JPH02193972A - Heterocyclic compound, production thereof and insecticide using same compound as active component - Google Patents

Abstract

NEW MATERIAL:Heterocyclic compounds represented by formula I (R1 is halogen or haloalkoxy; R2 is H or halogen). EXAMPLE:3-(4-Difluoromethoxyphenyl)-4-phenyl-1-(4- trifluoromethanesulfonyloxyphenylcarbamoyl)-4,5-dihydropyrazole. USE:An insecticide. PREPARATION:A heterocyclic compound of formula II is reacted with 4- trifluoromethanesulfonyloxyphenyl isocyanate of formula III to obtain the objective compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel heterocyclic compound, a method for producing the same, and an insecticide containing the same as an active ingredient.

<Prior Art> It has already been known from JP-A-51-41858 that certain pyrazoline compounds have insecticidal activity.

<Problems to be Solved by the Invention> However, these compounds are not necessarily fully satisfactory in terms of insecticidal activity and the like.

Means for Solving the Problems> In view of the above circumstances, the present inventors conducted various studies in order to find a compound with better insecticidal activity, and as a result, they found 4-
The inventors have discovered that a heterocyclic compound represented by the following linear formula [1] in which a trifluoromethanesulfonyloxyphenylcarbamoyl group is used as a t substituent has excellent insecticidal efficacy, leading to the present invention.

That is, the present invention represents a general formula xy group, and R2 represents a hydrogen atom or a halogen atom. ] A heterocyclic compound represented by (hereinafter referred to as the compound of the present invention).

), a method for producing the same, and an insecticide containing the same as an active ingredient.

In the above-mentioned linear formula [1], examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and examples of the haloalkoxy group include a difluoromethoxy group, a trifluoromethoxy group, and a 2,2,2-trifluoro Examples include ethoxy group and 1°1.2.2-tetrafluoroethoxy group.

Next, a method for producing the compound of the present invention will be explained.

The compound of the present invention has a -linear formula [wherein R1 is a halogen atom or a haloalco]
Ri and R2 have the same meanings as above. ] It can be produced by reacting the heterocyclic compound represented by the following with 4-trifluoromethanesulfonyloxyphenylisocyanate represented by the formula.

The reaction is carried out without a solvent or in an inert organic solvent, and the amount of reagents used in the reaction is 0.1 to IO equivalent of compound [11] relative to 1 equivalent of the compound represented by the -linear formula [1]. The amount is preferably 0.8 to 1.2 equivalents.

The reaction temperature range in this reaction is from the melting point to the boiling point of the reaction mixture, and is usually -50 to 150°C. Moreover, the range of reaction time is usually 0.5 to 50 hours.

Examples of the solvent used in the reaction include hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, O-dichlorobenzene, methylene chloride, chloroform, trichloroethylene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran,
Acetonitrile, ethyl acetate, dimethylformamide,
Examples include N-methylpyrrolidone, dimethylsulfoxide, and sulfolane.

After the reaction is completed, usual post-treatments such as concentration are performed, and if necessary, operations such as chromatography and recrystallization are performed to obtain the target compound.

Next, the compound of the present invention produced according to this production method is added to the first
Shown in the table.

Table 1 Compounds of the present invention can be produced from lepidopterans of diamondback moths, armyworms, etc. Compounds used in the production of compounds of the present invention can be produced, for example, by the following route.

It has an excellent insecticidal effect against insects of the order Pteroptera, such as corn rootworms, and insects of the order Pteroptera, such as Culex mosquito, and is also effective against pests that have developed resistance to existing insecticides. The compound of the present invention can be widely used as an active ingredient of agricultural and horticultural insecticides.

When using the compound of the present invention as an active ingredient of an insecticide,
Usually mixed with a solid carrier, liquid carrier, gaseous carrier, bait,
If necessary, surfactants and other formulation auxiliaries can be added to form oils, emulsions, wettable powders, flowables such as suspensions and emulsions in water, granules, powders, aerosols, and self-combustion. It is formulated and used in heated smokers such as type smokers, chemical reaction type smokers, porous ceramic plate smokers, fogging agents, ULV agents, poison baits, etc.

