JP2009023910A - Biphenyl sulfide compound and insecticidal or acaricidal agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound which has high activity against various insects and/or mites harmful in agricultural and horticultural fields, is excellent in aftereffects, exhibits sufficient control effects even against various resistant insect pests at low doses, and has an excellent acaricidal activity especially against Aculops pelekassi that is an important insect pest against citrus fruits. <P>SOLUTION: Provided is a biphenyl sulfide compound represented by formula [I] [wherein, (n) is 0 or 1; R is a 1 to 6C haloalkyl]. Provided further are the insecticidal or acaricidal agents containing the biphenyl sulfide compound as an active ingredient, and a method for controlling harmful insect pests, mites in agricultural and horticultural fields, applying an effective amount of the biphenyl sulfide compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel biphenyl sulfide compound and an insecticide / acaricide containing the same as an active ingredient.

  In the field of agriculture and horticulture, various insecticides and acaricides for the purpose of controlling various pests have been developed and used. However, conventionally used agricultural and horticultural insecticides / acaricides are not necessarily satisfactory in terms of insecticidal / acaricidal effects, insecticidal / acaricidal spectrum, residual effects, and the like. Moreover, it cannot be said that the request | requirement, such as the frequency | count of application and reduction of an applied chemical quantity, is satisfied.

  In recent years, the emergence of pests that have acquired resistance to insecticides and acaricides that have been used in the past has also become a problem, and the control of various pests caused by these resistant pests has become difficult year by year. .

  Therefore, it shows a sufficient control effect at low doses against various pests that have acquired resistance to agricultural and horticultural insecticides and acaricides that have been used in the past, has a wide spectrum, and has little impact on the environment The development of new insecticides and acaricides is eagerly desired.

On the other hand, 3-arylphenyl sulfide derivatives are known as known insecticides / acaricides (Patent Document 1). Although the compound group described in Patent Document 1 shows a high effect on the spider mite, the activity against citrus mite, which is an important citrus pest, is not always sufficient.
JP 2000-198768 A

  The problem of the present invention is to solve the above-mentioned problems that the insecticide / miticide of Patent Document 1 has, and has high activity on various insects and / or mites that are harmful in the field of agriculture and horticulture, In particular, an object of the present invention is to provide a compound having excellent acaricidal activity against citrus mite which is an important pest of citrus fruits.

  In order to develop an insecticidal / miticidal agent having the above-mentioned preferable characteristics, the present inventors have synthesized various biphenyl sulfide compounds not described in Patent Document 1 and repeatedly studied their insecticidal / miticidal activity. . As a result, in the (4-fluoro-2-methylphenyl) 2,2,2-trifluoroethyl sulfide compound, a novel biphenyl sulfide compound in which a tri-substituted phenyl group was introduced at the 5-position of the phenyl group was developed. Has been found to have high activity against various harmful insects and / or ticks, and in particular, has excellent acaricidal activity against citrus mite. Thus, the present invention has been completed.

That is, the present invention relates to the following (1) to (5).
(1) Formula [I]

(N represents 0 or 1, and R represents a C1-C6 haloalkyl group).
(2) The biphenyl sulfide compound according to (1), wherein in formula [I], n is 1, and R is a C1-C3 haloalkyl group.
(3) An insecticide and / or acaricide containing the biphenyl sulfide compound according to (1) or (2) as an active ingredient.
(4) A method for controlling harmful insects and / or ticks in the field of agriculture and horticulture by applying an effective amount of the biphenyl sulfide compound according to (1) or (2).

  INDUSTRIAL APPLICABILITY According to the present invention, a novel biphenyl having a high activity against various insects and / or mites that are harmful in the field of agriculture and horticulture, and particularly having an excellent acaricidal activity against citrus mite, an important pest of citrus fruits. Sulfide compounds are provided. In addition, an insecticide / acaricide containing the biphenyl sulfide compound as an active ingredient, and a method for controlling harmful insects and / or ticks in the field of agriculture and horticulture by applying an effective amount of the biphenyl sulfide compound are provided. .

  Here, the symbols and terms used 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 C1 to C6 indicates that the number of carbon atoms of the subsequent substituent is 1 to 6 in this case.

  The C1-C3 haloalkyl group means a linear or branched alkyl group having 1 to 3 carbon atoms which is mono-substituted or poly-substituted with the same or different halogen atoms, unless otherwise specified, and is difluoromethyl, dichloromethyl , Trifluoromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, bromodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 2-chloro-1,1,2,2-tetrafluoroethyl, 3,3,3-trifluoropropy 2,2,3,3-tetrafluoropropyl, 2,3,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoro-1- Trifluoromethylethyl, heptafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 3-chloro-1,1,2,3,3-pentafluoropropyl, 2-chloro-1,1 , 3,3,3-pentafluoropropyl and the like.

  The C1-C6 haloalkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms that is mono-substituted or poly-substituted with the same or different halogen atoms, unless otherwise specified, In addition to group examples, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 1,1,2,3,3,4,4-heptafluorobutyl, 2, 2,3,3,4,4,4-heptafluorobutyl, 5,5,5-trifluoropentyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,3 3,4,4,5,5,5-nonafluoropentyl, 6,6,6-trifluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 2, 2,3,3,4,4,5,5,6,6,6-undecafluo Hexyl include a group such as 1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro hexyl.

In the formula [I], a preferred group of compounds includes a group of compounds in which R is a C1-C3 haloalkyl group substituted with 2-6 fluorine atoms, chlorine atoms, bromine atoms, and n is 0 or 1. .
In a more preferred compound group, R is a difluoromethyl group, a bromodifluoromethyl group, a 2,2,2-trifluoroethyl group or a 1,1,2,3,3,3-hexafluoropropyl group, and n is 1 is a group of compounds.

  Next, specific examples of the compound of the present invention represented by the formula [I] are described in Table 1, but the compound of the present invention is not limited to these compounds. These compounds also include individual pure optical isomers, racemates and mixtures of optical isomers in any proportion. The compound numbers in Table 1 will be referred to in the following description.

  The compounds of the present invention represented by the formula [I] can be produced according to the production methods shown below, but are not limited to these methods.

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

(In the formula, R represents the same meaning as described above, and L represents a halogen atom or a trifluoromethanesulfonyloxy group.)
(Process A)
By reacting the compound represented by the formula [III] and the compound represented by the formula [II-a] in a solvent in the presence of a base and a transition metal catalyst, the compound represented by the formula [Ia] is represented. This invention compound can be manufactured.

The amount of the compound represented by the formula [III] used here is 0.7 to 10.0 mol, preferably 0, relative to 1.0 mol of the compound represented by the formula [II-a]. .8 to 1.5 moles.
(Process B)
By reacting the compound represented by the formula [IV] and the compound represented by the formula [II-b] in a solvent in the presence of a base and a transition metal catalyst, the compound represented by the formula [Ia] is represented. This invention compound can be manufactured.

  The amount of the compound represented by the formula [II-b] used here is 0.7 to 10.0 mol, preferably 0, relative to 1.0 mol of the compound represented by the formula [IV]. .8 to 1.5 moles.

  Examples of transition metal catalysts used in Step A and Step B include palladium compounds such as palladium-activated carbon, palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, and tris (dibenzalacetone) palladium. And nickel compounds such as bis (triphenylphosphine) nickel chloride and tetrakis (triphenylphosphine) nickel.

  The amount of the transition metal catalyst used is preferably 0.01 to 1.0 mol with respect to 1.0 mol of the compound represented by the formula [III] or the compound represented by the formula [II-b]. Is 0.02 to 0.1 mol.

  Examples of the solvent used in Step A and Step B include ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; N, N-dimethylformamide (DMF) ), Aprotic polar solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate and ethyl propionate; Examples thereof include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane; protic solvents such as water and ethanol; or a mixed solvent thereof.

