JP2007284385A - 2-Phenylimidazole derivatives and insecticides, acaricides, nematicides containing them as active ingredients - Google Patents

Abstract

The present invention includes a novel 2-phenylimidazole derivative or a salt thereof having an excellent soil treatment activity as an agricultural / horticultural insecticidal / acaricidal / nematicidal agent, and the derivative or a salt thereof as an active ingredient. Provide agricultural, horticultural insecticidal, acaricidal and nematicidal agents.
The general formula [I]
[Chemical 1]

(In the formula, R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group or a cyclopropylmethyl group, n represents 0 or 1, and A ¹ and A ² each independently represent hydrogen. atom, a halogen atom, a cyano _group, a C 1 -C ₆ alkyl or _C 1 -C ₆ haloalkyl group, ^{a 3} represents a hydrogen _atom, C 1 -C ₆ alkyl group, ^{B 1} is a hydrogen atom, a halogen atom Or a C ₁ -C ₆ alkyl group, and B ² represents a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group) and a salt thereof.
[Selection figure] None

Description

  The present invention relates to a novel 2-phenylimidazole derivative and an agricultural / horticultural insecticide / acaricide / nematicide containing the same as an active ingredient.

  Conventionally, regarding 2-phenylimidazole derivatives, the compounds described in Patent Document 1, Patent Document 2, and Patent Document 3 are known. However, the compound of the present invention is not described in these documents, and further, its usefulness as an insecticidal / miticidal / nematicidal agent is not known.

  On the other hand, as known agricultural and horticultural insecticides, acaricides, and nematicides, Patent Document 4 already discloses 3-arylphenyl sulfide derivatives. However, 2-phenylimidazole derivatives are not described in this document. Furthermore, although it is described that the compound group described in this document exhibits a high effect on spider mites by directly spraying on a plant body, there is no description regarding soil treatment. The compound group described in this document has insufficient transferability in soil and transferability into plants by soil treatment. Therefore, sufficient effects may not be obtained due to uneven drug spraying or transpiration, photolysis, drug outflow due to rainfall, or the like.

At present, there are very few known acaricides having practical soil treatment activity. Drugs that can be treated with soil have the advantage of being safer and more labor-saving for farmers. Therefore, development of an acaricide having soil treatment activity is required.
WO95 / 33730 gazette (claims and others) US Pat. No. 3,682,949 (Claims and others) German Patent Publication No. 19653355 (claims and others) JP 2000-198768 A (Claims and others)

  The problem of the present invention is to solve the above-mentioned problems of conventional insecticides, acaricides and nematicides in such circumstances, and further, safety, control effect, residual effect, etc. It is to provide an insecticide, acaricide and nematicide that are excellent in the field.

  In order to develop an insecticidal, acaricidal, and nematicidal agent having the above-mentioned preferable characteristics, the present inventors synthesized various 2-phenylimidazole derivatives and studied their physiological activities. As a result, a novel 2-phenylimidazole derivative represented by the following general formula [I] (hereinafter, also referred to as the compound of the present invention) is a variety of agricultural and horticultural pests, particularly spider mites represented by spider mites, kanzawa spider mites, citrus spider mites, etc. For example, lepidopterous insect pests such as white-tailed moth, leafhopper, white-winged beetle, hemipod pests typified by leafhoppers, leafhoppers, cotton aphids, nematodes such as Coleoptera The present invention has been completed by finding that it exhibits a superior effect and has a soil treatment activity that enables a safe and labor-saving application method.

  That is, this invention has the summary characterized by the following.

  (1) General formula [I]

[Wherein R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ haloalkenyl group or a cyclopropylmethyl group,
n represents 0 or 1,
A ¹ and A ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ haloalkyl group, a hydroxyl group, a C _{1 to} C ₆ alkoxy group, or a C _{1 to} C ₆ halo. alkoxy group, cyano _group, C 1 -C ₇ acyl _group, C 2 -C ₇ haloalkylcarbonyl ^group, -CY 1 = N-OY ² group, a nitro group, -N ^(Y 3) Y ⁴ group, a thiocyanate group, a thiol a group or -S (O) _m Y ⁵ group,
A ³ is a hydrogen atom, a C ₁ -C ₆ alkyl group (the group may be mono-substituted by a C ₁ -C ₆ alkoxy group or a cyano group), a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl a group or a _C 2 -C ₆ alkynyl group,
B ¹ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,
B ² represents a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ¹ and Y ² each independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ³ and Y ⁴ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, or a C ₁ -C. ₇ acyl _group, a C 2 -C ₇ haloalkylcarbonyl group or _C 2 -C ₇ alkoxycarbonyl group,
Y ⁵ represents a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
m shows the integer of 0-2. An insecticidal / acaricidal / nematicidal agent for agricultural and horticultural use containing a 2-phenylimidazole derivative or a pharmacologically acceptable salt thereof as an active ingredient.

  (2) General formula [I]

[Wherein R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ haloalkenyl group or a cyclopropylmethyl group,
n represents 0 or 1,
A ¹ and A ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₆ alkyl group, a hydroxyl group, a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ haloalkoxy group, a cyano group, or C _1. -C ₇ acyl _group, C 2 -C ₇ haloalkylcarbonyl ^group, -CY 1 = N-OY ² group, -N ^(Y 3) Y ⁴ group, a thiocyanate group, a thiol group or a -S (O) _m Y ⁵ group Indicate
A ³ is a hydrogen atom, a C ₁ -C ₆ alkyl group (the group may be mono-substituted by a C ₁ -C ₆ alkoxy group or a cyano group), a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl a group or a _C 2 -C ₆ alkynyl group,
B ¹ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,
B ² represents a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ¹ and Y ² each independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ³ and Y ⁴ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, or a C ₁ -C. ₇ acyl _group, a C 2 -C ₇ haloalkylcarbonyl group or _C 2 -C ₇ alkoxycarbonyl group,
Y ⁵ represents a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
m shows the integer of 0-2. Or a pharmacologically acceptable salt thereof.

