WO2007034755A1 - Biphenyl sulfide compounds and insecticides and miticides - Google Patents

Abstract

Compounds exerting high activities against various destructive insects and/or mites in agricultural and horticultural field, particularly excellent miticidal activity against Panonychus citri which is a weighty pest to citrus fruits, namely, biphenyl sulfide compounds represented by the general formula [I]: [I] wherein n is 0 or 1; X1 is hydrogen or halogeno; X2 is halogeno; and when X1 is hydrogen, X3 is halogeno, difluoromethyl, or difluoromethoxy and X4 is halogeno, while when X1 is halogeno, X3 is halogeno and X4 is hydrogen.

Description

 Specification

 Biphenylsulfide compounds and insecticides

 Technical field

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

 [0002] In the field of agriculture and horticulture, various insecticides and acaricides for the purpose of controlling various pests have been developed and used. However, agricultural and horticultural insecticides and acaricides, which have been used in the past, are not necessarily satisfactory in terms of insecticidal and acaricidal effects, insecticidal and acaricidal spectrum, and residual efficacy. In addition, the fact that the requirements such as the number of times of application and the reduction of the applied dose were satisfied was inevitably.

 [0003] 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 a problem. It has become difficult year after year.

 [0004] In view of this, a low dose of the insecticide for agro-horticultural and insecticides that have acquired resistance to the acaricide that has been used in the past shows a sufficient control effect with a low dose, and the spectrum is wide and the environment. The development of new insecticides and acaricides with little impact is eagerly desired.

 On the other hand, 3-arylpropylsulfide derivatives are known as known insecticides and acaricides (Patent Document 1). Although the compound group described in Patent Document 1 shows a high effect on namihada, its activity against citrus mite, an important citrus pest, is not always sufficient.

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-198768

 Disclosure of the invention

 Problems to be solved by the invention

[0006] An object of the present invention is to solve the above-mentioned problems of the insecticide / acaricide of Patent Document 1 and to have high activity against various insects and Z or mites that are harmful in the field of agriculture and horticulture. In particular, it has an excellent acaricidal activity against citrus mite, an important pest of citrus fruits. To provide things.

 Means for solving the problem

 [0007] In order to develop an insecticide 'acaricide having the above-mentioned preferable characteristics, the present inventors synthesized various biphenylsulfide compounds not described in Patent Document 1, Insecticidal activity was investigated for acaricidal activity. As a result, in (4-Fluoro-2-methylphenol) -2,2,2-trifluoroethylsulfide, a new bisulfursulfide was introduced in which a tri-substituted phenol group was introduced at the 5-position of the phenyl group. A compound was developed, and the compound was found to have high activity against various harmful insects and Z or ticks, and particularly excellent acaricidal activity against citrus mite, which led to the completion of the present invention. It was.

 [0008] That is, the present invention has the gist of the following features.

 (1) General formula [I]

[0009] [Chemical 1]

(n represents 0 or 1,

X ¹ represents a hydrogen atom or a halogen atom, X ² represents a halogen atom,

When X ¹ is a hydrogen atom, X ³ is a halogen atom, a difluoromethyl group or a difluoromethoxy group, X ⁴ is a halogen atom, and when X ¹ is a halogen atom, X ³ is a halogen atom, and X ⁴ is a hydrogen atom. Indicates an atom. Bisulfursulfide compounds represented by

[0010] (2) X ¹ is a hydrogen atom, X ² is a chlorine atom, X ³ is a chlorine atom, a difluoromethyl group or a difluoromethoxy group, X ⁴ is a fluorine atom or a chlorine atom, n is 0. The bisulfur sulfide compound according to (1).

[0011] (3) The biphenyl sulfide compound according to (1), wherein X ¹ is a hydrogen atom, X ² , X ³ and X ⁴ are fluorine atoms, and n is 1.

(4) The substituted biphenyl as described in (1) above, wherein X \ X ² and X ³ are fluorine atoms and n is 1 Sulfide compounds.

[0012] (5) General formula [Π] (X ⁵ is —B (OH), which is a useful production intermediate of the biphenylsulfide compound described in any one of (1) to (4) above. , Halogen atom or trifluoromethane

 2

 Represents a sulfo-loxy group).

 [0013] [Chemical 2]

[0014] (6) An insecticide / acaricide comprising the biphenylsulfide compound according to any one of (1) to (4) as an active ingredient.

 [0015] (7) Applying an effective amount of the biphenylsulfide compound described in any one of (1) to (4) above to control harmful insects, mites and Z or nematodes in the field of agriculture and horticulture. how to.

 (8) The method for controlling according to (7), wherein the mites are citrus mites.

 The invention's effect

 [0016] According to the present invention, it has high activity against various insects and Z or mites that are harmful in the field of agriculture and horticulture, and in particular it has excellent acaricidal activity against mandarin oranges, which are important pests of citrus fruits. There is provided a novel bisulfur sulfide compound having the formula: In addition, an insecticide containing a biphenylsulfide compound as an active ingredient and an effective amount of the biphenyl-sulfide compound are applied to control harmful insects, mites and Z or nematodes in the field of agriculture and horticulture. A method is provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

Next, specific examples of the compound of the present invention represented by the general formula [I] are shown in Table 1. The compound numbers in Table 1 may be cited in the following description.

