JPH05262741A - Phenylpyrazole derivative and noxious life controlling agent - Google Patents

Abstract

PURPOSE:To provide a new phenylpyrazole derivative having excellent insecticidal activity on various kinds of farm vermin and giving little adverse effect on mammals, fish and beneficial insects. CONSTITUTION:The compound of formula I [R is 1-4C (halo)alkyl, 1-4C (halo) alkylsulfonyl or 2-5C (halo)alkylcarbonyl; X is halogen, haloalkyl, NO2, 1-4C alkylthio, 1-4C alkylsulfinyl or 1-4C alkylsulfonyl; m is 3 or 4; Y is halogen, NO2, CN, CO-R<1> (R<1> is alkyl, alkoxy, H, etc.) or SOnR<2> (n is 0-2; R<2> is alkyl, phenyl, etc.); Z is 1-4C (halo)alkyl, 1-4C haloalkoxy or NH2], e.g. 3-methoxy-5- methyl-4-perfluorohexylthio-1-(2,4,6-trichlorophenyl)pyrazole. The compound of formula I wherein Y is SOnR<2> can be produced by reacting a compound of formula II with a compound of the formula hal-SR<2> and, as necessary, oxidizing the reaction product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phenylpyrazole derivative and a pest control agent containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, phenylpyrazole derivatives have been described in patents and literatures. Arch. Phar
m. , 321 , 879 (1988) and JP-B-48-
No. 2541 discloses 5-amino-3-alkoxy-1.
-Phenylpyrazole is described. Also, Arc
h. Pharm. , 321 , 863 (1988),
3,5-Diethoxy-1-phenylpyrazole is described.

However, these documents do not show any insecticidal or acaricidal activity. Furthermore, in the compounds described in these documents, the 4-position of pyrazole is unsubstituted.
Also, Chem. Ber. , 118 , 403 (198
5) includes 5-amino-4-cyano-3-methoxy-1.
-Phenylpyrazole is described, but no indication of insecticidal and acaricidal activity. Further, the 1-position of pyrazole is an unsubstituted phenyl group.

Further, JP-A-62-228065 and JP-A-62-273958 describe phenylpyrazole derivatives having insecticidal activity. However, in the phenylpyrazole derivatives disclosed in these publications, the substituent at the 3-position of the pyrazole ring is an alkylthio group, an alkyl group, a haloalkyl group, a cyano group, etc.
No phenylpyrazole derivative having a substituent bonded by an oxygen atom is shown. Therefore, the compounds of the present invention are novel compounds not included in these prior arts.

[0005]

Due to the long-term use of insecticides, pests have acquired resistance in recent years, making it difficult to control them with conventional insecticides. In addition, some insecticides are highly toxic and some are disturbing the ecosystem due to persistence. Therefore, development of new insecticides with low toxicity and low residue is always expected.

[0006]

The present invention has the general formula (1):

[0007]

[Chemical 2]

[Wherein R is a C ₁ -C ₄ alkyl group, C ₁
To C ₄ haloalkyl group, C _{1 to} C ₄ alkylsulfonyl group, C _{1 to} C ₄ haloalkylsulfonyl group, C _{2 to} C ₅
Represents an alkylcarbonyl group or a C _{2 to} C ₅ haloalkylcarbonyl group, and X represents a halogen atom, a haloalkyl group, a nitro group, a C _{1 to} C ₄ alkylthio group, a C _{1 to} C ₄
Represents an alkylsulfinyl group or a C ₁ -C ₄ alkylsulfonyl group, m represents 3 or 4, Y represents a halogen atom, a nitro group, a cyano group, —CO—R ¹ (provided that R
¹ represents a C ₁ -C ₄ alkyl group, C ₁ -C ₄ haloalkyl groups, C ₁ -C ₄ alkoxy group, a hydroxyl group or a hydrogen atom. ) Or —SO _n R ² (wherein R ² is C _{1 to} C
_{4 represents} an alkyl group, a C ₁ -C ₁₀ haloalkyl group or a phenyl group which may be substituted with a halogen atom, a haloalkyl group, a nitro group or a haloalkoxy group, and n represents 0, 1 or 2. And Z represents a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₄ haloalkoxy group or an amino group. ] The present invention relates to a phenylpyrazole derivative represented by the following formula and a pest control agent containing one or more of the derivatives as an active ingredient.

The compounds of the present invention are effective against various pests at extremely low drug concentrations. Examples of the pest include agricultural pests such as the leafhopper leafhopper, the brown planthopper, the green peach aphid, the pearl moss foxtail, the red-winged beetle, the red-spotted moss, the spider mites, the citrus spider mites, the citrus spider mites, the mosquito mosquitoes, the house fly, and the yellow antler. , Hygiene pests such as lice, weevil, stag beetle,
Examples thereof include storage shell pests such as Stripedeye moth, house pests such as termites, livestock pests such as mites, fleas, and lice, indoor dust mites such as mites, leopard mites and claw mites, and molluscs such as slugs and snails.

That is, the compound of the present invention can effectively control pests of Orthoptera, Hemiptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Termites and mites and lice at low concentrations.
On the other hand, it was found that the compound of the present invention is a very useful compound having almost no adverse effect on mammals, fish, crustaceans and beneficial insects, and completed the present invention. This effect was specifically described in the biological test example described later.

The compounds of the present invention can be prepared by a number of methods. These methods are as follows, for example.

[0012]

[Chemical 3]

In the above formula, X, m, R, Z, R ² and n
Represents the same meaning as described above, and hal represents a halogen atom. The compounds represented by the general formula (4) and the general formula (5) are the compounds of the present invention. More specifically, in Method A, the compound of the present invention represented by the general formula (4) is produced by reacting the pyrazole derivative (2) with the sulfenyl halides (3) in the step 1 in an inert solvent, Further, in step 2, the compound represented by the general formula (4) is m-
It is shown that the compound of the present invention represented by the general formula (5) can be produced by reacting with an oxidizing agent such as chloroperbenzoic acid or hydrogen peroxide.

As the solvent used in Method A, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran and the like. , Ethers such as 1,4-dioxane,
Examples thereof include ketones such as acetone, amides such as dimethylformamide, and dimethyl sulfoxide. The reaction temperature can be set to any temperature from -30 ° to the reflux temperature of the reaction mixture.

The compound represented by the general formula (2) is Arc
h. Pharm. , 321 , 879 (1988), Ar
ch. Pharm. , 321 , 863 (1988) and the like.

[0016]

[Chemical 4]

Also, Pharmaceutical Journal, 87 , 42 (1967)
And J. Am. Chem. Soc. , 65 , 53 (1
General formula (6) which can be synthesized according to the method described in 943).
(X and m have the same meanings as described above, Z'represents a lower alkyl group or an amino group.), In the presence of a base, in an inert solvent, methyl iodide, ethyl iodide, iodo Propyl chloride, 2,2,2-trifluoroethyl iodide, methyl bromide, ethyl bromide, methyl chloride,
Alkyl halides such as dibromodifluoromethane and chlorodifluoromethane, dialkyl sulfates such as diethylsulfate and dimethylsulfate, fluorinated olefins such as tetrafluoroethylene, acid chlorides such as acetyl chloride, acid anhydrides such as acetic anhydride and trifluoroacetic anhydride. , Methanesulfonyl chloride and other sulfonic acid chlorides, trifluoromethane, sulfonic acid anhydrides and other sulfonic acid anhydrides, alkyl sulfonates, alkyl tosylates, haloalkyl sulfonates, haloalkyl tosylates, etc. The pyrazole derivative can be synthesized.

Examples of the base used include alkali metal alkoxides such as sodium ethoxide, sodium methoxide and potassium t-butoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkalis such as sodium carbonate and potassium carbonate. Examples thereof include metal carbonates, organic bases such as triethylamine and pyridine, and sodium hydride.

As the solvent, lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,
4-dioxane, 1,2-dimethoxyethane, 1,2-
Examples thereof include ethers such as diethoxyethane, halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, and mixed solvents thereof. Depending on the case, a mixed solvent of these solvents and water can also be used,
In some cases, good results may be obtained by adding a quaternary ammonium salt such as tetra-n-butylammonium bromide as a catalyst.