  The compounds of the present invention are semilepidopterous insects, lepidopterous pests, coleopterous pests, diptera pests, hymenoptera pests, straight moth pests, termite pests, thrips pests, spider mites, plant parasitic nematodes It exhibits an excellent control effect against a wide range of pests such as, and can also control pests with resistance.

  In particular, the compound of the present invention is an agro-horticultural pest, spider mites represented by spider mites, kanzawa spider mites, citrus spider mites, etc., lepidopteran pests represented by spider mites, spider mites, white spider mites, etc. Since it exhibits excellent effects on nematodes such as Coleoptera, such as Coleoptera and Azuki beetle, and nematodes such as sweet potato root nematodes, and has excellent osmotic migration, a safe and labor-saving application method by soil treatment is possible.

    The symbols and terms described in this specification will be described.

  A halogen atom shows a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The notation such as C _{1 to} C ₆ indicates that the number of carbon atoms of the subsequent substituent is 1 to 6 in this case.

The C ₁ -C ₆ alkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms unless otherwise specified, and includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, s -Butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, n-hexyl 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 2,2-trimethyl-propyl, 1-ethyl-1-methylpropyl, it may be mentioned groups such as 1-ethyl-2-methylpropyl.

The C ₂ -C ₆ alkenyl group means a straight or branched alkenyl group having 2 to 6 carbon atoms unless otherwise specified. For example, vinyl, 1-propenyl, isopropenyl, 2-propenyl, 1, 2-propadienyl, 1-butenyl, 1-methyl-1-propenyl, 2-butenyl, 1-methyl-2-propenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1, 3-butadienyl, 1-pentenyl, 1-ethyl-2-propenyl, 2-pentenyl, 1-methyl-1-butenyl, 3-pentenyl, 1-methyl-2-butenyl, 4-pentenyl, 1-methyl-3- Butenyl, 3-methyl-1-butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl-2-propenyl, 2-methyl-2-butenyl, 3-methyl 2-butenyl, 1,2-dimethyl-1-propenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,3-pentadienyl, 1-vinyl-2-propenyl, 1-hexenyl, 1-hexenyl Propyl-2-propenyl, 2-hexenyl, 1-methyl-1-pentenyl, 1-ethyl-2-butenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-4-pentenyl, 1-ethyl -3-butenyl, 1- (isobutyl) vinyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-2-propenyl, 1- (isopropyl) -2-propenyl, 2-methyl- 2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1,3-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 3-methyl -4-pentenyl, 4-methyl-4-pentenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1,5-hexadienyl , 1-vinyl-3-butenyl or 2,4-hexadienyl.

The C ₂ -C ₆ alkynyl group means a straight-chain or branched alkynyl group having 2 to 6 carbon atoms unless specifically limited, and includes, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1 -Methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-methyl -3-butynyl, 2-methyl-3-butynyl, 1-hexynyl, 1- (n-propyl) -2-propynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-methyl-2 -Pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, 1-ethyl-3-butynyl, 1-ethyl 1-methyl-2-propynyl, 1- (isopropyl) -2-propynyl, it may be mentioned 1,1-dimethyl-2-butynyl or 2,2-dimethyl-3 group butynyl.

The C ₁ -C ₆ haloalkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms, which is substituted with the same or different halogen atoms 1 to 9 unless otherwise limited, for example, fluoromethyl , Chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, bromodifluoromethyl, 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl, 2, 2-difluoroethyl, 1,2-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 1,1,2,2-tetrafluoroethyl, Pentafluoroethyl, 2-bromo-2-chloroethyl, 2-chloro-1,1,2,2 Tetrafluoroethyl, 1-chloro-1,2,2,2-tetrafluoroethyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 2-bromopropyl, 3-bromopropyl, 2-bromo-1 -Methylethyl, 3-iodopropyl, 2,3-dichloropropyl, 2,3-dibromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 3-bromo-3,3- Difluoropropyl, 3,3-dichloro-3-fluoropropyl, 2,2,3,3-tetrafluoropropyl, 1-bromo-3,3,3-trifluoropropyl, 2,2,3,3,3- Pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, heptafluoropropyl, 1,2,2,2-tetrafluoro-1 Trifluoromethylethyl, 2,3-dichloro-1,1,2,3,3-pentafluoropropyl, 2-chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 2-chloro-1,1-dimethylethyl, 4- Bromobutyl, 3-bromo-2-methylpropyl, 2-bromo-1,1-dimethylethyl, 2,2-dichloro-1,1-dimethylethyl, 2-chloro-1-chloromethyl-2-methylethyl, 4 , 4,4-trifluorobutyl, 3,3,3-trifluoro-1-methylpropyl, 3,3,3-trifluoro-2-methylpropyl, 2,3,4-trichlorobutyl, 2,2, 2-trichloro-1,1-dimethylethyl, 4-chloro-4,4-difluorobutyl, 4,4-dichloro-4-fluorobutyl, 4-bromo-4,4-difluorobuty 2,4-dibromo-4,4-difluorobutyl, 3,4-dichloro-3,4,4-trifluorobutyl, 3,3-dichloro-4,4,4-trifluorobutyl, 4-bromo -3,3,4,4-tetrafluorobutyl, 4-bromo-3-chloro-3,4,4-trifluorobutyl, 2,2,3,3,4,4-hexafluorobutyl, 2,2 , 3,4,4,4-hexafluorobutyl, 2,2,2-trifluoro-1-methyl-1-trifluoromethylethyl, 3,3,3-trifluoro-2-trifluoromethylpropyl, , 2,3,3,4,4,4-heptafluorobutyl, 2,3,3,3-tetrafluoro-2-trifluoromethylpropyl, 1,1,2,2,3,3,4,4 -Octafluorobutyl, nonafluorobutyl, 4-c B -1,1,2,2,3,3,4,4- octafluoro butyl group can be mentioned.