  The amount of the solvent used is 0.1 to 100 L (liter), preferably 1.0 to 1.0 mol of the compound represented by the formula [III] or the compound represented by [II-b]. -5.0L.

  Examples of the base used in Step A and Step B include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; sodium carbonate and carbonate Alkali metal carbonates such as potassium; inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydrides such as sodium hydride and potassium hydride; sodium methoxide and sodium ethoxide , Alcohol metal salts such as potassium tert-butoxide; or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc. Organic bases.

  The amount of the base used is 1.5 to 4.0 moles with respect to 1.0 mole of the compound represented by the formula [III] or the compound represented by [II-b], preferably 2.0. ~ 2.5 mol.

  What is necessary is just to select reaction temperature from arbitrary ranges from -70 degreeC to the reflux temperature in a reaction system, Preferably it is the temperature range of -20 degreeC-150 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but may be selected from the range of 10 minutes to 20 hours, preferably 1 to 3 hours.

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

(Wherein R represents the same meaning as described above, and X represents a leaving group such as a halogen atom, an alkylsulfonyloxy group, a (substituted) arylsulfonyloxy group, a haloalkylsulfonyloxy group, etc. Can be exemplified by perfluoroethene, perfluoropropene, chlorotrifluoroethene, etc.)
By reacting a compound represented by the formula [V] with a compound represented by the formula RX or a C2-C6 haloalkene in a solvent in the presence of a base, the compound represented by the formula [Ia] is represented. This invention compound can be manufactured.

  The amount of the compound represented by the formula R—X or the C2 to C6 haloalkene used here is 1.0 to 10 mol with respect to 1.0 mol of the compound represented by the formula [V], preferably 1.0-1.5 mol.

  Examples of the solvent to be used include ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; N, N-dimethylformamide (DMF), N, N— Aprotic polar solvents such as dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate and ethyl propionate; pentane, hexane, cyclohexane, Examples thereof include aliphatic hydrocarbons such as heptane; pyridines such as pyridine and picoline; or a mixed solvent thereof.

  The usage-amount of the solvent in the above is 0.1-100L with respect to the compound represented by Formula [V], Preferably it is 0.5-5.0L.

  Examples of the base to be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal hydroxides such as sodium carbonate and potassium carbonate. Carbonates; Inorganic bases such as 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 tert-butoxide and the like Or organic bases such as triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene It is done.

  The usage-amount of a base is 1.0-10 mol with respect to 1.0 mol of compounds represented by Formula [V], Preferably it is 1.0-2.0 mol.

  What is necessary is just to select reaction temperature from the arbitrary ranges from -10 degreeC to the reflux temperature in a reaction system, Preferably it is a temperature range of 0 to 60 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but may be selected from the range of 10 minutes to 20 hours, preferably 1 to 3 hours.

<Manufacturing method 3>
The compound of the present invention represented by the formula [Ib] can be produced by a method comprising the reaction formulas exemplified below.

(Wherein R represents the same meaning as described above.)
The compound of the present invention represented by the formula [Ib] is produced by reacting the compound represented by the formula [Ia] with an oxidizing agent in a solvent in the presence or absence of a catalyst. be able to.

  Examples of the oxidizing agent include hydrogen peroxide, m-chloroperbenzoic acid, perbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI DuPont, potassium peroxosulfate), N- Examples include chlorosuccinimide, N-bromosuccinimide, tert-butyl hypochlorite, and sodium hypochlorite.

  The usage-amount of the oxidizing agent used here is 1.0-6 mol with respect to 1.0 mol of compounds represented by Formula [Ia], Preferably it is 1.0-1.5 mol. .

  Examples of the catalyst include sodium tungstate.

  The amount of the catalyst used here is 0.001 to 1.0 mol, preferably 0.01 to 0.05 mol, relative to 1.0 mol of the compound represented by the formula [Ia]. is there.

  The solvent to be used may be any solvent that does not inhibit the reaction, and examples thereof include halogenated alkanes such as chloroform, dichloromethane and dichloroethane; aromatic hydrocarbons such as chlorobenzene and trifluoromethylbenzene; acetic acid and the like. .

  The usage-amount of the said solvent is 0.1-100L with respect to 1.0 mol of compounds represented by [Ia], Preferably it is 1.0-5.0L.

  What is necessary is just to select reaction temperature from the arbitrary ranges from -30 degreeC to the reflux temperature in a reaction system, Preferably it is a temperature range of -10 degreeC-20 degreeC.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, and the like, but is preferably selected from the range of 10 minutes to 20 hours.

  When the compound of the present invention is used as an active ingredient of an insecticide / acaricide, the compound of the present invention may be used as it is, but a solid carrier, a liquid carrier, a surface activity generally used for formulation as an agrochemical adjuvant. Contains emulsions, suspensions, powders, granules, tablets, wettable powders, aqueous solvents, liquids, flowables, wettable granules, aerosols, pastes, oils, milk It can be formulated into various forms such as a suspending agent and a smoke agent. It is preferable that these compounding ratios are 0.1-90 mass% of this invention compound which is an active ingredient normally, and 10-99.9 mass% of an agricultural chemical adjuvant.

  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, Examples thereof include inorganic powders such as urea.

  Examples of the liquid carrier include water; alcohols such as isopropyl alcohol and ethylene glycol; ketones such as cyclohexanone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran (THF); aliphatic hydrocarbons such as kerosene and light oil; xylene , Trimethylbenzene, tetramethylbenzene, methylnaphthalene, solvent naphtha and other aromatic hydrocarbons; chlorobenzene and other halogenated hydrocarbons; N, N-dimethylacetamide and other acid amides; fatty acid glycerol esters and other esters 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, naphthalene sulfonic acid formalin condensate sodium salt, alcohol sulfate ester salt, alkyl aryl sulfonate, lignin sulfonate, polyoxyethylene. Examples thereof include glycol ether, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan monoalkylate, 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, Physical property improvers such as paraffin, 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 livestock with the above-mentioned active ingredient mixed with feed and to control the occurrence and growth of harmful insects, particularly harmful insects, by their 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 mixing ratio of the active ingredient is appropriately selected as necessary, but preferably 0.1 to 20% by mass when used as a powder and granule, and preferably 1 to 80% by mass when used as an emulsion and a wettable powder. Is appropriate.

  The application of the insecticide / acaricide of the present invention is generally carried out at an active ingredient concentration of 0.1 to 5000 ppm when used after being 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.