[0020]

[Chemical 5]

In the above formula, X, Z ', m, n, hal, R
And R ² have the same meaning as described above. In the method B, a compound represented by the general formula (6) is reacted with a sulfenyl halide to obtain a pyrazolone derivative represented by the general formula (7),
Further, in Step 2, it is shown that the compound of the present invention represented by the general formula (10) can be synthesized by oxidation, and then alkylation, acylation, alkylsulfonylation, haloalkylsulfonylation or haloalkylation in the presence of a base. In addition, in step 2, this order can be reversed.

As the solvent used in Method B, lower alcohols such as methanol and ethanol, benzene,
Aromatic hydrocarbons such as toluene, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, ethers such as 1,2-diethoxyethane, methylene chloride, chloroform, 1,2-dichloroethane, etc. And halogenated hydrocarbons, amides such as dimethylformamide and dimethylacetamide, acetonitrile, dimethylsulfoxide, and mixed solvents thereof. In some cases, a mixed solvent of these solvents and water can also be used, and good results may be obtained by adding a quaternary ammonium salt such as tetra-n-butylammonium bromide as a catalyst.

Examples of the base used include alkali metal alkoxides such as sodium ethoxide, sodium methoxide and potassium t-butoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkalis such as sodium carbonate and potassium carbonate. Examples thereof include metal carbonates, organic bases such as triethylamine and pyridine, and sodium hydride. Examples of the oxidizing agent include m-chloroperbenzoic acid and hydrogen peroxide.

Examples of the alkylating agent include alkyl halides such as methyl iodide, ethyl iodide, methyl bromide, ethyl bromide, and methyl chloride; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl sulfonates and alkyl tosylates. Can be used. As the acylating agent, for example, acetyl chloride, acetic anhydride, trifluoroacetic acid, etc. can be used.

Examples of the haloalkylating agent include 2,2
Alkyl halides such as 2-trifluoroethyl iodide, dibromodifluoromethane and chlorodifluoromethane, boiled olefins such as tetrafluoroethylene and haloalkyl sulfonates can be used. Examples of the alkylsulfonyl agent include methanesulfonyl chloride and the like. As the haloalkylsulfonylating agent, for example, trifluoromethanesulfonic acid anhydride can be used.

[0026]

[Chemical 6]

In the above formula, X, m, R and Z have the same meanings as described above, and Y'represents a nitro group, a halogen atom, a formyl group, an alkylcarbonyl group or a haloalkylcarbonyl group. The method C is carried out by nitrating, halogenating or acylating the pyrazole derivative represented by the general formula (2) in a suitable inert solvent, if necessary.
It shows that the compound of the present invention represented by 1) can be produced.
As the nitrating agent, for example, mixed acid can be used.

Examples of the halogenating agent include chlorine, bromine,
N-bromosuccinimide, N-chlorosuccinimide or iodine monochloride can be used. As the formylating agent, for example, Vilsmeier reagent such as phosphorus oxychloride-dimethylformamide can be used. As the acylating agent, for example, an acid chloride such as acetyl chloride or an acid anhydride such as trifluoroacetic anhydride can be used, and a Lewis acid such as anhydrous aluminum chloride, anhydrous ferric chloride or titanium tetrachloride is used as a desolvent. ..

Examples of the solvent usable in the method C include halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and 1,2-dichloroethane, amides such as dimethylformamide, carbon disulfide, nitrobenzene and acetic acid. Be done. The reaction temperature is in accordance with Method A.

[0030]

[Chemical 7]

In the above formula, X, m, Z'and R have the same meanings as described above, and Y "represents a halogen atom or a nitro group. Method D is a pyrazolone derivative represented by the general formula (6). If necessary, the compound represented by the general formula (12) is synthesized by nitration or halogenation in a suitable inert solvent, and then by alkylation, acylation, alkylsulfonation or haloalkylsulfonation A method for synthesizing the compound of the present invention represented by the formula (13) is shown.

The nitrating agent, halogenating agent, solvent, reaction temperature and the like in step 1 are in accordance with those described in [Method C]. The alkylating agent, haloalkylating agent, acylating agent, alkylsulfonylating agent, haloalkylsulfonylating agent, solvent and reaction temperature in Step 2 are as described in [Method B].

[0033]

[Chemical 8]

In the above formula, X, m, Z ', and R have the same meanings as described above, and Y''' represents an alkylcarbonyl group or a haloalkylcarbonyl group. Method E is represented by the general formula (6)
Acylating the pyrazolone derivative represented by the formula (1) in an inert solvent in the presence of a base to obtain a pyrazole derivative represented by the general formula (14), and then reacting it with a Lewis acid in an inert solvent. By synthesizing the compound represented by the general formula (15) and further alkylating, haloalkylating, acylating, alkylsulfonylating or haloalkylsulfonylating the compound of the present invention represented by the general formula (16) Indicates that it can be manufactured.

As the acylating agent in step 1, for example, an acid halide such as acetyl chloride or an acid anhydride such as trifluoroacetic anhydride or acetic anhydride can be used. The solvent and the reaction temperature are in accordance with those described in [Method B] Step 2. As the Lewis acid in step 2, for example, anhydrous aluminum chloride, anhydrous ferric chloride, titanium tetrachloride or the like can be used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane or carbon disulfide can be used, and the reaction temperature can be arbitrarily set from -30 ° C to 300 ° C. Alkylating agent in step 3, haloalkylating agent, acylating agent, alkylsulfonylating agent,
The haloalkyl sulfonylating agent, the solvent and the reaction temperature are the same as those described in [Method B] Step 2.

[0036]

[Chemical 9]

In the above formulas, X and m have the same meanings as described above, W represents a cyano group or a lower alkyloxycarbonyl group, and R'and R "represent a lower alkyl group. The ketene dithioacetal derivative represented by the formula (1) is treated with sodium alkoxide, and then the phenylhydrazine derivative is reacted to give a compound of the general formula (1
It is shown that the compounds of the present invention represented by 8) and (17) are obtained. Further, the compound of the present invention represented by the general formula (19) can be hydrolyzed to be a pyrazolecarboxylic acid derivative represented by the general formula (20). The compound represented by the general formula (20) is also included in the compound of the present invention. The solvent and reaction temperature in step 1 are [B
Method].

[0038]

[Chemical 10]

In the above formula, V represents bromine, iodine or a hydrogen atom, and X, R, Z, R ² and m have the same meanings as described above. In the method G, the pyrazole derivative represented by the general formula (2) is treated with an alkyllithium such as n-butyllithium, s-butyllithium, t-butyllithium, or methyllithium, and then reacted with dimethyldisulfide. It shows that the compound of the present invention represented by (21) is obtained. Further, the compound represented by the general formula (21) is treated with an oxidizing agent to obtain a compound represented by the general formula (21), and this is reacted with an acid anhydride such as acetic anhydride or trifluoroacetic anhydride. Next, it is shown that the compound of the present invention represented by the general formula (22) can be obtained by treating with triethylamine and then alkylating or haloalkylating.

As the solvent used in the step 1, ethers such as tetrahydrofuran and diethyl ether, and hydrocarbons such as n-hexane are desirable. Further, the oxidizing agent and the solvent in step 2 are in accordance with those described in Method A. The solvent used in step 3 is as described in Method B. As the alkylating agent, alkyl halides such as methyl iodide and ethyl iodide and dialkyl sulfates such as dimethylsulfate and diethylsulfate can be used. As the haloalkylating agent, fluoroalkanes such as dibromodifluoromethane and chlorodifluoromethane, fluorinated olefins such as tetrafluoroethylene and S-trifluoromethyldibenzothiophenium triflate can be used. Good results can be obtained by reacting in the presence of a base as described in the method.

In the production method, the molar ratio of each reaction substance is not particularly limited, but it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto. When the compound of the present invention needs to be purified, it can be separated and purified by any purification method such as recrystallization, column chromatography, thin layer chromatography and the like.

Among the compounds included in the present invention, the compounds having an asymmetric carbon atom include optically active compounds (+) and (−). Further, when the configurational isomers exist, cis isomers and trans isomers are included. The compounds included in the present invention include, for example, the compounds shown in Tables 1 and 2, but the compounds in Tables 1 and 2 are for exemplification, and the present invention includes only these compounds. It is not limited to. The symbols in the table have the following meanings.

