JPS62108885A - Organosilicon compound, production thereof and insecticide containing said compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is halogen, lower alkyl or lower alkoxy; X is H or F). EXAMPLE:(4-Chlorophenyl)dimethyl[3-(3-phenoxyphenyl)propyl]silane. USE:An insecticide capable of exhibiting remarkable effect particularly on injuring insects of the order Lepidoptera. PREPARATION:A halogenosilane expressed by formula II (Y is halogen), e.g. (4-chlorophenyl)dimethylchlorosilane, is reacted with a Grignard reagent expressed by formula III (Z is halogen), e.g. a reagent prepared from Mg and 3-(gamma- chloropropyl)diphenyl ether, preferably in the presence of an inert solvent e.g. THF, at 0-100 deg.C for 0.5-10hr.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is based on the general formula (1) (wherein R represents a halogen atom, a lower alkyl group, or a lower alkoxyfur group, and X represents a hydrogen atom or a fluorine atom) ), a method for producing the same, and an insecticide containing the same as an active ingredient.

The compounds of the present invention are useful in various industrial fields, and are particularly useful as insecticides in the agricultural field.

[Conventional technology]

Through many years of research and development into insecticides, many chemicals,
For example, organochlorine insecticides such as D D TXB HC,
Organophosphorus insecticides such as parathion and malathion, and carbamate insecticides such as carbaryl and methomyl have been developed and put into practical use, and these insecticides have played an extremely important role in improving agricultural productivity. In recent years, these pesticides remain
Due to problems such as accumulation and environmental pollution, their use has been regulated, and some products have developed resistant pests due to long-term use.

Pyrethroid insecticides have been developed and put into practical use because they have low toxicity to humans and livestock, are easily decomposed in the natural environment, have little residue, and their decomposition products are nontoxic.

However, some insect pests that are resistant to pyrethroid insecticides have appeared, and there is a demand for the development of new agents with excellent insecticidal properties.

[Problems to be Solved by the Present Invention] The present invention provides an excellent insecticidal compound that has a new structure, a wide insecticidal spectrum, and exhibits high insecticidal activity even against resistant pests, in order to solve the problems of the prior art. That is the issue.

[Means and effects for solving the problem] As a result of the inventors' intensive study on organosilicon compounds to solve the above problem, we found that the general formula (1) (wherein R is a halogen atom,
It represents a lower alkyl group or a lower alkoxyl group, and X represents a hydrogen atom or a fluorine atom. We have completed the present invention by discovering that the organosilicon compound represented by ) has a wide insecticidal spectrum and high insecticidal activity even against resistant pests. The organosilicon compound represented by the general formula (1) has not been described in any literature, and is a new compound discovered for the first time by the present inventors.

In the general formula (1), the halogen atom for the substituent R is preferably a fluorine atom, a chlorine atom, or a bromine atom, and the lower alkyl group has 1 or more carbon atoms, such as methinopethyl, propyl, isopropinopeptyl, or pentyl. Branched alkyl groups may be cited as straight-chain groups, and lower alkoxyl groups include straight-chain or branched alkoxyl groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and pentyloxy. can give.

The compound of the present invention represented by general formula (1) can be produced by the following method.

(■) (Ill) (wherein,
RlX, Y and Z have the above meanings. ) i.e.
A dimethylphenyl...Lonran derivative represented by general formula (II) and a Grignard reagent (G) represented by general formula (1)
The compound (1) of the present invention can be obtained by reacting the compound (Rignard reagent) in the presence of an inert solvent. Tetrahydrofuran (hereinafter T) is used as an inert solvent.
(abbreviated as HF), ethyl ether, hexamethylphosphoramide, etc. can be used.

The reaction temperature and reaction time can vary widely depending on the starting materials, but generally the reaction temperature is -100
C to 120 C, preferably from 0 C to 100 C, and the reaction time is from 01 to 20 hours, preferably from 05 to 10 hours. 1
Next, in the above reaction formula, the loginated silane represented by the general formula (II) and the Grignard reagent represented by the general formula (m) can be synthesized, for example, according to the following reaction formula.

(lIl) (wherein R and or the above meaning is shown), that is,
A bromobenzene derivative is reacted with metallic magnesium to obtain a Grignard reagent according to a conventional method, and dichlorodimethylsilane is reacted with this to obtain aryldimethylchloro7rane ([1)]. On the other hand, a corresponding cinnamic acid ester derivative is obtained by the Perkin ReaCl I On reaction of a benzaldehyde derivative, and the corresponding alcohol is obtained by reducing it with lithium aluminum hydride (LiAIH). This is chlorinated with a rogogenation reagent, such as thionyl chloride, to synthesize the corresponding chloride. A Grignard derivative (Ill) can be obtained by reacting this with metallic magnesium according to a conventional method.

