amine such as pyridine or triethylamine in an amount of 1 to 3 molar equivalents based on the substituted benzyl alcohol at room temperature or under heating. The desired substituted benzyl ester is obtained. (Production method b) Method by reaction of alcohol and carboxylic acid anhydride Substituted benzyl alcohol represented by the general formula () and the general formula (R CO ) ₂ O [wherein R is the general formula ()
has the same meaning as in. ] in an inert solvent such as benzene, toluene, xylene, hexane, acetone, etc.
The desired substituted benzyl ester is preferably obtained by reacting at room temperature or with heating in the presence of an acid such as sulfuric acid or p-toluenesulfonic acid or a tertiary amine such as pyridine or triethylamine. (Production method c) Method by reaction of alcohol and carboxylic acid A substituted benzyl alcohol represented by the general formula () and a carboxylic acid represented by the general formula () are mixed in an inert solvent such as benzene, toluene, or xylene, for example, with dicyclohexyl. carbodiimide,
Alternatively, the desired substituted benzyl ester is obtained by reacting 2-chloro-1-methylpyridinium iodide with a dehydration condensation agent such as triethylamine at room temperature or with heating. (Production method d) Method by reaction of alcohol with lower alkyl ester of carboxylic acid A substituted benzyl alcohol represented by the general formula () and a carboxylic acid represented by the general formula () are transesterified using a suitable transesterification catalyst, such as an alkali metal alkoxide. , in the presence of a titanium metal compound such as sodium hydride or tetramethyl titanate, in an inert solvent such as toluene or xylene, and remove the low-boiling alcohol generated from the reaction system using a rectification column. The desired substituted benzyl ester is obtained by removing . (Manufacturing method e) Method by reaction of alcohol halide or arylsulfonate with alkali metal salt of carboxylic acid Halide or arylsulfonate of substituted benzyl alcohol represented by general formula () and alkali of carboxylic acid represented by general formula () The desired substituted benzyl ester is obtained by reacting the metal salt with the metal salt in a solvent such as dimethylformamide, benzene, or acetone at room temperature or with heating. The substituted benzyl alcohol represented by the general formula (), which is an alcohol component, can be easily and inexpensively produced, for example, by the following method. That is, by ethylating the substituted benzaldehyde represented by the general formula () with sodium acetylide in a liquid ammonia solvent or ethynylating it with ethylmagnesium bromide in a tetrahydrofuran solvent, the substituted benzyl alcohol represented by the general formula () can be obtained. can get. On the other hand, the acid components substituted cyclopropanecarboxylic acid and substituted isovaleric acid are known, and the above-mentioned reactive derivatives of these carboxylic acids can be prepared from the corresponding free acids by conventional methods. When the compound of the present invention is actually applied, it can be used alone without adding other ingredients, but in order to make it easier to use as an insecticide, a carrier may be added to form a preparation. It is generally applied after dilution. For formulation, we use emulsions, wettable powders, powders, granules, fine granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.), follicles, etc. in accordance with conventional techniques for agricultural chemical formulations. It can take any form such as aerosols, non-heated fumigants, poison baits, etc., and can be used for various purposes depending on the purpose. In addition, unlike general chrysanthemum acid ester compounds,
The compounds of the present invention have high stability against light, heat, oxidation, etc., but if it is particularly necessary under severe oxidative conditions, antioxidants or ultraviolet absorbers, such as
Phenol derivatives like BHT, BHA, bis-
By adding appropriate amounts of phenol derivatives, arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, condensates of phenetidine and acetone, or benzophenone compounds as stabilizers, compositions with more stable effects can be obtained. Obtainable. The formulation generally contains 0.01 to 95% by weight of the compound of the present invention.
