JPS6352035B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, R ₁ and R ₂ are the same or different, 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 a methylenedioxy group is represented by R ₁ and R ₂ . X is an oxygen atom or a methylene group, and A represents an oxygen atom, a methylene group, an amino group, a methylamino group, or a formylamino group. R ₃ represents a hydrogen atom or a fluorine atom, and R ₄ 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 aromatic alkane derivative represented by the following as an active ingredient, 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 ₁ , R ₂ , R ₃ , and R ₄ have the same meanings as above.) In addition to the compound group represented by High insecticidal activity was found in the compound represented by (JP-A-58-201737). Although these compounds are being widely developed as pesticides 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 the high toxicity of compounds in () to fish, have not yet been sufficiently resolved. The inventors of the present invention continued their intensive research to find even more useful insecticidal and acaricidal ingredients. As a result, the above drawbacks were significantly improved by introducing silicon element, which is an alternative element to carbon element. On the other hand, the present invention was completed based on the knowledge that the insecticidal efficacy is enhanced and the toxicity to warm-blooded animals is further reduced compared to the original compound. Although there are still many unknowns as to why the introduction of silicon is effective, it is presumed that it is due to the empty 3D orbitals that exist in the outer shell of silicon atoms. 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 and R ₂ are the same or different, 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 a methylenedioxy group is represented by R ₁ and R ₂ . Also, M is a metal atom (Na, K, Li
etc.). ) Organosilicon aromatic compounds and general formulas (In the formula, X is an oxygen atom or a methylene atom, and A represents an oxygen atom, a methylene group, an amino group, a methylamino group, or a formylamino group.
R ₃ represents a hydrogen atom or a fluorine atom, and R ₄ represents a hydrogen atom, a halogen atom, or a methyl group. Also Y
represents a reactive derivative of a halogen atom or a hydroxyl group. ) 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. Representative examples of the compound represented by the above formula () are as follows, but the present invention is of course not limited to these. (1) Dimethyl (4-ethoxyphenyl) {3-(3-
phenoxy)phenylpropyl}silane
n ²⁰ _D 1.5641 (2) Dimethyl(4-ethoxyphenyl)(3-phenoxybenzyloxymethyl)silane
n ²⁰ _D 1.5653 (3) Dimethyl (4-ethoxyphenyl) {3-(3-
Phenoxy-4-fluoro)phenylpropyl}silane n ²⁰ _D 1.5638 (4) Dimethyl (4-ethoxyphenyl) {3-(3-
Anilino) phenylpropyl}silane
n ²⁰ _D 1.5690 (5) Dimethyl(4-ethoxyphenyl)(3-benzylbenzyloxymethyl)silane
n ²⁰ _D 1.5682 (6) Dimethyl (4-ethoxyphenyl) [3-{3-
(N-methyl-4-chloroanilino)phenyl}
Propylsilane n ²⁰ _D 1.5706 (7) Dimethyl (3,4-dichlorophenyl) {3-
(4-fluorophenoxy)-4-fluorobenzyloxymethyl}silane n ²⁰ _D 1.5612 (8) Dimethyl (4-difluoromethoxyphenyl)
[3-{3-(N-formyl-4-methylanilino)phenyl}propyl]silane n ²⁰ _D 1.5738 (9) Dimethyl(3,4-methylenedioxyphenyl)(3-anilino-4-fluorobenzyloxymethyl)silane n ²⁰ _D 1.5790 (10) Dimethyl (4-tert-butylphenyl)
[3-{3-(4-bromobenzyl)phenyl}
Propylsilane n ²⁰ _D 1.5765 (11) Dimethylphenyl 3-{3-(3-phenoxy)
Phenylpropyl}silane n ²⁰ _D 1.5477 (12) Dimethyl (4-methoxyphenyl) {3-(N-
methylanilino-4-fluorobenzyloxymethyl}silane n ²⁰ _D 1.5692 (13) Dimethyl (3-chloro-4-trifluoromethylphenyl) {3-(N-formyl-4-fluoroanilino)-4-fluorobenzyloxymethyl}silane n ²⁰ _D 1.5728 (14) Dimethyl (3,4-dimethylphenyl) [3-
{3-(4-fluorophenoxy)phenyl}propyl]silane n ²⁰ _D 1.5586 (15) Dimethyl (3-chloro-4-ethylphenyl)
{3-(4-bromoanilino)benzyloxymethyl}silane n ²⁰ _D 1.5833 (16) Dimethyl(3-methoxy-4-chloromethylphenyl) {3-(3-benzyl-4-fluorophenyl)propyl}silane n ²⁰ _D 1.5725 (17) Dimethyl (3-methyl-4-fluorophenyl) {3-(4-bromophenoxy)-4-fluorobenzyloxymethyl}silane
n ²⁰ _D 1.5780 (18) Dimethyl (4-isopropylphenyl) {3-
(N-methylanilino)benzyloxymethyl}
