JPS61109793A - Tin compound, its preparation and insecticide and acaricide containing same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is H, F; Z is methine or N). USE:Insecticide, acaricide. PREPARATION:The reaction of an alcohol of formula II with a halide of formula III (Y is halogen) is carried out, preferably in an inert solvent such as DMF or sulfolane in the presence of a base such as sodium or potassium hydroxide at 0-100 deg.C for 1-50hr.

Description

DETAILED DESCRIPTION OF THE INVENTION State of the Invention A novel tin compound represented by the following general formula (Il, its production method, and its active ingredient [wherein, X represents a hydrogen atom or a fluorine atom, and 2 represents a methine atom] represents a group or a nitrogen atom] As a result of repeated research for the purpose of developing a compound with excellent insecticidal and acaricidal activity, the present inventors have found that the general formula α)
The compound of the present invention represented by 1 has extremely high insecticidal and acaricidal efficacy. 2. The present invention was completed based on the discovery that the product has properties such as 〇, which makes it highly effective even against pests resistant to insecticides and acaricides.

Examples of specific pests to which the compounds of the present invention are particularly effective include Hemiptera such as planthoppers, planthoppers, leafhoppers, aphids, and stink bugs; Lepidoptera such as armyworms, cutworms, and diamondback moths; and Diptera such as Culex mosquitoes and houseflies. Examples of the orders of the order, Reticoptera such as the German cockroach, the orders of the order Pteroptera, the order Coleoptera, and the order Aniformes include the two-spotted spider mite, the red-spotted spider mite, the orange spider mite, and the like.

The compound of the present invention is, for example, an alcohol compound represented by the general formula (2) [wherein X and 2 have the same meanings as above] and a general formula (2) c in which Y
represents a halogen atom and a halide represented by ] in an inert solution (e.g., dimethylformamide, diethylformamide, dimethylsulfoxide, sulfolane, tetrahydrofuran, dimethoxyethane, etc.). ) IJium, potassium hydride, n-butyllithium, t-butoxypotassium, etc.)
When reacted for 1 to 50 hours at 100"cK, K. is obtained. Examples of compounds produced according to the above production method are shown in Table 1, but the compounds of the present invention are not limited to these examples. 〇Explain in detail〇Example 1 Production of compound (1) In a nitrogen atmosphere, 190 mf of sodium hydride (68%
Add 40 mjK of t-dry a-dimethyformamide (hereinafter abbreviated as dry DMP).
m-Fenoki V Benji Akko lv1. Add Of and continue heating and stirring at 40°C to 60°C for 1 hour. ◇After confirming that hydrogen is no longer generated, add trimethy/I/! to room temperature.
- Dry domestic μ stannane L22f in DMF 6ml K
Add the dissolved liquid and leave at room temperature for one night, then 400~500 ml.
Continue the reaction at 0°C for 1 hour. ◎ Cool the reaction solution, pour into ice water, and extract twice with ether μ. The ether layers were combined and washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica column μ column chromatography (developing solvent: n-hexane: ethyl acetate/I/ 50:1), target compound (1)
0.99 f was obtained. Hz (approximately 9%) and (5n11?=-C-H)50Hz (
0) 8.7'O(s, 2H) (where J (8n 111,11?-C-H) about 18
A satellite band coupling at Hz (approximately 17%) is observed. )4.88 (s, 2H) 6,80-7.50 (m, 9H) Example 2 Production of compound (2) Drying 189 mF (68% oil disbarge) of sodium hydride in a kiln atmosphere Suspend in DMF 50mjK. To this, 6-phenoxypyridine-2-methano-1v
1. Add Of, heat and stir at 40°C to 50°C for 21 hours, cool to 0 room temperature, and add trimethy A/! A solution obtained by dissolving 1.86 F of 1-tomethylstannane in 5 mJ of dry DMF is added, and heating is continued for -X nights at room temperature, and then for 1 hour at 50'CK. The reaction solution was poured into ice water and extracted with ether. The combined layers were washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified with silica gel. Along with column chromatography, developing solvent + n-hexane: ethyl acetate μ = 5
0:1), the target compound (2) obtained 0.67 F. , J (an"""'-C-H) A satellite band coupling at 52 Hz (about 16%) is observed0) 8.81 (s, 2K) (However, J (an"""-C -H) A satellite band coupling at 2 GHz (approximately 16%) is observed 0) 4.46 (a, 2H) 6, 70-7.8 0 (m, 8H) Reference example Trimethi1vW1-Domethy Synthesis of stannane Trimethyfi1m-domethyμstannane was synthesized from trimethyμchlorostannane according to the method described in the 12th Spring Yoki Metal Chemistry New Experimental Chemistry Course (Maruzen), page 897.01)-1) us, s 69 ~70°C (LiL b-p
(@, s 54-65°C) When using the compound of the present invention as an active ingredient of an insecticide, 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, It can be mixed with gaseous carriers, surfactants, other formulation auxiliaries, baits, etc., or impregnated into base materials such as incense sticks and mats to produce emulsions, irrigation agents, powders, granules, oils, air sea μ, etc.
It is used in formulations as heating fumigants for mosquito repellent lines, electric mosquito mats, porous ceramic plate mats, fogging agents, non-heating fumigants, poison baits, etc.