It is preferably contained in an amount of 0.1 to 90% by weight. The compounds of the present invention may be used in the form of the various types of preparations mentioned above, or these preparations may be further formulated into usage forms. The content of the compound of the present invention in the usage form can be appropriately selected within a very wide range such as 0.0000001 to 100% by weight, but is preferably 0.001 to 10% by weight. The insecticides according to the invention are used in the customary manner appropriate to the particular use type. Below, synthesis examples and test examples of the compounds of the present invention,
Although formulation examples and effect examples are shown, the present invention is not limited thereto. In addition, "parts" in the formulation examples mean parts by weight. The compound number is substituted benzyl ester (1) represented by the general formula () above.
- Corresponds to (11). Synthesis Example 1 Cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride
2.28 g (0.01 mol) and 1.77 g (0.01 mol) of α-ethynyl-3-nitrobenzyl alcohol were dissolved in 20 ml of dry benzene. Next, 1.58 g (0.02 mol) of pyridine was added dropwise to this solution at room temperature, and the mixture was stirred overnight. Thereafter, the reaction solution was poured into water and extracted with diethyl ether, and the extract was washed with diluted hydrochloric acid water and saturated brine. After drying the organic layer over anhydrous magnesium sulfate, low-boiling substances were distilled off under reduced pressure to obtain a viscous oily product. The obtained product was purified by silica gel high performance liquid chromatography (solvent: n-hexane/isopropyl ether = 85/15 volume ratio) to produce the following:
α-ethynyl-3-nitrobenzyl cis-2,2-dimethyl-3- with NMR spectrum
3.30 g of (2,2-dichlorovinyl)cyclopropanecarboxylate [compound (1), cis form] was obtained (yield 90%). NMR spectrum (90MHz) δ ^CDCl3 _HMS : 1.13-1.26 (m, 6H); 1.79-2.21 (m, 2H);
2.67-2.72 (m, 1H); 6.13, 6.17 (each d,
1H); 6.45-6.53 (m, 1H); 7.68 (d, 2H);
8.22 (d, 2H) Synthesis Examples 2 to 6 In Synthesis Example 1, trans-2,2 was used instead of 0.01 mol of cis-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride. -dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride, cis-2,2-dimethyl-3-(2,2-dibromvinyl)cyclopropanecarboxylic acid chloride, trans-2,2-dimethyl-3 -(2,2-dibromvinyl)cyclopropanecarboxylic acid chloride, 2,2-dimethyl-3-(2-methyl-1-
Propenyl) cyclopropanecarboxylic acid chloride and α-isopropyl-4-chlorophenylacetic acid chloride were used in the same manner as in Synthesis Example 1, except that 0.01 mol each was used, and the corresponding α-ethynyl-3-nitrobenzyl trans-
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate [Compound
(1), trans form], α-ethynyl-3-nitrobenzyl cis-2,2-dimethyl-3-(2,2
-Dibromvinyl)cyclopropanecarboxylate [Compound (2), cis form], α-ethynyl-3-
Nitrobenzyl trans-2,2-dimethyl-
3-(2,2-dibromvinyl)cyclopropanecarboxylate [Compound (2), trans form], α
-ethynyl-3-nitrobenzyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate [compound (4)] and α
-ethynyl-3-nitrobenzyl α-isopropyl-4-chlorophenylacetate [compound
(7)] was obtained. Yield and NMR of each product
The spectra are shown in Table 1.

