JPH0356467A - Bromodifluoromethoxybenzene-based compound and insecticide or miticide containing thereof as active ingredient - Google Patents

Abstract

NEW MATERIAL:Bromodifluoromethoxybenzene-based compound expressed by formula I (R1 is Cl, Br or methyl; R2 is H or 1-4C alkyl). USE:Used as insecticide or miticide. Also effective to harmful insect having developed resistance against conventional drug and also having preventive effect and remedy effect to various plant diseases. PREPARATION:For instance, pyridazinone-based compound expressed by formula II is reacted with halide-based compound expressed by formula III (X is halogen)in the presence of deoxidizer to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Application Field The present invention relates to a novel bromodifluoromethoxybenzene compound and an insecticide and acaricide containing it as an active ingredient.

BACKGROUND ART The fact that certain pyridazinone compounds have insecticidal and acaricidal activity is described, for example, in JP-A-6014178.

Problems to be Solved by the Invention> However, these compounds cannot necessarily be said to be sufficient in terms of their activity, insecticidal spectrum, etc.

Means for Solving the Problems> In view of the above circumstances, the present inventors have conducted various studies in order to develop a compound having excellent insecticidal and acaricidal activity, and as a result, the following general formula [I] has been developed. It was discovered that the shown bromodifluoromethoxybenzene compound has excellent insecticidal and acaricidal activity, leading to the present invention.

That is, the present invention relates to the general formula CI) R! [In the formula, Rl represents a chlorine atom, a bromine atom, or a methyl group, and Rl represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] The present invention provides a bromodifluoromethoxybenzene compound (hereinafter referred to as the compound of the present invention) represented by the following and an insecticide or acaricide containing the same as an active ingredient.

The pests and mites to which the compound of the present invention is effective include, for example, lepidopterans such as the diamondback moth, the two-spotted moth, the brown borer moth, the armyworm, the snail moth, the common white moth, the burr, and the carp moth, the Culex mosquito, the Aedes aegypti mosquito, the Anopheles mosquito, the striped mosquito, the house fly, etc. Diptera, German cockroach, black cockroach,
Ophthalmoptera such as the Japanese brown cockroach and American cockroach; Coleoptera such as the bean weevil, southern corn rootworm, northern corn rootworm, scarab beetles; planthoppers such as the brown planthopper and brown planthopper; leafhoppers such as the black leafhopper; and green leafhoppers such as the green leafhopper. aphids,
Pests of Hemiptera such as stink bugs and whiteflies, as well as other insects such as Hymenoptera, Thyroptera, and Orthoptera; spider mites such as the two-spotted spider mite, orange spider mite, and false red spider mite; ticks such as animal-parasitic mites such as the American spider mite; It is also effective against pests that have developed resistance to existing insecticides and acaricides. It also has preventive and therapeutic effects against various plant diseases.

Typical methods for producing the compounds of the present invention include, for example, the following methods.

Production method A General formula [■] [In the formula, Rl represents the same meaning as above. ] and a pyridazinone compound represented by the general formula ('l[I)R] [wherein R! represents the same meaning as above, and X represents a halogen atom. ] A method for producing by reacting a halide compound represented by the following in the presence of a deoxidizing agent.

This reaction is generally carried out in the presence of a solvent, and examples of suitable solvents include alcohols such as methanol, ethanol, n-butanol, and tert-butyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene; Pyridines such as pyridine and picoline, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, tetrahydrofuran, and dioxane, nitriles such as acetonitrile, water, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Polar solvents such as sulfoxide, N-methylpyrrolidone, etc. or mixtures thereof can be mentioned. The reaction temperature is usually 0
-160°C, preferably room temperature (20°C) - 120°C, and the reaction time is usually 0. It is 5 to 100 hours. Further, the halide compound represented by the general formula (II[) is usually used in a proportion of 0.8 to 1.5 mol per 1 mol of the pyridazinone compound represented by the general formula (II).

Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, and 1'mum carbonate, and organic bases such as pyridine and triethylamine. Usually, for 1 mol of the compound represented by general formula (II),
The deoxidizing agent is used in a proportion of 1 to 6 moles.

Production method B General formula (ff) 0 [In the formula, Rl represents the same meaning as above, and Y represents a halogen atom. ] A pyridazinone compound represented by the general formula [▼]R! [In the formula, R represents the same meaning as above. ] A method for manufacturing by reacting a mercabutan compound shown in the following in the presence of a deoxidizing agent.