The C ₂ -C ₆ haloalkenyl group means a linear or branched alkenyl group having 2 to 6 carbon atoms, which is substituted with the same or different halogen atoms 1 to 3 unless otherwise limited, Examples thereof include 2-chloro-2-propenyl, 3-chloro-2-propenyl, 3,3-dichloro-2-propenyl and the like.

C ₁ -C ₆ alkoxy group refers to an (alkyl) -O— group in which the alkyl moiety has the above meaning, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, Groups such as pentyloxy, isopentyloxy or hexyloxy can be mentioned.

C ₁ -C ₆ haloalkoxy group refers to a (haloalkyl) -O— group wherein the haloalkyl moiety is as defined above, eg, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1 , 2,2-Tetrafluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,3,3,4,4,4-hexa Fluorobutoxy, 2,2,3,3,4,4,5,5,5-nonafluoropentyloxy or 2,2,3,3,4,4,5,5,6,6,6-undeca Examples include groups such as fluorohexyloxy.

The C ₁ -C ₇ acyl group refers to a (alkyl) -C (═O) — group having 1 to 6 carbon atoms in which the formyl group or the alkyl portion has the above meaning, for example, a group such as acetyl or propionyl. I can give you.

The C ₂ -C ₇ haloalkylcarbonyl group means a (haloalkyl) -C (═O) — group having 1 to 6 carbon atoms in which the haloalkyl moiety has the above meaning, for example, chloroacetyl, trifluoroacetyl, pentafluoro Groups such as propionyl can be mentioned.

The C ₂ -C ₇ alkoxycarbonyl group means an (alkyl) -O—C (═O) — group having 1 to 6 carbon atoms in which the alkyl portion has the above-mentioned meaning, for example, methoxycarbonyl, ethoxycarbonyl, n -Groups such as propoxycarbonyl or isopropoxycarbonyl may be mentioned.

  In the general formula [I], a preferable group of compounds includes a group of compounds in which R is a 2,2,2-trifluoroethyl group and n is 0 or 1.

As a more preferred compound group, R is a 2,2,2-trifluoroethyl group, B ¹ is a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group, B ² is a chlorine atom or a methyl group, Examples include compounds in which n is 0 or 1.

  Next, although the specific example of this invention compound represented by general formula [I] is described in Table 1-Table 5, this invention compound is not limited to these compounds. These compounds include compounds containing optical isomers. The compound number is referred to in the following description.

  The following notations in the tables in the present specification represent the corresponding groups as follows.

Me: methyl, Et: ethyl,
Pr: n-propyl, Pr-i: isopropyl,
Pr-c: cyclopropyl, Bu: n-butyl,
Bu-i: isobutyl, Bu-s: sec-butyl,
Bu-t: tert-butyl, Bu-c: cyclobutyl,
Pen: n-pentyl, Ac: The acetyl example _CH 2 Pr-c, showing a cyclopropylmethyl group.

  Although this invention compound of general formula [I] can be manufactured in accordance with the manufacturing method shown below, it is not limited to these methods.

<Manufacturing method 1>
The compound of the present invention represented by the general formula [I] can be produced by a method comprising the reaction formulas exemplified below.

(In the formula, A ¹ , A ² , A ³ , B ¹ , B ² , R and n represent the same meaning as described above, and L ¹ represents a bromine atom or an iodine atom.)
Compound [I] of the present invention can be produced by reacting compound [II] with compound [III] in a solvent in the presence of a transition metal catalyst and a base.

  What is necessary is just to select the usage-amount of compound [III] from the range of 0.5-5.0 mol suitably with respect to 1 mol of compound [II], Preferably it is 0.5-2.0 mol.

  Solvents that can be used in this reaction are, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, dioxane, ketones such as acetone and methyl ethyl ketone, acetonitrile, Nitriles such as propionitrile, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, pyridines such as pyridine and picoline, water Alternatively, a mixed solvent thereof or the like can be given.

  The amount of the solvent used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [II].

  Examples of the base that can be used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, and barium hydroxide, sodium carbonate, Alkali metal carbonates such as potassium carbonate, inorganic bases such as sodium bicarbonate, alkali metal bicarbonates such as potassium bicarbonate, alkali metal phosphates such as sodium phosphate and potassium phosphate, sodium methoxide, Metal salts of alcohols such as sodium ethoxide and potassium tert-butoxide or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7 -Organic bases such as undecene.

  What is necessary is just to select the usage-amount of a base suitably from the range of 1.0-10.0 mol with respect to 1 mol of compound [II], Preferably it is 1.0-6.0 mol.

  Transition metal catalysts that can be used here include palladium compounds such as palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) nickel and And nickel compounds such as tetrakis (triphenylphosphine) nickel.

  What is necessary is just to select the usage-amount of a transition metal catalyst suitably from the range of 0.01-1.0 mol with respect to 1 mol of compound [II], Preferably it is 0.01-0.5 mol.

  What is necessary is just to select reaction temperature from the arbitrary ranges from 0 degreeC to the recirculation | reflux temperature in a reaction system, Preferably it is the temperature range of 20-100 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is completed in 10 minutes to 20 hours.

<Manufacturing method 2>
Compound [Ib] represented by the compound of the present invention can be produced by a method comprising the reaction formulas exemplified below.

[Wherein, A ¹ , A ² , B ¹ , B ² , R and n have the same meaning as described above, and A ⁴ represents a C _{1 to} C ₆ alkyl group (the group is a C _{1 to} C ₆ alkoxy group or cyano A C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group or a C ₂ -C ₆ alkynyl group, L ² is a halogen atom, C ₁ -C ₆ alkylsulfonyloxy group shown, arylsulfonyloxy _group, a C 1 -C ₆ haloalkylsulfonyl group. ]
Compound [Ib] of the present invention can be produced by reacting compound [Ia] with compound [IV] in a solvent in the presence of a base.