[Table] Synthesis Examples 7 to 11 Following the same procedure as Synthesis Example 1, 1.77 g of α-ethynyl-4-nitrobenzyl alcohol
(0.01 mol) to cis-2,2-dimethyl-3-
(2,2-dichlorvinyl)cyclopropanecarboxylic acid chloride, trans-2,2-dimethyl-
3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride, cis-2,2-dimethyl-
3-(2,2-dibromvinyl)cyclopropanecarboxylic acid chloride, 2,2-dimethyl-3-
0.01 mol each of (2-methyl-1-propenyl)cyclopropanecarboxylic acid chloride and α-isopropyl-4-chlorophenylacetic acid chloride were reacted, and the corresponding α-ethynyl-4-nitrobenzyl cis-2,2-dimethyl -3-
(2,2-dichlorvinyl)cyclopropanecarboxylate [compound (8), cis form], α-ethynyl-4-nitrobenzyl trans-2,2-dimethyl-3-(2,2-dichlorvinyl)cyclopropanecarboxylate [Compound (8), trans form], α-ethynyl-4-nitrobenzyl cis-2,2-dimethyl-3-(2,2-dibromvinyl)cyclopropanecarboxylate [compound
(9), cis form], α-ethynyl-4-nitrobenzyl 2,2-dimethyl-3-(2-methyl-1-
Propenyl) cyclopropanecarboxylate [Compound (10)] and α-ethynyl-4-nitrobenzyl α-isopropyl-4-chlorophenylacetate [Compound (11)] were obtained. The yield and NMR spectrum of each product are shown in Table 2.

[Table] Synthesis Example 12 Following the same procedure as Synthesis Example 1, 1.77 g of α-ethynyl-3-nitrobenzyl alcohol
(0.01 mol) to trans-2,2-dimethyl-3
-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylic acid chloride 3.87g
(0.01 mol) was reacted with α-ethynyl-3-nitrobenzyl trans-2,2-dimethyl-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate having the following NMR spectrum [ Compound (6), trans isomer]
Obtained 4.20g. NMR spectrum (90MHz) δ ^CDCl3 _HMS : 1.17-1.37 (m, 6H), 1.65-2.45 (m, 2H),
2.69-2.76 (m, 1H), 4.19-4.54 (m, 1H),
6.50 to 6.56 (m, 1H), 7.42 to 8.44 (m, 4H) Test Example 1 Insecticidal test against house flies by microdrop test method Each of the compounds of the present invention and the control compound were accurately weighed as specimens, and an acetone solution of a predetermined concentration was added. Prepared. The above preparation was applied to the dorsal prothorax of an adult female house fly (Musca domestica) anesthetized with ether.
Drop 1μ and put it in a waist-high shear dish with the bait.
It was covered with a wire mesh lid and stored at a temperature of 25°C. The test insects were sent to 30 insects in one ward. After 24 hours, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. The results are shown in Table 3.

[Table] Test Example 2 Insecticidal test against Spodoptera trifoliata by micro-drop test method Each of the compounds of the present invention was accurately weighed as a specimen, and an acetone solution of a predetermined concentration was prepared. Using a microsyringe, 0.5μ of the above prepared solution was dropped onto the dorsal surface of the thorax of the third instar Spodoptera larvae. Thereafter, the test insects were released together with food onto paper in a 9 cm diameter Peer tray and stored at a temperature of 25°C. The test insects were sent to 20 insects in one ward. After 24 hours, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. The results are shown in Table 4.

[Table] Formulation example 1 Add 50 parts of xylol and 20 parts of the surfactant Nucalgen ST-50 (trade name, Takemoto Yushi Co., Ltd.) to 30 parts of compound (1), and mix well with stirring to obtain 30 parts.