Me: methyl group, Et: ethyl group, Pr:
Propyl group, Bu: butyl group, n: normal, i: iso, t: tertiary [Table 1]

[0044]

[Chemical 11]

[0045]

[Chemical 12]

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

[0055]

[Table 10]

[0056]

[Table 11]

[0057]

[Table 12]

[0058]

[Table 13]

[Table 2]

[0060]

[Chemical 13]

[0061]

[Chemical 14]

[0062]

[Table 14] ─────────────────────────────────── RYZ ────────── ───────────────────────── Me NO ₂ Me Me Br Me Me SMe Me Me SCF ₃ Me Me SO ₂ CF ₃ Me Me SOCF ₃ Me Me SC ₆ H ₄ -4-CF ₃ Me Me SO ₂ C ₆ H ₄ -4-CF ₃ Me Me NO ₂ NH ₂ Me SCF ₃ NH ₂ Me SO ₂ CF ₃ NH ₂ Me SOCF ₃ NH ₂ Et NO ₂ Me Et Br Me Et SMe Me Et SCF ₃ Me Et SO ₂ CF ₃ Me Et SOCF ₃ Me Et SCF ₃ NH ₂ Et SO ₂ CF ₃ NH ₂ Et SOCF ₃ NH ₂ ─────────────── ─────────────────────

[0063]

[Table 15] Table 2 (continued) ─────────────────────────────────── RYZ ──── ─────────────────────────────── n-Pr NO ₂ Me n-Pr Br Me n-Pr SMe Me n-Pr SCF ₃ Me n-Pr SO ₂ CF ₃ Me n-Pr SOCF ₃ NH ₂ i-Pr SC ₆ H ₄ -4-CF ₃ Me i-Pr SO ₂ C ₆ H ₄ -4-CF ₃ Me i-Pr NO ₂ NH ₂ i-Pr SCF ₃ NH ₂ n-Bu SO ₂ CF ₃ NH ₂ n-Bu SOCF ₃ NH ₂ n-Bu NO ₂ Me i-Bu Br Me i-Bu SMe Me i-Bu SCF ₃ Me t- Bu SO ₂ CF ₃ Me CHF ₂ SOCF ₃ Me CHF ₂ SCF ₃ NH ₂ CHF ₂ SO ₂ CF ₃ NH ₂ CHF ₂ SOCF ₃ NH ₂ CHF ₂ NO ₂ Me ─────────────── ─────────────────────

[0064]

[Table 16] Table 2 (continued) ─────────────────────────────────── RYZ ──── ─────────────────────────────── CHF ₂ SC ₆ H ₄ -4-CF ₃ Me CF ₂ CHF ₂ Br Me CF ₂ CHF ₂ SMe Me CF ₂ CHF ₂ SCF ₃ Me CF ₂ CHF ₂ SO ₂ CF ₃ Me CF ₂ CHF ₂ SOCF ₃ NH ₂ CF ₂ CHF ₂ SC ₆ H ₄ -4-CF ₃ Me CF ₂ CHF ₂ SO ₂ C ₆ H ₄ -4-CF ₃ Me CF ₂ CHF ₂ NO ₂ Me CF ₂ CHFCF ₃ SCF ₃ NH ₂ CF ₂ CHFCF ₃ SO ₂ CF ₃ NH ₂ CF ₂ CHFCF ₃ SOCF ₃ NH ₂ CF ₂ CHFCF ₃ NO ₂ Me CF ₂ CHFCF (CF ₃ ) ₂ NO ₂ Me CF ₂ CHFCF (CF ₃ ) ₂ SMe Me CF ₂ CHFCF (CF ₃ ) ₂ SCF ₃ Me CF ₂ CHFCF (CF ₃ ) ₂ SO ₂ CF ₃ Me CF ₂ CHFCF (CF ₃ ) ₂ SOCF ₃ Me CF ₃ SCF ₃ NH ₂ CF ₃ SO ₂ CF ₃ NH ₂ CF ₃ SOCF ₃ NH ₂ CF ₃ NO ₂ Me ───────────────────── ───────────────

[0065]

[Table 17] Table 2 (continued) ─────────────────────────────────── RYZ ──── ─────────────────────────────── CF ₃ SO ₂ CF ₃ Me CBrF ₂ Br Me CBrF ₂ SMe Me CBrF ₂ SCF ₃ Me CBrF ₂ SO ₂ CF ₃ Me CBrF ₂ SOCF ₃ NH ₂ CBrF ₂ SC ₆ H ₄ -4-CF ₃ Me CBrF ₂ SO ₂ C ₆ H ₄ -4-CF ₃ Me CBrF ₂ NO ₂ Me SO ₂ Me SCF ₃ NH ₂ SO ₂ Me SO ₂ CF ₃ NH ₂ SO ₂ Me SOCF ₃ NH ₂ SO ₂ Me NO ₂ Me SO ₂ Et NO ₂ Me SO ₂ Et SMe Me SO ₂ Et SCF ₃ Me SO ₂ Pr-n SO ₂ CF ₃ Me SO ₂ Pr-n SOCF ₃ Me SO ₂ Pr-n SCF ₃ NH ₂ SO ₂ Bu-n SO ₂ CF ₃ NH ₂ SO ₂ Bu-n SOCF ₃ NH ₂ SO ₂ Bu-n NO ₂ Me ──── ───────────────────────────────

[0066]

[Table 18] Table 2 (continued) ─────────────────────────────────── RYZ ──── ─────────────────────────────── SO ₂ CF ₃ SO ₂ CF ₃ Me SO ₂ CF ₃ Br Me SO ₂ CF ₃ NO ₂ Me SO ₂ CF ₃ SCF ₃ Me SO ₂ CF ₃ SO ₂ CF ₃ Me SO ₂ CF ₃ SOCF ₃ NH ₂ COMe SC ₆ H ₄ -4-CF ₃ Me COMe SO ₂ C ₆ H ₄ -4-CF ₃ Me COMe NO ₂ Me COMe SCF ₃ NH ₂ COEt SO ₂ CF ₃ NH ₂ COEt SOCF ₃ NH ₂ COEt NO ₂ Me COPr-n NO ₂ Me COPr-n SMe Me COBu-n SCF ₃ Me COBu-n SO ₂ CF ₃ Me COBu-t SOCF ₃ Me COBu-t SCF ₃ NH ₂ COCF ₃ SO ₂ CF ₃ NH ₂ COCF ₃ SOCF ₃ NH ₂ COCF ₃ NO ₂ Me ───────────────── ──────────────────

In using the compound of the present invention as a pest control agent, generally, a suitable carrier, for example, solid carrier such as clay, talc, bentonite, diatomaceous earth or the like, water, alcohols such as methanol, ethanol, benzene, toluene, Aromatic hydrocarbons such as xylene, chlorinated hydrocarbons, ethers, ketones, esters such as ethyl acetate, acid amides such as dimethylformamide can be mixed and applied with a liquid carrier, and if desired, can be applied. By adding an emulsifier, a dispersant, a suspending agent, a penetrating agent, a spreading agent, a stabilizer, etc., it can be put into practical use as an arbitrary formulation such as an emulsion, an oil, a wettable powder, a granule, a flowable agent. ..

If desired, it may be mixed with other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like during formulation or spraying. The application dose of the compound of the present invention varies depending on the application scene, application time, application method, target pests, cultivated crops, etc., but in general, the amount of the active ingredient is preferably about 0.005 to 50 kg per hectare.

Next, Table 3 shows the compounding ratios and types of the various preparations of the present invention.

[0070]

[Table 19] Table 3 Table ─────────────────────────────────── Active ingredient Carriers Surfactants, etc. Ingredient (adjuvant) ─────────────────────────────────── Milk emulsion 1-25 52-95 3 ~ 200-20 Oil agent 1-30 57-99 Flowable agent 1-70 10-90 1-20 0-10 Wettable powder 1-70 15-93 3-100-5 Powder 0.01-30 67-99.5 0 to 3 granules 0.01 to 30 67 to 99.5 0 to 8 ─────────────────────────────────── Above Numerical values in the table indicate% by weight.

