JPH0349911B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, A is a -CH ₂ -CH ₂ - group or -CH=CH
- group, and R ₁ represents a methyl group or general formula (). Here, R ₄ and R ₅ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a 1 to 3 carbon atom.
~2 haloalkyl group, haloalkoxy group, or R ₄ and R ₅ represent a methylenedioxy group. Y is
Represents an oxygen atom, methylene group, amino group, methylamino group, formylamino group, or carbonyl group. In addition, R ₂ is a hydrogen atom or a fluorine atom,
R ₃ represents a hydrogen atom, a halogen atom or a methyl group. ) The present invention relates to an insecticide and acaricide characterized by containing an organosilicon compound represented by the following formula, and a method for producing the same. In recent years, research has been widely conducted on analogs with modified chemical structures of pyrethrin, a natural insecticidal ingredient, and the general formula () (Here, R ₂ , R ₃ , R ₄ , and R ₅ have the same meanings as above.) In addition to the compound group represented by High insecticidal activity was found in the compound represented by (Japanese Unexamined Patent Publication No. 58-201737). Although these compounds are being widely developed as agricultural chemicals to replace conventional organic phosphorus agents and carbamate agents, they are unable to adequately deal with the problem of pyrethroid resistance that will arise in the future. Poor penetration into the plant body. In particular, the problems inherent to pyrethroids, such as high toxicity to fish, have not been sufficiently improved for compounds of type (). In addition, the present inventors previously discovered the general formula (In the formula, R ₁ and R ₂ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a halomethyl group, a methoxy group, an ethoxy group, a difluoromethoxy group, or R ₁ and R ₂ represents a methylenedioxy group. X is an oxygen atom or a methylene group _, A represents an oxygen atom, a methylene group, an amino group, a methylamino group, or a formylamino group. , R ₄ represents a hydrogen atom, a halogen atom, or a methyl group. This insecticide and acaricide improves the above-mentioned drawbacks, has good insecticidal efficacy, and has low toxicity to warm-blooded animals, making it an excellent product. As a result of intensive research into silicon-based aromatic alkane derivatives, we have found that, like the insecticides and acaricides described in the above-mentioned JP-A-61-87687, they have improved the drawbacks of , and have low toxicity to warm-blooded animals. However, we have discovered an insecticide and acaricide that is even more excellent in insecticidal efficacy and residual efficacy than the insecticide and acaricide described in the publication. The compound represented by the above formula () used as an active ingredient in the present invention has the general formula () (In the formula, R ₁ represents a methyl group or general formula (). Here, R ₄ and R ₅ are the same or different, a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
Alkoxy group having 1 to 3 carbon atoms, haloalkyl group having 1 to 2 carbon atoms, haloalkoxy group or R ₄
R ₅ represents a methylenedioxy group. Also, M is a chlorine atom or a metal atom (Li, Na, K, etc.)
represents. ) Organosilicon compounds and general formulas (In the formula, A is a -CH ₂ -CH ₂ - group or -CH=CH
- group, and Y represents an oxygen atom, a methylene group, an amino group, a methylamino group, a formylamino group, or a carbonyl group. Further, R ₂ represents a hydrogen atom or a fluorine atom, and R ₃ represents a hydrogen atom, a halogen atom, or a methyl group. Further, Z represents a halogen atom or a reactive derivative thereof. ) can be prepared by reacting a compound represented by The reaction is carried out in a suitable solvent, optionally in the presence of a catalyst, and optionally with heating. In addition, when A is a -CH=CH- group, geometric isomers based on double bonds exist, and each of them or a mixture thereof is included in the present invention. Representative examples of the compound represented by the above formula () are as follows, but the present invention is of course not limited to these. Dimethyl (4-ethoxyphenyl) {3-(2-