% emulsion was obtained. Formulation example 2 Add 50 parts of xylene and 20 parts of the surfactant Solpol SM-200 (Toho Chemical Industry Co., Ltd., trade name) to 30 parts of compound (1), and mix and dissolve these by stirring well to make a 30% emulsion. I got it. Formulation Example 3 0.5 parts of compound (1) was dissolved in 20 parts of acetone, then 99.5 parts of clay was added and thoroughly stirred, the acetone was removed by evaporation, and 0.5% powder was prepared by further stirring thoroughly in a grinder. Obtained. Formulation Example 4 0.2 part of compound (1) was stirred and dissolved in white kerosene to make a total of 100 parts to obtain an oil solution. Combination example 5 20 parts of compound (1) and surfactant Solpol SM-
200 (same as above) was added and mixed well, and 75 parts of talc was added thereto and sufficiently stirred in a grinder to obtain a wettable powder. Effect Example 1 A 30% emulsion of each of compounds (1) to (11) obtained in the same manner as in Formulation Example 1 was diluted with water to prepare a chemical solution so that the concentration of each compound was 400 ppm. Spray 7 ml/pot of the above chemical solution on rice planted in pots (6 cm diameter pot, 7 rice seedlings) 4 weeks after sowing, air dry, cover with a wire mesh cage, and incubate 20 female adult leafhoppers in the cage. Released. a pot
The test insects were stored in a constant temperature room at 25°C, and after 24 hours, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. In all cases, the mortality rate was over 90%. Effect Example 2 Compounds (1), (2), obtained in the same manner as Formulation Example 1
A chemical solution was prepared by diluting each of the 30% emulsions (4), (5), (8), (9), and (10) with water to give a compound concentration of 40 ppm. Spray 7 ml/pot of the above drug solution on rice planted in pots (6 cm diameter pot, 7 rice seedlings) 4 weeks after sowing, air dry, cover with a wire mesh cage, and incubate 30 female adult leafhoppers in the cage. Released. The pots were stored in a constant temperature room at 25°C, and 24 hours later, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. In all cases, the mortality rate was over 90%. Effect Example 3 Compounds (1) and (8) obtained in the same manner as Formulation Example 1
A drug solution was prepared by diluting each 30% emulsion with water to give a compound concentration of 400 ppm. Spray 7 ml/pot of the above chemical solution on rice planted in pots (pots with a diameter of 6 cm, 7 rice seedlings) 4 weeks after sowing, and after air-drying, cover with a wire mesh cage and release 20 adult brown planthoppers into the cage. I kept it. Pot at 25℃
After 24 hours, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. In all cases, the mortality rate was over 90%. Effect Example 4 A 30% emulsion of each of compound (1) and permethrin obtained in the same manner as in Formulation Example 1 was diluted with water to prepare a drug solution so that the concentration of each compound was 40 ppm. Rice planted in pots 4 weeks after sowing (diameter 6
Spray 7 ml/pot of the above chemical solution on 7 cm pots and 7 rice seedlings, and after air-drying, cover with a glass cylinder.
Twenty female adult leafhoppers were released into the cylinder, and the cylinder was covered with gauze. The pots were stored in a constant temperature room at 25°C, and 24 hours later, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. As a result, the mortality rate of compound (1) was 90% or more, and that of permethrin was 60% or less. Effect Example 5 A 30% emulsion of each of compound (1) and permethrin obtained in the same manner as in Formulation Example 2 was diluted with water to prepare a drug solution so that the concentration of each compound was 20 ppm. After immersing the leaves in this chemical solution, air-dry the leaves, place the leaves in a plastic container with a diameter of about 6 cm and a capacity of about 60 cm, and place ³ to 4 diamondback moths in the container.
Ten instar larvae were released. The container was stored in a constant temperature room at 25°C, and two days later, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. The above test was conducted in duplicate. As a result, the mortality rate of compound (1) was 100%, and that of permethrin was 90%.

Claims (1)

[Claims] 1. General formula [In the formula, R represents a group represented by the general formula [Formula] or [Formula]. Here, R ¹ represents a [formula] group or a [formula] group, Q represents a halogen atom, X and X' are the same or different and each represents a halogen atom, Y and Y' are the same or different and each represents a halogen atom. represents an atom or a methyl group, and Z represents a halogen atom. ]
A substituted benzyl ester represented by 2 General formula [In the formula, R represents a group represented by the general formula [Formula] or [Formula]. Here, R ¹ represents a [formula] group or a [formula] group, Q represents a halogen atom, X and X' are the same or different and each represents a halogen atom, Y and Y' are the same or different and each represents a halogen atom. represents an atom or a methyl group, and Z represents a halogen atom. ] An insecticide containing a substituted benzyl ester represented by the following as an active ingredient.