In application, emulsions, oils, flowables and wettable powders are diluted with a predetermined amount of water and then sprayed, while powders and granules are directly sprayed without being diluted with water. Next, examples of each component in each of the above formulations will be given.

Emulsion active ingredient: Compound of the present invention Carrier: Xylene, dimethylformamide, methylnaphthalene, cyclohexanone, dichlorobenzene,
Isophorone Surfactant: Solpol 2680, Solpol 3005X, Solpol 3353 Other components: Piperonyl butoxide, benzotriazole

Oil agent Active ingredient: Compound of the present invention Carrier: Xylene, methyl cellosolve, kerosene

Flowable agent Active ingredient: Compound of the present invention Carrier: Water Surfactant: Lunox 1000C, Solpol 3353, Soprofer FL, Nipol, Aglycol S-710, Sodium lignin sulfonate Other ingredients: Zansan gum, formalin, ethylene glycol ,Propylene glycol

Wettable powder Active ingredient: Compound of the present invention Carrier: Calcium carbonate, kaolinite, Sikhlite D, Sikhlite PFP, diatomaceous earth, talc Surfactant: Solpol 5039, Lunox 1000C, calcium lignin sulfonate, dodecylbenzene sulfone Acid soda, Solpol 5050, Solpol 005D, Solpol 5029-0 Other ingredients: Carplex # 80

Dust active ingredient: Compound of the present invention Carrier: Calcium carbonate, kaolinite, Sikhlite D, talc Other ingredients: Diisopropyl phosphate, Carplex # 80

Granules (1) Active ingredient: Compound of the present invention Carrier: Calcium carbonate, kaolinite, bentonite, talc Other ingredients: Calcium lignin sulfonate, polyvinyl alcohol

Granules (2) [Bait] Active ingredient: Compound of the present invention Carrier: Wheat flour, bran, corn grit, Sieglite D Other ingredients: Paraffin, soybean oil

[0079]

【Example】

Examples (Synthesis Examples, Formulation Examples, Test Examples) Hereinafter, the present invention will be specifically described with reference to Examples (Synthesis Examples, Formulation Examples, Test Examples).

[Synthesis Example] The compounds included in the present invention are
It could be produced based on the synthesis example shown below,
The present invention is not limited to only these compounds.

Synthesis Example 1 3-methoxy-5-methyl-4-perfluorohexylthio-1- (2,4,6-trichlorophenyl) pyrazole (invention compound No. 1) 3-hydroxy-5-methyl- A mixture of 1.5 g of 1- (2,4,6-trichlorophenyl) pyrazole, 3.6 g of perfluorohexylsulfenyl chloride and 15 ml of carbon tetrachloride was refluxed for 10 hours. Evaporate the solvent,
The obtained solid was washed with hexane and dried to give 3-hydroxy-5-methyl-4-perfluorohexylthio-1-.
(2,4,6-Trichlorophenyl) pyrazole 2.1
g was obtained.

Next, 3-hydroxy-5-methyl-4-
To a solution of 0.5 g of perfluorohexylthio-1- (2,4,6-trichlorophenyl) pyrazole and 5 ml of N, N-dimethylformamide, 0.07 g of sodium hydride was added under ice-cooling, and 2 I stirred the time. A mixture of 0.36 g of methyl iodide and 2 ml of N, N-dimethylformamide was added to this solution under ice cooling, and the mixture was further stirred at room temperature overnight. The reaction solution was poured into water, extracted with ethyl ether, washed with water and dried. The solvent is distilled off, and the residue is treated with hexane to give the desired 3-methoxy-5-methyl-
0.05 g of 4-perfluorohexylthio-1- (2,4,6-trichlorophenyl) pyrazole was obtained. m
p172-174 ° C

Synthesis Example 2 3-Bromodifluoromethoxy-5-methyl-4-nitro-1- (2,4,6-trichlorophenyl) pyrazole (inventive compound No. 2) 3-hydroxy-5-methyl-1 -(2,4,6-trichlorophenyl) pyrazole 16.1 g was added to concentrated sulfuric acid 50 m.
It was dissolved in 1 l, 6.1 g of 60% nitric acid was added under ice cooling, and the mixture was stirred overnight at room temperature. The reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried over sodium sulfate, the solvent was distilled off, and the obtained crude crystals were washed with isopropyl ether.
-Hydroxy-5-methyl-4-nitro-1- (2,
18.1 g of 4,6-trichlorophenyl) pyrazole
Obtained.

Next, 2.0 g of 55% sodium hydride was suspended in 50 ml of N, N-dimethylformamide, and under ice cooling, 3-hydroxy-5-methyl-4-nitro-1-.
(2,4,6-trichlorophenyl) pyrazole 10.
A solution prepared by dissolving 0 g in 30 ml of N, N-dimethylformamide was added. After stirring at room temperature for 1 hour, 37 g of dibromodifluoromethane and 0.5 g of potassium iodide
g was added and reacted at 130 ° C. for 1.5 hours. Under vacuum,
The solvent was distilled off, water was added, the mixture was extracted with ethyl ether, washed with water, and dried over sodium sulfate. After distilling off the solvent,
The obtained oily substance was purified by high performance liquid chromatography to give 3-bromodifluoromethoxy-5-methyl-4-.
3.5 g of nitro-1- (2,4,6-trichlorophenyl) pyrazole were obtained. mp59-62 ° C

Synthesis Example 3 5-amino-4-cyano-3-methoxy-1- (2,
4,6-Trichlorophenyl) pyrazole (inventive compound No. 3) Sodium methoxide 1 dissolved in a solution of 16 g of 3,3-bis (methylthio) -2-cyanoacrylonitrile and 200 ml of methanol in 50 ml of methanol under ice cooling.
0.2 g was added. After stirring at room temperature for 2.5 hours, 20 ml of acetic acid and 21 g of 2,4,6-trichlorophenylhydrazine were added, and the mixture was refluxed for 2.5 hours. After cooling to room temperature, water was added and the precipitated crystals were collected by filtration, washed with water and dried to obtain a crude product. Recrystallize with benzene-hexane,
Targeted 5-amino-4-cyano-3-methoxy-1
-(2,4,6-Trichlorophenyl) pyrazole 1.
I got 6g. mp188.5-190.0 ° C

Synthesis Example 4 5-Amino-3-methoxy-4-trichloromethylthio-1- (2,4,6-trichlorophenyl) pyrazole (invention compound No. 4) 5-amino-3-methoxy-1- (2,4,6-trichlorophenyl) pyrazole 1 g chloroform 20 ml
Was dissolved in water, and 0.64 g of trichloromethylsulfenyl chloride was added dropwise under ice cooling, followed by stirring at room temperature overnight. The precipitated solid was collected by filtration and washed with cold chloroform to obtain 0.5 g of the target compound. Melting point 155.8-16
3.1 ° C

Synthesis Example 5 4-formyl-3-methoxy-5-methyl-1- (2,
4,6-Trichlorophenyl) pyrazole (inventive compound No. 5) 2 g of 3-methoxy-5-methyl-1- (2,4,6-trichlorophenyl) pyrazole was dissolved in 6 ml of N, N-dimethylformamide, Vilsmeier reagent prepared from 1.2 g of phosphorus oxychloride and 3 ml of N, N-dimethylformamide was added dropwise under ice cooling, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water, diluted with dilute aqueous sodium hydroxide to make it alkaline, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product. This was purified by preparative thin layer chromatography (benzene / n-hexane = 2/1) to obtain 1 g of the target compound. Melting point 93.8-98.7
℃

Synthesis Example 6 Methyl-5-amino-3-methoxy-1- (2,4,6
-Trichlorophenyl) pyrazole-4-carboxylate (Compound No. 6 of the present invention) 2.8 g of sodium methoxide was dissolved in 40 ml of methanol, and methyl-3,3-bis (methylthio) -2- under ice cooling. It was added dropwise to a methanol solution of 5 g of cyanoacrylate (200 ml of methanol). After stirring at room temperature for 15 minutes, 10 ml of glacial acetic acid and 2,4,4 under ice cooling.
5.2 g of 6-trichlorophenylhydrazine was added.
After stirring at room temperature for 2 hours and then heating under reflux for 2 hours, the solvent was distilled off under reduced pressure, and the residue was extracted with chloroform. The organic layer was washed with an aqueous sodium hydrogen carbonate solution and then with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Benzene and isopropyl ether were added to the residue, and the precipitated crystals were collected by filtration and methyl 5-amino-3-
5.3 g of methoxy-1- (2,4,6-trichlorophenyl) pyrazole-4-carboxylate were obtained. Melting point 211.5-212.5 [deg.] C.