Other insecticide compounds that can be mixed or used together are exemplified below.
Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, thiamethoxam, ethiprole, protoprol , Chromafenozide, halofenozide, methoxyfenozide, tebufenozide, acrinathrin, allethrin, alpha-cypermethrin, beta-cyfluthrin (beta) ), Beta-cypermethrin), bifenthrin, bioallethrin, bioresmethrin, cycloprothrin, Flutrin (cyfluthrin), cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenpropathrin, fenvalerate ), Flucythrinate, flumethrin, gamma-cyhalothrin, imiprothrin, lambda-cyhalothrin, methothrin, permethrin, phenothrin ), Prarethrin, Resmethrin, Kadesthrin, Tau-fluvalinate, Tefluthrin, Tetramethrin, Zeta cypermethrin (Zeta-cypermethrin), tralomethrin, transfluthrin, (transfluthrin), etofenprox, halffenprox, silafluofen, bensultap, cartap, thiocyclam ( thiocyclam, thiosultap-sodium, acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, Chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, Daiji Dizinon, dichlorvos, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, etoprophos, famphur, fenamiphos (Fenamiphos), fenitrothion, fenthion, fosthiazate, heptenophos, isocarbophos, isoxathion, malathion, mecarbam, memidamphos, methamiphos, methamiphos (Methidathion), mevinphos, monocrotophos, nared, omethoate, oxydemeton-methyl, parathion, parathion me Parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos ( profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, temephos, tersfos Chlorvinphos, thiometon, triazophos, trichlorfon, bamidothion, imicyafos, flupyrazofos, aldicarb, bendiocal Bendiocarb, benfuracarb, carbaryl, carbofuran, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formethanate, furathiocarb, isoprocarb ), Methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, trimethacarb, XMC, xylylcarb, alanycarb Carboxyme (butocarboxim), butoxycarboxim, thiodicarb, thiofanox, bistrifluron, chlorfluazuron, di Rubenzuuron (diflubenzuron), flucycloxuron (flucycloxuron), flufenoxuron (flufenoxuron), hexaflumuron (lufenuron), novaluron, nobiflumuuron (noviflumuron), teflubenzuron (teflubenzuron), teflubenzuron (teflubenzuron) (Triflumuron), abamectin, emamectin, chlorfenapyr, phenoxycarb, hydroprene, kinoprene, metoprene, pyriproxyfen, dienochlor dienochlor, cyenopyrafen, cyflumetofen, spiromesifen, spirodiclofen, spirotetramat, fulvenge Flubendiamide, flurimfen, flonicamid, metaflumizon, linnaxypyr, lepmectin, pyridalyl, fluacrypyrim, oxaxacarb , Bromopropylate, triazamate, fenazaquin, fenpyroximate, pyridaben, tebufenpyrad, clofentezine, etoxazole, hexathiazox, hexytazox , Pymetrozine, buprofezin, 1.3 dichloropropene (1.3-D), isocarbophos, ammonium N-methyldithiocarbamate (NCS), azosic Rotin (azocyclotin), endosulfan, chlordane, chloropicrin, cyhexatin, spinosad, sodium dimethyldithiocarbamate, fenbutatin oxide , Flusulfamide, methyl isothiocyanate (MITC), rotenone, CL900167, sodium aluminum fluoride, NNI-0101, RU-15525, XDE-175, ZXI-8901
Other fungicidal compounds that can be used together or in combination are exemplified below.

Amisulbrom, benomyl, benthiavalicarb, benopirad etaboxam, bitertanol, blasticidin-S, boscalid, captan (Captan), carbendazol, carpropamid, chlorothalonil, cyazofamid, cyflufenamid, cymoxanil, diclomezine, dimoxystrobin, dimoxystrobin dithianon, edifenphos, fenamidone, fenarimol, fenbuconazole, fluazinam, fluopicolide, fluoxastrobin (fluoxast) robin), flutolanil, folpet, fosetyl, fthalide, guazatine, hexaconazole, hydroxyisoxazole, hymexazol, iprobenphos (Iprobenfos), iprodione, iprovalicarb, isoprothiolane, isotianil, kasugamycin, mandipropamid, manneb, mepanipyrim, mepronyl, mepronyl , Metrafenone, myclobutanyl, orysastrobin, oxadixyl, oxolinic acid, pefurazoate, pencicurn (pencycur) on), phenazine oxide, picoxystrobin, polycarbamate, polyoxin, probenazole, prochloraz, procymidone, propamocarb hydrochloride (propamocarb) , Propiconazole, propineb, proquinazid, pyraclostrobin, pyribencarb, pyroquilon, simeconazole, streptomycin, clocloamte, ft Thiabendazole, thiophanate-methyl, thiuram, thiadinyl, tolnifanide, triadimefon, tricyclazole tricyclazole), trifloxystrobin (trifloxystrobin), triflumizole (triflumizole), triforine (triforine), validamycin (validamycin), vinclozolin (vinchlozoline), zineb (zineb), ziram (ziram)
Other herbicide compounds that can be used in combination or in combination, plant growth regulating compounds are exemplified below.

Diphenamid, naproanilide, napropamide, pentanochlor, propanil, flamprop-M, MCPA-thioethyl, clodinafop- propargyl), cyhalofop-butyl, diclofop-methyl, fenoxaprop-P-ethyl, fenoxaprop-ethyl, fluazifop -butyl), Fluazifop-P-butyl, Haloxyfop, Haloxyfop-P, Haloxyfop-P-methyl, Metamifop, Propizahop (Propaquizafop), quizalofop-ethyl, quizalofop-P quizalofop-P), quizalofop-P-ethyl, quizalofop-P-tefuryl, isoxaben, propyzamide, chlorthal-dimethyl, Benfuresate, ethofumesate, 2,3,6-TBA, dicamba, dichlobenil, bentazone, benazolin, diquat dibromide, paraquat dichloride, Asuram, carbetamide, chlorpropham, propham, acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, Metazachlor, Metrac Metolachlor, pethoxamid, pretilachlor, propachlor, propisochlor, S-metolachlor, tenylchlor, alloxydim, butoxydim (Butroxydim), clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim, benfluralin, butralin, dinitramine (di) , Ethalluralin, oryzalin, pendimethalin, trifluralin, dinoterb, DNOC, acifluorfen, bifenox , Fluoroglycofen-ethyl, fomesafen, HC-252, lactofen, oxyfluorfen, aclonifen, glyphosate, glyphosate-trimesium salt (glyphosate- trimesium, bromoxynil, ioxynil, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazathir (Isoxaflutole), clomazone, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, oxadiargyi, oxadia Oxadiazon, pentoxazone, flufenacet, mefenacet, 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop- P (dichlorprop-P), MCPA, MCPB, mecoprop (mecoprop), mecoprop-P potassium salt (mecoprop-P), desmedipham, phenmedipham, pyraflufen-ethyl , Pyridate, forchlorfenuron, thidiazuron, bilanafos, glufosinate-ammonium, glufosinate-sodium, butamifos, bensulide , Naptalam, benzophenap (b enzofenap), pyrazolynate (pyrazolynate), pyrazoxifene (pyrazoxyfen), pyrasulfotole, maleic hydrazide, norflurazon, chloridazon, dithiopyr (thiazopyr), thiazopyr , Diflufenican, picolinafen, clopyralid, fluroxypyr, picloram, triclopyr, diflumetorim, butafenacil, fenclolim, fenclolim ancymidol, flurprimidol, bispyribac-sodium, pyribenzoxim, pyrifalid, pyriminobacmethyl (pyrimi) nobac-methyl), pyrithiobac-sodium, chlormequat chloride, mepiquat chloride, quinoxyfen, quinclorac, quinmerac, diflufenzopyr (Diflufenzopyr), flucarbazone sodium salt (flucarbazone-sodium), propoxycarbazone sodium salt (propoxycarbazone-sodium), propoxycarbazone (amidosulfuron), azimsulfuron, azimsulfuron, bensulfuron methyl (Bensulfuron-methyl), chlorimuron-ethyl, chlorsulfuron (chlorsulfuron), cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxys Ruflon (ethoxysulfuron), flazasulfuron, flupirsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron -methyl-sodium), mesosulfuron-methyl, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron (Prosulfuron), pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron ), Ribenuron-methyl, trifloxysulfuron-sodium, triflusulfuron-methyl, tritosulfuron, flucetosulfuron, fentrazamide (fentrazamide) , Flutiacet-methyl, butyrate, cycloate, dimepiperate, EPTC, esprocarb, molinate, orbencarb, pebulate, losulfocarb prosulfocarb, thiobencarb, thiocarbazil, tri-allate, pyributicatb, ametryn, atrazine, cyanazine, dimetamethrin (dim) ethametryn, prometon, promethrin, proazine, propazine, simazine, simetryn, terbumeton, terbuthylazine, terbutryn, trietazine, trietazine, trietazine hexazinone, metamitron, metribuzin, amitrole, flupoxame, amicarbazone, carfentrazone-ethyl, sulfentrazone sulfentrazone chloranthram methyl ( cloransulam-methyi, diclosulam, florasulam, flumetsulam, metosulam, penoxsulam, mesotrione, sulcotrione, tefuri Tefuryltrion, bromacil, lenacil, terbacil, chlorotoluron, dimefuron, diuron, fluometuron, isoproturon, isoproturon, isouron Carbutilate, linuron, methabenzthiazuron, metbenzuron, metoxuron, monolinuron, neburon, siduron, tebuturon Oxaziclomefone, anilofos, benzobicyclon, prodiamine, cinmethylin, pyraclonil, pyroxysulam, triadifram (tria) ziflam, etobenzanid, bromobutide, daimuron, cafenstrole, benzfendizone, benzfendizone, pinoxaden, aminopyralid, topramezone, tembotrione (temone) , Indanofan, pyrimisulfan, thiencarbazone, TM-435, KIH-485
These pesticides are, for example, The Pesticide Manual 13th edition (British Crop Protection Council (2004)), Shibuya Index 10th edition, 11th edition (SHIBUYA) INDEX 10th Edition, 11th Edition, Publisher: SHIBUYA INDEX Study Group), Monthly Fine Chemical 2006, Vol. 35, No. 7 (issued by CMC Publishing, 2006) or publicly known.