  What is necessary is just to select the usage-amount of compound [IV] from the range of 1.0-10.0 mol suitably with respect to 1 mol of compound [Ia], Preferably it is 1.0-5.0 mol.

  Solvents that can be used in this reaction are, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N -Aprotic polar solvents such as methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol and methyl cellosolve, pentane, hexane, cyclohexane and heptane Aliphatic hydrocarbons, pyridines such as pyridine and picoline, water or a mixed solvent thereof.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [Ia].

  Examples of the base that can be used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate, potassium carbonate and the like. Inorganic bases such as alkali metal carbonates, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, sodium ethoxide, potassium Metal salts of alcohols such as tert-butoxide or organic compounds such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene Bases and the like.

  What is necessary is just to select the usage-amount of a base from the range of 1.0-10.0 mol suitably with respect to 1 mol of compound [Ia], Preferably it is 1.0-5.0 mol.

  What is necessary is just to select reaction temperature from the arbitrary ranges from 0 degreeC to the recirculation | reflux temperature in a reaction system, Preferably it is the temperature range of 0-60 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is completed in 10 minutes to 70 hours.

  <Manufacturing method 3>

(In the formula, A ¹ , A ² , A ³ , B ¹ , B ² and R have the same meaning as described above.)
The compound of the present invention represented by the general formula [Id] can be produced by reacting the compound [Ic] with an oxidizing agent in a solvent in the presence or absence of a catalyst.

  Examples of the oxidizing agent that can be used in this reaction include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI DuPont; potassium peroxohydrogensulfate-containing product), N-chloro. Examples thereof include succinimide, N-bromosuccinimide, tert-butyl hypochlorite, and sodium hypochlorite.

  What is necessary is just to select the usage-amount of an oxidizing agent from the range of 1.0-6.0 mol suitably with respect to 1 mol of compound [Ic], Preferably it is 1.0-1.2 mol.

  Examples of the catalyst that can be used in this reaction include sodium tungstate.

  What is necessary is just to select the usage-amount of a catalyst suitably from the range of 0-1.0 mol with respect to 1 mol of compound [Ic], Preferably it is 0.01-0.1 mol.

  Solvents usable in this reaction include, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide. , Aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol and isopropyl alcohol, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, pentane and hexane And aliphatic hydrocarbons such as cyclohexane and heptane, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetic acid, water, or a mixed solvent thereof.

  The amount of the solvent to be used is 0.1 to 100 liters, preferably 0.3 to 10 liters, per 1 mol of compound [Ic].

  The reaction temperature may be selected from an arbitrary temperature range from −30 ° C. to the reflux temperature in the reaction system, preferably in the range of −10 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 10 minutes to 20 hours.

  When the compound of the present invention is used as an active ingredient of a pest control agent, the compound of the present invention may be used as it is, but carriers, surfactants, and other auxiliary agents generally used for formulation as agricultural chemical adjuvants. Formulated with emulsion, suspension, powder, granule, tablet, wettable powder, water solvent, liquid, flowable, granule wettable powder, aerosol, paste, oil, emulsion, smoke It can be formulated into various forms such as an agent. These blending ratios are usually 0.1 to 90% by weight of the active ingredient and 10 to 99.9% by weight of the agrochemical adjuvant.

  Carriers used in the formulation herein are classified into solid carriers and liquid carriers. Examples of solid carriers include animal and vegetable powders such as starch, activated carbon, soybean flour, wheat flour, wood flour, fish flour, and milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, ammonium sulfate, and urea. Inorganic powders such as Examples of the liquid carrier include water; alcohols such as isopropyl alcohol and ethylene glycol; ketones such as cyclohexanone, methyl ethyl ketone and isophorone; ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as kerosene and light oil; xylene and trimethyl. Aromatic hydrocarbons such as benzene, tetramethylbenzene, methylnaphthalene and solvent naphtha; Halogenated hydrocarbons such as chlorobenzene; Acid amides such as dimethylacetamide; Esters such as glycerin esters of fatty acids; Nitriles such as acetonitrile And sulfur-containing compounds such as dimethyl sulfoxide.

  Examples of the surfactant include alkylbenzene sulfonic acid metal salt, dinaphthylmethane disulfonic acid metal salt, alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, Examples thereof include polyoxyethylene sorbitan monoalkylate, salt of naphthalenesulfonic acid formalin condensate, and the like.

  Other adjuvants include, for example, carboxymethyl cellulose, gum arabic, sodium alginate, guar gum, tragacanth gum, polyvinyl alcohol and other sticking agents or thickeners, metal soap and other antifoaming agents, fatty acids, alkyl phosphates, silicones, paraffins And the like, and physical property improvers, colorants and the like can be used.

  In actual use of these preparations, they can be used as they are or diluted to a predetermined concentration with a diluent such as water. Application of various preparations containing the compound of the present invention, or dilutions thereof, is usually carried out by a commonly used application method, ie, spraying (eg spraying, misting, atomizing, dusting, dusting, water surface application, box application). Etc.), soil application (for example, mixing, irrigation, etc.), surface application (for example, application, powder coating, coating, etc.), immersion, poison bait, smoke application, etc. It is also possible to feed the livestock with the active ingredient in a feed to control the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra-high concentration and small quantity spraying method. In this method, it is possible to contain 100% of the active ingredient. The blending ratio of the active ingredient is appropriately selected as necessary, but 0.1 to 20% (weight) when used as a powder and granule, and 1 to 80% (weight) when used as an emulsion and wettable powder. Is appropriate.

  Application of the pest control agent of the present invention is generally carried out at an active ingredient concentration of 0.1 to 5000 ppm when it is diluted with a diluent. When the preparation is used as it is, the application amount per unit area is 0.1 to 5000 g per ha as an active ingredient compound, but is not limited thereto.

  In addition, it goes without saying that the compound of the present invention alone is sufficiently effective, but if necessary, other fertilizers, agricultural chemicals such as insecticides, acaricides, nematicides, bactericides, antiviral agents, It can be mixed and used in combination with attractants, herbicides, plant growth regulators, and the like, and in this case, a more excellent effect may be exhibited.