Synthesis Example 7 4-Acetyl-3-methoxy-5-methyl-1- (2,
4,6-Trichlorophenyl) pyrazole (inventive compound No. 7) 1 g of 3-acetoxy-5-methyl-1- (2,4,6-trichlorophenyl) pyrazole was added to 10 ml of carbon disulfide.
And add 0.84 g of anhydrous aluminum chloride and add 5
After heating under reflux for a period of time, diluted hydrochloric acid was added under ice cooling and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried, and the solvent was evaporated under reduced pressure. The residue was dissolved in 5 ml of N, N-dimethylformamide, 0.05 g of sodium hydride was added, and the mixture was stirred at room temperature for 30 minutes.
It was stirred for a minute. After adding 1 g of methyl iodide and stirring at room temperature overnight, the solvent was distilled off under reduced pressure. The residue was extracted with benzene, washed with water, dried, and concentrated under reduced pressure to obtain an oily substance, which was then purified by preparative thin layer chromatography (benzene / n-hexane = 2/1) to give the resinous target compound. 200 mg
Got

¹ H-NMR (CDCl ₃ , TMS, δp
pm): 2.30 (3H, s), 2.49 (3H,
s), 4.01 (3H, s), 7.50 (2H, s)

Synthesis Example 8 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-5-methyl-4-nitropyrazole (invention compound No. 8) N, N-dimethylformamide 1- (2, 100 ml
6-dichloro-4-trifluoromethylphenyl) -3
5.7 g of -hydroxy-5-methylpyrazole was dissolved, 7.6 g of potassium carbonate was added, and chlorodifluoromethane was blown in for 3 hours while stirring at an external temperature of 80 ° C. Then, the reaction mixture was subjected to solvent removal under reduced pressure, water was added to the obtained residue, extracted with chloroform, washed with saturated saline,
It was dried over anhydrous sodium sulfate and treated with activated carbon. The residue obtained by distilling off the solvent was purified by silica gel column chromatography (eluent: benzene) to give 1- (2,
6-dichloro-4-trifluoromethylphenyl) -3
-Difluoromethoxy-5-methyl-pyrazole 1.8
g was obtained as a pale yellow viscous liquid.

1- (2,6-dichloro-obtained above
870 mg of 4-trifluoromethylphenyl) -3-difluoromethoxy-5-methylpyrazole was added to 3 m of concentrated sulfuric acid.
l, and stirred under ice cooling, concentrated nitric acid 253 mg
Was dripped. After stirring the reaction mixture at room temperature overnight,
It was poured little by little on ice, extracted with chloroform, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: normal hexane: benzene = 2: 1) to give 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-. 5
720 mg of -methyl-4-nitropyrazole were obtained as a viscous liquid.

¹ H-NMR (CDCl ₃ , TMS, δp
pm): 2.44 (3H, s), 6.94 (1H, t,
J = 70 Hz), 7.67 (2H, s)

Synthesis Example 9 4-Bromo-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-methoxy-5-methylpyrazole (invention compound No. 9) 1- (2,6- Dichloro-4-trifluoromethylphenyl) -3-methoxy-5-methylpyrazole 0.49
g was dissolved in 5 ml of acetic acid, and bromine (0.1 ml) was added while stirring at room temperature.
24 g was dropped. The reaction mixture was stirred at room temperature for another 2 hours and left overnight. Water was added to the residue obtained by distilling off acetic acid, the mixture was extracted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and then the solvent was evaporated. The obtained residue was purified by silica gel column chromatography (solvent: benzene) to give 4-bromo-1- (2,6-dichloro-4).
-Trifluoromethylphenyl) -3-methoxy-5-
0.5 g of methylpyrazole was obtained as colorless crystals. Melting point 64.5-65.5 ° C

Synthesis Example 10 3-methoxy-5-methyl-1- (2,4,6-trichlorophenyl) -4-{(4-trifluoromethylphenyl) thio} pyrazole (invention compound No. 10) and 3-methoxy-5-methyl-1- (2,4,6-trichlorophenyl) -4-{(4-trifluoromethylphenyl) sulfonyl} pyrazole (present compound No.
11) 0.86 g of 3-methoxy-5-methyl-1- (2,4,6-trichlorophenyl) pyrazole was added to 5 m of carbon tetrachloride.
It was dissolved in 1 and 0.75 g of 4-trifluoromethylphenylsulfenyl chloride was added with stirring under ice-cooling, and then the mixture was stirred at room temperature overnight. Then, the reaction mixture was diluted with chloroform, washed with diluted NaOH aqueous solution and water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was washed with normal hexane to give 3-methoxy-5-methyl-1- (2,4,6-trichlorophenyl) -4-{(4-trifluoromethylphenyl) thio} pyrazole 0. 0.41 g was obtained as colorless crystals. Melting point 150-152 [deg.] C.

3-methoxy-5-methyl-1 obtained above
0.3 g of-(2,4,6-trichlorophenyl) -4- (4-trifluoromethylphenylthio) pyrazole was dissolved in 5 ml of dichloromethane, and the mixture was stirred while cooling with ice.
-0.22 g of chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 1 hour and a half. Then, this reaction mixture was diluted with dichloromethane, washed with a saturated sodium hydrogen carbonate aqueous solution and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by preparative thin layer chromatography to give 3-methoxy-5-methyl-1- (2,4,6-
0.15 g of trichlorophenyl) -4- (4-trifluoromethylphenylsulfonyl) pyrazole was obtained as a colorless amorphous.

¹ H-NMR (CDCl ₃ , TMS, δp
pm): 2.37 (3H, s), 3.94 (3H,
s), 7.49 (2H, s), 7.78 (2H, d, J
= 8.3 Hz), 8.16 (2H, d, J = 8.3H)
z)

Synthesis Example 11 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-nitro-3-tetrafluoroethoxypyrazole (invention compound No. 12) 5-amino-1 -(2,6-Dichloro-4-trifluoromethylphenyl) -3-hydroxypyrazole 1.0
g was dissolved in 10 ml of N, N-dimethylformamide, 1.3 g of potassium carbonate was added, and tetrafluoroethylene was blown therein for 1 hour with stirring at 90 ° C. After stirring at 90 ° C. for another two and a half hours, ice was added to the reaction mixture, extraction with ethyl acetate, washing with water, drying over anhydrous sodium sulfate, and evaporation of the solvent. The obtained residue was purified by silica gel column chromatography (eluent: chloroform) to give 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-tetrafluoroethoxypyrazole 0.61 g. Got

The 5-amino-1- (2,6 obtained above was obtained.
-Dichloro-4-trifluoromethylphenyl) -3-
0.61 g of tetrafluoroethoxypyrazole was dissolved in 5 ml of concentrated sulfuric acid, and 0.16 of concentrated nitric acid was added while stirring under ice cooling.
g was added dropwise, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was allowed to stand overnight, poured into ice, and the precipitated crystals were collected by filtration.
By purifying the obtained crude product by silica gel column chromatography (eluent: chloroform), 5-
0.35 g of amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -4-nitro-3-tetrafluoroethoxypyrazole was obtained as colorless crystals. Melting point 165-170 ° C

Synthesis Example 12 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-methoxy-4-nitro-5-tetrafluoroethoxypyrazole (invention compound No. 13) 2- (2 6-Dichloro-4-trifluoromethylphenyl) -5-methoxy-3 (2H) -pyrazolone 1.4
7 g was dissolved in 10 ml of N, N-dimethylformamide, 1.86 g of potassium carbonate was added, and tetrafluoroethylene was blown thereinto for 1.5 hours while stirring at 90 ° C. After allowing to cool, ice was added to the reaction mixture, which was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue is filtered through silica gel to give crude 1-
1.05 g of (2,6-dichloro-4-trifluoromethylphenyl) -3-methoxy-5-tetrafluoroethoxypyrazole was obtained as a brown oily substance.