Silane n ²⁰ _D 1.5686 (19) Dimethyl(3-bromo-4-bromofluoromethylphenyl[3-{3-(4-methylphenoxy)-4-fluorophenyl}propyl]silane n ²⁰ _D 1.5794 (20) Dimethyl (3,4-methylenedioxyphenyl) {3-(4-iodobenzylbenzyloxymethyl}silane) n ²⁰ _D 1.5751 (21) Dimethyl (4-chlorophenyl) [3-{3-
(4-fluoroanilino)phenyl}propyl]
Silane n ²⁰ _D 1.5677 (22) Dimethyl(3-fluoro-4-propylphenyl) {3-(N-formyl-4-chloroanilino)benzyloxymethyl}silane
n ²⁰ _D 1.5740 (23) Dimethyl (4-difluoromethoxyphenyl)
{3-(4-chlorophenoxy)-4-fluorobenzyloxymethyl}silane n ²⁰ _D 1.5659 (24) Dimethyl(4-chlorophenyl){3-(3-phenoxyphenyl)propyl}silane
n ²⁰ _D 1.5592 (25) Dimethyl (4-chlorophenyl) {3-(4-fluorophenoxy)benzyloxymethyl}silane n ²⁰ _D 1.5605 The compound used as an active ingredient in the insecticide and acaricide of the present invention is a new compound, and is solid or solid at room temperature. It is a liquid and generally easily soluble in organic solvents. Therefore, insecticides and acaricides for spraying can be used in the form of emulsions, oils, powders, wettable powders, aerosols, etc., and can also be mixed with wood flour or other suitable base materials for fumigation such as mosquito coils. It can be used as an insecticide and acaricide. 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, has a broader spectrum of insecticidal and acaricidal properties, has low toxicity, low toxicity to fish, and is inexpensive, so it is better than conventional organic phosphorus agents. It can be used as an agricultural and horticultural insecticide and acaricide in place of organochlorine insecticides. 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 effect can be further enhanced by adding a synergist such as toxide. In addition, in addition to the insecticide and acaricide of the present invention, other insecticides, such as organic phosphorus agents such as fenitrothion, DDVP, diazinon, propafos, and pyridafentione,
Carbamates such as NAC, MTMC, BPMC, PHC, conventional pyrethroid insecticides such as pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decametrin, fuenvalerate, fuenpropanate, cartap, chlorphenamide Insecticides or acaricides such as gin, methomyl, etc.
By mixing fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, saving labor and providing sufficient synergy between the drugs. This is something to look forward to. Next, examples of synthesizing compounds used as active ingredients in the present invention will be shown. The metal organosilicon aromatic compound represented by the general formula () is based on chlorosilane containing Na, K,
Obtained by reacting metal elements such as Li. [Figure 1] On the other hand, the compound of general formula () can be prepared according to FIG. 2 using the alcohol component constituting the pyrethroid. [Figure 2] Synthesis Example 1 0.4 g of metallic lithium was added to 50 ml of dry tetrahydrofuran under a nitrogen stream. The suspension was cooled to -50 DEG C. with dry ice-acetone, and a solution prepared by dissolving 4.1 g of dimethyl(4-chlorophenyl)chlorosilane in 20 ml of dry tetrahydrofuran was added dropwise to this suspension over 30 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 4.9 g of 3-(3-phenoxy)phenylpropyl chloride dissolved in 40 ml of dry tetrahydrofuran was added dropwise under a nitrogen stream over 1 hour. 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 brine 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-chlorophenyl) {3-(3
-Phenoxyphenyl)propyl}silane 6.4g
I got it. Synthesis Example 2 0.9 g of potassium metal was added to 40 ml of dry ether under a stream of nitrogen, and the suspension was cooled to -40°C.
Dimethyl(4-methoxyphenyl)chlorosilane
A solution of 4.0 g dissolved in 20 ml of dry ether was added dropwise to the suspension over 30 minutes. After stirring at -40°C for 2 hours, the liquid temperature was gradually raised to 0°C, and stirring was further continued for 1 hour to complete the production of potassium silane.
The reaction solution was cooled again to -40°C and heated under a nitrogen stream for 3
-(N-Methylanilino)-4-fluorobenzyloxymethyl chloride (5.6 g) in dry ether 40
ml of the solution was added dropwise over 1 hour. 1 at -40℃
After reacting at room temperature overnight, water was added and the ether layer was separated. After distilling off the solvent, the resulting residue was purified by column chromatography on 100 g of silica gel to obtain the desired dimethyl (4-methoxyphenyl).