  Representative examples of insecticides, fungicides, acaricides and the like that can be used by mixing with the compound of the present invention are shown below.

For example, organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon, chlorpyrifos, oxydeprofos, bamidothion, phenthoate, dimethoate , Formothion, malathion, trichlorfon, thiometon, phosmet, dichlorvos, acephate, EPBP (EPBP), parathion-methyl, oxydimethone Methyl (oxydemeton-methyl), ethion, dioxabenzofos, cyanophos, isoxathion, pyridaphenthion, phosalone, methidathio (Methidathion), sulprofos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, disulfoton, profenofos ), Pyraclofos, monocrotophos, azinphos-methyl, aldicarb, metomyl, thiodicarb, carbofuran, carbosulfan, benfuracarb ), Furathiocarb, propoxur, fenobucarb, metolcarb, isoprocarb, carbaryl, pirimicarb, ethiophene Ethiofencarb, dichlofenthion, pirimiphos-methyl, quinalphos, chlorpyrifos-methyl, prothiofos, nared, EPN (EPN), XMC (XMC), Bendiocarb, bendiocarb, oxamyl, alanycarb, chlorethoxyfos, etc. Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate , Fenpropathrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, proparthrin, phenothrin, protothrin (Prothrin), fluvalinate, cyfluthrin, cyhalothrin, flucythrinate, etofenprox, cycloprothrin, tralomethrin, silafluofen Tefluthrin, bifenthrin, acrinathrin and the like.

Acylurea, other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, teflubenzuron, flufenoxuron, flucyclooxuron flucycloxuron, buprofezin, pyriproxyfen, lufenuron, cyromazine, metoprene, endosulfan, diafenthiuron, imidacloprid (imidacloprid), acetamiprid, nitenpyram, clothianidin, dinotefuran, thiamethoxam, thiacloprid, pymetrozine, fipronil (Fipronil), pyridalyl, nicotine-sulfate, rotenone, metaldehyde, machine oils, microbial pesticides such as BT and entomopathogenic viruses, phenoxycarb , Cartap, thiocyclam, bensultap, tebufenozide, chlorfenapyr, emamectin-benzoate, acetamiprid, aceticiprid, nitenpyram, oleic acid sodium salt), rape seed oil and the like.
Nematicides: fenamiphos, fosthiazate, ethoprophos, methyl isothiocyanate, methyl isocyanate, 1,3-dichloropropene, DCIP (DCIP) and the like.
Acaricides: chlorobenzilate, phenisobromolate, dicohol, amitraz, propargite, benzomate, hexythiazox, fenbutatin oxide oxide, polynactins, quinomethionate, chlorfenson, tetradifon, abamectin, milbemycin, clofentezine, pyridaben, fenpyroximate (fenpyroximate) ), Tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor, etoxazole, bifenazate, acequinosyl ( acequinocyl), halfenprox, spirodiclofen, etc.

  Bactericides: thiophanate-methyl, benomyl, carbendazol, thiabendazole, folpet, thiuram, ziram, zineb, maneb ), Polycarbamate, iprobenfos, edifenphos, fthalide, probenazole, isoprothiolane, chlorothalonil, captan, polyoxin, blastsai Gin S (blasticidin-S), kasugamycin, streptomycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil mepronil, flutolanil, pencicuron, iprodione, hymexazol, metalaxyl, triflumizole, triforine, triadimefon, ertanol, bitteranol Fenarimol, propiconazole, cymoxanil, prochloraz, pefurazoate, hexaconazole, microbutanyl, diclomezine, tecloftal, tecloftal (Propineb), dithianon, fosetyl, vinchlozoline, procymidone, oxadixyl, guazatine, propamocarb hydrochloride (propineb) propamocarb), fluazinam, oxolinic acid, hydroxyisoxazole, mepanipyrim, etc.

  The compounds of the present invention are semilepidopterous insects, lepidopterous pests, coleopterous pests, diptera pests, hymenoptera pests, straight moth pests, termite pests, thrips pests, spider mites, plant parasitic nematodes It shows excellent control effect against such pests. Examples of such pests include the following pests.

  Hemiptera pests such as Riptortus clavatus, Nezara viridula, Lyme sp., Blissus leucopterus, Stephanitis nashi, etc. Heteroptera), leafhoppers (Nephotettix cincticeps), leafhoppers such as Empoasca sp., Erythroneura sp., Circulifer sp. Planthoppers, Psylla sp. And other killer whales, Silver leaf whitefly (Bemisia tabaci), Whitefly whitefly (Trialeurodes vaporariorum) whitefly, Grape aphid (Viteus vitifolii), Peach aphid (Myzus persicae), Aphis aphid pomi), cotton aphid (A aphids such as phis gossypii), Aphis fabae, Rhopalosiphum psedobrassicas, Aulacorthum solani, Schizaphis graminum, Pseudococ Scale insects such as the scale insect (Comstockaspis perniciosa) and the scale insect (Unaspis yanonensis), and the scale turtle (Rhodnius sp.).

  Lepidopterous pests, such as Homona magnanima, Adoxophyes orana, Sparganothis pilleriana, Grapholitha molesta, Leguminivora glycinivorella, Spaspanobea , Mosquitoes such as Eupoecillia ambiguella, minoga such as Bambalina sp., Nesting moths (Nemapogon granellus), squirrels (Tinea translucens), and hummingbirds such as lingon moth (Lyonetia prunifoliella) Hosogaga such as Phyllonorycter rigoniella, Pseudomonas such as Phyllocnistis citrella, Suga such as Plutella xylostella, Prays citri, Paranthrene regalis, Paranthreneon moth, Synanthedon sp. (Pectinophora gossypiella), Potato moth (Phthorimaea operculella), Stomopteryx sp. ), Ostrinia nubilalis, Ostrinia furnacalis, Hellula undalis, Honey moth (Galleria mellonella), Elasmopalpus lignosellus, Loxostege sticticalis, etc., Pieris rapae ) And other species, such as male moth (Malacosoma neustria), male moths such as Manduca sexta, giant moths (Euproctis pseudoconspersa), Japanese moths (Lymantria dispar) and other species, Hyphantria cunea, etc. Taba Bad worms (Heliothis virescens), ball worms (Helicoverpa zea), scallop moth (Spodoptera exigua), giant cigarette moth (Helicoverpa armigera), Spodoptera litura, mamestra brassicae, paramedo, iron Yagas such as Trichoplusia ni.