As solid carriers, kaolin clay, attaba rho gite clay, bentonite, acid clay, pyrophyllite,
Examples include fine powders or granules of diatomite, diatomaceous earth, corn cob powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrous silicon oxide, etc., and liquid carriers include kerosene, Aliphatic hydrocarbons such as kerosene, aromatics such as benzene, toene, xylene, methylnaphthalene, aromatic hydrogen aX,
Halogenated hydrocarbons such as dichloroethane, trichloroethylene, carbon tetrachloride, alcohols such as methanol, ethanol, inzolopanol, ethylene glycol, heptarosop, etc., acetone, methyl ethyl ketone, cyclohexanone, isophorone, etc. Ketone, jechi〃ete〃,
Aether μ such as dioxane, ketone and dorofuran, ester μ such as methyl acetate, nitric rho such as acetonitrile, inbutyronitrile, acid amides such as dimethymu formamide and dimethylacetamide, dimethyme phosphoxide, soybean oil, cottonseed oil and other vegetable oils. Examples of gaseous carriers include 70% gas, LPG (liquefied petroleum gas), dimethylate μ, etc. Surfactants used for emulsification, dispersion, wet layer, etc. include alkyl sulfate ester Jv
woodcutter, alkyl/I/(ary-/I/) sulfonate, cyasyl phosphosuccinate, polyoxyethylene alkyl
Ali-ether sinoic acid ester lv salt, naphthalene μ
Anionic surfactants such as formalin condensate, polyoxyethylene ether, polyoxyethylene polyoxyderobylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Examples of formulation adjuvants such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (boxymethylcellulose), Examples include pine oil, agar, etc., and stabilizers include PAP (isopropyl acid cynate lv), T
Phosphoric acid 7〃kiμ such as CP (J + phosphoric acid tricrezi / I /) etc.
, vegetable oil, epoxidized oil, the above-mentioned surfactant, BHT,
Antioxidants such as BHA, sodium oleate, fatty acid salts such as stearic acid, methi oleate,
These formulations include fatty acid esters such as methyl stearate. Examples of formulations containing 0.01% to 95% by weight of the compound of the present invention as an active ingredient are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 Compound of the present invention (110.2 parts, xylene 2 parts, white kerosene 9
7.8 parts are mixed to obtain an oil solution. Preparation Example 2 Compound of the present invention (1) - (3310 parts, polyoxyethylene chloride 14 parts, 14 parts of decimubeninsulphonic acid 6) 1 part, xylene 70 parts are thoroughly mixed to obtain an emulsion ◇Formulation Example 8 Inventive compound (2) 20 parts, fenitrothion 101 parts
1S, 8 parts of lignin sulfonic acid, 2 parts of sodium sulfate, and 65 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain an irrigation agent. Formulation Example 4 1 part of the compound of the present invention (3), 1 part of lignin sulfonic acid y −/l/2 parts, 87 parts of kaolin clay, and 10 parts of kaolin clay are thoroughly ground and mixed to obtain a powder.

Formulation Example 5 - 5 parts of the compound (l) of the present invention, 1 part of synthetic hydrous silicon oxide,
2 parts of lignin-nulphonic acid lvvum, 8 parts of bentonite
0 parts and 62 parts of kaolin clay are thoroughly ground and mixed, water is added thereto, the mixture is kneaded, and the mixture is granulated and dried to obtain granules.