  The compound of the present invention is a grasshopper pest, a thrips pest, a stink bug, a coleopteran insect, a fly eye pest, a butterfly pest, a bee eye pest, a stag beetle, a spotted pest, a cockroach pest, a termite pest, Against pests such as Chatteridae, Pteridomycete, Lice, Pest, Plant parasitic mites, Plant parasitic nematodes, Plant parasitic molluscs, Other harmful animals, Unpleasant animals, Sanitary pests, Parasites, etc. Show excellent control effect. Examples of such pests include the following biological species.

  Grasshopper pests, such as the grasshopper (Ruspolia lineosa), the cricket (Teleogryllus emma), etc., the gryllotalpa orientalis, the grasshopper (Oxya hyla intricate), the locust migra The grasshopper (Atractomorpha lata, Eucyrtus japonicus), the grasshopper (Xya japonicus), etc., such as the Mygratley grasshopper (Melanoplus sanguinipes).

  Thrips of the order Thrips, such as Frankliniella intonsa, Frankliniella occidentalis, Scirtothrips dorsalis, Thrips, Thrips, Thrips Oyster Thrips (Ponticulothrips diospyrosi), Thrips thrips (Haplothrips aculeatus), etc.

  Stink bugs, for example, Cicaceae, Mogannia minuta, Aphrophora intermedia, etc., Machaerotypus sibiricus, etc. Empoasca onukii, Nephotettix cincticeps, Recilia dorsalis, etc., Pentastiridius apilaaog ), Etc., Nisia nervosa, etc., Kamendaka saccharivora, etc., Red fungus bags (Achilus flammeus), etc. Lomos (Orosanga japonicus), etc. Adelges laricis, Adelges tsugae, etc., Acyrthosiphon pisum, Aphis gossypii, spira phi Radish aphids (Lipaphis erysimi), peach aphids (Myzus persicae), barley beetle (Schizaphis graminum), barley beetle (Rhopalosiphum padi), etc. Tobacco whitefly (Bemisia tabaci), silver leaf whitefly (Bemisia argentifolii), Onsatsu whitefly (Trialeurodes vaporariorum), etc. (Dysmicoccus brevipes), citrus scale insect (Planococcus citri), stag beetle scale (Pseudococcus comstocki), etc. Lygas back (Aonidiella aurantii), Nasimaru scale (Diaspidiotus perniciosus), Buprestidae (Unaspis yanonensis), etc. esperus, Trigonotylus caelestialium, etc., Stephanitis pyrioides, Stephanitis nashi, etc., Eysarcoris aeneus, La gym The stink bug (Nezara viridula), the Platypia crossota, etc. japonicus, etc., Dysdercus cingulatus, etc., Hosohelamidae, Leptocorisa acuta, Leptocorisa chinensis, etc. (Anacanthocoris striicornis), etc., Hime, such as helicopter stink bug family of red Hime helicopter stink bug (Rhopalus maculatus), bed bugs of bed bugs family (Cimex lectularis) and the like.

  Coleoptera pests, for example, Anomara cuprea, Anomara rufocuprea, Japanese beetle (Popillia japonica), Oryctes rhinoceros, etc. (Melanotus okinawensis), Markubikushimetsume (Melanotus fortnumi fortnumi), etc., Anthrenus verbasci, etc. , Leopardidae (Pitinus clavipes), etc., Tenebroides manritanicus, etc., Necrobia rufipes, Nephibia rufipes, Carpophilus hemipterus), etc. ), Etc., Tenebrio molitor, Tribolium castaneum, etc., Epicauta gorhami, etc. pyrrhoderus), pine beetle beetle (Monochamus alternatus), etc., beetle weevil (Callosobruchus chinensis), etc., beetle family Colorado potato beetle (Leptinotarsa decemlineata), western corn rootwa Diabrotica virgifera, Phaedon brassicae, Phyllotreta striolata, etc., Cylas formicarius, etc. costirostris), weevil (Euscepes postfasciatus), etc. Tomicus piniperda) and other species, such as Crosswormar niponicus and other species such as Lyctus brunneus.

  For example, flies, such as Tipula aino, Plecia nearctica, Exechia shiitakevora, Pechixia, Pnyxia scabiei, etc., Soybean flies (Asphondylia yushimai), Hessian flies (Mayetiola destructor), etc., Aedes aegypti, Culex pipiens pallens, etc., Simulium takahashii Chironomus oryzae, etc., Chrysops suavis, Abuba (Tabanus trigonus), etc., Eumerus strigatus, etc., Bactrocera dorsalis, Drosophila Euphranta japonica), Cerato fruit fly (Cerati) tis capitata), etc., D. ros, Drosophila, Drosophila, Drosophila Hydrellia griseola, etc., Hempobosca equina, etc., Parallelpmma sasakawae, etc. (Fannia canicularis), etc., Musca domestica, Stomoxys calcitrans, etc., Sarcophaga peregrina, etc., Gasterophilus intestina lis), etc., Hypoderma lineatum, etc., Oestrus ovis, etc.

  Lepidoptera, for example, Endoclita excrescens, etc., Antitispila ampelopsia, etc., Zeuzera leuconotum, etc. Adoxophyes orana fasciata, Grapholita molesta, Chamonaki (Homona magnanima), Beansinkiga (Leguminivora glycinivorella), Codlinga (Cydia pomonella), etc. ), Eumeta minuscula, etc., Nemapogon granella, Tinea translucens, etc., Bucculatrix pyrivorella, etc., Lyonetia clerkella Caloptilia theivora), golden moth (Phyllonorycter ringoniella), etc. Argyresthia conjugella, etc., Nokona regalis, etc., Phthorimaea operculella, Sitotroga cerealella, Pectinophora gossypiella, etc. Carposina sasakii), etc., Illiberis pruni, etc., Iraga monema flavescens, etc. (Ostrinia furnacalis), European corn borer (Ostrinia nubilalis), etc. , White butterflies (Pieris rapae), etc. , Agrius convolvuli, etc., Arna pseudoconspersa, Lymantria dispar, etc., Hyphantria cunea, etc., Agrotis ipsilon, Tamanagin Autographa nigrisigna), cotton bollworm (Helicoverpa armigera), corn bollworm (Helicoverpa zea), tobacco Bud worm (Heliothis virescens), beet armyworm (Spodoptera exigua), common cutworm (Spodoptera litura) and the like.

