JPH01131104A - Insecticidal and miticidal agent containing organic silicon compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain an insecticidal and miticidal agent having high permeability into plant body, low toxicity to warm-blooded animal and excellent insecticidal activity and applicable without causing the problem of the development of pyrethroid resistance, by using a novel organic silicon compound as an active component. CONSTITUTION:The objective agent contains an organic silicon compound of formula I [A is -CH2-CH2- or -CH=CH-; R is methyl or group of formula II (R4 and R5 are same or different H, halogen, 1-4C alkyl, 1-3C alkoxy, etc.); X is N or methyl; Y is O, methylene, amino, etc., provided that Y is solely carbonyl when A is -CH2-CH2, R is group of formula II and X is methylene; R2 is H or F; R3 is H, halogen or methyl] as an active component. The agent is used in the form of emulsifiable concentrate, wettable powder, etc. The compound of formula I is a novel compound which can be synthesized by reacting a compound of formula III (M is Cl, etc.) with a compound of formula IV.

Description

Detailed description of the invention (wherein A is a -CH2=CH2- group or -CH=CH-
group, and 9 represents a methyl group or general formula 0, where R
s, Ft+ 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, haloalkyl μ group having 1 to 2 carbon atoms, haloa μkoxy A group or 1 and a tortoise represent a methylenedioxy group. Or represents a nitrogen atom or a methine group.

Y represents an M elementary atom, a methylene group, an amino group, a methylamino group, a formylamino to pony/L/ group, where A is one CH2-CH2- group, nine is the general formula (■), and X When is a methine group, Y represents only a carbonyl group.

Also, crows have hydrogen atoms or fluorine atoms, turtles have hydrogen atoms,
Represents 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. In addition to the group of compounds represented by ), high insecticidal activity has been found in compounds represented by (to), for example, in which the ester moiety is replaced with another group (Japanese Patent Application Laid-Open No. 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. (2) In particular, the problems inherent to pyrethroids, such as the high toxicity of compounds of type (V) to fish, have not been sufficiently improved.

The inventors of the present invention continued their intensive research to search for more useful insecticidal and acaricidal ingredients, and as a result, by introducing silicon element, which is an alternative element to carbon element, the above-mentioned ①. The present invention was completed after discovering that the disadvantages of (1) and (3) are significantly improved, while the insecticidal efficacy is enhanced compared to the original compound, and the toxicity to warm-blooded animals is further reduced. Although there are still many unknown points as to why the introduction of silicon element is effective, it is presumed that it is due to empty 3d orbitals existing in the outer shell of silicon atoms.

The compound represented by the above formula (I) used as an active ingredient in the present invention has the general formula (I) C)Is (wherein R represents a methyl group or the general formula (ID).

Here, R1 and R1 are the same or different, and are a hydrogen atom, a halogen atom, a C1-4 a[mu]kyl group, a C1-3
An alkoxy group, a haloalkyl group having 1 to 2 carbon atoms, a haloalkoxy group, or a methylenedioxy group is represented by an alkoxy group or a haloalkoxy group having 1 to 2 carbon atoms.

Furthermore, M is a chlorine atom or a metal atom (Ll).

Ha, K, etc.). ) is an organic silicon (
In the formula, A is a -CH2-CH2- group or a -0H=CH- group, or represents a nitrogen atom or a methine group. Y represents an oxygen atom, a methylene group, an amino group, a methylamino group, a formylamino group, or a carbonyl group;
When H2-CH2- is a general formula (ID) and X is a methine group, Y represents only a carbonyl group.

- is a hydrogen atom or a fluorine atom, a turtle is a hydrogen atom,
Represents a halogen atom or a methyl group. Further, 2 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 in the presence of an appropriate catalyst and, if necessary, 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 (I) are as follows, but the present invention is of course not limited to these.