[0018] [Table 1]

Compound number X ¹ X ² X ³ X ⁴ n Physical properties

1-1 Η C1 CI CI 0 Refractive index (n _D ^2Q ): 1.5833

1-2 Η C1 OCHF ₂ CI 0 Refractive index (n _D ^2D ): 1.5490

1-3 Η FFF 0 Refractive index (n _D ² °>: 1.5235

1-4 FFFH 0 Refractive index (n _D ² °>: 1.5210

1-5 Η F F F 1 Melting point: 104 ~ 105

1-6 F F F H 1 Melting point: 95-97 "C

1-7 Η C1 CHF ₂ F 0 Refractive index (n _D ^2D ): 1.5335

1-8 Η C1 Br F 0 Refractive index (n _D ^M ): 1.5887

1-9 Η C1 F CI 0 Melting point: 31 to 32: The compound of the present invention represented by the general formula [I] can be produced according to the production method shown below, and is not limited to these methods. Nah ...

 <Production method 1>

 The compound of the present invention represented by the general formula [Ia] can be produced by a method having the reaction process power exemplified below.

[0020] [Chemical 3]

 [IV] [Π +]

(Wherein X \ X ² , X ³ and X ⁴ represent the same meaning as described above, and L represents a halogen atom or trifluoro Represents an chloromethanesulfuroxy group. )

 [0021] (Process A)

 By reacting a compound represented by the general formula [III] with a compound represented by the general formula [Π-a] in a solvent in the presence of a base group and a transition metal catalyst, A compound represented by the formula [I a] can be produced.

[0022] The amount of the compound represented by the general formula [III] used here is preferably 0.8 to 10 mol, more preferably 1 mol of the compound represented by the general formula [Π-a]. Is 1 to 1.5 moles

[0023] (Process B)

 A compound represented by the general formula [IV] and a compound represented by the general formula [Π-b] are reacted in a solvent in the presence of a base group and a transition metal catalyst to give a compound of the present invention. formula

A compound represented by [I a] can be produced.

 The amount of the compound represented by the general formula [Π-b] used here is preferably 0.8 to 10 mol, more preferably 1 to 1 mol with respect to 1 mol of the compound represented by the general formula [IV]. 1. 5 moles.

 [0024] Transition metal catalysts used in Step A and Step B include palladium-activated carbon, palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tris (dibenzalacetone). Palladium compounds such as palladium, and nickel compounds such as bis (triphenylphosphine) nickel chloride and tetrakis (triphenylphosphine) -packet.

 [0025] The amount of the transition metal catalyst used is preferably 0.01 to 1 mol, more preferably 1 mol per 1 mol of the compound represented by the general formula [ΠΙ] or the compound represented by the general formula [Π-b]. Use 0.03 to 0.1 moles.

[0026] Examples of the solvent used in Step A and Step B include ethers such as jetyl ether, tetrahydrofuran (THF), and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and black benzene; N , N Dimethylformamide (DMF), N, N Dimethylacetamide, N-Methyl-2-pyrrolidone, Dimethylsulfoxide, Sulfolane and other aprotic polar solvents; Acetonitrile, propio-tolyl and other tolyls; Ethyl acetate And esters such as ethyl propionate; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane; protic solvents such as water and ethanol; and mixed solvents thereof.

 [0027] The amount of the solvent used in the above is 0.1 to 100 liters per 1 mol of the compound represented by the general formula [III] or the compound represented by [Π-b]. More preferably, it is 1.0 to 5.0 liters.

 [0028] 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 water such as calcium hydroxide and magnesium hydroxide. Acid salts; carbonates of alkali metals such as sodium carbonate and potassium carbonate; inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydrogen such as sodium hydride and potassium hydride Compounds; alcohol metal salts such as sodium methoxide, sodium methoxide, 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.

 [0029] The amount of the base used may be 1 to 4 mol per 1 mol of the compound represented by the general formula [ΠΙ] or the compound represented by [Π-b]. More preferably, it is 1.5-2 mol.

 [0030] The reaction temperature may be selected in an arbitrary range from 70 ° C to the reflux temperature in the reaction system, and is preferably in the temperature range of -20 ° C to 150 ° C.

 [0031] 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.

 [0032] <Production method 2>

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

[0033] [Chemical 4]

(Wherein X ¹ , x ² , x ³ and x ⁴ represent the same meaning as described above.)

[0034] By reacting the compound represented by the general formula [Ia] and an oxidizing agent in a solvent in the presence or absence of a catalyst, the compound of the present invention represented by [Ib] Can be manufactured.

[0035] Examples of the oxidizing agent include hydrogen peroxide, m-peroxybenzoic acid, perbenzoic acid, sodium peroxyphosphate, and oxone (OXONE, i-i 'DuPont's trade name; potassium peroxosulfate, hydrogen hydrogen Content), N chlorosuccinimide, N bromosuccinimide, tert butyl hypochlorite, sodium hypochlorite and the like.