The compound of the present invention represented by the general formula (+) is effective against sanitary pests such as flies, mosquitoes, and cockroaches, as well as Hemiptera (Hem1
ptera) Pests, such as goldenrod, diamondback moth, fall armyworm, fall armyworm, fall armyworm, fall armyworm, etc., V! AW order (Lepidptera) pests, rice weevil, etc. Coleoptera (Coleoptera)
It is also effective against agricultural pests such as insect pests, household pests such as ants, bark insects, and other pests. It is particularly effective against Lepidoptera pests. When the compound of the present invention is actually applied, it can be used alone without the addition of other ingredients, but in order to make it easier to use as a pesticidal agent, it is generally applied with a carrier added thereto. The compounds of the present invention can be formulated into emulsions, wettable powders, powders, granules, fine granules, oils, aerosols, poison baits, etc. without any special conditions and by methods well-known in the art industry in accordance with general agricultural chemicals. These can be adjusted to any desired dosage form and used for various purposes depending on the purpose.

The carrier here refers to synthetic, natural, inorganic or organic substances that are blended to help the active ingredient reach the area to be treated and to facilitate the storage, transportation, and handling of the active ingredient compound. means.

Suitable solid carriers include clays such as montmorillonite and kaolinite, diatomaceous earth, white clay, talc, vermicileite, gypsum, calcium carbonate, mineral gel, ammonium sulfate, and plants such as soybean flour, sawdust, and wheat flour. These include organic substances and urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene; paraffinic hydrocarbons such as kerosene and mineral oil; halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane; ketones such as acetone and methyl ethyl ketone; Examples include ethers such as dioxane and tetrahydrofuran, alcohols such as methanol, furopanol, and ethylene glycol, dimethylformamide, dimethyl sulfoxide, and water.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used individually or in combination depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as genin sulfonate, nonionic surfactants such as alkylbenzene sulfonate, alkyl sulfate, calcium stearate, wax, etc. lubricants, stabilizers such as inflovir hydrodiene phosphate, and other ingredients such as methyl cellulose, carboxyl methyl cellulose, casein, and gum arabic.However, these ingredients are not limited to the above.

Furthermore, by using two or more of these compounds of the present invention in combination, it is possible to develop even more excellent insecticidal power.
``Also other physiologically active substances, such as allethrin, N-(chrysanthemoylmethyl)-6゜4.5.6-ketonehydrophthalimide, 5-benzyl-5-furylmethyl chrysanthemate, 3-phenoxybenzyl chrysante mate, 5-propargyl furfuryl chrysanthemate, its (also known cyclopropane carboxylic acid ester,
3-phenoxybenzyl 2,2-dimethyl-3-(2
゜2-dichlorovinyl)-cyclopropane-1-carboxylate, 6-phenoxy-α-cyanobenzyl 2
,2-dimethyl-z, -(2,2-dichlorovinyl)-
Cyclopropane-1-carboxylate, 6-fe,'
x-α-cyanobenzyl 2,2-dimethyl-5-(
2,2-dibromovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl
Synthetic pyrethroids such as α-inpropyl-4-chlorophenylacetate and their various isomers or pyrethrum extract, 0.0-diethyl-〇-(3-oxo-
2-phenyl-2H-pyridazin-6-yl) phosphorothioate (Offnac, a registered trademark of Mitsui Toatsu Chemical), 0.
○-dimethyl-(2,2-dichlorovinyl)phosphate (DDVP), 0.0-dimef-0-(5-methyl-4-nitrophenyl)phosphorothioate, diazinon, 0゜O-dimethyl-○-4 -cyanophenylphosphorothioate, o,o-dimethyl-5-(α-(
Organophosphorus insecticides such as ethoxycarbonyl)benzyl cophosphorodithioate, 2-methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide, and 〇-ethyl〇-4-cyanophenylphosphonothionitona. agent, 1-naphthyl N-methyl carbamate (NAC),
m-tolyl N-methyl carbamate (MTMC), 2
-dimethylamino-5,6-dimethylpyrimidine-4-
yl-dimethylcarbamate (bilimer), 3.4-/
'Carbamate insecticides such as methylphenyl N-methylcarbamate, 2-isoprophoki/phenyl N-methylcarbamate, 3-phenoquinbenzyl 2-
(4-chlorophenyl)-2-)f luproyl ether, 6-phenoxy-4-fluorobenzyl 2-(4-
chlorophenyl) 2-methylpropyl ether, 5-
Phenoquinbenzyl 2-(4-ethoxyphenyl)-
2-Methylpropyl ether, phenoxy-4-
Fluorobenzyl 2-(4-ethoxyphenyl)-2
-Arylpropyl such as methylpropyl ether
Ether insecticide, 1-(3-phenoxyphenyl)
-4-(4-10lophenyl)-4-methylpentane,
1-(ro-phenoquine-4-fluorophenyl)-4-
(4-chlorophenyl)-4-)f-rubentane, 1-(
3-phenoquinphenyl)-4-(4-ethoxyphenyl)=4-methylpentane,' (3-phenoxy-
Aromatic alkane insecticides such as 4-(4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methylpentane, other insecticides, acaricides or fungicides, nematicides, herbicides, plants By mixing it with growth regulators, fertilizers, BT agents, insect hormones, other agricultural chemicals, etc., it is possible to create multipurpose compositions with even greater efficacy, and a synergistic effect can also be expected. The compound of the present invention is stable against light, heat, oxidation, etc., but if necessary, it may be added with an antioxidant or an ultraviolet absorber, such as BHT (2,6-di-t-butyl-
4-methylphenol), phenol derivatives such as BHA (butylhydroxyanisole), bisphenol derivatives, arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, condensates of phenetidi/and acetone, or benzophenone compounds. By adding appropriate amounts of these as stabilizers, a composition with more stable effects can be obtained.