These preparations usually contain 0.01 to 96% by weight of the compound of the present invention as an active ingredient.

Examples of solid carriers used in formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, fubasamiclay, acid clay, etc.), talcs, ceric, and other inorganic minerals (sericite, etc.). ,quartz,
Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc.), and other fine powders or granules.As liquid carriers, for example, water, alcohol, etc. (methanol, ethanol, etc.),
Ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N,
(N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc.; Examples of propellants include chlorofluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide, and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and their polyoxyethylenic products, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol m-conductors, etc. can be given.

Examples of formulation auxiliaries such as fixing agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol, etc.) , polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (isopropyl acid phosphate), BIT (2,6-sheeter
t-butyl-4-methylphenol), BHA (2-t
ert-butyl-4-; methoxyphenol and 3-t
mixture with ert-butyl-4-methoxyphenol)
, vegetable oil, mineral oil, surfactant, fatty acid or its ester, etc.

Examples of base materials for self-combusting smoke agents include nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethylcellulose, combustion exothermic agents such as wood flour, alkali metal salts, alkaline earth metal salts, heavy Pyrolysis stimulators such as chromate, chromate, oxygen supply agents such as potassium nitrate,
Examples include combustion supporting agents such as melamine and wheat starch, fillers such as diatomaceous earth, and binders such as synthetic glues.

The base materials for chemically reactive smoke agents include, for example, exothermic agents such as alkali metal sulfides, polysulfides, hydrosulfides, hydrated salts, and calcium oxide, and catalyst agents such as carbonaceous substances, iron carbide, and activated clay. , organic blowing agents such as azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetraene, polystyrene, polyurethane, natural fiber pieces,
Examples include fillers such as synthetic delicate pieces.

Examples of base materials for poison bait include shell powder, plant essential oil, sugar,
Feed components such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaceretic acid, preservatives such as dehydroacetic acid, agents to prevent accidental ingestion such as chili pepper powder,
Attractive flavoring agents such as cheese flavoring and onion flavoring may be mentioned.

The formulation of flowables (suspensions or emulsions in water) generally consists of 1-75% compound, 0.5-16% dispersing agent, 0.1-10% suspending aid (e.g. colloidal or thixotropic compounds), 0 to 10% of suitable auxiliary agents (e.g. antifoaming agents, rust preventives, stabilizers,
It is obtained by finely dispersing it in water containing a spreading agent, penetration aid, antifreeze agent, antibacterial agent, anti-dispersion agent, etc.). It is also possible to use an oil in which the compound is hardly soluble instead of water to create a suspension in oil. Examples of protective colloids used include geranin, casein, gums, cellulose ether, and polyvinyl alcohol. Examples of compounds that impart thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, and polyacrylic acid.

The preparation thus obtained is used as it is or diluted with water or the like. It may also be used with or without mixing with other insecticides, acaricides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, and soil conditioners. It can also be used at the same time.

When the compound of the present invention is used as an active ingredient of an agricultural and horticultural insecticide, the application rate is usually 1 to 1000 per 10 are.
F, and when applying emulsions, wettable powders, flowable agents, etc. diluted with water, the application concentration is 10 to 1000 pp.
Granules, powders, etc. are applied as they are without any dilution.

These application amounts and concentrations vary depending on the type of formulation, application time, application location, application method, type of pest, and degree of damage, and may be increased or decreased without regard to the above range. be able to.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to production examples, reference examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, a manufacturing example will be shown.

Production Example 1 8-(4-difluoromethoxyphenyl)-4-phenyl-4,5-dihydropyrazole 1.0 Of (8,
47 mmol) was dissolved in 10 ml of toluene, a toluene solution Loss/ containing 0.98 f (8.47 mmol) of 4-trifluoromethanesulfonyloxyphenyl isocyanate was added thereto, and the mixture was stirred at room temperature for 10 hours.