[0036] The amount of the oxidizing agent used here is preferably 1 to 6 mol, more preferably 1 mol, per 1 mol of the compound represented by the general formula [I a].

[0037] Examples of the catalyst include sodium tungstate.

 Here, the amount of the catalyst used is preferably 0.001 to 1 monolayer with respect to 1 mol of the compound represented by the general formula [Ia]. More preferably, it is from 0.01 to 0.05 mono.

[0038] The solvent to be used is not particularly limited as long as it does not inhibit the reaction, for example, halogenated alkanes such as black mouth form, dichloromethane and dichloroethane; aromatic hydrocarbons such as black mouth benzene and trifluoromethylbenzene; Mention may be made of acetic acid.

[0039] The amount of the solvent used is preferably 0.1 to: LO with respect to 1 mol of the compound represented by [I a].

0 liters. More preferably, it is 1.0 to 5.0 liters.

[0040] The reaction temperature may be selected from an arbitrary range force from 30 ° C to the reflux temperature in the reaction system, and is preferably in the temperature range of -10 ° C to 20 ° C.

[0041] The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but preferably a force in the range of 10 minutes to 20 hours can be selected.

[0042] Next, Table 2 shows specific examples of the intermediate product of the biphenylsulfide compound of the present invention. [0043] [Table 2]

[0044] When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, the compound of the present invention itself may be used, but a carrier generally used for formulation as an agrochemical adjuvant, Contains surfactants and other adjuncts, emulsions, suspensions, powders, granules, tablets, wettable powders, aqueous solvents, liquids, flowable powders, granular wettable powders, aerosols, pastes, oils It can be formulated into various forms such as an agent, an emulsion, and a smoke agent. These blending ratios are preferably 0.190% by weight of the active ingredient and 109.99% by weight of the agricultural chemical adjuvant.

 [0045] Carriers used in the formulation are classified into solid carriers and liquid carriers. Solid carriers include, for example, 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 inorganic powders such as urea. Examples of liquid carriers 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 (THF); kerosene, light oil, and the like. Aliphatic hydrocarbons: xylene, trimethylbenzene, tetramethylbenzene, methylnaphthalene, solvent naphtha and other aromatic hydrocarbons; halogenated hydrocarbons such as black benzene; N, N-dimethylacetamide, etc. Acid amides; esters of fatty acids such as glycerin esters; -tolyls such as acetonitryl; and sulfur-containing compounds such as dimethyl sulfoxide.

[0046] Surfactants include, for example, alkylbenzene sulfonic acid metal salts, dinaphthyl methane disulfonic acid metal salts, alcohol sulfate esters, alkyl aryl sulfonates, lignite sulfonates, polyoxyethylene glycol ethers, polyoxyethylenes. Examples thereof include salts of alkylaryl ether, polyoxyethylene sorbitan monoalkylate, naphthalenesulfonic acid formalin condensate, and the like.

 [0047] Other adjuvants include, for example, carboxymethylcellulose, gum arabic, sodium alginate, guar gum, tragacanth gum, polyvinyl alcohol, and other sticking agents or thickeners, antifoaming agents such as metal sarcophagus, fatty acids, Physical property improvers such as alkyl phosphates, silicones and paraffins, colorants and the like can be used.

 [0048] 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. Various preparations containing the compound of the present invention, or dilutions thereof, are usually applied by a commonly used application method, that is, spraying (for example, spraying, misting, atomizing, dusting, dusting, water surface application, box application) Application), soil application (eg, mixing, irrigation, etc.), surface application (eg, application, powder coating, coating, etc.), immersion, poison bait, and smoke application. It is also possible to feed livestock with the above-mentioned active ingredient mixed with 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 it is preferably 0.1 to 20% by mass in the case of powders and granules, and preferably 1 to 80% by mass in the case of emulsions and wettable powders. Is appropriate.

 [0049] 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 not limited to the force used at an amount of preferably 0.1 to 5000 g per lha as the active ingredient compound.

 [0050] Needless to say, the compound of the present invention alone is sufficiently effective, but if necessary, other fertilizers, agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, It can be used in combination with antiviral agents, attractants, herbicides, plant growth regulators, etc., and in this case, even better effects may be shown.