1- (2,6-dichloro-obtained above
4-trifluoromethylphenyl) -3-methoxy-5
-Dissolve 0.99 g of tetrafluoroethoxypyrazole in 5 ml of concentrated sulfuric acid and add 0.1 ml of concentrated nitric acid while stirring under ice cooling.
5 g was added dropwise, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into ice, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. If the residue is purified by preparative high performance liquid chromatography, 1-
0.26 g of (2,6-dichloro-4-trifluoromethylphenyl) -3-methoxy-4-nitro-5-tetrafluoroethoxypyrazole was obtained as colorless crystals.
Melting point 113.9-122.3 ° C

Synthesis Example 13 5-amino-3-difluoromethoxy-1- (2,4,
6-trichlorophenyl) -4-{(4-trifluoromethylphenyl) thio} pyrazole (the present compound N
o. 14) and 5-amino-3-difluoromethoxy-1- (2,4,6-trichlorophenyl) -4-
{(4-trifluoromethyl) sulfonyl} pyrazole (inventive compound No. 15) 3.43 g of 5-amino-3-hydroxy-1- (2,4,6-trichlorophenyl) pyrazole was dissolved in 50 ml of chloroform, While stirring under ice cooling, 3.2 g of 4-trifluoromethylphenylsulfenyl chloride
Was added dropwise, and the mixture was stirred at room temperature for 3.5 hours. By distilling off the solvent and recrystallizing from benzene-normal hexane, 5-
4.03 g of amino-3-hydroxy-1- (2,4,6-trichlorophenyl) -4- (4-trifluoromethylphenylthio) pyrazole was obtained as flesh color crystals.

The above 5-amino-3-hydroxy-1-
2.36 g of (2,4,6-trichlorophenyl) -4- (4-trifluoromethylphenylthio) pyrazole was dissolved in 20 ml of N, N-dimethylformamide, 1.8 g of potassium carbonate was added, and 70-80 ° C. Chlorodifluoromethane was blown in for 5 hours and a half with stirring. After cooling, the reaction mixture was added with ice, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography (eluent: benzene: normal hexane = 2: 1) to give 5-amino-3-difluoromethoxy-1-.
(2,4,6-Trichlorophenyl) -4-{(4-trifluoromethylphenyl) thio} pyrazole 0.59
g was obtained as a brown amorphous.

¹ H-NMR (CDCl ₃ , TMS, δp
pm): 4.12 (2H, brs), 7.04 (1H,
t, J = 73 Hz), 7.21 (2H, d, J = 8.6)
Hz), 7.52 (2H, d, J = 8.5 Hz), 7.
53 (2H, s) 5-amino-3-difluoromethoxy-obtained above
1- (2,4,6-trichlorophenyl) -4- (4-
0.59 g of trifluoromethylthio) pyrazole was dissolved in 7 ml of dichloromethane, and m- was added while stirring under ice cooling.
0.36 g of chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with dichloromethane, washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was purified by preparative thin layer chromatography to give 0.39 g of 5-amino-3-difluoromethoxy-1- (2,4,6-trichlorophenyl) -4- (4-trifluoromethylphenylsulfonyl) pyrazole. Obtained as pale yellow crystals. Melting point 61.3-67.1 ° C

Synthesis Example 14 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-methyl-4-nitro-3-trifluoromethanesulfonyloxypyrazole (Compound No. of the present invention.
16) 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-hydroxy-5-methylpyrazole 1.0
g was dissolved in 5 ml of concentrated sulfuric acid, 0.34 g of concentrated nitric acid was added dropwise with stirring under ice-cooling, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ice, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was evaporated. 0.75 g of crude 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-hydroxy-5-methyl-4-nitropyrazole by washing the residue with normal hexane.
Was obtained as brown crystals.

The above-obtained 1- (2,6-dichloro-
4-trifluoromethylphenyl) -3-hydroxy-
0.53 g of 5-methyl-4-nitropyrazole was dissolved in 7 ml of benzene, 0.18 g of pyridine was added, and trifluoromethanesulfonic anhydride 0.6 was added while stirring at room temperature.
3 g was added dropwise, and the mixture was further stirred at room temperature for 10 minutes. The reaction mixture was diluted with benzene, washed with water, diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was filtered through silica gel and 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-methyl-4-nitro-3-
Trifluoromethanesulfonyloxypyrazole 0.6
9 g was obtained as brown crystals. Melting point 138-140 ° C

Synthesis Example 15 Synthesis of 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-5-methyl-4-methylthiopyrazole (invention compound No. 69) In 70 ml of normal hexane. 4-bromo-1- (2,6
-Dichloro-4-trifluoromethylphenyl) -3-
5.6 g of difluoromethoxy-5-methylpyrazole was dissolved, cooled to -40 ° C, and 11 ml of n-butyllithium (1.57M hexane solution) was slowly added dropwise, followed by stirring at the same temperature for 20 minutes. 1.5 ml of dimethyl disulfide dissolved in 2 ml of normal hexane
6 g was slowly added dropwise, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature overnight. The reaction solution was poured into ice water, extracted with chloroform, washed with water, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: chloroform / normal hexane = 1/4) to obtain the desired 1- (2,
6-dichloro-4-trifluoromethylphenyl) -3
3.72 g of -difluoromethoxy-5-methyl-4-methylthiopyrazole was obtained as a colorless viscous liquid. (N ²⁰
= 1.5153)

Synthesis Example 16 Synthesis of 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-5-methyl-4-methylsulfinylpyrazole (invention compound N
o. 70) Crude 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-5-methyl-4-methylthiopyrazole in 50 ml methylene chloride 8.
9 g was dissolved, 2.04 g of metachlorobenzoic acid was added with stirring under ice cooling, and the mixture was stirred at room temperature for 4 hours. Then, the reaction solution was diluted with methylene chloride, washed with a saturated aqueous solution of sodium hydrogen carbonate and water, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: chloroform) to obtain the desired 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-5-methyl-4. 2.58 g of -methylsulfinylpyrazole was obtained as a colorless viscous liquid.

¹ H-NMR (CDCl ₃ , TMS, δ
_ppm ) 2.32 (3H, s), 3.10 (3H, s),
7.07 (1H, t, J = 72Hz), 7.80 (2
H, s)

Synthesis Example 17 Synthesis of 1- (2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-4-trifluoromethylthio-5-methylpyrazole (invention compound No. 71) Methylene chloride 1- (2,6-dichloro-4- in 20 ml
2.58 g of trifluoromethylphenyl) -3-difluoromethoxy-5-methyl-4-methylsulfinylpyrazole was dissolved in the solution, and trifluoroacetic anhydride 2.5 m
1 was added, and the mixture was heated under reflux for 30 minutes, allowed to cool, and the solvent was removed under reduced pressure. The residue obtained is methanol (30 m
It was dissolved in a mixed solution of 1) and triethylamine (30 ml), stirred for 1-2 minutes, and then the solvent was removed under reduced pressure. The obtained residue was dissolved in chloroform, washed with a saturated aqueous solution of ammonium chloride, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained residue was dissolved in 5 ml of N, N-dimethylformamide, 0.27 g of sodium hydride was suspended, and the mixture was added dropwise to 20 ml of ice-cooled N, N-dimethylformamide and stirred for 5 minutes, and then S-
2.4 g of trifluoromethyldibenzothiophenium triflate was added, and the mixture was further stirred for 30 minutes. The reaction solution was poured into ice water, extracted with chloroform, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: chloroform / normal hexane = 1/8) to give the desired 1
1.35 g of-(2,6-dichloro-4-trifluoromethylphenyl) -3-difluoromethoxy-4-trifluoromethylthio-methylpyrazole were obtained as a colorless viscous liquid. (N ²⁰ = 1.4801) Table 4 shows compounds produced according to any of the methods shown in the above Synthesis Examples. In addition, Q1 to Q6 in Table 4 are groups represented by the following formula.