The insecticide of the compound of the present invention is the compound i04)001-9
The content is 5% by weight, preferably 0001 to 50% by weight. To apply the insecticide of the present invention, the active ingredient is generally 0.0
1 to 5000 ppm, preferably 1 to 0.1 to 200+)I
) It is preferable to use it at the discretion of ITT. The amount applied per 10a is generally 200g to 0.1g of active ingredient.
It is.

〔Example〕

All representative examples of the compound of the present invention represented by the general formula (1) are listed in Table 1 below, but the present invention is not limited thereto.

Table 1 Compound RX Physical properties, 716 Refractive index (℃)
(1) CI H1,5682 (20
,1)(2) CI F 1.
5698 (20,5)(3) 0H3H15
440(20,1)(4) CH3F 1
．． 5474 (20,3)(5) C2H1O
H1,5664(20,1)(6) (,H2O
F 1.5678 (20,1) Next, the method for producing the compound of the present invention will be explained with reference to synthesis examples.

Synthesis Example 1 Synthesis of Compound AI of the Present Invention (4-chlorophenyl)dimethylC3-(5-phenoxyphenyl)furobyl]ranmagneum 0.35g and anhydrous THFM
Ome was stirred at room temperature under a nitrogen stream. 4-
Bromokuoo benzene 235g (0,0122mol
) anhydrous THF 5 ml! The solution dissolved in
The mixture was added dropwise over 0 minutes and stirred at room temperature for 1 hour. After cooling the reaction mixture with water and adding 1.8 g of dichlorodimethyl,
Stirred at room temperature for 2 hours. A THF solution of (4-chlorophenyl)dimethylchlorosilane thus obtained was added to an anhydrous THF solution of a Grignard reagent prepared from 0.19 g of magnesium and 2.00 g of 3-(r-chloropropyl)diphenyl ether at room temperature under a nitrogen atmosphere. The mixture was stirred and heated to reflux for 5 hours. 2 parts water to the reaction mixture
0 ml was added, insoluble matter was separated by ρ on a Hycross-Purcel, and P'tL was extracted with hexane.

The extract was washed with water, and after drying, the solvent was completely distilled off under reduced pressure.

The oily residue was purified by column chromatography (
116 g of 4-chlorophenyl)dimethyl [6-(6-phenoxyphenyl)propyl]/run were obtained as a total colorless oil.

1250, 1220 0.6-1.0 (2H, m).

14-1.8 (2H, m).

2.55 (2H, t, J=8.37(z).

6.7-7.4 (13H, m) Elemental analysis value: C23H2, Cl08iCHC1 Calculated value (ch) 72,51 6.61 9.3
1d111 constant value (@72,74 6,42 9.
10 Synthesis Example 2 Synthesis of Compound A63 of the Present Invention (4-Mefulfenyl)dimethyl[3-(3-phenoxyphenyl)propyl]/Ran In Synthesis Example 1, 4-bromotoluene was used instead of 4-bromochlorobenzene as a raw material. The desired compound was obtained as a colorless oil by using the same name as a compound.

1250, 1220 0.3-0.9 (2H, ml.

1.3-1.7 (2H, m).

2.27 (2H, t, J=8.0Hz).

6.5-7.4 (13H, m) Elemental analysis value "C24H2+1O8+ CH Calculated value (@79.94 7.83 Measured value
(%) 80.11 7.77 Next, the composition of the present invention will be specifically explained by giving formulation examples.

Formulation Example 1 20 parts of the compound of the present invention, Nlupol 355 (Toho Chemical Co., Ltd.)
10 parts of solidified surfactant) and 70 parts of xylene were uniformly mixed with H' to obtain an emulsion.