Phenoxy-6-pyridyl)propyl}silane n ²⁰ _D 1.5684 Dimethyl (4-ethoxyphenyl) [3-{2-
(4-Fluorophenoxy)-6-pyridyl}propyl]silane n ²⁰ _D 1.5675 Trimethyl {3-(2-benzyl-3-fluoro-6-pyridyl)-1-propenyl}silane n ²⁰ _D 1.5558 Trimethyl[3-{2-(4-chlorophenoxy)-6-pyridyl}propyl]silane n ²⁰ _D 1.5603 Trimethyl {3-(2-benzoyl-6-pyridyl)propyl}silane n ²⁰ _D 1.5570 Dimethyl(3,4-methylenedioxyphenyl)[3-{2-(N-methyl-4-fluoroanilino-6-pyridyl}propyl)silane n ²⁰ _D 1.5720 Dimethyl (4-tert-butylphenyl)
{3-(2-anilino-3-fluoro-6-pyridyl)propyl}silane n ²⁰ _D 1.5704 Dimethyl(3,4-methylenedioxyphenyl)[3-{2-(4-methylbenzoyl)-6-pyridyl}propyl]silane n ²⁰ _D 1.5704 Dimethyl (3,4-dimethylphenyl) {3-
(2-phenoxy-6-pyridyl)-1-propenyl}silane n ²⁰ _D 1.5694 Dimethyl (3-chloro-4-ethylphenyl)
{3-(2-benzyl-3-fluoro-6-pyridyl)-1-propenyl}silane n ²⁰ _D 1.5723 Dimethyl (3-methoxy-4-chloromethylphenyl) [3-{2-(4-chloroanilino)-6-
(pyridyl)-1-propenyl]silane n ²⁰ _D 1.5786 Dimethyl(3-methyl-4-fluorophenyl)[3-{2-(N-methylanilino)-6-pyridyl)-1-propenyl]silane n ²⁰ _D 1.5790 Dimethyl (4-isopropylphenyl) [3-
{2-(N-formyl-4-fluoroanilino)-
6-pyridyl)-1-propenyl]silane n ²⁰ _D 1.5788 Trimethyl [3-{2-(3-methylanilino)
-3-Fluoro-6-pyridyl}-1-propenyl]silane n ²⁰ _D 1.5595 Trimethyl [3-{2-(N-methylanilino)
-6-pyridyl}propyl]silane n ²⁰ _D 1.5581 Trimethyl[3-{2-(N-formyl-4-fluoroanilino)-6-pyridyl}-1-propenyl]silane n ²⁰ _D 1.5575 Dimethyl (3-bromo-4-bromofluoroethylphenyl) {3-(2-benzyl-6-pyridyl)propyl}silane n ²⁰ _D 1.5779 Dimethyl(3-fluoro-4-propylphenyl)[3-{2-(N-formyl-4-bromoanilino)-6-pyridyl}propyl]silane n ²⁰ _D 1.5802 Dimethyl(4-chlorophenyl) {3-(2-phenoxy-3-fluoro-6-pyridyl)propyl}silane n ²⁰ _D 1.5760 Trimethyl {3-(2-benzoyl-3-fluoro-6-pyridyl}-1-propenyl}silane n ²⁰ _D 1.5585 Dimethyl (4-pentafluoroethoxyphenyl) {3-(2-phenoxy-3-fluoro-6-
pyridyl)propyl}silane n ²⁰ _D 1.5697 The compound used as an active ingredient in the insecticide and acaricide of the present invention is a new compound, solid or liquid at room temperature, and generally easily soluble in organic solvents. Therefore, as an insecticide or acaricide for spraying, it can be used as an emulsion, oil, powder, aerosol, etc.
It can also be mixed with wood flour or other suitable base material and used as an insecticide or acaricide for fumigation such as mosquito coils. Also, when used as a so-called electric mosquito repellent, in which the active ingredient is dissolved in an appropriate organic solvent and soaked in a mount, or dissolved in an appropriate solvent and heated and evaporated with an appropriate heating element, it can be used in the same way as a mosquito coil. Shows excellent effects. The compound of the present invention is more stable to light than conventional pyrethroids, and has insecticidal and
Because it has a wide acaricidal spectrum, low toxicity, low fish toxicity, and low price, it can be used as an agricultural and horticultural insecticide and acaricide in place of conventional organophosphates and organochlorine insecticides. can. The insecticide and acaricide of the present invention can be used for flies,
In addition to sanitary pests such as mosquitoes and cockroaches, organophosphorus and carbamate resistant leafhoppers, planthoppers, stinkbugs, armyworms, diamondback moths, tobacco moths, bean weevils, nocturnal moths, cabbage moths, chestnut beetles, leafhoppers, aphids, and scale insects. It is extremely useful for the control of agricultural pests such as, grain storage pests such as brown elephant, mites, etc.