Bees, for example, Arge pagana, etc., Apethymus kuri, Athalia rosae ruficornis, etc., Dryocosmus kuriphilus, etc. xanthoptera), ants of the ant family (Solenopsis invicta), etc., honeybee (Megachile nipponica), etc.
Coleoptera, for example, Bourletiella hortensis from the family Maltovicidae.

  Spotted pests, such as Lepisma saccharina, Ctenolepisma villosa, etc.

  Cockroach insect pests, such as the cockroach family Periplaneta americana and the German cockroach family Blattella germanica.

  Termite pests, for example, the American termite (Incisitermes minor) of the Lepidoptera family, the termites of the termite family (Coptotermes formosanus) and the like, the Odontotermes formosanus of the family termite.

  Pterodoptera, for example, Trogium pulsatorium, etc., Liposcelis corrodens, etc.

  White-headed pests, for example, the chicken lice of the family Abysidae, the Damalinia bovis, etc.

  Lice insect pests, for example, Haematopinus suis, etc., Human lice, Pediculus humanus, Linognathus setosus, etc., lice, etc.

  Plant parasitic mites, such as Penthaleus major, such as Penthaleus major, Phytonemus pallidus, Polyphagotarsonemus latus, etc. Grape spider mite (Brevipalpus lewisi) etc., Phytoseiidae spider mite (Tuckerella pavoniformis), etc. Etc., Trisetacus pini, etc., Acarops pelekassi, Epitrimerus pyri, Phyllocoptruta oleivora, etc. Fushidani (Diptacus crenatae), etc., Mugikonadani (Aleuroglyphus ovatus) of mites family, Tyrophagus (Tyrophagus putrescentiae), the bulb mite, Rhizoglyphus (Rhizoglyphus robini) and the like.

  Plant parasitic nematodes, for example, the Xiphinema index of the Longidoridae, Paratrichodorus minor of the Trichodols family, Rhabditella sp. Aglenchus sp.), A kind of Tyrodolceceae (Cephalenchus sp.), Etc., Anguinaceae strawberry mesenchu (Nothotylenchus acris), Imogusaresenchu (Ditylenchus destructor), etc. Helicotylenchus dihystera, etc., Paratylencus curvitatus, etc., Meloidogyne incognita, Meloidogyne hapla, etc. a rostochiensis), soybean cyst nematode (Heterodera glycines), etc., Tylenchorhynchus claytoni, etc., Psilenchus sp. .), Tylenchulus semipenetrans, etc., Sphaeronema camelliae, etc., Sphaeronema camelliae, Radophorus citrophil , Banophore similis, Nacobbus aberrans, Pratylenchus penetrans, Pratylenchus coffeae, etc. Iotonchium ungulatum, etc., Aphelenchus avenae, etc., Aphelenchoides besseyi, Aphelenchoides fragariae, etc. Nematode (Bursaphelenchus xylophilus) etc.

  Plant parasitic molluscs, for example, Pomacea canaliculata, etc., Leavicaulis alte, etc., Achatina fulica, etc. Meghimatium bilineatum), etc. Noharamakukuji (Deroceras reticulatum), etc., Parakeliella harimensis, etc., Onusidai, Acusta despecta sieboldiana, Bradybaena similaris, etc.

  Pests such as other pests, unpleasant animals, sanitary pests, livestock pests, and parasites, for example, Ornithonyssus sylvialum, such as tick-spotted mites, Varroa jacobsoni, etc. Dermanyssus gallinae, etc., Mite, Ornithonyssus sylvialum, etc., Tick, Boophilus microplus, Rhipicephalus sanguineus, Haemaphysalis, Tick, etc. scabiei), etc., Isodaceae, Armadillidium vulgare, etc., Shrimp, Crayfish, Procambarus clarkii, etc., Paramecidae, Armadillidium vulgare, etc. Gezi and centipede eyes tobism Deer (Scolopendra subspinipes) and other centipede net pests, Oxidus gracilis, millipede pests such as the Oxidus gracilis, Theridiidae hasseltii, and the like , Scorpion Afghan death stalkers (Androctonus crassicauda), linear animal endoparasites (Ascaris lumbricoides), worms (Syphacia sp.), Filariaes (Wuchereria bancrofti), flat animals, etc. Parasites such as liver dystoma (Distomum sp.), Lung dystoma (Paragonimus westermanii), Metagonimus yokokawai, Schistosoma japonicum, Taenia solium, Taeniarhynchus saginatus ), Echinococcus sp., Diphyllobothrium latum, etc.

  The compound of the present invention also exhibits a control effect on the above-mentioned pests that have acquired resistance to existing pest control agents. It is particularly effective against pests that are resistant to organophosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, acylurea compounds, or existing insecticides.

  The compounds of the present invention can be used for plants that have acquired characteristics such as pest resistance, disease resistance, and herbicide resistance by genetic recombination, artificial mating, and the like.

  Hereinafter, although the manufacturing method of this invention represented by a formula [I], a formulation example, and a use are demonstrated in detail in the following Example, this invention is not restrict | limited at all to these Examples. In the following description, “%” indicates a mass percentage, and “part” indicates a mass part.

[Production Example 1]
[5- (4-Chloro-5-difluoromethoxy-2-fluorophenyl) -4-fluoro-2-methylphenyl] Preparation of 2,2,2-trifluoroethyl sulfide (Compound No. 1):
A mixture of 5-bromo-2-chloro-4-fluorophenol (1.25 g), potassium carbonate (1.2 g) and N, N-dimethylformamide (10 mL) was blown with chlorodifluoromethane at 70 ° C. for 2 hours. Stir. The reaction mixture was poured into water and extracted with diethyl ether. 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 (elution solvent; hexane: ethyl acetate = 50: 1) to obtain 1.45 g of 1-bromo-4-chloro-5-difluoromethoxy-2-fluorobenzene.

2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid (0.81 g), 1-bromo-4-chloro-5-difluoromethoxy-2-fluorobenzene (0 .83 g), sodium carbonate (0.64 g), tetrakis (triphenylphosphine) palladium (0.20 g), tetrahydrofuran (12 mL), and water (3 mL) were heated to reflux for 8 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 50: 1) to give [5- (4-chloro-5-difluoromethoxy-2-fluorophenyl) -4- Fluoro-2-methylphenyl] 0.81 g of 2,2,2-trifluoroethyl sulfide was obtained (64% yield).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.54 (3H, s), 3.34 (2H, q), 6.54 (1H, t), 7.09 (1H, d), 7.28 (1H, d), 7.30 (1H, d), 7.55 (1H, d)

[Production Example 2]
[5- (4-Chloro-5-difluoromethoxy-2-fluorophenyl) -4-fluoro-2-methylphenyl] Preparation of 2,2,2-trifluoroethyl sulfoxide (Compound No. 2):
[5- (4-Chloro-5-difluoromethoxy-2-fluorophenyl) -4-fluoro-2-methylphenyl] 2,2,2-trifluoroethyl sulfide (0.44 g) synthesized by the method of Production Example 1 ) In chloroform (10 mL) was added m-chloroperbenzoic acid (0.26 g, purity 70%) under ice-cooling and stirred for 1 hour. To the reaction mixture was added aqueous sodium hydrogen sulfite solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (elution solvent; hexane: acetic acid). Ethyl = 4: 1) and purified from [5- (4-chloro-5-difluoromethoxy-2-fluorophenyl) -4-fluoro-2-methylphenyl] 2,2,2-trifluoroethyl sulfoxide. 37 g was obtained (yield 81%).