Formulation Example 6 Compound of the present invention (2) 0.05 parts, tetramethrin 0,
Mix and dissolve 2 parts of Resmethrin, 0.05 parts of xylene, and 32.7 parts of deodorized kerosene, fill it into an aerosol container, attach the pulp part, and then spray the propellant (liquefied petroleum gas) through the pulp part. If 60 parts are filled under pressure, Air Sea P will be obtained.

Formulation Example 7 Compound of the Invention (3) 0.8 f and allethrin d-tofunne tertiary chrysanthemum acid ester/L10. Add stwo, methanol
/L' 20 mJ, carrier for mosquito coil (ffi combination of tag powder: lees powder: wood flour in the ratio of 8:5:1) 99.4
After uniformly stirring and mixing with r, methanol is evaporated, 150 mJ of water is added, the mixture is thoroughly kneaded, and the well-mixed product is molded and dried to obtain each mosquito coil.

These preparations can be used as they are or diluted with water.
It can also be used in combination with herbicides, plant growth regulators, fertilizers, soil conditioners, etc. When the compound of the present invention is used as an insecticide or acaricide, the application amount is usually 10 ar. When diluting 5oot, emulsion, irrigation agent, etc. with water, the application concentration is 10 ppm to 11000 pp], powder,
Granules, oils, aerosols, etc., can be used without any dilution.
Apply in the formulation ◇ Next, test examples are shown. 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 Compound Symbol Structural Formula Name Test Example 1 2 mJ of a predetermined concentration dilution with water of an emulsion of the following inventive compound and control compound obtained according to Formulation Example 2 was diluted with 18 mJ.
Impregnated with F. Spodoptera lupus artificial food, diameter 11
10 4th instar larvae of Spodoptera were placed in a 51 polyethylene cup, and 6 days later, their survival and death were investigated.
The LCso value (50% lethal concentration) was determined (2 repetitions)0 The results are shown in Table 80 Table 8 Test Example 2 Each of the following inventive compound and control compound diluted with acetone was placed in 10 diameter cubes. 1 on the bottom of the aluminum pan.
After the loacetone was uniformly applied at a dose of 78 mf/rIf and evaporated, 10 adult German cockroaches (5 males and 5 females) were released onto the treated surface and forced into contact with the surface.
After 24 hours of treatment, the test insects were collected in a new container, watered, and allowed to stand for another 24 hours, and the mortality rate was determined by examining whether they were alive or dead (2 repetitions).The results are shown in Table 4. Table Test Example 8 A piece of paper of the same size was placed at the bottom of a polyethylene cup with a diameter of 5.5 CIn, and a 200-fold dilution (equivalent to 500 ppm) of an emulsion of the following compound prepared in accordance with Formulation Example 2 with water was used.
Drop 7 mjl onto two pieces of paper and use 1 sugar as bait at 80 mW.
was added evenly. 10 female adult house flies were released into the chamber, the lid was closed, and 48 hours later, their survival and death were investigated.
[(50% lethal concentration) @ The results are shown in Table 5.

Table 5 Test Example 4 Potted green beans (primary leaf stage) K, - 7 days after sowing
A leaflet was parasitized with 10 female adult spider mites, and 2
After 06 days of storage in a constant temperature room at 5°C, a drug solution prepared by diluting an emulsion of the following inventive compound and control compound with water to 500 ppm of active ingredient prepared according to Formulation Example 2 was poured into one pot on a turntable (F). Spray 10wj and 2m of both liquids at the same time.
J above*: 4 Notes After 08 days, the degree of damage caused by spider mites on each plant was investigated and the effectiveness criteria were 90.

The results are shown in Table 6. Table 6

Claims (3)

[Claims] (1) General formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is a hydrogen atom or a fluorine atom and Z represents a methine group or a nitrogen atom. represent ] A tin compound represented by (2) General formula▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X represents a hydrogen atom or a fluorine atom, and Z represents a methine group or a nitrogen atom. ] There are alcohol compounds and general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Y represents a halogen atom. [In the formula, X and Z have the same meanings as above. ] A method for producing a tin compound shown in (3) General formula▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X represents a hydrogen atom or a fluorine atom, and Z represents a methine group or a nitrogen atom. ] An insecticide and acaricide characterized by containing a tin compound represented by the following as an active ingredient.