Here, other pesticides that can be mixed or used together are exemplified below. Chlorfenavir, abamethatin, emamethatin, bromopropyrate, bistrifnorerone, chlorfluururon, difluvensulon, fullcycloxuron, furfenoxuron, hexaflum Ron, Norefenuron, Novaluron, Novifnoremuron, Teflubensulon, Triflumuron, Aldicarp, Bendayo Calp, Benfuracarb, Force Rubaril, Carbofuran, Carbosulfan, Etiofen Calp, Fuenocarp, Formethanate, Fraciocarp, Mesopromil, Mesopromil , Pirimicarb, propoxyl, trimetacarp, XMC, xylylcarp, triazamate, chlorden, endosulfan, chromaphenoid, halophenozide, methoxyphenozide, tebufenozide, bensultap, cartap, thiocyclam, thiosultap, ethiprole, fipronil, phenol Plane, quinoprene, methoprene, pyriproxyfen, fu Nazakin, fenpyroximate, pyridaben, tebufenvirad, clofentezine, etoxazol, hexathiazotas, acetamiprid, clothiazidine, dinotefuran, imidacloprid, ditenviram, thiacloprid, thiamethoxam, etofenprox, halfenprofens Acetephate, azamethiphos, azinphos 'ethyl, azinphos' methyl, kazusafos, chloroethoxyphos, chronorefenbinphos, chlormefos, chlorpyrifos, chlorpyrifos'methyl, coumaphos, cyanfos, demeton 'S' methyl, diazinon, dichlorvos, dicrotophos, dimethoate, Dimethylvinphos, disulfoton, EPN, ethion, etoprophos, famful, fenamiho , Fenitrothion, fenthion, phosthiazete, heptenofos, isocarbophos, isoxathion, malathion, mecarbam, methamidophos, metidathion, mevinphos, monocrotophos, nared, ometoate, oxydimethone 'methyl, parathion, parathion' methyl, fentoate, folate, phosphatophos , Phoxime, pyrimifos' methyl, profenofos, propetamfos, prochifos, pyracrofos, pidafenci, quinanorefos, sulfotepe, tebupyrimfos, temefos, terbufos, tetrachlorbinphos, thiometone, triazophos, trichronolephone, nomidion, Cihexatin, phenbutanthin oxide, aranicarp, butocarboxy , Butoxycarboxyme, thiozi, rub, thiophanox, acrinathrin, allethrin, alpha-cypermethrin, beta 'cynoretrin, beta-cypermethrin, bifenthrin, bi-areslin, violesmethrin, cycloprotorin, cynoretrin, cyhalothrin Cyphenothrin, denoretamine, empentrin, esfenvalerate, fenpronotrin, fenvalerate, full Citrinate, Funoremethrin, Gamma'Cyhalothrin, Imiprothrin, Lambda'Cyhalothrin, Methrin, Permethrin, Phenothrin, Praretrin, Resmethrin, Taufluvalinate, Tefluthrin, Tetramethrin, Tetramethrin, Zeta'Cipermethrin, Tralomethrin, Transflutrizein Cypermethrin, ZXI-8901, Pymetrozine, Acequinosinore, Acetopro Monore, Imisiafos, Indoxacarp, Quinomethionate, Sanobirafen, Dienochlor, Difluvidazine, Sifnoremethofene, Spiromethifene, Spirodiclofen, Spirotetramat, Tolphira , Bifenazate, pyrafluprolol, pyridalyl, pyriprole, fluclipirim, fluazinam, flupirazofos, Didiamide, flurimphene, buprofin, floni force amide, metaflumizone, linaxyl, repimectin, CL900167, XDE-175.

 These pesticides are, for example, The Pesticide Manual, 1st 3rd Edition [British Crop Protection Council, 2004], Shibuya Index 10th Edition, The force described in the 11th edition (SHIBUYA INDEX 10th Edition, 11th Edition, Publisher: SHIBUYA INDEX Study Group) is a publicly known one.

 [0051] The compound of the present invention is a semilepidopterous insect, lepidopterous insect, coleoptera insect, diptera insect, hymenopteran insect, straight-eye insect, termite insect, azamuma insect, hada, plant Excellent control effect against pests such as parasitic nematodes. Examples of such pests include the following pests.

[0052] Hemiptera pests, for example, Riptortus clavatus, Nez ara viridula, Lygus sp., Blisssus leu copterus, Stephanitis nashi ) And other stink bugs (heteroptera; heteroptera); (Sogatella forcifera), sea cucumbers such as Laodelphax striatellus, killer whales such as Ps ylla sp. ), Peach aphid (Myzus persicae), apple aphid (Aphis pomi), ヮ Aphids such as aphis (Aphis gossypii), Aphis fabae, black radish aphids (Rhopalosiphum ps edobrassicas), potato aphids (Aulacorthum solani), wheat aphids (Schizaphis graminum), oc rubens), San Jose scale insects (Comsto ckaspis perniciosa), silkworm rotifers such as the fieldworm worm (Unaspis yanonensis), and the sand turtle (Rhodnius sp.).