(-R3 dimethy/l/(4-ethoxypheny/v)[3-(2-
7 enoxy 6-viridi/L/) propihehirane n20
1.5684 Shi'))flVc4-xToxipheni/I/)[3-(3
-Fujimechi/I/(4-xtoxifz=l')ε
3-(3-vezimethyA/(4-ethoxyphenyl)(3
-42-(dimethyA/(4-x-toxyy z=tv
) (3-(3-phtrimethyl(3-13-(3-chlorobenzyl→fufu~olophenylv1propyl)silane n DL5580 C￥13 trimethy~13-(2-benzyl-3-fluoro-6-
Viridi, 11/)-1-propenylj silane n ”D
l-5558 Trimethyl(3-(2-(4-chlorophenoxy)-6
-Viridiμ■propyl]silane n20 1.5603
Propyl,) Shihun n”D
1.5570 dimethyl (3,4-dichlorophenyl) (
3-(3-(4-fluorophenoxy)-4-fluorophenyl)-1-propenylxilane nXi 1.56
42 dimethy/v(4-difluoromethoxyphenylene/L'
) I:3-(3-(N-formi/v-2-bromoanilino)phenyl)-1-propenyl]silanedimethy/L/(3,4-methylenedioxyphenyl→[
3-(2-(N-methy/I/-4-fluoroanilino-
6-viridi lvJ propyl) sila7 n”
n I-5720 dimethy/u(3,4-methylenedioquinpheni/I/)(3-(2-(4-methylbency/L/)-6-pyridyl)propylcosilane
n n 1.5704 Shimechi ρ Feni ~ (
3-[3-(3-methylbendi/l/)phenyl)-1
-globenyl]silane n 1.5655 dimethyfi/(4-methoxyphenyzv)13-(3-
Anilinophenyl/l/)-1-propenyl]Sion M3 Dimethy/l/(3-chloro-4-trifluoromethylphenyl)(3-(3-(N-methyl-2-fluoroanilino)-4-fluorophenyl #)-t-propenylxilane n”DI-5729
Dimethy/I/(3,4-dimethylphenyl)[3-(2
-phenoxy-6-pyridyl)-1-10benyl)sifunn ”n L5694
(2-bendi/L/-3-fluoro-6-pyridyl)-
1-proveni/L/]silane n ”n
1.5723 dimethyl(3-methoxy-4-chloromethylphenyl)(3-[2-(4-chloroanilino)-
6-Pyricidimethy/L/(3-methyl-4-fluoropheny/L')(3-(N-HomiIv-4-fluoroanilino)-6-pyridipy)-1-propenylxilane n201. 5788 Trimethyl (3-(3-(N-homi/l/-3-)μ
Ooanilino)phenyl)propylxilane n D
I-5563 TrimethyllI/c3-(2-<3-methylanilino)-
3-Fluoro-6-pyridiρ)-1-propenylxilane n”D i,s
595q3 trimethy~(3-[2-(N-formiA/-4-7μ oloanilino)-6-pyridiA/)-1-probenip]silane n”01.5575 dimethy1v(3-bromo-4-promo Fluoroethyl μdimethy, A/(3-]]~Olo-4-probilpheni/l/
(3-(2-(N-formyl-4-bromoanilino)-
6-Viridi/I/J Propi〃〃Sion n” 1.58
02 dimethiμ(4-rioo7.=lv)E3-(3--yz
noxypheni) v ) -1-proveni) VΔsilane n
n I-5743 Trimethyl (3-(z-pensy A/-3-fluoro-
6-pyridyl)-1-proveni/L/l sifundimethyl(4-difluorochloromethoxyphenyl)(3-(3
-Pency 1v-4-7/L/oa 7, =)v
) Propyl) Shihun n20 1
．． 5653 Dimethy/L/(3-isopropoxyphenyl) [3-[3-(N-methy1v-3-bromoanilino)
phenyl)-1-probeni~]silane nchi 1.5
764 Dimethy/I/(4-pentafluoroethoxypheny/I/)(3-(2-phenoxyly-fluoro-6-
Pyridi/L/)propyl]silane n20 1
．． 5697 Dimethy/L/(4-ethoxyphenyl)(3
-(3-(The compound used as an active ingredient in the insecticide and acaricide of the present invention is a new compound, is solid or liquid at room temperature, and is generally easily soluble in organic solvents. Therefore, it can be used as an insecticide and acaricide for spraying. It can be used as an emulsion, an oil, a powder, a wettable powder, a near-sea μ agent, etc. It can also be used as an insecticide or acaricide for fumigation such as mosquito coils by mixing with wood flour or other suitable base material. be able to.