Furthermore, the compound of the present invention has significantly reduced toxicity to fish compared to conventional pyrethroids, and has good permeability into plants, making it possible to apply it as an insecticide for paddy rice. In addition, the insecticide and acaricide of the present invention may include N-
Octylbicycloheptenedicarboximide (trade name MGK-264), mixture of N-octylbicycloheptenedicarboximide and aryl sulfonate (tradename MGK-5026), Cinepirin 500, octachlorodipropyl ether, piperonylbutylene The insecticidal and acaricidal effects can be further enhanced by adding a synergist such as toxide.
In addition, other insecticides such as fenitrothion, DDVP, diazinon,
Organic phosphorus agents such as propaphos and pyridafenethione, carbamate agents such as NAC, MTMC, BPMC, and PHC, pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decamethrin, fuenvalerate, fuenpropanate, and fluvali Conventional pyrethroid insecticides such as nate, insecticides or acaricides such as cartap, chlorphenamidine, methomyl, fungicides, nematicides, herbicides,
By mixing plant growth regulators, fertilizers, and other agricultural chemicals, a multipurpose composition with excellent effects can be obtained, and labor savings and synergistic effects between the drugs can be fully expected. Next, examples of synthesizing compounds used as active ingredients in the present invention will be shown. The organosilicon compound represented by the general formula () is
If R ₁ is a methyl group, it can be obtained as a commercially available product, and R ₁
When is represented by the general formula (), it can be easily obtained using the Grignard reaction as shown in FIG. Note that the compound () can be reacted with a metal element to lead to a lithium, sodium, or potassium silane compound if necessary. on the other hand,
The compound of general formula () is prepared by using an alcohol component constituting a pyrethroid, for example, when A is -CH ₂ -
In the case of CH ₂ - group, it can be easily prepared according to FIG. The compound of the general formula () can be easily coupled with the silicon compound of the general formula () by using, for example, a Grignard reaction to synthesize the compound () of the present invention. Also, A is -
In the case of CH=CH- group, as shown in Figure 3, the general formula () is α-bromonated using N-bromosucciimide, and then selectively HBr is removed to lead to the general formula (). It can be prepared by coupling with a silicon compound of the general formula () as shown below, and then migrating the double bond in the presence of a base such as n-butyllithium. Synthesis Example 1 0.4 g of metallic lithium was added to 50 ml of dry tetrahydrofuran under a nitrogen stream. Cool to -50°C with dry ice-acetone, and add 4.2 g of dimethyl(4-ethoxyphenyl)chlorosilane to this suspension.
30ml of solution dissolved in 20ml of dry tetrahydrofuran
It was dripped in minutes. After reacting at this temperature for 1 hour, the liquid temperature was gradually raised to 0° C. and stirred for an additional 1 hour to generate lithium silane. The reaction solution was cooled to -20 DEG C., and then a solution of 5.0 g of 3-(2-phenoxy-6-pyridyl)propyl chloride dissolved in 40 ml of dry tetrahydrofuran was added dropwise over 1 hour under a nitrogen stream. After further stirring at room temperature for 2 hours, water was carefully added dropwise to the reaction solution while cooling to decompose excess lithium. After extraction with benzene, the benzene solution was washed with saturated saline and dried over sulfur salt. The oil obtained by distilling off benzene under reduced pressure was purified by column chromatography on 100 g of silica gel, and dimethyl (4-ethoxyphenyl) was purified.
6.2 g of {3-(2-phenoxy-6-pyridyl)propyl}silane was obtained. Synthesis Example 2 0.6 pieces of magnesium metal in 40 ml of dry ether
1.7 g of 3-{2-(N-formyl-4-fluoroanilino)-6-pyridyl}-2-propenyl bromide and a small amount of iodine were added. Warm to 40℃,
After the reaction started, 20 ml of an ether solution containing 5.6 g of 3-{2-(N-formyl-4-fluoroanilino)-6-pyridyl}-2-propenyl bromide was added dropwise so as to continue boiling. After further stirring for 15 minutes to prepare a Grignard reagent, 50 ml of an ether solution containing 4.4 g of dimethyl(4-isopropylphenyl)chlorosilane was added dropwise over 3 hours with vigorous stirring, and the mixture was stirred under reflux for an additional hour. While stirring the reaction mixture, add 30 g of ice, 10 g of ammonium chloride, and 20 g of water.
and the ether layer was separated. The aqueous layer was extracted twice with 50 ml of ether, combined with the ether layer, washed with brine, and the ether was distilled off.