Lepidopterous pests such as Homona magnanima, Adoxop hyes orana, Anguinoma = (Sparganothis pillenana), Nanhimeme squirrel (urapholitha molesta), Ma, No, Nokui 7J (Leguminivora glycinivorella), aspor 7 ), Eucosma sp. ゝ Lobesia botrana, etc., Grape Hosono ヽ Maki (Eupoe cillia ambiguella), etc., Bambalina sp. Etc. Minoka, Nekopo (Nemapog on granellus), Iga (Tinea translucens), etc. Common moths, Common moths such as Lyo netia prunifoliella, Common moths such as Phyllonorycter rigoniella, Common moths such as Phyllocnistis citrella, Plu tella xys , Grape scab (Paranthrene regalis), Synanthedon sp. hora gossypiella), potato moth (Phthorimaea operculella), Stomopteryx sp. medinalis, Ostnnia nubilalis, ostrichia fornacalis, yellowtail moth (Hellula undalis), honey honey (Eualmoria mellonella), Eiasmopalpus lignoselms, Loxostege sticticalis, etc. (Asco tis selenaria), Prunus moth (Malacosoma neustria), Kalehaga (Manauca sexta), Sueda swords (Euproctis pseudoconspersa), Douguga (Lymantria dispar), cunea), Tanoconod ヮ¹ ~~ mu (Helio this virescens), Bore ~~ Norewa ~~ Mu (Helicoverpa zea), Nro Timosho-to (Spodoptera exigua), Otano, Helicopa (Helicoverpa armigera), Spodoptera litura, Mamestra brassicae (Mamestra brassicae), Agrotis ipsiron), Pseudaletia separata, Trichoplusia ni, etc.

[0054] Coleopterous pests, for example, Anomala cuprea, bean pupae (Popillia japo nica), himeko! (. Agriotes sp) not (Anomala rufocuprea), co-7 Nemushi such as Eutheola rugiceps, Wa Iyawamu, click beetles such Conodeus sp, etc., -. Jiyuuyahoshiten ^door, Roh (Epilachna vigintioctopunctata Roh, Ί Sindelfingen Anne toe insect (Epilachnavanvestis), etc. Ladybirds, Tribolium castaneum and other beetles, sesame squirrels ^ ³ r, noplophora malasiaca), pine beetles ^ ³ r (Monochamus alternatus) and other longhorn beetles Bean beetles such as calli (Callosobruchus chinensis), Colorado worm (Leptinotarsa d ecemlineata no, Koburu ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ (Diabrotica sp.), Noemun (Chaetocnema concinna ^ Phaedon cochleanas, Oulema m elanopus, Dicladispa armigera and other bugs, Apion godmani and others Chizoumu down such, Ί Ne Zuzowamun (Lissorhoptrus oryzophilus, Watamizoumun (Anthonomus gr andis) Zoumushi such as, Osazoumushi such as Kokuzoumushi (Sitophilus zeamais), wooden pile insects, Katsuobushimushi class, beetles, and the like.

 [0055] Diptera pests, for example, Tipra ano, Inanyuris (Tanytarsus oryza e), Inseolia oryzae, Ceratitis capitata, Hydrellia griseola, Drosophila suzukii, Fritz fly (Oscinella frit), Rice flies (chlorops oryzae), Common beetle (Ophiomyia phaseoli), Bumble beetle (Liriomyza trifolii), Pyomya hyacinth (os) Tanenoe (Hylemia platura, Sonore; V Mufufi (Athengona soccata), Yenoe (Musca domestica), Kumanoe (Gastrophilus sp.), Sasinoye (St omoxys sp.), Aedes aegypti, Culexa (Culex) pipiens), Shichoha Madaf force (Anopheles sinensis), Cucatakayae force (Culex tritaeniorhynchus), etc.

[0056] Hymenopteran pests, for example, Cephus sp., Harmolita sp., Athalia sp., Vespa _sp ., Fire Iant and the like.

[0057] Diptera, for example, Blatella germanica, Peripla neta americana), Kera (Gryllotalpa africana), Notta (Locusta migratoria migratori odes), Melanoplus sanguinipes, etc.

[0058] Termite insect pests, for example, reticulitermes speratus, termite termosanus and the like.

[0059] Azamuma pests, for example, Scirtothrips dorsalis, Thrips palmi, Helothothrips haemorrhoidalis, Frankalis, Kudaazamuma (Haplothrips acul eatus) etc.ο

[0060] Acarid mites, such as Nami Hada (Tetranychus urticae), Kanza Hada (Tetranychus kanzawai), Kanony Tani (Panonychus citri), Rincono Tani (Panonychus ulmi), Erotic ■ ~ "Mite (Eotetranychus carpin , ^{3 3} r Susunthusmite (Eotetranychus banksi), Misunsabitani (Phyllocoptruta oleivora), Chiyanokokoritani (Polyphagot ars onemus latus), Himeno mite (Brevipalpus sp.), Robinneda-(Rhizoglyphus robinigus), escent ),etc.

 [0061] Plant-parasitic nematodes, such as Meloidogyne sp., Pratylenchus sp., Dizzyst (Heterodera glycines, Globodera rostochiensis) ), Bananamemo Sentiyu (Radopholus similis), Strawberry Sentiyu (Aphelenchoides fragariae), Rice Singale Sentiyu (.Aphelenchoides besseyi no, Bursaphelenchus xylophilus) and the like.

 [0062] Other harmful animals, unpleasant animals, sanitary pests, parasites such as gastropods such as Pomacea canaliculata, slugs (Incilaria sp.), African maimai (Achatina fiilica), armadillidium sp .), Isopods such as mussel, centipede etc. Usopoda), scallops such as Liposcelis sp., Stains such as Ctenolepisma sp., Such as Pule X sp. And tenocephalides sp. Examples include bed bugs such as nymphs, imex sp., Animal parasitic mites such as Boophilus microplus, Haemaphy sails longicornis, and ticks.