Also, when used as a so-called electric mosquito repellent by dissolving this active ingredient in an appropriate organic solvent and soaking it in a mount, or dissolving it in an appropriate solvent and heating and evaporating it with an appropriate heating element, it is as good as a mosquito coil. Show effectiveness. 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 insecticides and acaricides of the present invention can be used against sanitary pests such as flies, mosquitoes, and cockroaches, as well as organophosphorus agent- and carbamate-resistant leafhoppers, planthoppers, stink bugs, armyworm moths, diamondback moths, tapa moths, bean weevils, Yaga, cabbage butterfly, chestnut beetle, ha, maki,
It is extremely useful for controlling agricultural pests such as aphids and scale insects, grain storage pests such as brown elephants, mites, and the like. 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 include N-octylbicyclohebutene dicarboximide (trade name MGK-264), a mixture of N-octylbicyclohebutene dicarboximide and an arylsulfonate salt (trade name MoK- 5026), cinepirin 500, octachlorodipropyl ether, piveronyl gutoxide, etc., the insecticidal and acaricidal effects can be further enhanced. 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 pyridafenthione, NAC% MTMC, BPM, etc.
C.

Carbamate agents such as PHC, conventional pyrethroid insecticides such as pyrethrin, allethrin, phenotrin, fumetrin, phenotrin, pepmethrin, cypermethrin, decametrin, fenvalerate, fenpropanate, fluparinate, force μ tap, cloy phenamidine, By mixing insecticides such as methomyl, acaricides, fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, saving labor. , a synergistic effect 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 (g) is available as a commercial product when ~ is a methyl group, and when ~ is the general formula (2), it can be easily obtained using a Grignard reaction as shown in FIG.

In addition, if necessary, the compound (or) can be reacted with a metal element to lead to a lithium, sodium, or botany compound.

On the other hand, in the compound of general formula (5), for example, A is -CH2-CH2 using an alcohol component constituting a pyrethroid.
- group can be easily prepared according to FIG.

The compound of the general formula (Yl) can be easily coupled with the silicon compound of the general formula (2) by using, for example, a Grignard reaction to synthesize the compound (I) of the present invention. In addition, when A is a -CH=CH- group, as shown in FIG. ), coupled with the silicon compound of general formula (2) as described above, and then migrating the double bond in the presence of a base such as n-butyllithium.

0.4 g of metallic lithium was added to 50 ml of dry tetrahydrofuran under a nitrogen stream. The suspension was cooled to -50°C with dry ice-acetone, and dimethyl (4-
A solution prepared by dissolving 4.2 g of ethoxyphenylene/V) chlorosilane in 20 rne of dry tetrahydrofufun was added dropwise over 30 minutes. After reacting at this temperature for 1 hour, the liquid temperature was gradually raised to 0°C and stirred for 1 hour to generate lithium silane. The reaction solution was cooled to -20'C, and then 5.0 g of 3-(2-phenoxy-6-pyridi/L/)propyl chloride was added to 4 ml of dry tetrahydrofuran under a nitrogen stream.
A solution dissolved in 0 ml was added dropwise over 1 hour. After 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 f8 liquid was washed with saturated saline and dried with sulfur salt. The oil obtained by distilling off benzene under reduced pressure was purified by cuff chromatography using silicage/I/100 g to obtain dimethy Iv (4-ethoxypheny A/) (3
6.2 g of -(2-phenoxy-6-pyridyl)propyl)silane was obtained.

Synthesis Example 2 0 pieces of magnesium metal in 40 ml of dry ether tV
．． 6g, 3-t3-(4-chlorobenzoyl)-4-
Fluorophenyl)-2-propenylpromyF1.5
g and a small amount of iodine were added. After heating to 40'C and starting the reaction, 3-(3-(4-chlorobencyA/)-4
-20- of an ether solution containing 5.6 g of -fluoro)-2-propenyl bromide was added dropwise while continuing to boil. After stirring for 15 minutes to prepare a Grignard sample, 4.2 g of Dimethy A/(4-chlorophenylene/L/) aa silane was prepared.
(D knee flL/solution 50rne was added dropwise over 3 hours while stirring vigorously. The reaction mixture was stirred and refluxed for 1 hour. While stirring the reaction mixture, 0 g of ice and 10 g of ammonium chloride were added.
The mixture was poured into a mixture of 1 and 20 g of water, and the ether layer was separated. The aqueous layer was extracted twice with 50% ether, combined with the ether layer, washed with brine, and the ether was distilled off. 8.1 g of the obtained residue was dissolved in 50 me of dry tetrahydrofuran, and n-butyllithium was dissolved in n-hexane at -50°C under a nitrogen stream. (1,35 molar solution) 16-
added.