8.1g of the resulting residue was dried in tetrahydrofuran 50g.
ml, and 16 ml of n-hexane solution (1.35 mol solution) of n-butyllithium was added thereto at -50°C under a nitrogen stream. After continuing the reaction at the same temperature for 1 hour, the reaction solution was heated to nitrogen temperature and stirred overnight to complete the reaction. Next, the reaction solution was cooled to -50°C, 30 ml of 10% hydrochloric acid was added thereto, extracted with ethyl acetate, and the ethyl acetate solution was diluted with saturated brine for 2 hours.
Washed twice. After further drying with anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography to obtain the desired dimethyl (4-
isopropylphenyl) [3-{2-(N-formyl-4-fluoroanilino)-6-pyridyl}-1
7.7 g of -propenyl]silane were obtained. According to Synthesis Example 2, dimethyl(3-chloro-4-ethylphenyl)chlorosilane and 3-(2-benzyl-
3-fluoro-6-pyridyl)-2-propenylmagnesium bromide to dimethyl(3-chloro-4-ethylphenyl){3-(2-benzyl-
3-fluoro-6-pyridyl)-1-propenyl}
I got silane. Next, in order to make it clearer that the composition provided by the present invention is excellent, the results of testing the effectiveness will be shown. Test Example 1 Insecticidal test by spraying 0.2% white light solution of the compound of the present invention (A), 0.2% and cinepirin 500 0.8% white light solution (B), 0.1% and phthalthrin 0.1% white light solution (C), and The falling and turning rate of houseflies was calculated for a 0.2% white light solution of phthalthrin and compound (A), the relative effectiveness of the test agent was calculated, and the mortality rate after 24 hours was calculated as follows. . The numbers in parentheses indicate the mortality rate after 24 hours.

[Table] Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of insecticidal ingredients were prepared and tested for their effectiveness in causing adult Culex mosquitoes to fall and roll over. This experiment was published in Insect Control Science Volume 16 (1951).
The relative effectiveness of the incense stick was calculated according to the method of Nagasawa, Katsuta et al., p. 176, and the results were as follows. The sample drug number is the same as that of the active ingredient example above.

[Table] Test Example 3 Insecticidal test using microdropping method Piperonyl butoxide was added to each of the control compound (A) and the compound of the present invention in an amount twice the amount of the active ingredient to prepare an acetone solution with a predetermined concentration. The compound was applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the insecticidal power relative to the control compound and the synergistic effect with piperonyl butoxide were investigated based on the mortality rate after 24 hours.The results are as follows.

[Table] Next, examples of formulation are shown, but the formulation does not require any special conditions similar to general agricultural chemicals, and can be prepared by a method familiar to those skilled in the art. . Example 1 White kerosene was added to 0.2 parts of the compound of the present invention (1) and the whole was mixed.
Obtain 0.2% oil solution as 100 parts. Example 2 White kerosene was added to 0.2 parts of the compound (11) of the present invention and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil agent. Example 3 To 20 parts of the compound of the present invention (4), 10 parts of Sorbol SM-200 (registered trademark of Toho Chemical) and 70 parts of xylol were added, stirred and mixed to dissolve, to obtain a 20% emulsion. Example 4 Compound of the present invention (13) 0.4 parts, resmethrin 0.1
1 part, 1.5 parts of octachlorodipropyl ether is dissolved in 28 parts of refined kerosene, and the solution is filled into an aerosol container.
After installing the valve part, 70 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol. Example 5 0.5 g of the compound (17) of the present invention and 0.5 g of BHT were added to base materials for mosquito coils such as pyrethrum extract lees powder, wood flour, and starch powder.
Mix 99.0g of the mixture uniformly and obtain a mosquito coil by a known method. Example 6 Compound of the present invention (25) 0.4g, MGK-5026 1.0g
was uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Example 7 0.3 parts of the compound of the present invention (30) and 99.7 parts of clay are ground and mixed to obtain a 0.3% powder. Example 8 40 parts of the compound of the present invention (38), 35 parts of diatomaceous earth, 20 parts of clay
1 part, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 4 5 to 5 on a surface where a large number of green peach aphids appeared
Among the emulsions obtained in Example 3 in a radish field at the 6-leaf stage, compounds of the present invention (13), (17), (22), (25),
A 1000 times diluted solution of each emulsion containing (31), (34) and (38) with water was sprayed at 100 times per area.