  Coleopterous insects, for example, Anomala cuprea, Popillia japonica, Scarabae (Anomala rufocuprea), Eutheola rugiceps, etc., wire worms (Agriotes sp.), Connodeus sp. (Epilachna vigintioctopunctata), ladybirds such as common beetle (Epilachna varivestis), bark beetles such as Tribolium castaneum, Anoplophora malasiaca, tusnoaccelus tuss, Monochamus alternatus ), Beetle weevil (Callosobruchus chinensis), Colorado potato beetle (Leptinotarsa decemlineata), corn root worm (Diabrotica sp.), Rice plant beetle (Oulema oryzae), chaetococci beetle (Chaetoc) nema concinna), Phaedon cochlearias, Oulema melanopus, Dicladispa armigera and other potato beetles, Apion godmani and other weevil weevil (Lissorhoptrus oryzophilus) Large weeviles, bark beetles, cutworms, beetles, etc.

  Diptera pests such as Tipra ano, Tanytarsus oryzae, Oreseolia oryzae, Ceratitis capitata, Hydrellia griseola, Sutro ros D (Oscinella frit), rice flies (Chlops oryzae), common beetle (Ophiomyia phaseoli), bean fly (Liriomyza trifolii), red beetle (Pegomya hyoscyami), fly fly (Hylemia platura), sorghum fly (Atherigona soccae) Musca domestica, Gastrophilus sp., Stomoxys sp., Aedes aegypti, Culex pipiens, Anopheles slnensis, Culex tritaeniorhynchus, etc.

  Hymenopteran pests, for example, Cephus sp., Harmolita sp., Athalia sp., Vespa sp., Fire ant, etc.

  Diptera, such as German cockroach (Blatella germanica), American cockroach (Periplaneta americana), Kera (Gryllotalpa africana), Grasshopper (Locusta migratoria migratoriodes), Melanoplus sanguinipes, etc.

  Termite pests, for example, Yamato termites (Reticulitermes speratus), termites (Coptotermes formosanus) and the like.

  Thrips of the order Thrips thrips (Scirtothrips dorsalis), Southern thrips (Thrips palmi), Croton thrips (Heliothrips haemorrhoidalis), Citrus thrips (Frankliniella occidentalis), rip

  Spider mites, such as the spider mite (Tetranychus urticae), the Kanzawa spider mite (Tetranychus kanzawai), the mandarin spider mite (Panonychus citri), the apple spider mite (Panonychus ulmi), the yellow mito (Eotetranychus carpini), the Texas citrus mito (Eotetranychus carite), Chinese mite (Polyphagotarsonemus latus), Japanese red spider mite (Brevipalpus sp.), Robin mite (Rhizoglyphus robini), Japanese black tick (Tyrophagus putrescentiae), etc.

  Plant parasitic nematodes, for example Meloidogyne sp., Pratylenchus sp., Soybean cyst nematode (Heterodera glycines), Potato cyst nematode (Globodera rostochiensis), Banana moth nematode (Radopholus similis) , Strawberry nematode (Aphelenchoides fragariae), rice scented nematode (Aphelenchoides besseyi), pine wood nematode (Bursaphelenchus xylophilus) and the like.

  Other harmful animals, unpleasant animals, sanitary pests, parasites such as Pomacea canaliculata, slugs (Incilaria sp.), Gastropods such as Achatina fulica (Gastropoda), armadillidium sp. Isopods such as barley beetle and centipede (Isopoda), Chatterus such as Liposcelis sp., Spots such as Ctenolepisma sp., Fleas such as Pulex sp. And Ctenocephalides sp., Hazel worms such as Trichodectes sp., Cimex Examples include bed bugs such as sp., animal parasitic mites such as Boophilus microplus, Haemaphysalis longicornis, and leopard mites.

  Furthermore, it is also effective against pests that are resistant to organophosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, acylurea compounds, or existing insecticides.

  Next, the production method, formulation method and use of the compound of the present invention will be described specifically by way of examples.

[Example 1]
2- [2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1-methyl-1H-imidazole-4,5-dicarbonitrile (present compound number 3) (1) A mixture of 2-bromo-1H-imidazole-4,5-dicarbonitrile (1.97 g), iodomethane (1.7 g), potassium carbonate (1.8 g), and acetonitrile (10 ml) was stirred at room temperature for 24 hours. To the reaction mixture, 40 ml of ethyl acetate and 5 g of florisil were added and filtered. The solvent was distilled off under reduced pressure to obtain 1.85 g of 2-bromo-1-methyl-1H-imidazole-4,5-dicarbonitrile.

(2) Production of 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1-methyl-1H-imidazole-4,5-dicarbonitrile 2- Bromo-1-methyl-1H-imidazole-4,5-dicarbonitrile 0.79 g, 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid 1.10 g, A mixture of 1.52 g of triethylamine, 0.22 g of tetrakis (triphenylphosphine) palladium, 8 ml of N, N-dimethylformamide and 2 ml of water was stirred at 100 ° C. for 8 hours. After cooling to room temperature, ethyl acetate was added, the organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1-methyl-1H-imidazole- 0.47 g of 4,5-dicarbonitrile was obtained.

  According to this method, Compound No. 21 of the present invention was produced.