After continuing the reaction at the same temperature for 1 hour, the reaction solution was heated to room temperature and stirred overnight to complete the reaction. Next, the reaction solution was cooled to -50°C, and 30% of 10% hydrochloric acid was added to it.
After adding me, extraction was performed with ethyl acetate, and the ethyl acetate solution was washed twice with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain the desired dimethyl/L/(
77.5 g of 4-chlorophenyl→(3-43-(4-chloropency/l/)-4-fluorophenylvj-1-propenyl)silica were added.

Similarly to Synthesis Example 1, Sodium Trimethic acid and 3
-(3-(4-methylanilino)-4-fluorophenyl)propyl bromide to trinotyl(3-[3-(
According to Synthesis Example 2, dimethyl(3-
Chloro-4-ethylphenylv) chlorosilane and 3-(
2-benzyl-3-fluoro-6-pyridyl/)-2
- Dimethylene from propenylmagnesium bromide/1/
(3-chloro-4-ethylphenyl)(3-(2-benzyl-3-fluoro-6-viridi/L')-1-probeni p)-ran was obtained.

Next, in order to clearly demonstrate that the composition provided by the present invention is excellent, the results of test results will be shown.

Test example 1. Insecticidal test by spraying 0.2% white light solution of the compound of the invention (A), 0.2% and 0.8% Cinepirin 500 in white light solution (B), 0.2% white light solution (B) of 0.8% Cinepirin 500, 0.2% white light solution of the compound of the present invention (A),
The drop-upside-down rate of houseflies was determined for each of 0.2% white light solution (C) of 1% and 70.1% lid μsuri, and 0.2% white light solution of lid μsuri and compound (A). The effectiveness was calculated and the mortality rate after 24 hours was determined as follows. Values within 0 indicate the mortality rate after 24 hours.

Test example 2. Insecticidal test by fumigation Mosquito coils containing 0.5% of the insecticidal ingredient were prepared and tested for their effectiveness in making adult Culex mosquitoes fall and roll over. This experiment was carried out in accordance with the method of Insect Control Science Vol. 16 (1951), p. 176, Nagasawa, Katsuta et al., and the relative effectiveness of the incense sticks was calculated as follows. The sample drug number is the same as that of the active ingredient example above.

Test example 3. Insecticidal test control compound (A) by microdropping method and the compound of the present invention, biveronyl ptoxide was added in twice the amount of the active ingredient to each of them, and an acetone solution of a predetermined concentration was prepared using a microsyringe. The compound was applied to the thoracic dorsal plate of adult house flies, and the insecticidal activity relative to the control compound and the synergistic effect with piveronyl ptoxide were investigated based on the mortality rate after 24 hours, and the results were as follows.

Next, an example of formulation will be shown, but the formulation does not require any special conditions similar to general agricultural chemicals, and can be prepared by a method familiar to art technicians.

Example 1 White kerosene was added to 0.2 parts of the compound of the present invention (1) to obtain a 0.2% oil solution, making the total 100 parts.

Example 2 White kerosene was added to 0.2 parts of the compound (5) of the present invention and 0.8 parts of Piveroni-butoxide to make a total of 100 parts to obtain an oil solution.

Example 3゜Compound of the present invention (8) 20 parts of Sorbo-/l/5M-2
00 (registered trademark of Toho Chemical) and 70 parts of Xylo-y were added and stirred and dissolved to obtain a 20% emulsion.

Example 4 The compound of the present invention (1310.4 parts, 0.1 part of resmethrin, 1.5 parts of octachlorodipropyl ether IV) was dissolved in 28 parts of refined kerosene, filled into an aerosol container, and 1 part of Pal was attached. , 70 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the pulp portion to obtain an aerosol.

Example 5 0.5 g of the compound (17) of the present invention (0.5 g% BIT) was added to a base material for mosquito coils such as pyrethrum extract lees powder, wood flour, and starch powder.
The mixture is uniformly mixed with Og and a mosquito coil is obtained by a known method.

Example 6゜Compound 34 of the present invention 0.4g%MGK-50261.0g
was uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method.

Example 7 3 parts of the compound of the present invention (3010.3 parts) and 99.7 parts of clay were ground and mixed to obtain a 0.3% powder.

Example 8゜40 parts of the compound of the present invention (to), 35 parts of diatomaceous earth, 20 parts of clay
part, lauryl sulfonate 3 parts, carboxymethy
Grind and mix 2 parts of rose to obtain an irrigation agent.

Test Example 4 In a radish field at the 5th to 6th leaf stage where a large number of green peach aphids were infested, among the emulsions obtained in Example 3, compounds of the present invention (3), (8), 110+, H+ (to), +lη.