[0111]

[Chemical 15]

[Table 4]

[0113]

[Chemical 16]

[0114]

[Table 20] ─────────────────────────────────── No. QRYZ Melting point (° C) ─── ──────────────────────────────── 17 Q1 CHF ₂ Br CH ₃ oil 18 Q1 CHF ₂ SO ₂ C ₆ H ₄ -4-CF ₃ NH ₂ 61.3-67.7 19 Q1 CHF ₂ NO ₂ CH ₃ oil 20 Q1 CH ₂ CF ₃ NO ₂ CH ₃ 123-124 21 Q1 CH ₃ I CH ₃ 95-97 22 Q1 CH ₃ NO ₂ OCHF ₂ 125-131 23 Q1 CH ₃ SC ₆ H ₅ CH ₃ 125-129 24 Q1 CH ₃ SC ₆ H ₅ NH ₂ 154.5-156 25 Q1 CH ₃ SOC ₆ H ₅ NH ₂ 74-78 26 Q1 CH ₃ SOC ₆ H ₅ CH ₃ oil 27 Q1 CH ₃ SO ₂ C ₆ H ₅ CH ₃ 122-123.5 28 Q1 CH ₃ SO ₂ C ₆ H ₅ NH ₂ 156-158 29 Q1 CH ₃ SC ₆ H ₄ -4-Cl CH ₃ 110-115 ───────────────────────────────────

[0115]

[Table 21] Table 4 (continued) ─────────────────────────────────── No. QRYZ Melting point ( ° C) ─────────────────────────────────── 30 Q1 CH ₃ SC ₆ H ₄ -4-Cl NH ₂ 162-166 31 Q1 CH ₃ SOC ₆ H ₄ -4-CF ₃ CH ₃ Resin 32 Q1 CH ₃ SC ₆ H ₄ -3-CF ₃ CH ₃ 108.5-111 33 Q1 CH ₃ SOC ₆ H ₄ -3 -CF ₃ CH ₃ Resin 34 Q1 CH ₃ SO ₂ C ₆ H ₄ -3-CF ₃ CH ₃ Resin 35 Q1 CH ₃ SO ₂ C ₆ H ₃ -2,4-F ₂ CH ₃ 199-207 36 Q1 CH ₃ SOC ₆ H ₃ -2-Cl-4-NO ₂ CH ₃ 192.8-193 37 Q1 CH ₃ SO ₂ C ₆ H ₃ -2-Cl-4-NO ₂ CH ₃ 205.7-207.9 38 Q1 CH ₃ SC ₆ F ₁₃ NH ₂ oil 39 Q1 CH ₃ SCH ₃ CH ₃ 57-67 40 Q2 CHF ₂ Br CH ₃ oil 41 Q2 CHF ₂ SO ₂ C ₆ H ₄ -4-Cl CH ₃ 115.4-117.5 42 Q2 CF ₂ CHF ₂ NO ₂ CH ₃ 82-85 43 Q2 CHF ₂ SOC ₆ H ₄ -4-CF ₃ CH ₃ 40.9-45 44 Q2 CHF ₂ SO ₂ C ₆ H ₄ -4-CF ₃ CH ₃ 43.2-45.9 45 Q2 CH ₃ NO ₂ CH ₃ 115-117 46 Q2 CH ₃ NO ₂ NH ₂ 240-245 47 Q2 CH ₃ NO ₂ OCBrF ₂ 95.3-100.9 48 Q2 CH ₃ NO ₂ OC HF ₂ 124.8-129.8 49 Q2 CH ₃ NO ₂ CF ₃ 94.5-95.3 50 Q2 CH ₃ SC ₆ H ₄ -4-OCF ₃ CH ₃ 112.4-116.6 51 Q2 CH ₃ SOC ₆ H ₄ -4-OCF ₃ CH ₃ oil ───────────────────────────────────

[0116]

[Table 22] Table 4 (continued) ─────────────────────────────────── No. QRYZ Melting point ( ° C) ─────────────────────────────────── 52 Q2 CH ₃ SO ₂ C ₆ H ₄ -4 -OCF ₃ CH ₃ 150.1-152.5 53 Q2 CH ₃ SC ₆ H ₃ -2,4-F ₂ CH ₃ 140-146.2 54 Q2 CH ₃ SOC ₆ H ₃ -2,4-F ₂ CH ₃ Resin 55 Q2 CH ₃ SO ₂ C ₆ H ₄ -4-Br CH ₃ 200.6-202.4 56 Q2 CH ₃ SOC ₆ H ₄ -4-CF ₃ CH ₃ 107.8-108.6 57 Q2 CH ₃ SO ₂ C ₆ H ₄ -4-CF ₃ CH ₃ 150.6-154.4 58 Q2 CH ₃ SO ₂ C ₆ H ₄ -4-NO ₂ CH ₃ 187.9-191.2 59 Q2 CH ₃ SOC ₆ H ₄ -3-CF ₃ CH ₃ 168.3-172.3 60 Q2 CH ₃ SO ₂ C ₆ H ₄ -3-CF ₃ CH ₃ 142.3-147.9 61 Q2 Et NO ₂ CH ₃ 95-100 62 Q2 Et NO ₂ NH ₂ 180-185 63 Q2 SO ₂ CH ₃ NO ₂ CH ₃ 154-156 64 Q2 SO ₂ CH ₃ Br CH ₃ 152-155 65 Q3 CHF ₂ NO ₂ CH ₃ 143-147 66 Q4 CH ₃ Br CH ₃ Resin 67 Q5 CH ₃ Br CH ₃ Resin 68 Q6 CH ₃ Br CH ₃ Resin 72 Q1 CH ₃ SOCH ₃ CH ₃ Resin 73 Q1 CH ₃ SCBrF ₂ CH ₃ 137-139 74 Q1 C H ₃ SO ₂ CBrF ₂ CH ₃ Resin 75 Q1 CH ₃ SCHF ₂ CH ₃ 98-101 76 Q1 CH ₃ SCF ₃ CH ₃ 116-121 ────────────────── ─────────────────

[0117]

[Table 23] Table 4 (continued) ─────────────────────────────────── No. QRYZ Melting point ( ° C) ─────────────────────────────────── 77 Q1 CH ₃ SOCF ₃ CH ₃ 122-124.5 78 Q1 CH ₃ SO ₂ CF ₃ CH ₃ 85.5-88 79 Q2 CH ₃ SCF ₃ CH ₃ n _D ²⁰ = 1.5153 80 Q2 CH ₃ SOCF ₃ CH ₃ n _D ²⁰ = 1.5044 81 Q2 CH ₃ SO ₂ CF ₃ CH ₃ 127.2- 129.1 82 Q2 CHF ₂ SOCF ₃ CH ₃ 59-63 83 Q2 CHF ₂ SO ₂ CF ₃ CH ₃ Resin 84 Q2 CH ₃ COCF ₃ CH ₃ Resin 85 Q2 CHF ₂ COCF ₃ CH ₃ Resin ─────── ─────────────────────────────

Compound No. in Table 4 72, No. 7
4, No. 83, No. 84, No. 85 of ¹ H-NM
The R spectrum is as follows. Compound No. 72 NMR (CDCl ₃ , δ value, ppm): 2.21 (3H,
s), 3.08 (3H, s), 4.00 (3H, s),
7.56 (2H, s) Compound No. 74 NMR (CDCl ₃ , δ value, ppm): 2.32 (3H,
s), 4.02 (3H, s), 7.56 (2H, s) Compound No. 83 NMR (CDCl ₃ , δ value, ppm): 2.40 (3H,
s), 7.04 (1H, t, J = 71 Hz), 7.84
(2H, s) Compound No. 84 NMR (CDCl ₃ , δ value, ppm): 2.37 (3H,
s), 4.01 (3H, s), 7.80 (2H, s) Compound No. 85 NMR (CDCl ₃ , δ value, ppm): 2.42 (3H,
s), 7.08 (1H, t, J = 72Hz), 7.83
(2H, s)

[Formulation Examples] Next, formulation examples of pest control agents containing the compound of the present invention as an active ingredient are shown, but the present invention is not limited thereto. In the following formulation examples, "part" means part by weight.

Formulation Example 1 Emulsion Compound of the present invention: 5 parts Xylene: 70 parts N, N-Dimethylformamide: 20 parts Solpol 2680: 5 parts (nonionic surfactant Mixture of agent and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd. The above is uniformly mixed to obtain an emulsion.