[Production Example 3]
[5- (5-Bromodifluoromethoxy-4-chloro-2-fluorophenyl) -4-fluoro-2-methylphenyl] Preparation of 2,2,2-trifluoroethyl sulfide (Compound No. 5):
A mixture of 5-bromo-2-chloro-4-fluorophenol (0.83 g), dibromodifluoromethane (1.54 g), potassium carbonate (0.76 g), N, N-dimethylformamide (10 mL) was sealed in a sealed tube. The mixture was stirred at 100 ° C. for 10 hours. The reaction mixture was poured into water and extracted with diethyl ether. 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 (elution solvent; hexane) to obtain 0.81 g of 1-bromo-5-bromodifluoromethoxy-4-chloro-2-fluorobenzene.

2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid (0.61 g), 1-bromo-5-bromodifluoromethoxy-4-chloro-2-fluorobenzene ( 0.91 g), sodium carbonate (0.48 g), tetrakis (triphenylphosphine) palladium (0.20 g), tetrahydrofuran (12 mL), and water (3 mL) were heated to reflux for 20 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 30: 1) to give [5- (5-bromodifluoromethoxy-4-chloro-2-fluorophenyl) -4 as an oily substance. -Fluoro-2-methylphenyl] 2,8,2-trifluoroethyl sulfide 0.88 g was obtained (yield 78%).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.54 (3H, s), 3.34 (2H, q), 7.10 (1H, d), 7.34 (1H, d), 7.42 (1H, d), 7.56 (1H, d)

[Production Example 4]
[5- (5-Bromodifluoromethoxy-4-chloro-2-fluorophenyl) -4-fluoro-2-methylphenyl] Preparation of 2,2,2-trifluoroethyl sulfoxide (Compound No. 6):
[5- (5-Bromodifluoromethoxy-4-chloro-2-fluorophenyl) -4-fluoro-2-methylphenyl] 2,2,2-trifluoroethyl sulfide synthesized by the method of Production Example 3 (0. M-chloroperbenzoic acid (0.21 g, purity 70%) was added to a chloroform (10 mL) solution of 42 g) under ice cooling, and the mixture was stirred for 1 hour. To the reaction mixture was added aqueous sodium hydrogen sulfite solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 4: 1) to give a candy-like substance [5- (5-bromodifluoromethoxy-4-chloro-2-fluorophenyl)- 4-Fluoro-2-methylphenyl] 0.42 g of 2,2,2-trifluoroethyl sulfoxide was obtained (yield 97%).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.47 (3H, s), 3.38-3.59 (2H, m), 7.14 (1H, d), 7.37 (1H, d), 7.45 (1H, d), 8.01 (1H, d)

[Production Example 5]
{5- [4-Chloro-2-fluoro-5- (2,2,2-trifluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfide (Compound No. 7) Production:
5-bromo-2-chloro-4-fluorophenol (0.83 g), 2,2,2-trifluoroethyl trifluoromethanesulfonate (0.94 g), potassium carbonate (0.76 g), N, N-dimethylformamide (10 mL) was stirred at room temperature for 3 days. The reaction mixture was poured into water and extracted with diethyl ether. 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 (elution solvent; hexane: ethyl acetate = 20: 1), and 1-bromo-4-chloro-2-fluoro-5- (2,2,2-trifluoroethoxy). ) 1.09 g of benzene was obtained.

2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid (0.67 g), 1-bromo-4-chloro-2-fluoro-5- (2,2, A mixture of 2-trifluoroethoxy) benzene (0.77 g), sodium carbonate (0.53 g), tetrakis (triphenylphosphine) palladium (0.15 g), tetrahydrofuran (12 mL), water (3 mL) was heated to reflux for 4 hours. did. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 20: 1) to give {5- [4-chloro-2-fluoro-5- (2,2,2- Trifluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfide (0.75 g) was obtained.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.54 (3H, s), 3.34 (2H, q), 4.41 (2H, q), 7.00 (1H, d), 7.09 (1H, d), 7.27 (1H, d), 7.55 (1H, d)

[Production Example 6]
{5- [4-Chloro-2-fluoro-5- (2,2,2-trifluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfoxide (Compound No. 8) Production:
{5- [4-Chloro-2-fluoro-5- (2,2,2-trifluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2 synthesized by the method of Production Example 5 -To a chloroform (10 mL) solution of trifluoroethyl sulfide (0.40 g) was added m-chloroperbenzoic acid (0.22 g, purity 70%) under ice cooling, and the mixture was stirred for 1 hour. To the reaction mixture was added aqueous sodium hydrogen sulfite solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 4: 1), and {5- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethoxy) was obtained. ) Phenyl] -4-fluoro-2-methylphenyl} 2,0,2-trifluoroethyl sulfoxide (0.30 g) was obtained (yield 72%).

[Production Example 7]
{5- [4-Chloro-5- (2-chloro-2,2-difluoroethoxy) -2-fluorophenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfide (compound Production of number 9):
Perfluorobutanesulfonyl fluoride (19.0 g) was added dropwise to a solution of 2-chloro-2,2-difluoroethanol (5.0 g) and triethylamine (6.9 g) in dichloromethane (300 mL) and heated for 1 hour. After refluxing, the mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated and purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 9: 1) to obtain 8.5 g of 2-chloro-2,2-difluoroethyl perfluorobutanesulfonate.

[5- (4-Chloro-2-fluoro-5-hydroxyphenyl) -4-fluoro-2-methylphenyl] 2,2,2-trifluoroethyl sulfide (0.50 g), 2-chloro-2,2 -A mixture of difluoroethyl perfluorobutane sulfonate (0.54 g), potassium carbonate (0.22 g) and dimethyl sulfoxide (10 mL) was stirred at room temperature for 20 hours. The reaction mixture was poured into water and extracted with ethyl acetate. 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 (elution solvent; hexane: ethyl acetate = 20: 1) to give an oily product {5- [4-chloro-5- (2-chloro-2,2-difluoroethoxy). ) -2-Fluorophenyl] -4-fluoro-2-methylphenyl} 2,5,2-trifluoroethyl sulfide (0.35 g) was obtained (55% yield).
1H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.53 (3H, s), 3.33 (2H, q), 4.49 (2H, t), 7.02 (1H, d), 7.08 (1H, d), 7.25 (1H, d), 7.55 (1H, d)

[Production Example 8]
{5- [4-Chloro-5- (2-chloro-2,2-difluoroethoxy) -2-fluorophenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfoxide (compound Production of number 10):
{5- [4-Chloro-2-fluoro-5- (2-chloro-2,2-difluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2, synthesized by the method of Production Example 7 M-Chloroperbenzoic acid (0.10 g, purity 70%) was added to a chloroform (10 mL) solution of 2-trifluoroethyl sulfide (0.20 g) under ice cooling, and the mixture was stirred for 1 hour. To the reaction mixture was added aqueous sodium hydrogen sulfite solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 4: 1), and the residue was converted to the {5- [4-chloro-5- (2-chloro-2,2-difluoro) -like substance. Ethoxy) -2-fluorophenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfoxide (0.10 g) was obtained (yield 53%).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.45 (3H, s), 3.40-3.56 (2H, m), 4.50 (2H, t), 7.05 (1H, d), 7.11 (1H, d), 7.27 (1H, d), 7.98 (1H, d)

[Production Example 9]
{5- [4-Chloro-2-fluoro-5- (1,1,2,2-tetrafluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfide ( Preparation of compound number 11):
[5- (4-Chloro-2-fluoro-5-hydroxyphenyl) -4-fluoro-2-methylphenyl] 2,2,2-trifluoroethyl sulfide (1.0 g), potassium carbonate (0.04 g) , N, N-dimethylformamide (50 mL) was stirred at 90 ° C. for 1 hour while perfluoroethene was blown into the mixture. The reaction mixture was poured into water and extracted with ethyl acetate. 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 (elution solvent; hexane: ethyl acetate = 20: 1) to give {5- [4-chloro-2-fluoro-5- (1,1,2,2, 2-tetrafluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfide was obtained (yield 9%).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.53 (3H, s), 3.34 (2H, q), 5.99 (1H, tt), 7.09 (1H, d), 7.31 (1H, d), 7.37 (1H, d), 7.56 (1H, d)

[Production Example 10]
{5- [4-Chloro-2-fluoro-5- (1,1,2,2-tetrafluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfoxide ( Preparation of compound number 12):
{5- [4-Chloro-2-fluoro-5- (1,1,2,2-tetrafluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2 synthesized by the method of Production Example 9 , 2-Trifluoroethyl sulfide (0.12 g) in chloroform (10 mL) was added with m-chloroperbenzoic acid (0.07 g, purity 70%) under ice-cooling and stirred for 1 hour. To the reaction mixture was added aqueous sodium hydrogen sulfite solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 4: 1), and {5- [4-chloro-2-fluoro-5- (1,1,2,2-tetra Fluoroethoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfoxide was obtained (yield: 100%).