A parasitic rate survey two days later showed that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 5 Compound of the present invention among the emulsions obtained in Example 3
(1), (4), (12), (18), (23), (29) and (34)
of
Fresh leaves were immersed in the 2000-fold diluted solution for about 5 seconds, and after the solution had dried, they were placed in a shear dish, and 10 healthy armyworm larvae were released. The test insects were released twice, once on the day of soaking the fresh leaves, and once 5 days later, and the mortality rate after 24 hours was determined.

[Table] From the results of Test Example 5, the drug of the present invention has superior insecticidal efficacy and residual efficacy compared to the commercially available salithion emulsion and control drugs A and B. In particular, the drug of the present invention (1)
Comparisons between the drug (34) and the control drug A, as well as the drug (34) of the present invention and the control drug B confirmed the usefulness of introducing a substituted pyridyl group in place of the substituted phenyl group. Test Example 6 One day before applying the insecticidal ingredient to potted fava beans, one tree was infested with approximately 200 aphids. Among the hydrating agents obtained in Example 8, (11)
Spray 4000 times diluted solutions of (16), (24), (28), (35) and (38) onto leaves infested with compressed air.
Sprayed 10ml/pot and observed the degree of damage two days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 7 Each of the powders (1), (17), (26), and (30) obtained in Example 7 was uniformly sprinkled on the bottom of a waist-high glass shear dish with a diameter of 14 cm at a rate of ² g/m2. Spread butter on the wall, leaving about 1cm at the bottom. If adult German cockroaches were released into the container in groups of 10, and the cockroaches were left in contact for 30 minutes and then transferred to a new container, more than 80% of the cockroaches could be killed by either powder after three days. Test Example 8 1 for 4 leaves of potted green beans 5 days after sowing
Infested with 10 female adult spider mites per leaf.
Store in a constant temperature room at 27℃. After 6 days, a chemical solution prepared by diluting the emulsions (1), (4), (22), (32) and (34) obtained in Example 3 with water to 100 ppm of active ingredient was sprayed on a turntable in 10 ml per pot. After 10 days, the number of parasitic spider mites on the plants was observed.

[Table] Results of Test Example 8, especially the drug (1) of the present invention and control drug A, and the drug (34) of the present invention and target drug B
From the comparison with JP 61-87687, the drug of the present invention
It can be seen that the compound exhibits a higher acaricidal effect compared to the compound disclosed in the publication. Test Example 9 Carp was used as the subject, and the compound of the present invention ((11)), (16), (29)
When the TLm48 (ppm) of (35) was determined, it was 10 or more in all cases.

Claims (1)

[Claims] 1. General formula [In the formula, A is -CH ₂ -CH ₂ - group or -CH=CH
- represents a group, R ₁ is a methyl group or the following formula () (In the formula, R ₄ and R ₅ are the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 3 carbon atoms, or 1 to 2 carbon atoms)
represents a haloalkyl group, a haloalkoxy group, or R ₄ and R ₅ together represent a methylenedioxy group. ) represents a group represented by
Y represents an oxygen atom, methylene group, amino group, methylamino group, formylamino group or carbonyl group, R ₂ represents a hydrogen atom or a fluorine atom, and R ₃ represents a hydrogen atom, a halogen atom or a methyl group . ] An insecticide and acaricide characterized by containing an organosilicon compound represented by the following. 2 General formula [In the formula, R ₁ is a methyl group or the following formula () (In the formula, R ₄ and R ₅ are the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 3 carbon atoms, or
2 represents a haloalkyl group or a haloalkoxy group, or R ₄ and R ₅ together represent a methylenedioxy group. ) represents a group represented by
And M represents a chlorine atom or a metal atom. ]
Organosilicon compounds and general formulas represented by (In the formula, A is a -CH ₂ -CH ₂ - group or -CH=CH
- group, Y represents an oxygen atom, methylene group, amino group, methylamino group, formylamino group, or carbonyl group, R ₂ represents a hydrogen atom or a fluorine atom, and R ₃ represents a hydrogen atom, a halogen atom, or It represents a methyl group, and Z represents a halogen atom or a reactive derivative thereof. ) General formula obtained by reacting compounds represented by (In the formula, A, Y, R ₁ , R ₂ and R ₃ have the same meanings as above.) A method for producing an insecticide or acaricide, characterized by containing an organosilicon compound represented by the above formula.