[0063] Furthermore, it is also effective against pests that are resistant to organophosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, acylurea compounds, or existing insecticides. Example

 Next, the present invention will be specifically described with reference to examples. The method for producing the synthetic intermediate of the compound of the present invention is also described.

[0065] Example 1

 [4 Fluoro-2-methyl-5- (3, 4, 5 Triclonal Methyl) Fuel] — 2, 2, 2 —Trifluoroethylsulfide (Compound No. I-1):

 2 Fluoro-4-methyl-5- (2, 2, 2 trifluoroethylthio) benzeneboronic acid 0.6 g, 1-bromo 3, 4, 5 Trichlorobenzene 0.58 g, sodium carbonate 0.5 g, tetrakis (Trife -Luphosphine) A mixture of 0.13 g of palladium, 50 ml of tetrahydrofuran and 50 ml of water was heated to reflux for 2 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate, the organic layer was 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: n— Hexane) to obtain 0.85 g of oily [4 fluoro-2-methyl-5- (3,4,5 trichlorophle) phenol] 2,2,2 trifluoroethylsulfide (Yield 94%).

 1H—NMR data (CDC1 / TMS δ (ppm) value)

 Three

 2.53 (3H, s), 3.33 (2H, q), 7.08 (lH, d), 7.53 (2H, s), 7.58 (lH, d)

[0066] Example 2

[5- (4 Difluoromethoxy-1,3,5-dichlorophenyl) 4 Fluoro-2-methylphenyl] 2, 2, 2-Trifluoroethylsulfide (Compound No. 1-2) Production: 1-bromo-3,5 dichloro-4-difluoromethoxybenzene 0.65 g, 2 fluoro 4-methyl-5- (2, 2, 2 trifluoroethylthio) benzeneboronic acid 0.6 g, sodium carbonate 0.5 g Then, a mixture of tetrakis (triphenylphosphine) palladium (0.13 g) and water (50 ml) was heated to reflux for 2 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate, the organic layer was 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: n— Hexane) and purified oily [5- (4 difunoleolomethoxy-1,3,5-dichlorophenol) 4-funoleoro 2-methylphenol] 2, 2, 2 trifluoroethylsulfide 0.82 g (91% yield). 1H—NMR data (CDC1 / TMS δ (ppm) value) 2.53 (3H, s), 3.34 (2H, q), 6.64 (lH, t), 7.08 (lH, d), 7.52 (2H, s), 7.57 (lH, d)

[0067] Example 3

 [4 Fluoro-2-methyl-5- (3, 4, 5 trifluorophenyl) phenol] Preparation of 2, 2, 2-trifluoroethylsulfide (Compound No. I-3):

 2 Fluoro-4-methyl-5- (2,2,2 trifluoroethylthio) benzeneboronic acid 1. Og, 1-bromo 3, 4, 5 trifluorobenzene 0.72 g, sodium carbonate 0.80 g, tetrakis (triphenyl) -Luphosphine) A mixture of 0.2 g of palladium, 50 ml of tetrahydrofuran and 50 ml of water was heated to reflux for 2 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate, the organic layer was 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: n— [4 Fluoro-2-methyl-5- (3, 4, 5 trifluorophenyl) phenol] —2, 2, 2 trifluoroethylsulfide 1. lg (Yield 85%)

[0068] Example 4

 [4 Fluoro-2-methyl-5- (3,4,5 trifluorophenyl) phenol] Preparation of 2,2,2 trifluoroethyl sulfoxide (Compound No. I-5):

 [4 Fluoro-2-methyl-5- (3,4,5 trifluorophenol) phenol]-2, 2, 2 trifluoroethylsulfide 0.55 g synthesized by the method of Example 3 The resultant was dissolved in 2 Oml, and 0.27 g of m-chloroperbenzoic acid was added at room temperature over 15 minutes, followed by further reaction for 1 hour. The reaction mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. [4 Fluoro-2-methyl-5- (3, 4, 5-trifluorotrifluoro ) Fuel] 2,2,2 Trifluoroethyl sulfoxide 0.55 g was obtained (yield 97%).

[0069] Example 5

 [4 Fluoro-2-methyl-5- (2, 3, 4 trifluorophenyl) phenol] Preparation of 2, 2, 2 trifluoroethylsulfide (Compound No. (I-4)):

2 Fluoro-4-methyl-5- (2,2,2 trifluoroethylthio) benzeneboronic acid 1.0 g, 1-bromo 2,3,4 trifluorobenzene 0.72 g, sodium carbonate 0.80 g, tetrakis (triphenyl) -Luphosphine) palladium 0.2g, tetrahydrofuran 50ml, water 50m The mixture of 1 was heated to reflux for 2 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate, the organic layer was 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: n— [4 Fluoro-2-methyl-5- (2, 3, 4 trifluorophenyl) phenol] —2, 2, 2 trifluoroethylsulfide 0.95 g (Yield 73%).