[Production Example 11]
{5- [4-Chloro-2-fluoro-5- (1,1,2,3,3,3-hexafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-tri Production of fluoroethyl sulfide (Compound No. 21):
[5- (4-Chloro-2-fluoro-5-hydroxyphenyl) -4-fluoro-2-methylphenyl] 2,2,2-trifluoroethyl sulfide (1.30 g), triethylamine (10 mL), N, While perfluoropropene was blown into an N-dimethylformamide (20 mL) solution, the mixture was stirred at 50 ° C. for 1 hour. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed with water, dilute hydrochloric acid 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 (elution solvent; hexane: ethyl acetate = 20: 1) to give {5- [4-chloro-2-fluoro-5- (1,1,2,2, 3,3,3-Hexafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfide (0.77 g) was obtained (42% yield).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.54 (3H, s), 3.34 (2H, q), 4.96-5.20 (1H, m), 7.09 (1H, d), 7.32 (1H, d), 7.36 (1H, d), 7.55 (1H, d)

[Production Example 12]
{5- [4-Chloro-2-fluoro-5- (1,1,2,3,3,3-hexafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-tri Production of fluoroethyl sulfoxide (Compound No. 22):
{5- [4-Chloro-2-fluoro-5- (1,1,2,3,3,3-hexafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl synthesized by the method of Production Example 11 } To a chloroform (10 mL) solution of 2,2,2-trifluoroethyl sulfide (0.42 g), m-chloroperbenzoic acid (0.20 g, purity 70%) was added under ice cooling, and the mixture was stirred for 1 hour. . To the reaction mixture was added aqueous sodium hydrogen sulfite solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 4: 1), and {5- [4-chloro-2-fluoro-5- (1,1,2,3,3) , 3-hexafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl sulfoxide (yield: 93%).

[Production Example 13]
{5- [4-Chloro-2-fluoro-5- (2,2,3,3,3-pentafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl Production of sulfide (Compound No. 19):
Perfluorobutanesulfonyl fluoride (75.0 g) was added to a solution of 2,2,3,3,3-pentafluoro-1-propanol (25.0 g) and triethylamine (27.0 g) in dichloromethane (300 mL). The mixture was added dropwise and heated to reflux for 1 hour, and then stirred at room temperature for 1 hour. The reaction mixture was concentrated and purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 9: 1) to obtain 30 g of 2,2,3,3,3-pentafluoropropyl perfluorobutanesulfonate.

  [5- (4-Chloro-2-fluoro-5-hydroxyphenyl) -4-fluoro-2-methylphenyl] 2,2,2-trifluoroethyl sulfide 0.50 g, 2,2,3,3,3 -A mixture of pentafluoropropyl perfluorobutane sulfonate (0.59 g), potassium carbonate (0.22 g) and dimethyl sulfoxide (10 mL) was stirred at room temperature for 20 hours. The reaction mixture was poured into water and extracted with ethyl acetate. 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 (elution solvent; hexane: ethyl acetate = 50: 1), and {5- [4-chloro-2-fluoro-5- (2,2,3,3,3) -Pentafluoropropoxy) -4-fluoro-2-methylphenyl] phenyl} 2,2,2-trifluoroethyl sulfide 0.50 g was obtained (yield 74%).

  According to this method, compounds of compound numbers 23, 25 and 27 were synthesized.

[Production Example 14]
{5- [4-Chloro-2-fluoro-5- (2,2,3,3,3-pentafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl} 2,2,2-trifluoroethyl Production of sulfoxide (Compound No. 20):
{5- [4-Chloro-2-fluoro-5- (2,2,3,3,3-pentafluoropropoxy) phenyl] -4-fluoro-2-methylphenyl} 2 synthesized by the method of Production Example 11 , 2,2-trifluoroethyl sulfide (0.40 g) in chloroform (10 mL) was added m-chloroperbenzoic acid (0.20 g, purity 70%) under ice-cooling and stirred for 1 hour. To the reaction mixture was added aqueous sodium hydrogen sulfite solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 4: 1), and the residue was converted to the {5- [4-chloro-2-fluoro-5- (2,2,3] , 3,3-pentafluoropropoxy) phenyl] -4-fluoro-2-methyl-phenyl} 2,2,2-trifluoroethyl sulfoxide was obtained (68% yield).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.46 (3H, s), 3.40-3.56 (2H, m), 4.48 (2H, t), 7.00 (1H, d), 7.12 (1H, d), 7.29 (1H, d), 7.99 (1H, d)

  According to this method, compounds of Compound Nos. 24, 26 and 28 were synthesized.

  The structural formula and physical property values of the compound [1] of the present invention synthesized according to the above production example are shown in Table 2, including the production example. In addition, the compound number in a table | surface represents the same meaning as the above.

For compound numbers 23, 24, 25, 26, 27, and 28, ¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value) is shown below.
Compound No. 23:
2.54 (3H, s), 3.34 (2H, q), 4.51 (2H, t), 6.99 (1H, d), 7.09 (1H, d), 7.27 (1H, d), 7.55 (1H, d)
Compound No. 24:
2.46 (3H, s), 3.40-3.57 (2H, m), 4.52 (2H, t), 7.01 (1H, d), 7.12 (1H, d), 7.29 (1H, d), 7.99 (1H, d)
Compound No. 25:
2.54 (3H, s), 3.34 (2H, q), 4.52 (2H, t), 6.99 (1H, d), 7.09 (1H, d), 7.27 (1H, d), 7.55 (1H, d)
Compound No. 26:
2.46 (3H, s), 3.40-3.57 (2H, m), 4.53 (2H, t), 7.01 (1H, d), 7.12 (1H, d), 7.30 (1H, d), 7.99 (1H, d)
Compound No. 27:
2.54 (3H, s), 3.34 (2H, q), 4.52 (2H, t), 6.99 (1H, d), 7.09 (1H, d), 7.27 (1H, d), 7.55 (1H, d)
Compound No. 28:
2.46 (3H, s), 3.40-3.57 (2H, m), 4.53 (2H, t), 7.01 (1H, d), 7.12 (1H, d), 7.30 (1H, d), 7.99 (1H, d)

[Reference Example 1] (Production intermediate)
Preparation of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid:
4-Bromo-3-fluorotoluene (500 g) was added dropwise to chlorosulfonic acid (910 g) at 50 to 60 ° C., followed by further reaction at 50 to 60 ° C. for 1 hour. The reaction mixture was cooled to room temperature and then 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.

  To a mixture of acetic acid (1 L), red phosphorus (240 g) and iodine (2 g), add a solution of 5-bromo-4-fluoro-2-methylbenzenesulfonyl chloride (750 g) in acetic acid (750 mL) 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 the reaction mixture 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- 800 g of acetylthiobenzene was obtained.