A 1,000-fold dilution of each emulsion containing solid, +251, (31+, +341 and (to)) with water was
00//sprayed per counter. 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 Among the emulsions obtained in Example 3, the compound of the present invention (2),
(4), (8), +1 chain, j151,
Country f, +231, @, (33 and 2 of □□□
Fresh leaves were immersed in a 1:000 diluted solution for about 5 seconds, and after drying, they were placed in a petri dish and 10 healthy armyworm larvae were released. The test insects were released twice, once on the day of immersion in the fresh leaves and 5 days later, and the mortality rate was determined 24 hours later.

Test Example 6: Approximately 200 aphids were infested on each tree one day before applying the insecticidal ingredient to potted fava beans. Example 8
Of the irrigation agents obtained by (2), (6),
(9), 01, Qφ, +19), (En, +
28), (g) and 4. of μs. The OQ 0 times diluted solution was sprayed on leaves infested with pests using a compressed air spray method at 10 me/per pot, and the degree of damage was observed 2 days later. As a result, no increase in the degree of damage was observed in either case.

Test Example 7゜(1)*(s), (obtained in Example 7)
s) *H* 071゜tall, 翰, (fi
, +33) and (9) to a diameter of 14 (
141! + 2 g/rrr on the bottom of the waist-high glass petri dish
Apply the putter to the wall surface by uniformly distributing it at a ratio of 1. I saw an adult German cockroach in it.
If the cockroaches were released as 0 and left in contact for 30 minutes and then transferred to a new container, more than 80% of the cockroaches could be killed by any of the powders after 3 days.

Test Example 8: Four leaves of potted green beans 5 days after sowing are infested with 10 female adult spider mites per leaf and stored in a constant temperature room at 27°C. Emulsion (4) obtained in Example 3 after 6 days
, (8) , (+o) , ! +51, spider.

+2'J, (2η, 0 audience and □□□ diluted with water to 100 pptn of active ingredient) was sprayed on a turntable in an amount of 1 Ome per pot, and 10 days later, the number of parasitic spider mites on the plants was observed. As a result, all of the insecticides and acaricides of the present invention were used against test example 9゜ carp,
Compounds of the present invention (2), (8), (n
j.

11B+, +211+! A and (to) TL
When m48 (ppm) was calculated, it was 10 in both cases.
That was it.

Procedural amendment April 23, 1988 1, Indication of the case 1986 Patent Application No. 194730 2, Name of the invention Insecticides and acaricides containing organosilicon compounds and their manufacturing method 3, Person making the amendment 6 , Full text of the specification to be amended 7, Reprint of the specification of the contents of the amendment (no change in content)

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, A is -CH_2-CH_2- group or -CH=C
It is a H- group, and R_1 represents a methyl group or general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) Here, R_4 and R_5 are the same or different, hydrogen atom, halogen atom, alkyl group with 1 to 4 carbon atoms, 1 carbon number
~3 alkoxy group, a haloalkyl group having 1 to 2 carbon atoms,
A haloalkoxy group, or R_4 and R_5 represent a methylenedioxy group. X represents a nitrogen atom or a methine group. Y represents an oxygen atom, methylene group, amino group, methylamino group, formylamino group or carbonyl group,
A is -CH_2-CH_2- group and R_1 is the general formula (
II) and when X is a methine group, Y represents only 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. ) An insecticide and acaricide characterized by containing an organosilicon compound represented by: (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, R_1 represents a methyl group or general formula (II).)▲There are mathematical formulas, chemical formulas, tables, etc.▼・...(II) 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 haloalkyl group having 1 to 2 carbon atoms. group, haloalkoxy group, or R_4 and R_5 represent a methylenedioxy group. Further, M represents a chlorine atom or a metal atom (Li, Na, K, etc.). ) Organosilicon compounds represented by the general formula ▲Mathematical formulas, chemical formulas, tables, etc.▼...(IV) (In the formula, A is -CH_2-CH_2- group or -CH=C
It is a H- group, and X represents a nitrogen atom or a methine group. Y
is an oxygen atom, methylene group, amino group, methylamino group,
Represents a formylamino group or a carbonyl group, but A
is a -CH_2-CH_2- group and R_1 is a general formula (I
I) and when X is a methine group, Y represents only 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. ) is a general formula obtained by reacting a compound represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) (In the formula, A, A method for producing an insecticide or acaricide, characterized by containing an organosilicon compound represented by: