JPH0449280A - Ester compound, its production and insecticidal and miticidal agent containing the compound as active component - Google Patents

Abstract

NEW MATERIAL:The ester compound of formula I (X is F, Cl or Br). EXAMPLE:(RS)-1-(6-phenoxy-2-pyridyl)-ethyl-(1R)-trans-2,2-dimethyl-3-( E/Z)-(2- chloro-2-fluorovinyl)cyclopropane-1-carboxylate. USE:An active component for insecticidal miticide. It has excellent insecticidal and miticidal activities against various vermin such as hemipterous insects (e.g. plant-hopper, leaf-hopper, aphid and stink bug), dipterous insects (e.g. house fly and common gnat) and mites (e.g. citrus red mite). It exhibits extremely quick action and high lethal activity and has remarkable effect even on vermin resistant to organophosphorus insecticides and carbamate insecticides. PREPARATION:The compound of formula I can be produced by reacting a carboxylic acid halide of formula II (Y is halogen) with 1-(6-phenoxy-2-pyridyl) ethanol in an inert solvent in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel ester compound, its production method, and its use as an insecticide or acaricide.

<Prior art> Until now, for example, JP-A-59-118768, JP-A-5
Certain ester compounds such as 4-12351 are insecticidal,
It is described that it has acaricidal effect.

<Problems to be Solved by the Invention> However, their insecticidal and acaricidal efficacy cannot necessarily be said to be satisfactory.

Means for Solving the Problems In view of the above circumstances, the present inventors conducted various studies to develop a compound with excellent insecticidal and acaricidal activity, and found that the general formula [υ] X represents a fluorine atom, a chlorine atom or a bromine atom. ] It was discovered that the ester compound represented by (hereinafter referred to as the compound of the present invention) has extremely high insecticidal and acaricidal efficacy, and the present invention was achieved.

That is, the present invention provides a novel ester compound represented by the general formula (J'J), a method for producing the same, and an insecticide and acaricide containing the same as an active ingredient.

The compound of the present invention has excellent properties such as acting extremely rapidly against various pests, having high lethal activity, and being highly effective against pests resistant to organophosphates or carbamates. It is something.

Specific pests for which the compounds of the present invention are particularly effective include Hemiptera such as planthoppers, leafhoppers, aphids, and stink bugs, Lepidoptera such as armyworms, Diptera such as Culex mosquitoes and houseflies, and German cockroaches. Insects such as the order Ophthalmoptera, subdivisions of the order Pteroptera, Orthoptera, and Isoptera, and mites such as the red-spotted spider mite, the two-spotted spider mite, the red spider mite, and the orange spider mite are included.

The compound of the present invention has, for example, the general formula (3) [wherein X represents a fluorine atom, a chlorine atom or a bromine atom, and Y represents a halogen atom]. ]Benzene, toluene, hexane,
It can be produced by reacting diethyl ether for 20 hours. After completion of the reaction, the reaction solution can be subjected to conventional post-treatments such as organic solvent extraction and concentration, and if necessary, purified by operations such as chromatography to obtain the compound of the present invention.

The compound of the present invention has various optical isomers and geometric isomers, and these isomers and mixtures thereof are also included in the present invention.

When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding any other ingredients, but it is usually used in combination with a solid carrier, liquid carrier, gaseous carrier, surfactant, It can be mixed with other formulation auxiliaries, baits, etc., or impregnated into base materials such as incense sticks and mats to produce emulsions, wettable powders, powders, granules, oils, aerosols, mosquito coils, electric mosquito mats, etc. It is used in formulations such as heating fumigants, fogging agents, non-heating fumigants, poison baits, etc.

These preparations usually contain 0.01% to 95% by weight of the compound of the present invention as an active ingredient.

The solid carriers used include fine powders or granules such as kaolin clay, attapulgite, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, walnut flour, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, halogenated hydrocarbons such as dichloroethane, trichloroethylene, and carbon tetrachloride, methanol, Alcohols such as ethanol, isopropanol, ethylene glycol, and cellosolve; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone; ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate; and nitrites such as acetonitrile and isobutyronitrile. , acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, and vegetable oils such as soybean oil and cottonseed oil.

Examples of the gaseous carrier include chlorofluorocarbon gas, LPG (liquefied petroleum gas), dimethyl ether, and the like.

Surfactants used for emulsification, dispersion, wet layer, etc. include alkyl sulfate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts,
Examples include anionic surfactants such as naphthalene sulfonic acid formalin condensate, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, and CMC.
Examples of stabilizers include alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate), vegetable oils, epoxidized oils, and the above-mentioned surfactants. , B
Antioxidant pressure agents such as HT and BHA, sodium oleate,
Examples include fatty acid salts such as calcium stearate, fatty acid esters such as methyl oleate, and methyl stearate.

The preparation thus obtained can be used as is or diluted with water. It can also be used in combination with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

When using the compound of the present invention as an active ingredient of an insecticide or acaricide: 1. The application amount is usually 0.57 to 0.57 per 10 ares.
5007, and when applying emulsions, wettable powders, etc. diluted with water, the application concentration is usually I T) T) m ~ 100
0 T)T)m, and powders, granules, oils, aerosols, etc. are applied without dilution in any way.

<Examples> Hereinafter, the present invention will be explained in more detail using production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, a production example of the compound of the present invention will be shown.

Production Example In 5d of dry toluene, (R5)-1-(6-phenoxy-2-pyridyl)ethanol 58G"'9 and (IR)-
)U:/Su2.2-Dimethi1z-3-(E/Z)-(
2-chloro-2-fluorovinyl)cyclopropane-1
- 500 m2 of carboxylic acid chloride was dissolved, and 244 mg of pyridine was added dropwise while cooling with water. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours, and then the reaction solution was pressurized into diluted hydrochloric acid water to separate the toluene layer.

Extract the aqueous layer once with toluene, combine it with the previous toluene layer,
After washing successively with water and saturated brine, it was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was subjected to silica gel thin layer chromatography (developing solvent: ethyl acetate: n-hexane = 1:15) to obtain the compound (2) of the present invention, i.e., (R5)-1-(6-phenoxy- 2-pyridyl)-ethyl (IR)-) lance-2,
2-dimethyl-3-(E/Z)-(2-chloro-2-fluorovinyl)cyclopropane-1-carboxyle)
I received 600 mg.

1.5331 1H-NMR (CDCJ a solvent; TMS internal standard)
δ value (ppm): 1.15 to 2.40 (m, 1
1H), 4.80-5.20 (m, IH
), 5.75 (Q, LH), 6.65 (d, LH), 6
85-7.40 (m, 6H), 7.60 (t, LH) 19F-NMR (CD Cps solvent; CFaCO
OH external standard) δ value (pI) m) knee 0.24 (d, 1
/2F) -4,09(d, 1/2F) Next, Table 1 shows some of the compounds of the present invention obtained in the same manner as above.

Compounds shown in Table 1 Next, (IR)-) lance (E/Z)-3-(2-bromo-2-fluorovinyl)-2, which is a raw material compound used in producing the compounds of the present invention. , 2-'; An example of producing methylcyclopropane-1-carboxylic acid is shown.

Reference production example (I) Dry N,N-dimethylformamide 50m/
To the solution were added 5.52 liters of dibromofluoromethane and 3.01 liters of methyl (IR)-trans-2,2-dimethyl-3-formylcyclopropanecarboxylate.

A solution of 4,32 potassium tert-butoxide dissolved in a mixed solvent of 36 rnl of tert-butyl alcohol and 18 ml of dry tetrahydrofuran was added dropwise to this solution under a nitrogen stream while maintaining the temperature at -50°C.

After the dropwise addition was completed, the reaction solution was gradually warmed to room temperature, poured into diluted hydrochloric acid-ice water, and extracted three times with diethyl ether. The diethyl ether layer was washed twice with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was dissolved by adding 50 rnl of pyridine and 50 ml of acetic anhydride, and left overnight at room temperature. This was poured into dilute hydrochloric acid and ice water, extracted twice with diethyl ether, diluted hydrochloric acid and ice water, and extracted twice with diethyl ether.
It was washed successively with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate:
(IR)-trans-2,2-dimethyl-3-(1-acetoxy-2,2-
4.12 of methyl dibromo-2-fluoroethyl)cyclopropanecarboxylate was obtained.

1H-NMR (CDC1g solvent; TMS internal standard) δ value (1)pm): 1.15-2.00 (m, 5H), 2.
15 (m, 3H), 8.65 (m, 3H), 5
．． 15 (m, 1B) (4) Add 2,37 ml of zinc powder to 30 ml of glacial acetic acid and heat at 50°C.
heated to. To this, (IR) −)− obtained in (1)
lance-2,2-dimethyl-3-(I-acetoxy2.
Methyl 2-dibromo-2-fluoroethyl)cyclopropanecarboxylate (4.02%) was dissolved in glacial acetic acid (20%). / was added dropwise with vigorous stirring.

After continuing stirring at 50°C for 30 minutes, insoluble matter was filtered off.
Washed with toluene. The filtrate and washing liquid were combined, and the solvent was distilled off under reduced pressure. Diethyl ether was added to the resulting residue, which was washed successively with water, saturated aqueous sodium bicarbonate, and water, dried over anhydrous magnesium sulfate, and then evaporated under reduced pressure. The solvent was distilled off. The obtained residue was distilled in a Kugelrohr distiller (90°C, 4 hours) to give (IR)-trans(E/Z)-8-(2-bromo-2-fluorovinyl)-2,2- 1.02 of methyl dimethylcyclopropane-1-carboxylate was obtained.

'H-NMR (CDCJ a solvent; TMS internal standard) δ
Value (1) pm): 1.15 (S, 3) (), 1.2
5 (d, 8H), 1.50 (dd, IH), 1.85~
2.30 (m, IH), 8.65 (m, 8H), 4
．． 80 (dd, 1/2H), 5.20 (dd.

1/2H), "F-NMR (CDCJ a solvent; CFsCOOH
external standard) δ value (1) pm) knee 5.49 (d, 1/2
F), -0,96(d, 1/2F'') (-CH=CFBr site had E/Z=1/1.)
(1.02 of the ester obtained in surface (i) was hydrolyzed with aqueous methanol to which twice the equivalent of potassium hydroxide was added,
(IR)-trans(E/Z)-3-(2-bromo-2
~Fluorovinyl)-2,2-ditylcyclopropane-
1-carboxylic acid o,sy was obtained.

1H-NMR (CDCJ a solvent; TMS internal standard)
δ value (pI) m): 1.20 (s, IH), 1.8
0 (S, 8B), 1.50 (dd, LH), 2.10 (
m, IH), 4.80 (dd, 1/2)1),
5.85 (dd.

1/2H) 19F-NMR (CDC7+ a solvent; CFaCO
OH external standard) δ value (1) pm): -6,00 (d
, 1/2F), 1.44 (d, 1/2F) Next, formulation examples are shown. The compounds of the present invention are indicated by the compound numbers listed in Table 1. Parts are parts by weight.

Formulation Example 1 Formulation Example 2 10 parts each of the compounds (1) to 00) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene were thoroughly mixed to obtain a mark Mi.

Formulation Example 3 20 parts each of the compounds of the present invention (1) to 00), 10 parts of fenitrothion, 3 parts of calcium ligninsulfonate Formulation Example 4 1 part each of the compounds of the present invention (1) to (10), Calpari-
Get the rules.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients for insecticides and acaricides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Formulation Example 5 5 parts each of the compounds (1) to 00) of the present invention, i part of synthetic hydrated uranium oxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 62 parts of kaolin clay Formulation Example 6 Compounds of the present invention ( 1) to Cl0), 02 parts of tetramethrin, 7 parts of xylene, and 32.7 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, and after attaching a valve part, the propellant is applied through the valve part. The results are shown in Table 3.

Table 3 Test Example 1 Ten adult female Culex mosquitoes were released in a 70ffi cubic (0.84 m) glass chamber. In this glass chamber, 0.0% of the test compound obtained according to Formulation Example 1 was placed.
0.7 ml of 1% oil agent was sprayed with a spray gun at a pressure of 0.8 atm. After 7 minutes and 00 seconds had elapsed, the number of knockdowns of the test insects was investigated and the number of knockdowns was determined (2 repetitions).
.

Test Example 2 An emulsion of a test compound obtained according to Formulation Example 2 was diluted with water so that the active ingredient was 50 ppm.

This diluted solution was applied to potted rice plants 14 days after sowing at 1 dose per pot.
0. / Sprayed. After air-drying, the rice plants were covered with cages, adult brown planthoppers (female:male = 1:1) were released, and the mortality rate was determined after 1 day. Furthermore, insects were released into the same pots 8 days and 12 days after the chemical spraying, and the mortality rate was determined after 1 day for each.
2 repetitions).

The results are shown in Table 4.

Table 4 Table 5 Test Example 3 Rice stems (length about 12 crn) were placed in a 20,000-fold dilution with water (active ingredient concentration 5 ppm) of the emulsion of the test compound obtained according to Formulation Example 2 for 1 minute. Soaked.

After air-drying, put the rice stem into a test tube and add one brown planthopper adult.
0 animals were released, and the mortality rate was determined 1 day later (2 repetitions).

The results are shown in Table 5.

Test Example 4 A filter paper of the same size was placed at the bottom of a polyethylene cup with a diameter of 5.5 cm. A 20° dilution of the emulsion of the test compound obtained according to Formulation Example 2 with water (active ingredient concentration 5°)
o ppm) 0.7 mzi/” JCM lower L on paper,
30~30 ml of sucrose was evenly added as bait. Ten female adult houseflies were released into the container, the container was covered with a lid, and the mortality rate was determined 24 hours later (2 repetitions).

The results are shown in Table 6.

Table 6 Table 7 Test Example 5 An emulsion of the test compound obtained according to Formulation Example 2 was diluted with water for 50 minutes.
It was diluted to 0 ppm. 2rnl of this diluted solution
18f (7) of artificial feed for Spodoptera were placed in a polyethylene cup with a diameter of 11 crn. Ten fourth-instar Spodoptera larvae were released into a container, and the mortality rate after 6 days was determined (2 repetitions).

The results are shown in Table 7.

Test Example 6 Rice stems (length about 12 crn) were immersed for 1 minute in a 6670-fold dilution of the emulsion of the test compound obtained according to Formulation Example 2 with water (active ingredient concentration 15 ppm). Windchi,
Mortality rate after 1 day was determined (2 replicates).

The results are shown in Table 8.

Table 8 The degree of damage is classified into the following three levels and is indicated by -10 and ox.

: No damage is observed.

10: Some damage is observed.

++: Damage similar to non-processing is observed.

The results are shown in Table 9.

Table 9 Test Example 7 -
10 adult female spider mites per leaf, 2
It was stored in a constant temperature room at 5°C. After 6 days, the emulsion of the test compound obtained according to Formulation Example 2 was diluted with water to an active ingredient concentration of 500.
The diluted solution was diluted to pI)m on a turntable for 10rn! Spreading and simultaneously pouring 2 m/m of soil*m. After 8 days, examine the degree of damage caused by spider mites to each string bean.

<Effects of the Invention> The compounds of the present invention are effective against Hemiptera such as planthoppers, Aphids, Aphids, and stink bugs, Diptera such as Culex and Culex mosquitoes, and Acarina such as N. chinensis and Citrus spider mite. Since it has excellent insecticidal and acaricidal effects against a variety of pests, it can be used for a variety of purposes.

Claims (3)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents a fluorine atom, chlorine atom, or bromine atom. ] An ester compound represented by (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X represents a fluorine atom, chlorine atom, or bromine atom, and Y represents a halogen atom. ] Carboxylic acid halide and 1-(6-phenoxy-2-pyridyl)
A method for producing an ester compound according to claim 1, which comprises reacting with ethanol. (3) An insecticide or acaricide containing the ester compound according to claim 1 as an active ingredient.