5-Bromo-4-fluoro-2-methyl-1-acetylthiobenzene (800 g) is dissolved in methanol (2 L), 20% aqueous sodium hydroxide solution (1.8 L) is added at 50 ° C. or lower, and this mixture is further added. Was stirred at 50 ° C. or lower for 30 minutes. Hydrochloric acid was added to this mixture so that the pH was 2 to 3 while cooling with ice. 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.
5-bromo-4-fluoro-2-methyl-benzenethiol 550 g, potassium carbonate 180 g, Rongalite (Rongalit, Sodium formaldehyde sulfoxylate, CH 2 OHSO 2 Na · 2H 2 O) (55g), N, N- dimethylformamide (3L) 1-iodo-2,2,2-trifluoroethane (380 g) was added dropwise at 40 ° C. or lower, and the mixture was further reacted at room temperature for 5 hours. The reaction mixture 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 resulting residue was distilled under reduced pressure (142-143 ° C., 4.67 KPa (35 mmHg)) to obtain 345 g of 5-bromo-4-fluoro-2-methylphenyl 2,2,2-trifluoroethyl sulfide.

  The following reaction was performed in a nitrogen atmosphere. 5-Bromo-4-fluoro-2-methylphenyl 2,2,2-trifluoroethyl sulfide (300 g) was dissolved in diethyl ether (3 L) and cooled to -70 ° C. To this solution, n-butyllithium (n-hexane solution, 1.54 mol / L) (625 mL) was added dropwise at −70 to −60 ° C. over 20 minutes. After 5 minutes, a solution of trimethoxyborane (104 g) in diethyl ether (100 mL) was added dropwise at −65 to −60 ° C. over 10 minutes, then the temperature was raised to −20 ° C., and 20% sulfuric acid (1 kg) was added dropwise. The mixture was further reacted at room temperature for 2 hours. The organic layer was separated from this reaction mixture, 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 of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid (melting point: 161 to 163 ° C.).

[Reference Example 2] (Production intermediate)
Production of 5-bromo-2-chloro-4-fluorophenol:
Sodium sulfite (5.2 g) was added to concentrated sulfuric acid (70 g) at 40 ° C. or lower, and then acetic acid (70 mL) was added at 40 ° C. or lower. To this solution, a solution of 4-chloro-2-fluoro-5-hydroxyaniline (10 g) in acetic acid (120 mL) was added dropwise at 5 ° C. to 10 ° C., and the mixture was further stirred at 5 ° C. for 1 hour to prepare a diazonium salt solution. Obtained.

  In a separate reaction vessel, copper (I) bromide (18 g) and 48% hydrobromic acid (100 mL) were added and heated to 60 ° C. The diazonium salt solution previously obtained was added dropwise to this solution at 60 ° C., and the mixture was further stirred at 70 ° C. for 1 hour. The reaction mixture was cooled to room temperature, poured into ice water, and extracted with diethyl ether. The organic layer was washed with water, aqueous sodium hydrogen carbonate solution and saturated brine, anhydrous magnesium sulfate and florisil were added, filtered and concentrated to obtain 12.7 g of 5-bromo-2-chloro-4-fluorophenol.

4-Chloro-2-fluoro-5-hydroxyaniline is prepared according to the method described in pages 2001-2004 (1989) of Agric. Biol. Chem. Synthesized.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
5.45 (1H, s), 7.14 (1H, d), 7.23 (1H, d)

[Reference Example 3] (Production intermediate)
[5- (4-Chloro-2-fluoro-5-hydroxyphenyl) -4-fluoro-2-methylphenyl] Preparation of 2,2,2-trifluoroethyl sulfide:
5-bromo-2-chloro-4-fluorophenol (1.13 g), 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid (1.34 g), tetrakis A mixture of (triphenylphosphine) palladium (0.35 g), sodium carbonate (1.80 g), tetrahydrofuran (25 mL) and water (7 mL) was heated to reflux for 4 hours. After cooling the reaction mixture to room temperature, the organic layer is dried over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure, and the resulting residue is subjected to silica gel column chromatography (elution solvent; hexane: ethyl acetate = 5: 1). ) To obtain 1.70 g of [5- (4-chloro-2-fluoro-5-hydroxyphenyl) -4-fluoro-2methyl-phenyl] 2,2,2-trifluoroethyl sulfide.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.53 (3H, s), 3.33 (2H, q), 5.40 (1H, s), 7.02 (1H, d), 7.07 (1H, d), 7,19 (1H, d), 7.54 (1H, d)
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.

[Formulation Example 1] Emulsion Compound No. 11 Compound 30 parts Cyclohexanone 20 parts Polyoxyethylene alkyl aryl ether 11 parts Calcium alkylbenzenesulfonate 4 parts Methyl naphthalene 35 parts or more were uniformly dissolved to prepare an emulsion. Further, an emulsion can be similarly obtained using each of the compounds shown in Table 1 instead of Compound No. 11.

[Formulation Example 2] Wetting agent Compound No. 11 Compound 10 parts Naphthalenesulfonic acid formalin condensate sodium salt 0.5 parts Polyoxyethylene alkyl aryl ether 0.5 parts Diatomaceous earth 24 parts Clay 65 parts or more are mixed and ground uniformly. To obtain a wettable powder. Further, a wettable powder can be obtained in the same manner using each of the compounds shown in Table 1 instead of Compound No. 11.

[Formulation Example 3] Powder Compound 2 of Compound No. 24 2 parts Diatomaceous earth 5 parts Clay 93 parts or more were mixed and ground uniformly to obtain a powder. Moreover, it can replace with the compound number 24 and can obtain a dust similarly using each of the compound of Table 1.

[Formulation Example 4] Granule Compound No. 24 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 24 and can obtain a granule similarly using each compound of Table 1.

  Next, the effect of the insecticide / miticide containing the compound of the present invention as an active ingredient will be described with test examples.

[Test Example 1] Citrus mite control test test method: A leaf piece infested with Citrus mite was placed on a leaf disc of citrus on wet cotton wool on a plastic cup and left overnight. One day after the inoculation, the number of adult worms moved on the leaf disk was counted, and the wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. This diluted solution was sprayed on a leaf disk (spraying amount 2 mg / cm ² ). After the treatment, it was placed in a thermostatic chamber at 25 ° C. for 3 days, and the number of live insects was examined.

  As comparative control compounds, compounds [I-356], [I-358], [I-361], and [I-414] exemplified in JP-A-2000-198768 (hereinafter referred to as Comparative Compound a, respectively). , B, c, and d.) Were prepared in the same manner as in Formulation Example 2, and the same test was performed.

  The above results are shown in Table 3.

[Test Example 2] 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 2. The test was conducted in a single run.

  Compounds having a control value of 100% in this test are compound numbers 1, 5, 9, 11, 22, 26 and the like.

[Test Example 3] Brown planthopper insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. Rice buds and rice bran were immersed in the chemical solution and placed in a plastic cup having a capacity of 60 ml. To this, 10 3rd instar larvae were released, covered and placed in a thermostatic chamber at 25 ° C. Six days later, the number of surviving insects was counted, and the mortality rate was determined by the formula of Formula 3. The test was conducted in a single run.

  In this test, the compounds having a control value of 100% are compound numbers 1, 5, 11, 19, 20, 23, 24, 26, 28, and the like.

Claims (4)

Formula [I]

(N represents 0 or 1, and R represents a C1-C6 haloalkyl group).   The biphenyl sulfide compound according to claim 1, wherein in formula [I], n is 1 and R is a C1-C3 haloalkyl group.   An insecticide and / or acaricide containing the biphenyl sulfide compound according to claim 1 or 2 as an active ingredient.   A method for controlling harmful insects and / or mites in the field of agriculture and horticulture by applying an effective amount of the biphenyl sulfide compound according to claim 1.