The reaction shown in Manufacturing Method B can be carried out under substantially the same conditions as the reaction shown in Manufacturing Corporation.

Production method C General formula (V[) [In the formula, R1 represents a chlorine atom and R] represents a hydrogen atom. ] A method for producing by reacting the compound represented by these with tert-butylhydrazine.

The reaction shown in Manufacturing Method C can be carried out under substantially the same reaction conditions as the reaction shown in Manufacturing Corporation.

When performing a heterogeneous reaction using water as a solvent,
Phase transfer catalysts such as tetra n-butylammonium bromide, penzyltriethylammonium chloride, etc. can be used.

Since tert-butylhydrazine is usually handled in the form of salts such as hydrochloride and sulfate, the deoxidizing agent shown in Production Method A is used to liberate tert-5-butylhydrazine from these salts. be done.

After the reaction is completed, the compound of the present invention (in the general formula (I), R1 is a chlorine atom and R2 is a hydrogen atom) can be obtained by carrying out a usual post-treatment.

The compounds of the present invention include R! There are optical isomers derived from these isomers, including any of the isomers and any mixtures of these isomers, each of which can be used as an insecticide or acaricide.

In the above general formula, the compounds represented by [■] and (ff) are known compounds, and the compound represented by the general formula (III) can be produced, for example, by the following method.

In addition, the compound represented by the general formula [▼] is the general 1101
(1984), Can. J. Chem. ．． 8
1. 1098 (1956)).

Furthermore, the compound represented by the general formula [■] is
It can be produced according to the known method described in JP-A-67076.

Examples of the compounds of the present invention include compounds shown in Table #Il below, but of course the present invention is not limited thereto.

Table 1 Compounds represented by the general formula 0 R2 When the present compound is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding any other ingredients, but it is usually used in a solid carrier. , liquid carrier, gaseous carrier, feed, etc., and if necessary, surfactants and other formulation auxiliaries are added to produce oils, emulsions, wettable powders, floor pulls, granules, powders, aerosols, etc. It is used as a poison bait etc.

These preparations usually contain 0.01% to 95% 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, ceramics, and other inorganic minerals (sericite, quartz). ,
Sulfur, activated carbon, calcium carbonate, Eiwa silica, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc.), and other fine powders or granules. Liquid carriers include, for example, water, alcohol, etc. (methano, alcohol, 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, imbutyronitrile, etc.), ethers (diisobrobyl 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. Gaseous carriers, that is, propellants, include, for example, chlorofluorocarbon gas,
Examples include butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

Examples of surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates,
Anionic surfactants such as polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin conjugates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters Nonionic surfactants such as

Examples of formulation aids such as fixing agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose S conductor, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl (alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (
isobrovir acid phosphate), BHT (2,6-te
rt-butyl-4-methylphenol), BHA (2-
tert-butyl-4-methoxyphenol and 3-
(mixtures with tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

Examples of base materials for poison bait include grain flour, vegetable essential oil, sugar,
Feed ingredients such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic 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.

Floor pulls (suspensions or emulsions in water) generally contain 1 to 76% of the active compound, 0.5 to 15% of dispersing agents, and 0.1 to 10% of suspending aids (e.g. protective agents). Compounds that impart colloidal and thixotropic properties), 0 to 10%
suitable adjuvants (e.g. antifoaming agents, rust inhibitors, stabilizers,
(spreading agent, penetration aid, antifreeze agent, antibacterial agent, antifungal agent, etc.)
obtained by finely dispersing it in water containing

It is also possible to use oil in which the active ingredient compound is hardly soluble instead of water to form a suspension in oil. Examples of protective colloids include gelatin, casein, gums, cellulose ether, and polyvinyl alcohol, and examples of compounds that impart thixotropic properties 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. In addition, it can be mixed with other insecticides, acaricides, nematicides, soil pest control agents, pest control agents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, and soil conditioners. Alternatively, they can be used simultaneously without being mixed.