In use, the above emulsion is added in an amount of 50 to 200.
Diluted to 00 times and the amount of active ingredient is 0.0 per hectare
Sprinkle so that the amount becomes 05 to 50 kg.

Formulation Example 2 Wettable powder Compound of the present invention ............ 25 parts Dikhlite PFP ………… 66 parts (mixture of kaolinite and sericite: trade name of Sikhlite Industry Co., Ltd.) Solpol 5039 4 parts (anionic surfactant: Toho Chemical Industry Co., Ltd. product name) Carplex # 80 ………… 3 parts (white carbon: Shionogi Pharmaceutical Co., Ltd. product name) Calcium lignin sulfonate ………… Two or more parts are uniformly mixed and pulverized to obtain a wettable powder.

In use, the above wettable powder is added to 50 to 20
It is diluted to 000 times and the amount of active ingredient is 0.1 per hectare.
Sprinkle so that it is 005 to 50 kg.

Formulation Example 3 Oil agent Compound of the present invention: 10 parts Methylcellosolve: 90 parts The above ingredients are uniformly mixed to obtain an oil agent. When used, the above oil agent is used in an amount of 0.005 to 5 per hectare.
Sprinkle so that it weighs 0 kg.

Formulation Example 4 Powder Compound of the present invention: 3.0 parts Carplex # 80: 0.5 parts (white carbon: Shionogi Pharmaceutical Co., Ltd. trade name) Clay: 95 Part Diisopropyl phosphate: 1.5 parts Uniformly mix and grind the above to make a powder.

At the time of use, the above powder is sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 5 particles Agent compound of the present invention 5 parts Bentonite 54 parts Talc 40 parts Calcium lignin sulfonate 1 part 1 part The above is uniformly mixed and pulverized in a small amount Water is added and mixed by stirring, granulated by an extrusion granulator, and dried to obtain granules.

At the time of use, the above granules are sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare.

Formulation Example 6 Flowable agent Compound of the present invention 35 parts Solpol 3353 10 parts (Nonionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Lunox 1000C ...... 5 parts (anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) 1% aqueous solution of xanthan gum ............ 20 parts (natural polymer) water ............ 4.5 parts Active ingredient (compound of the present invention) Except for the above components, the components are uniformly dissolved, the compound of the present invention is added, and the mixture is stirred well and then wet-milled in a sand mill to obtain a flowable agent.

At the time of use, 50 parts of the above flowable agent was used.
It is diluted to 20,000 times and sprayed so that the amount of the active ingredient is 0.005 to 50 kg per hectare. [Test Example] Next, the usefulness of the compound of the present invention as a pest control agent will be specifically described in the following test examples.

Test Example 1 Insecticidal test against brown planthopper 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent to give a concentration of 1000 ppm. Was prepared. A sufficient amount of this chemical solution was applied to the foliage of rice planted in a pot of 120,000 are. After air-drying, a cylinder was set up, 10 second-instar larvae of the brown planthopper were released per pot, covered with a lid, and stored in a temperature-controlled room. The investigation was conducted after 6 days, and the mortality rate was calculated from the following formula. The test was conducted in a two-division system.

Mortality of mortality (%) = (number of mortality / number of larvae) × 100 As a result, the following compounds showed a mortality of 100%. Inventive compound: No. 8, 12, 17, 19, 20, 2
1, 40, 42, 45, 61, 71, 73, 74, 7
5,76,77,78,79,80,81,82,8
3,84

Test Example 2 Insecticidal test against Cistanche salsa lucidum A 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent. Then, the tomato leaf is soaked in this chemical solution for about 10 seconds, adjusted to 1000 ppm concentration, air-dried and put in a petri dish, and 10 second-instar larvae of Nijiyahoushitentou are released into the petri dish, and 10 larvae are released per petri dish. It was then stored in a thermostatic chamber at 25 ° C., and the mortality rate after 6 days was calculated from the following formula.
The test was conducted in a two-division system.

Mortality of mortality (%) = (number of mortality / number of larvae) × 100 As a result, the following compounds showed a mortality of 100%. Inventive compound: No. 11, 17, 21, 24, 28,
31, 33, 38, 51, 56, 71, 74, 75, 7
6,77,78,79,80,82,83,84,85

Test Example 3 Insecticidal test against green peach aphid A moist filter paper was laid on a Petri dish having a diameter of 3 cm, and a leaf of gabbage was placed thereon. A 2.0 mg / cm ² chemical solution was sprayed onto the cabbage leaves using a rotary spraying tower. The test liquid was prepared by diluting a 5% emulsion of the compound of the present invention described in the specification (25% wettable powder depending on the compound) with a water containing a spreading agent to adjust the concentration to 1000 ppm. Was used. After air-drying, 10 peach aphid 1st-instar larvae were inoculated per petri dish, housed in a thermostatic chamber at 25 ° C., and the mortality rate after 6 days was calculated from the following formula. The test was repeated 4 times.

Mortality of mortality (%) = (number of mortality / number of larvae) × 100 As a result, the following compounds showed a mortality of 100%. Inventive compound: No. 80, 81, 82

Test Example 4 Acaricidal Activity Test against Nite Mites The green leaf was cut into a circle with a diameter of 3.0 cm using a leaf punch and placed on a damp filter paper on a styrene cup having a diameter of 7 cm. Add 1 larvae of the spider mite to each leaf
0 animals were inoculated. 5% of the compound of the invention described in the description
An emulsion (25% wettable powder depending on the compound was tested) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 1000 ppm, and this chemical solution was sprayed in an amount of 2 ml per styrene cup using a rotary spraying tower. And store it in a thermostatic chamber at 25 ° C for 9
The mortality rate after 6 hours was calculated from the following formula. still,
The test was conducted in a two-district system.

Mortality of mortality (%) = (number of mortality / number of mortality) × 100 As a result, the following compounds showed a mortality of 100%. Inventive compound: No. 74, 77, 78, 83

[0139]

INDUSTRIAL APPLICABILITY The compound of the present invention has excellent insecticidal and acaricidal activity against many agricultural pests and mites, and has almost no adverse effect on mammals, fish and beneficial insects. Therefore, the compound of the present invention can provide a useful pest control agent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location C07D 231/52 (72) Inventor Tatsuo Numata 722 Tsuboi-cho, Funabashi-shi, Chiba 1 Nissan Chemical Industries, Ltd. Central Research Institute (72) Inventor Toshiyuki Umehara 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd.Biological Sciences Research Institute (72) Inventor Masatake Kudo 1470, Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Prefecture Inside Institute of Science (72) Inventor Yoichi Inoue 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Nissan Chemical Industry Co., Ltd.

Claims (2)

[Claims] 1. General formula (1): [Wherein, R C ₁ -C ₄ alkyl group, C ₁ -C ₄ haloalkyl groups, C ₁ -C ₄ alkylsulfonyl group, C ₁ -C
Represents a ₄ haloalkylsulfonyl group, a C _{2 to} C ₅ alkylcarbonyl group or a C _{2 to} C ₅ haloalkylcarbonyl group, and X represents a halogen atom, a haloalkyl group, a nitro group,
C ₁ -C ₄ alkylthio group, a C ₁ -C ₄ alkylsulfinyl group or a C ₁ -C ₄ alkylsulfonyl group, m represents 3 or 4, Y is a halogen atom, a nitro group, a cyano group, -CO- R ¹ (However, R ¹ is C _{1 to} C
₄ alkyl groups, C _{1 to} C ₄ haloalkyl groups, C _{1 to} C ₄
Represents an alkoxy group, a hydroxyl group or a hydrogen atom. ) Or —SO _n R ² (wherein R ² is a C ₁ -C ₄ alkyl group,
C ₁ -C _{10 represents a} haloalkyl group or a phenyl group which may be substituted with a halogen atom, a haloalkyl group, a nitro group or a haloalkoxy group, and n is 0, 1 or 2
Represents. ), Z is a C _{1 to} C ₄ alkyl group, C ₁ to
It represents a C ₄ haloalkyl group, a C ₁ -C ₄ haloalkoxy group or an amino group. ] The phenyl pyrazole derivative represented by these. 2. A pest control agent containing, as an active ingredient, one or more of the phenylpyrazole derivatives according to claim 1.