Formulation Example 2 A wettable powder was obtained by uniformly stirring and mixing 20 parts of the compound of the present invention, 5 parts of alkylnaphthalene sulfone (sodium), 5 parts of white carbon, and 170 parts of diatom.

Formulation Example 5 Three parts of the compound of the present invention are dissolved in acetone, and the acetone is evaporated while mixing with 97 parts of clay to form a powder.

Formulation Example 4 6 parts of the compound of the present invention, 2 parts of sodium ligninsulfonate and 95 parts of bentonite were uniformly pulverized and mixed, water was added and kneaded, and after f'C, granulation was dried to obtain granules.

Formulation Example 5 An oil solution was obtained by uniformly mixing and dissolving 0.1 part of the compound of the present invention, 05 parts of biperonyl butoxide, and 994 parts of white kerosene.

Formulation Example 6 04 parts of the compound of the present invention, 20 parts of piperonyl butoxide, and 76 parts of deodorized kerosene were uniformly mixed and dissolved, filled into an aerosol container, and after the injection valve was removed, 90 parts of liquefied petroleum gas was pressurized. The aerosol was obtained by filling.

Formulation Example 7 B I T 0.05 to 0.05 g of the compound of the present invention
2.5 cm x 2.5 cm
i, 5cm.

The fiber composition was uniformly adsorbed onto the surface of asbestos having a thickness of Q and 3 cm and heated on an electric heating plate to obtain a fiber composition.

Formulation Example 8 1 part of the compound of the present invention, 5 parts of sugar, 50 parts of wheat bran, 20 parts of rice sugar
1 part and 24 parts of wheat flour were uniformly mixed, and an appropriate amount of water was added and kneaded to obtain a poison bait.

Formulation Example 9 After 10 parts of the compound of the present invention, 20 parts of a 10-polyvinyl alcohol aqueous solution and 5 parts of xylene were mixed uniformly with stirring, 65 parts of water was added and stirred again to obtain a flowable agent.

Next, the efficacy of the compounds and compositions of the present invention as insecticides will be explained using test examples.

Test Example 1 Paddy rice seedlings (3
During the leaf stage, an emulsion of the compound of the present invention prepared according to Formulation Example 1 was diluted with water to give an active ingredient concentration of 50 ppm, and the solution was sprinkled on a turntable to the extent that it dripped lightly. After air-drying, the seedlings were removed using a wire mesh cylinder, and 10 female adult resistant leafhoppers (native to intercultivation) were released into the seedlings and left to stand at room temperature. After 24 hours, all mortality rates were investigated.

All tests were conducted in two-luck mode, and the results are shown in Table 2.

Test Example 2 An acetone solution of the compound of the present invention (concentration 2
00 ppm) 1me was added and one hit was good.

I then released 10 final instar larvae of Akai nika there and left them to stand still.
Mortality rate was examined after 48 hours.

All tests were conducted in duplicate, and the results are shown in Table 3.

Test Example 3 Twenty female adult two-spotted spider mites were inoculated onto leaf disks (2 cm in diameter) of French bean leaves placed on moistened absorbent cotton. After 24 hours, the diluted emulsion prepared according to Formulation Example 1 (active ingredient concentration 50 ppm) was treated with a scattering base so that the amount of gold treated on the leaf disk was about 2 m9/crl K, and left to stand for 48 hours. Later, the mortality rate was investigated.

All tests were conducted in duplicate, and the results are shown in Table 4.

Table 2 Table 6 Table 4 [Effects of the Invention] As is clear from the above explanation, the organosilicon compound according to the present invention is an excellent compound having high insecticidal power and a wide insecticidal spectrum.

The organosilicon compound according to the present invention can be easily produced by the production method according to the present invention.

Further, the agricultural chemical containing the organosilicon compound according to the present invention has excellent properties and is useful as an insecticide.

Claims (3)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a halogen atom, a lower alkyl group, or a lower alkoxyl group, and X represents a hydrogen atom or a fluorine atom. ) is an organosilicon compound represented by (2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R represents a halogen atom, lower alkyl group, or lower alkoxyl group, and Y represents a halogen atom.) The halogenated silane and general formula (III) ▲ formula,
There are chemical formulas, tables, etc. ▼ (III) (X represents a hydrogen atom or a fluorine atom, Z represents a halogen atom.)
The general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) A method for producing an organosilicon compound represented by (in the formula, R and X have the above meanings). (3) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a halogen atom, a lower alkyl group, or a lower alkoxyl group, and X represents a hydrogen atom or a fluorine atom. ) An insecticide characterized by containing an organosilicon compound represented by the following as an active ingredient.