When the compound of the present invention is used as an active ingredient in agricultural insecticides and acaricides, the amount of the active ingredient to be applied is usually 11 to ioof per 10 ares, and emulsions, wettable powders, floor pull agents, etc. are diluted with water. When used as a preparation, the application concentration is 10 ppm to 1000 m) pm, and granules, powders, etc. are applied as they are without any dilution. In addition, when used as an insecticide or acaricide for epidemic prevention, emulsions, hydrating agents, floor pull agents, etc. should be used at a concentration of 10 ppm in water.
~1000 m) diluted to 1000 m) pm and applied,
Aerosols, fog agents, poison baits, etc. should be applied as is.

The above-mentioned application amount and application concentration vary depending on the situation such as the type of preparation, application time, application place, application method, type of pest, degree of damage, etc., and may be increased or decreased without regard to the above range. You can

The present invention will be explained in more detail below using production examples, formulation examples, and test examples, but the present invention is not limited thereto.

First, a manufacturing example will be shown.

Production Example 1 1-tert-butyl-5-chloro-4-mercabuto-6(IH)-pyridazinone 219η (1.00mM
), 4-promodifluoromethoxybenzyl bromide 8.
00t! A solution of 9 (1.00 mM) in anhydrous N,N-dimethylformamide (6-) was added under stirring, and the mixture was incubated at 70 °C for 1
Stirred for 0 hours. After the reaction was completed, the reaction mixture was added to cold water and extracted with ethyl acetate. The extracted ethyl acetate fB solution was washed successively with a saturated ammonium chloride aqueous solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.

The obtained Yukinkai IMk+ was obtained as crystals with a melting point of 115 to 120°C.

Production example 2 Sodium hydride (60% oil suspension) 40
4-Promo,difluoromethoxybenzylmercabutane 26911F (1.0
0mM) of anhydrous N,N-dimethylformamide (5-)
After adding the solution and stirring for 80 min at room temperature, l-ter
221q (1.0mM) of t-butyl-4,6-dichloro-6(IH)-pyridazinone was added and stirred at room temperature for 16 hours. After the reaction was completed, the reaction mixture was poured into cold water and extracted with ethyl acetate. The extracted ethyl acetate solution was washed with a saturated aqueous ammonium chloride solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography to obtain the desired compound of the present invention (1) 2 5 1 11
19 (yield 55%) was obtained as crystals with a melting point of 115-120°C.

Production Example 8 tert-butylhydrazine Hydrochloride 125"? (1.
0 OmM), 252 I? (8.00mM
) and stirred at room temperature for 80 minutes. Next, acetic acid 2- was added and stirred for 80 minutes. Then, 402g9 (1.00mM) of 8-(4-bromodifluoromethoxybenzylmerkabuto)-2-chloromalealdehyde acid was added, and the mixture was stirred at room temperature for 10 hours. After the reaction was completed, the mixture was diluted with toluene and separated, and the toluene solution was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained oil was subjected to silica gel column chromatography to obtain the desired compound of the present invention (1) 1 6 8 w? (
(Yield 87%) was obtained as crystals with a melting point of 115-120°C.

Examples of formulations are shown below. In addition, parts represent parts by weight, and the compounds of the present invention are represented by the compound numbers listed in Table 1.

Formulation Example I Emulsion 10 parts of the compound of the present invention (1) was dissolved in 85 parts of xylene and 85 parts of dimethylformamide, 14 parts of polyoxyethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added, and the mixture was thoroughly stirred and mixed. ! 058 emulsion is obtained.

Formulation Example 2 Wettable powder 20 parts of the compound of the present invention (1) was added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder, and 54 parts of silica clay. Stir and mix with a juice mixer to obtain a 20% hydrating powder.

Formulation Example 8 Granules (in the case of solid drug substance) To 5 parts of the compound of the present invention (1), 6 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 80 parts of bentonite, and 55 parts of clay were added, and the mixture was thoroughly stirred. Mix. Then, an appropriate amount of water was added to these mixtures, the mixture was further stirred, granulated using a granulator, and air-dried to give a 55'if
Obtain granules.

Formulation Example 4 Powder Dissolve 1 part of the compound of the present invention (1) in an appropriate amount of acetone,
To this, 6 parts of synthetic hydrated silicon oxide fine powder, P A P 0.
8 parts and 98.7 parts of clay were added, stirred and mixed using a juice mixer, and the acetone was evaporated to remove 1! Obtain i8 powder.