6.8 g of {3-(N-methylanilino)-4-fluorobenzyloxymethyl}silane was obtained. Similarly, sodium, dimethyl(3-methoxy-4-chloromethylphenyl)silane and 3-(3
-benzyl-4-fluorophenyl)propyl bromide to dimethyl(3-methoxy-4-chloromethylphenyl){3-(3-benzyl-4-
fluorophenyl)propyl}silane, lithium dimethyl(3-fluoro-4-propylphenyl)silane and p-(N-formyl-4-chloroanilino)benzyloxymethyl alcohol
Toluenesulfonic acid ester and dimethyl (3
-Fluoro-4-propylphenyl) {3-(N-
Formyl-4-chloroanilino)benzyloxymethyl}silane was obtained. 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 A 0.2% white light solution of the compound of the present invention (A), a white light solution of 0.2% and 0.8% Cinepirin 500 (B), a white light solution of 0.1% and phthalthrine 0.1% (C), The falling and turning rate of houseflies was determined for each 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 determined as follows. be.

[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 fall upside down. 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. . Reference example 1 White kerosene was added to 0.2 parts of the present compound (1) and the whole
Obtain 0.2% oil solution as 100 parts. Reference Example 2 White kerosene is added to 0.2 parts of the present compound (4) and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil solution. Reference Example 3 To 20 parts of the compound (7) of the present invention, 10 parts of Solpol SM-200 (registered trademark of Toho Chemical) and 70 parts of xylol were added and stirred and mixed to dissolve to obtain a 20% emulsion. Reference Example 4 0.4 parts of the present compound (9), 0.1 parts of resmethrin, and 1.5 parts of octachlorodipropyl ether were added to refined kerosene.
After dissolving in 28 parts and filling into an aerosol container and attaching a valve part, 70 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol. Reference Example 5 0.5 g of the compound (14) 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. Reference example 6 Compound of the present invention (17) 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. Reference Example 7 0.3 parts of the compound of the present invention (21) and 99.7 parts of clay are ground and mixed to obtain a 0.3% powder. Reference Example 8 40 parts of the present compound (24), 35 parts of diatomaceous earth, clay
20 parts of lauryl sulfonate, 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 Reference Example 3 in a radish field at the 6-leaf stage, compounds of the present invention (3), (7), (10), (13), (18),
by water of each emulsion containing (22) and (25).
A 1000-fold diluted solution was sprayed 100 times per area. Two days later, the parasitism rate was investigated and found that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 5 Among the emulsions obtained in Reference Example 3, the compound of the present invention
(2), (4), (7), (11), (15), (17) and (23)
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] Test Example 6 Approximately 200 aphids were infested on one tree one day before applying the insecticidal ingredient to potted fava beans. Among the hydrating agents obtained in Reference Example 8, (2)
(6), (7), (14), (16), (19) and (24) 4000
The diluted solution was sprayed onto leaves infested with insects using a compressed air spray method (10 ml/pot), and the degree of damage was observed 2 days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 7 (1), (5), (8), (12), obtained by Reference Example 7
Each of the powders (17) and (21) is uniformly sprinkled at a rate of 2 g/m ² on the bottom of a waist-high glass shear dish with a diameter of 14 cm, and the butter is applied to the wall leaving about 1 cm of the bottom. If you release 10 adult German cockroaches into the container, leave them in contact for 30 minutes, and transfer the cockroaches to a new container, after 3 days, 80.
It was possible to kill more than % of cockroaches. 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, emulsions (4), (7), (10), (15), (20) and (22) obtained in Reference Example 3 were
)
A chemical solution diluted with water to 100 ppm of active ingredient was sprayed on a turntable in 10 ml per pot, and 10 days later, the number of parasitic spider mites on the plants was investigated. As a result, all of the insecticides and acaricides of the present invention were found to have acaricidal effects superior to the control agents.

[Table] Test Example 9 Carp was used as the subject, and the tests were carried out in accordance with the Toxicity Test Method for Fish, Notification Agricultural Policy No. B 2735 (November 25, 1966), and the compounds of the present invention (2), (8), (11) were tested. ), (16)
When the TLm48 (ppm) of (21) was determined, it was 20 or more in both cases.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ and R ₂ are the same or different, 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 a methylenedioxy group is represented by R ₁ and R ₂ . X is an oxygen atom or a methylene group, and A represents an oxygen atom, a methylene group, an amino group, a methylamino group, or a formylamino group. R ₃ represents a hydrogen atom or a fluorine atom, and R ₄ represents a hydrogen atom, a halogen atom, or a methyl group. ) An insecticide and acaricide characterized by containing an organosilicon aromatic alkane derivative represented by: 2 General formula (In the formula, R ₁ and R ₂ are the same or different, 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 a methylenedioxy group is represented by R ₁ and R ₂ . Also, M is a metal atom (Na, K, Li
etc.). ) Organosilicon aromatic compounds and general formulas (In the formula, X is an oxygen atom or a methylene atom, and A represents an oxygen atom, a methylene group, an amino group, a methylamino group, or a formylamino group.
R ₃ represents a hydrogen atom or a fluorine atom, and R ₄ represents a hydrogen atom, a halogen atom, or a methyl group. Also Y
represents a reactive derivative of a halogen atom or a hydroxyl group. ) General formula obtained by reacting compounds represented by (Herein, R ₁ , R ₂ , R ₃ , R ₄ , X and A have the same meanings as above.) Method of manufacturing the agent.