[0070] Example 6

 [4 Fluoro-2-methyl-5- (2,3,4 trifluorophenyl) phenol] Preparation of 2,2,2-trifluoroethyl sulfoxide (Compound No. (I-6)):

 [4 Fluoro-2-methyl-5- (2,3,4 trifluorophenol) phenol] 2, 2, 2 trifluoroethylsulfide synthesized by the method of Example 5 0.5 g After dissolving in 20 ml, 0.25 g of m-chloroperbenzoic acid was added at room temperature over 15 minutes, and further reacted at room temperature for 1 hour. The reaction mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. [4 Fluoro-2-methyl-5- (2, 3, 4, trifluorophenyl) Phenyl] 0.5 g of 2,2,2 trifluoroethyl sulfoxide was obtained (yield 94%).

[0071] Example 7

 [4-Fluoro-2-methyl-5- (3--dichloromethyl-5-fluoro) phenol] — 2, 2, 2 Preparation of trifluoroethylsulfide (Compound No. 1-7): Fuming nitric acid To 69 g, 29.9 g of 2 6-fluorobenzaldehyde was added at 0 ° C for 15 minutes, and the mixture was allowed to stir at room temperature for 16 hours. The reaction mixture was poured into cold water, extracted with ethyl acetate, and the organic layer was 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 obtain 23.2 g of 2-chloro-3-fluorobenzene.

2 Black mouth 6 Fluoro 3-trobenzaldehyde 23.2 g was dissolved in 300 ml of methanol, 40.6 g of tin was added, and 100 ml of concentrated hydrochloric acid was added dropwise over 30 minutes. After cooling to room temperature, the reaction mixture was neutralized with 25% aqueous sodium hydroxide solution, and insolubles were filtered off. The filtrate was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 3 amino-2chloro-6fluorobenzaldehyde dimethyl alcohol was removed. Settal 20.2 g was obtained.

 6-Fluorobenzaldehyde dimethyl acetal (20.2 g), N, N dimethylformamide (100 ml) was dissolved in 1-chloro (N-bromosuccinimide) (16.4 g) and stirred at room temperature for 30 minutes. The reaction mixture is poured into water, extracted with ethyl acetate, the organic layer is dried over anhydrous magnesium sulfate, and the solvent is distilled off under reduced pressure. 25.8 g of benzaldehyde dimethylacetal were obtained.

 3-Amino 4 Bromo 2 Black mouth 6 Fluorobenzaldehyde Dimethylacetal 25. 8 g is dissolved in N, N-dimethylformamide 90 ml, t-butyl nitrite 12. Og at 50 ° C for 15 min. The solution was added dropwise and further stirred for 30 minutes. The reaction solution was poured into water, extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 4 bromo-2 chloroform 6 fluorbenzaldehyde dimethyl acetal. 8. 7g was obtained.

 4-Bromo 2 black 6 Fluorobenzaldehyde dimethylacetal 8.7 g, ethanol 20 ml and concentrated hydrochloric acid 5 ml were heated to reflux for 6 hours. After cooling at room temperature, water was added, extraction was performed 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 to obtain 4.7 g of 4-bromo-2-chlorobenzene-6-fluorobenzaldehyde.

 4-Bromo 2 Black mouth 6 Fluorobenzaldehyde 4.7 g dissolved in 50 ml dichloromethane, 3.9 g Jetylaminosulfur trifluoride was added over 15 minutes at room temperature and stirred for 1 hour. . The reaction mixture was poured into water, extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 4.lg of 5-bromo-1-chlorodi-2-difluoromethyl-3-fluorobenzene.

5 Bromo-1—Black 2 Difluoromethyl-3 fluorobenzene 0.78 g, 2-fluoro-4-methyl-5- (2, 2, 2 trifluoroethylthio) benzeneboronic acid 0.80 g tetrakis (triphenylphosphine) palladium A mixture of 0.31 g, sodium carbonate 0.64 g, tetrahydrofuran 50 ml and water 50 ml was heated to reflux for 3 hours. After cooling to room temperature, the organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (elution solvent: n-hexane), and [4-Fluoro-2-methyl-5- (3-chlorodiethyl 4-difluoromethyl 5-fluorophenol) phenol] 2, 2, 2 Trifluoroethylsulfide 1. Og (84% yield) was obtained.

1H-NMR data (CDC1 / TMS δ (ppm) value) is shown below.