Thereafter, it was concentrated under reduced pressure, and the resulting oil was subjected to silica gel column chromatography to form a white solid, 8-(
4-difluoromethoxyphenyl)-4-phenyl-1
-(4-)lifluoromethanesulfonyloxyphenylcarbamoyl)-4,5-dihydropyrazole (hereinafter referred to as
It is written as compound (1). ) 1.75f was obtained.

m, p, 1516°C Next, a production example of compound [1111], which is a production intermediate, is shown as a reference example.

Reference example 1 p-nitrophenol 6,96 f (50 mmol)
18.18 f (58 mmol) of trifluoromethanesulfonic anhydride was added dropwise to 80 yxl of an anhydrous pyridine solution containing the following while stirring at 0°C for 180 minutes. Then 60°
The mixture was stirred at C for 2 hours and poured into a concentrated hydrochloric acid-water mixture with stirring. This mixture was extracted with ether and 2.5N
Wash with aqueous sodium hydroxide solution and saturated saline,
After drying over anhydrous magnesium sulfate, it was concentrated under reduced pressure.
4-trifluoromethanesulfonyloxynitrobenzene 12.55F was obtained as a pale yellow solid.

Next, 4-trifluoromethanesulfonyloxynitrobenzene 12. δ6 f (461 mmol) was mixed with 5% palladium-activated carbon 5004, 101 t of concentrated hydrochloric acid and 100 ml of ethanol, and the mixture was stirred at room temperature and atmospheric pressure under a hydrogen atmosphere. The reaction was stopped when 8.11 of hydrogen was consumed and the catalyst was removed through Celite. Celite and the catalyst were washed with ethanol, and the washing liquid was combined with the filter and concentrated under reduced pressure to obtain 11.60y of 4-trifluoromethanesulfonyloxyaniline hydrochloride as a pale yellow solid.

Obtained hydrochloride 11.60 &Ki 0% (W, 'V)
Add 800xl of phosgene-toluene solution and stir at room temperature for 1
The mixture was then heated to reflux at 80°C for 20 hours. After completion of the reaction, the obtained homogeneous solution was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain 5.15 f of colorless liquid 4-trifluoromethanesulfonyloxyphenyl isocyanate.
I got it.

b, p, 140-150°C (15 Torr) Next, formulation examples are shown. In addition, parts represent parts by weight.

Formulation Example 1 10 parts of emulsion compound (1) was dissolved in 85 parts of xylene and 86 parts of dimethylformamide, 14 parts of polyoxyethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added, and the mixture was thoroughly stirred to dissolve 10 parts of emulsion compound (1).
% emulsion is obtained.

Formulation Example 2 20 parts of wettable powder compound (1), 4 parts of sodium lauryl sulfate,
Add 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder, and ±64 parts of diatom to a mixture,
Stir and mix in a juice mixer to obtain a 20% hydrating agent.

Formulation Example 8 Granules 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 80 parts of bentonite, and 56 parts of clay are added to 5 parts of Compound (1) and thoroughly mixed with stirring.

Next, an appropriate amount of water is added to the mixture, which is further stirred, granulated using a granulator, and dried through ventilation to obtain 5% granules.

Formulation Example 4 Powder Dissolve 1 part of Compound (1) in an appropriate amount of acetone, add 5 parts of synthetic hydrous silicon oxide fine powder, 8 parts of PAPo, and 98.7 parts of clay, and stir with a juice mixer. Mix and evaporate the acetone to obtain a 1% powder.

Formulation Example 5 Flowable agent (suspension in water) Compound (1)
20 parts of sorbitan trioleate and 1.5 parts of sorbitan trioleate were mixed with 28.6 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and after finely pulverizing the mixture with a sand grinder (particle size of 8μ or less), 0.05 parts of xanthan gum was added to the mixture. 40 parts of an aqueous solution containing 0.1 part of aluminum magnesium silicate
1 part, and further 10 parts of propylene glycol and stirring and mixing to obtain a 20% suspension in water.

Next, a test example is shown.