[Example 2]
2- [2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] -1-methyl-1H-imidazole-4,5-dicarbonitrile (Compound No. 4 of the present invention) Preparation of 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1-methyl-1H-imidazole-4,5-dicarbonitrile 0.25 g in chloroform It melt | dissolved in 5 ml and 0.18 g (purity 70%) of m-chloro perbenzoic acid was added under ice-cooling. After stirring for 1 hour under ice cooling, an aqueous sodium thiosulfate solution was added. Ethyl acetate was added to the reaction solution, and the organic layer was washed with water, aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to give 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl]- 0.16 g of 1-methyl-1H-imidazole-4,5-dicarbonitrile was obtained.

  According to this method, Compound Nos. 2, 6, 22, 81 of the present invention were produced.

[Example 3]
Production of 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1H-imidazole-4,5-dicarbonitrile (Compound No. 1 of the present invention) 2- Bromo-1H-imidazole-4,5-dicarbonitrile 4.40 g, 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid 3.76 g, triethylamine 6.00 g , Tetrakis (triphenylphosphine) palladium (1.00 g), N, N-dimethylformamide (30 ml), and water (8 ml) were stirred at 100 ° C. for 8 hours. After cooling to room temperature, ethyl acetate was added, and the organic layer was washed with aqueous citric acid solution, water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1H-imidazole-4,5- 2.58 g of dicarbonitrile was obtained.

[Example 4]
1-ethyl-2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1H-imidazole-4,5-dicarbonitrile (present compound number 5) Preparation of 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1H-imidazole-4,5-dicarbonitrile 0.55 g, iodoethane 0.60 g A mixture of 0.50 g of potassium carbonate and 8 ml of N, N-dimethylformamide was stirred at 50 ° C. for 3 days. Ethyl acetate was added to the reaction mixture, and the organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 1-ethyl-2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1H-imidazole- 0.49 g of 4,5-dicarbonitrile was obtained.

[Example 5]
2- [2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1- (1,2-propadienyl) -1H-imidazole-4,5-dicarbonitrile ( Preparation of the present compound No. 80) 2- [2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1H-imidazole-4,5-dicarbonitrile 0.50 g A mixture of 0.35 g of 1-bromo-2-propyne, 0.30 g of potassium carbonate and 5 ml of N, N-dimethylformamide was stirred at 50 ° C. for 2 days. Ethyl acetate was added to the reaction mixture, and the organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 2- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] -1- (1,2-propadienyl) was obtained. ) -1H-imidazole-4,5-dicarbonitrile 0.33 g was obtained.

  Next, production examples of the intermediate are shown.

<Intermediate Production Example 1>
Preparation of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid (1) To 910 g of chlorosulfonic acid, 500 g of 4-bromo-3-fluorotoluene was added at an internal temperature of 50 After dripping so that -60 degreeC may be maintained, it was further made to react at 50-60 degreeC for 1 hour. After allowing to cool, it was poured into a mixed solution of ice water and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to obtain 750 g of 5-bromo-4-fluoro-2-methylbenzenesulfonyl chloride.

  (2) A solution of 750 g of 5-bromo-4-fluoro-2-methylbenzenesulfonyl chloride in 750 ml of acetic acid in a mixture of 1 L of acetic acid, 240 g of red phosphorus, and 2 g of iodine is added so that the internal temperature is maintained at 110 to 120 ° C. The solution was added dropwise over a period of time and further heated to reflux for 2 hours. After cooling to room temperature, the solid was filtered off and the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl acetate, washed with water and saturated brine, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 5-bromo-4-fluoro-2-methyl-1-acetyl. 800 g of thiobenzene was obtained.

  (3) Dissolve 800 g of 5-bromo-4-fluoro-2-methyl-1-acetylthiobenzene in 2 L of methanol, add 1.8 L of 20% aqueous sodium hydroxide so that the internal temperature does not exceed 50 ° C., and The mixture was stirred for 30 minutes. While cooling with ice, the mixture was neutralized with hydrochloric acid so that the pH was 2 to 3. The reaction mixture was concentrated under reduced pressure, and the residue was extracted with ethyl acetate and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 550 g of 5-bromo-4-fluoro-2-methylbenzenethiol.

  (4) To a mixture of 550 g of 5-bromo-4-fluoro-2-methylbenzenethiol, 180 g of potassium carbonate, 55 g of Rongalite (trade name, sodium / formaldehyde / sulfoxylate) and 3 L of N, N-dimethylformamide, After 380 g of iodo-2,2,2-trifluoroethane was added dropwise at 40 ° C. or lower, the reaction was allowed to proceed at room temperature for 5 hours. The reaction solution was poured into water, extracted with n-hexane, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was distilled under reduced pressure (142-143 ° C., 35 mmHg) to obtain 345 g of 5-bromo-4-fluoro-2-methylphenyl 2,2,2-trifluoroethyl sulfide.

  (5) The reaction was performed in a nitrogen atmosphere. 300 g of 5-bromo-4-fluoro-2-methylphenyl 2,2,2-trifluoroethyl sulfide was dissolved in 3 L of diethyl ether and cooled to -70 ° C. To this solution, 625 ml of n-butyllithium (n-hexane solution, 1.54 mol / L) was added dropwise over a period of 20 minutes in a temperature range of −70 to −60 ° C. After 5 minutes, a solution of 104 g of trimethoxyborane in 100 ml of diethyl ether was added dropwise over 10 minutes in a temperature range of −65 to −60 ° C. The temperature was raised to −20 ° C., 1 kg of 20% sulfuric acid was added dropwise, and the mixture was further reacted at room temperature for 2 hours. The organic layer was separated, washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was washed with n-hexane to obtain 211 g (melting point: 161 to 163 ° C.) of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid.

The structural formula and physical property values of the compound [I] of the present invention produced according to the examples are shown in Table 6 including the examples. However, the symbols in the table have the same meaning as described above.
The compound number is referred to in the following description.

  Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “parts” means parts by weight.