Formulation Example 5 Flowable agent (solid drug substance) 20 parts of the compound of the present invention (1) and 1.6 parts of sorbitan trioleate were mixed with 28.6 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture was ground finely with a sand grinder. After pulverization (particle size: 8μ or less), 40 parts of an aqueous solution containing 0.06 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate were added, and 10 parts of propylene glycol was added, mixed with stirring, and dissolved in 20% water. Obtain a suspension.

Formulation Example 6 Oil Agent Compound of the Invention (1) 0. 1 part was dissolved in 5 parts of xylene and 6 parts of trichloroethane, and this was dissolved in 89% of deodorized kerosene.
9 parts to obtain a 0.1% oil solution.

Formulation Example 7 Oil-based aerosol Compound of the present invention (1) 0. 1 part, tetramethrin 0.
2 parts, 0.1 part of d-phenothrin, 10 parts of trichloroethane, and 69.6 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, and after attaching a pulp part, a propellant (liquefied petroleum gas) is passed through the pulp part. 80 parts were filled under pressure to obtain an oil-based aerosol.

Formulation Example 8 Aqueous Aerosol Compound of the Invention (1) 0. 2 parts, d-allethrin 0.
2 parts of d-phenothrin, 0.2 parts of xylene, 8.4 parts of deodorized kerosene, and 1 part of emulsifier {Atmos 800 (registered trademark of Atlas Chemical Co., Ltd.)} were mixed and dissolved;
An aerosol container is filled with 50 parts of pure water, a valve part is attached, and 40 parts of a propellant (fossil petroleum gas) is filled under pressure through the valve part to obtain an aqueous aerosol.

Formulation Example 9 Heat-smoking agent Compound (1) of the present invention 100 # was dissolved in an appropriate amount of acetone, 4.051×4.0 pieces, 1.0 mm thick. A hot smoking agent is obtained by impregnating a two-hole porous ceramic plate.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients for insecticides and acaricides.

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 Test Example 1 (Insecticidal test against house fly) Place oven paper of the same size on the bottom of a polyethylene cup with a diameter of 5.5 inverted, and dilute the emulsion of the test compound obtained according to Formulation Example 1 with water. wLC 500 1) pm) 0.7- was dropped onto the furnace paper, and 80 capes of sugar was evenly added as bait. Ten female adult house flies were released into the container, and the container was covered with a lid. After 48 hours, the survival rate was determined to determine the mortality rate (2 repetitions). The results are shown in Table 8.

Table 8 Test Example 2 (Insecticidal test against Chapane cockroach) Diameter 5. P of the same size at the bottom of a 5 am polyethylene cup.
Spread the paper and dilute the emulsion of the test compound obtained according to Formulation Example 1 with water! (50(H)I)m)0. 7- was dropped onto furnace paper, and 80 capes of citrus sugar were added uniformly as bait. Ten adult male Chapane cockroaches were released into the container, the container was covered with a lid, and 6 days later, their survival and death were determined to determine the mortality rate. The results are shown in Table 4.

Table 4 Test Example 8 (Insecticidal test against southern corn rootworm) A polyethylene cup with a diameter of 5.55 mm was lined with oven paper of the same size at the bottom, and an emulsion of the test compound obtained according to Formulation Example 1 was prepared.
Dilution with water! (500 ppm) 1- was dropped onto furnace paper, and one corn sprout was added as bait. Place about 80 southern corn rootworm eggs in it, cover it with a lid, and
After several days, the survival of the hatched larvae was investigated, and the mortality rate was calculated.

The results are shown in Table 5.

The insect mortality rate is determined according to the effectiveness criteria below. a: No living insects were observed.

b: Six or fewer living insects are observed.

C: 6 or more animals show.

Effects of the invention shown in Table 5> The compound of the present invention can be applied to Hemiptera calliform insects, Lepidoptera pests, Diptera pests, Coleoptera pests, Reticuloptera pests, Thymoptera pests, Orthoptera pests,
It has excellent insecticidal and acaricidal effects against Hymenoptera bookworms, spider mites, ticks, indoor dust mites, etc.

Claims (2)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a chlorine atom, a bromine atom, or a methyl group, and R_2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] A bromodifluoromethoxybenzene compound represented by (2) An insecticide or acaricide containing the bromodifluoromethoxybenzene compound according to claim 1 as an active ingredient.