Test Example 1 (Insecticidal test against Spodoptera trifoliata) The test compound was made into an emulsion according to Formulation Example 1, and the
0 times diluted solution (500PPm) 2 g/diameter 11al
It was soaked in 18f of artificial feed for Spodoptera japonica prepared in a polyethylene cup. We released 10 fourth-instar Spodoptera larvae into the larvae, and examined their survival and death after 6 days.
Mortality rate was determined (2 replicates). In the case of no treatment, the mortality rate is 0.
%, whereas when treated with compound (1), the mortality rate was 100%.

Test Example 2 (Insecticidal test against Southern corn rootworm) The test compound was made into an emulsion according to Formulation Example 1, and 1*l of the 2000-fold dilution (5 oppm) with water was made into a 5.5-fold diameter emulsion.
The solution was dropped onto a filter paper of the same size placed at the bottom of a cN polyethylene cup, 20 to 80 Southern corn rootworm eggs and one corn sprout were added, and the lid was placed on top. After 8 days, the survival of the larvae and the degree of damage to the corn were investigated. The criteria for evaluating effectiveness are as follows.

(mortality rate) (degree of feeding damage) A: 100%
-: No feeding damage B: 90% or more and less than 100% +: Slight feeding damage C: 9
Less than 0% ←: Eating damage equivalent to untreated results are shown in Table 2.

Table 2 Test Example 8 (Insecticidal test against Spodoptera trifoliata) The test compound was made into an emulsion according to Formulation Example 1, and the
26 ml of the 0-fold diluted solution (25 ppm) was sprayed on a citrus orchid planted in a plastic cup with a diameter of 91 mm and a depth of 71 mm.

After air-drying, 10 fourth-instar Spodoptera larvae were released, and 5 days later, survival and death were examined to determine the mortality rate (2 repetitions).

The results are shown in Table 8.

Table 8 Test Example 4 (Insecticidal test against drug-resistant diamondback moth) The test compound was made into an emulsion according to Formulation Example 1, and 8,000 times diluted with water (12.5 ppm) was placed in a diameter of 9 mm.
cWl, was sprayed on Orchid orchid planted in a plastic cup at a depth of 7 cm.

After air-drying, 10 8th instar larvae of drug (pyrethroids, organic phosphorus) resistant diamondback moths were released, and after 5 days, survival was examined to determine the mortality rate (2 repetitions).

In the case of no treatment, the mortality rate was 0%, whereas with the compound (
When treated with 1), the mortality rate was 100%.

Test Example 5 (Insecticidal test against Culex mosquito) The test compound was made into an emulsion according to Formulation Example 1, diluted 200 times with water, and the resulting solution was added to 0.7 l1ll x 100 txt of ion-exchanged water (active ingredients concentration 8.5 ppm). Twenty second-instar larvae were released into the larvae, and the mortality rate was investigated after one day. Thereafter, the animals were fed and reared for about 8 days until all of the untreated animals had emerged, and the inhibition rate of emergence was examined.

The effectiveness evaluation criteria are A: B: C: (mortality rate) (molding inhibition rate) 90% or more A: 90% or more, 10% or more, less than 90% B = 80% or more, less than 90%, less than 10% C: Less than 80% And so. The results are shown in Table 4.

Table 4 <Effects of the Invention> The compounds of the present invention have excellent insecticidal efficacy against Lepidoptera pests, Diptera pests, Coleoptera pests, etc., and are also effective against pests resistant to existing insecticides. It has excellent insecticidal efficacy and is therefore useful as an active ingredient in insecticides.

Claims (3)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a halogen atom or a haloalkoxy group, and R_2 represents a hydrogen atom or a halogen atom. ] A heterocyclic compound represented by (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a halogen atom or a haloalkoxy group, and R_2 represents a hydrogen atom or a halogen atom. ] The heterocyclic compound according to claim 1, characterized in that the heterocyclic compound represented by the formula ▲ is reacted with 4-trifluoromethanesulfonyloxyphenylisocyanate represented by the formula ▼ which includes a mathematical formula, a chemical formula, a table, etc. ▼ Manufacturing method. (3) An insecticide containing the heterocyclic compound according to claim 1 as an active ingredient.