[Formulation Example 1] Emulsion Compound No. 4 Compound 30 parts Cyclohexanone 20 parts Polyoxyethylene alkyl aryl ether 11 parts
Calcium alkylbenzenesulfonate 4 parts
Methyl naphthalene 35 parts or more was uniformly dissolved to prepare an emulsion. Moreover, it can replace with compound number 4 and can obtain an emulsion similarly using each of the compound of Tables 1-5.

[Formulation Example 2] Wetting agent Compound of Compound No. 4 10 parts Naphthalenesulfonic acid formalin condensate sodium salt 0.5 part
Polyoxyethylene alkyl aryl ether 0.5 part Diatomaceous earth 24 parts Clay 65 parts
The above was mixed and ground uniformly to obtain a wettable powder. Moreover, it can replace with compound number 4 and a wettable powder can be obtained similarly using each of the compound of Tables 1-5.

[Formulation Example 3] Powder Part 2 of Compound No. 4
Diatomaceous earth 5 parts Clay 93 parts
The above was uniformly mixed and pulverized to obtain a powder. Moreover, it can replace with the compound number 4 and can obtain a dust similarly using each of the compounds of Tables 1-5.

[Example 4] Granule Compound No. 4 Compound 5 parts Sodium salt of lauryl alcohol sulfate 2 parts Sodium lignin sulfonate 5 parts Carboxymethyl cellulose 2 parts Clay 86 parts or more were uniformly mixed and ground. The mixture was kneaded with an equivalent amount of 20 parts of water, processed into granules of 14 to 32 mesh using an extrusion granulator, and dried to give granules. Moreover, it can replace with the compound number 4 and can obtain a granule similarly using each of the compounds of Tables 1-5.

  Next, the effect of the pest control agent comprising the compound of the present invention as an active ingredient will be described with test examples.

[Test Example 1] Spider mite control test (immersion treatment)
A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. Soybean seedlings previously inoculated with adult spider mites were immersed in the chemical solution and air-dried. The treated soybean seedlings were placed in a thermostatic chamber at 25 ° C., and the number of living insects was examined after 13 days, and the control value was determined by the formula of Formula 1. The test was conducted in a single run.

  Compounds having a control value of 100 in this test are Compound Nos. 4, 22, and the like.

[Test Example 2] Spider mite control test (soil treatment)
A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 100 ppm as an active ingredient. 5 ml of the drug solution was irrigated into the soil (100 g) of a soybean seedling cup that had previously been inoculated with adult spider mites. The treated soybean seedlings were placed in a thermostatic chamber at 25 ° C., and the number of living insects was examined after 13 days, and the control value was determined by the formula of Formula 1. The test was conducted in a single run.

  Compounds having a control value of 100 in this test are Compound Nos. 4, 22, and the like.

Test Example 3 Root-knot nematode test The test compound was dissolved in an N, N-dimethylformamide solution containing 1% of tween 20, and this solution was diluted with distilled water to a concentration of 20 ppm as an active ingredient. 0.5 ml of the drug solution and 0.5 ml of a suspension containing about 30 larvae of the second stage of the sweet potato root nematode were mixed and placed in a thermostatic chamber at 25 ° C. Five days later, the number of immobile and viable nematodes was counted under a microscope, and the control nematode rate was determined by the formula of Formula 2. The test was conducted in a two-run system.

  The compound that showed 100% nematode rate in this test is Compound No. 4 and the like.

Claims (2)

Formula [I]

[Wherein R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ haloalkenyl group or a cyclopropylmethyl group,
n represents 0 or 1,
A ¹ and A ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ haloalkyl group, a hydroxyl group, a C _{1 to} C ₆ alkoxy group, or a C _{1 to} C ₆ halo. alkoxy group, cyano _group, C 1 -C ₇ acyl _group, C 2 -C ₇ haloalkylcarbonyl ^group, -CY 1 = N-OY ² group, a nitro group, -N ^(Y 3) Y ⁴ group, a thiocyanate group, a thiol a group or -S (O) _m Y ⁵ group,
A ³ is a hydrogen atom, a C ₁ -C ₆ alkyl group (the group may be mono-substituted by a C ₁ -C ₆ alkoxy group or a cyano group), a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl a group or a _C 2 -C ₆ alkynyl group,
B ¹ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,
B ² represents a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ¹ and Y ² each independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ³ and Y ⁴ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, or a C ₁ -C. ₇ acyl _group, a C 2 -C ₇ haloalkylcarbonyl group or _C 2 -C ₇ alkoxycarbonyl group,
Y ⁵ represents a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
m shows the integer of 0-2. An insecticidal / acaricidal / nematicidal agent for agricultural and horticultural use containing a 2-phenylimidazole derivative or a pharmacologically acceptable salt thereof as an active ingredient. Formula [I]

[Wherein R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ haloalkenyl group or a cyclopropylmethyl group,
n represents 0 or 1,
A ¹ and A ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₆ alkyl group, a hydroxyl group, a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ haloalkoxy group, a cyano group, or C _1. -C ₇ acyl _group, C 2 -C ₇ haloalkylcarbonyl ^group, -CY 1 = N-OY ² group, -N ^(Y 3) Y ⁴ group, a thiocyanate group, a thiol group or a -S (O) _m Y ⁵ group Indicate
A ³ is a hydrogen atom, a C ₁ -C ₆ alkyl group (the group may be mono-substituted by a C ₁ -C ₆ alkoxy group or a cyano group), a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl a group or a _C 2 -C ₆ alkynyl group,
B ¹ represents a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,
B ² represents a halogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ¹ and Y ² each independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
Y ³ and Y ⁴ are each independently a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, or a C ₁ -C. ₇ acyl _group, a C 2 -C ₇ haloalkylcarbonyl group or _C 2 -C ₇ alkoxycarbonyl group,
Y ⁵ represents a C ₁ -C ₆ alkyl group or a C ₁ -C ₆ haloalkyl group,
m shows the integer of 0-2. Or a pharmacologically acceptable salt thereof.