 Three

 2.54 (3H, s), 3.34 (2H, q), 7.09 (lH, t), 7.10 (lH, d), 7,25 (lH, d), 7.40 (lH, d), 7.60 (lH, d) Example 8

 Preparation of (5-bromo-4-fluoro-2-methylphenol) -2, 2, 2 trifluoroethylsulfide (intermediate compound number II 1):

To 40 g of chlorosulfonic acid, 20 g of 4 bromo 3 fluorotoluene was added so that the temperature in the system was maintained at 50 to 60 ° C., and further reacted at 50 to 60 ° C. for 1 hour. After allowing to cool, it was poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 29 g of 5 bromo 4 fluoro 2 methylbenzenesulfur chloride. Acetic acid (300 ml) was added to the obtained sulfo-urel chloride, and then red phosphorus (6.3 g) and iodine (0.5 g) were added, followed by heating under 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 extracted with ethyl acetate, washed with saturated brine, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give 5-bromo-4-fluoro-2-methyl-1-acetylthiobenzene. 26. 6g was obtained. This thiobenzene was dissolved in 300 ml of methanol, 100 ml of an aqueous potassium hydroxide (10%) solution was added, and the mixture was stirred at 50 ° C. for 30 minutes and neutralized with hydrochloric acid. 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 19.8 g of 5 bromo-4-fluoro-2-methylbenzenethiol. This thiol was added to 250 ml of N, N dimethylformamide, and further added with 13.6 g of potassium carbonate, 28 g of 2,2,2-trifluoro 1-3-doethane and 3.2 g of Rongalitz and reacted 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, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (elution solvent: Purification with n-hexane) gave 25. lg of (5-bromo-4 fluoro-2methylphenyl) -2,2,2 trifluoroethylsulfide (yield 93%). 1H-NMR data (CDC1 / TMS δ (ppm) value) is shown below.

 Three

 2.44 (3H, s), 3.33 (2H, q), 7.02 (lH, d), 7.70 (lH, d)

[0073] Example 9

 2 Fluoro-4-methyl-5- (2, 2, 2 trifluoroethylthio) benzeneboronic acid (intermediate compound number II-2):

 5 Bromo-4 fluoro-2 methylphenol 2, 2, 2 trifluoroethyl sulfide synthesized by the method of Example 8 was charged with 25 ml of dry ether under a nitrogen stream, and cooled to −60 ° C. with 350 ml of dry ether. . Under a nitrogen stream, 53.8 ml of n-butyllithium (n-hexane solution, 1.54 mol ZL) was added dropwise to the mixture over 15 minutes. After 5 minutes, a solution of trimethoxyborane 8.6 gZ in 50 ml ether was added dropwise over 10 minutes. The temperature was raised, and a 16 g Zl00 g aqueous solution of sulfuric acid was added dropwise at around 20 ° C, and the mixture was reacted at room temperature for 2 hours. The reaction mixture was separated, the organic layer was washed with saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and 2 fluoro-4-methyl-5- (2, 2, 2 Trifluoroethylthio) benzeneboronic acid 18. Og was obtained (yield 81%).

 [0074] Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and adjuvants are not limited to these, and can be changed over a wide range. In the following description, “part” means part by mass.

 [0075] Example 10

 Formulation Example 1 Emulsion

 Compound No. (I 1) 30 parts

 Cyclohexanone 20 parts

 11 parts of polyoxyethylene alkyl ether ether

 Calcium alkylbenzenesulfonate 4 parts

 Methylnaphthalene 35 parts

 The above was dissolved uniformly to obtain an emulsion. In addition, an emulsion can be obtained in the same manner using each of the compounds shown in Table 1 instead of the compound number (1-1).

[0076] Example 11

Formulation example 2 wettable powder Compound No. (I 1) 10 parts

 Naphthalenesulfonic acid formalin condensate sodium salt 0.5 part

 Polyoxyethylene alkyl ether ether 0.5 part

 Diatomaceous earth 24 parts

 Clay 65 咅

 The above was mixed and ground uniformly to obtain a wettable powder. In addition, a wettable powder can be obtained in the same manner using each of the compounds shown in Table 1 instead of the compound number (1-1).

[0077] Example 12

 Formulation Example 3 Powder

 Compound No. 2 of Compound No. (I 3)

 Diatomaceous earth 5 parts

 Clay 93 咅

 The above was uniformly mixed and ground to obtain a powder. In addition, powders can be obtained in the same manner using each of the compounds listed in Table 1 instead of Compound No. (I 3).

[0078] Example 13

 Formulation Example 4 Granules

 Compound No. 5 (I 3)

 Sodium salt of lauryl alcohol sulfate 2 parts

 5 parts sodium sulfonate sulfonate

 Canoleboxymethinorescenellose 2 parts

 Clay 86 咅

 The above was mixed and ground uniformly. The mixture was kneaded with an equivalent amount of 20 parts of water, and after crushing to 14-32 mesh granules using an extrusion granulator, it was dried to give granules. Further, a granule can be obtained in the same manner using each of the compounds shown in Table 1 instead of the compound number (I 3).

 [0079] Next, the effect of the insecticidal 'acaricide containing the compound of the present invention as an active ingredient will be described with reference to test examples.

[0080] Test Example 1 Acaricide test of citrus red mite A citrus leaf disc on an agar medium was inoculated with an adult mandarin mite mite. After 24 hours, the wettable powder of the reagent provided in accordance with Formulation Example 2 was diluted to a predetermined concentration, and this diluted solution was sprayed on a leaf disk (spraying amount 2 mg / cm ² ). Placed in a constant temperature room at 25 ° C for 2 days after treatment, the number of live insects was examined, and the death rate was calculated using the formula (1). The test was conducted in a single run. The results of this test are shown in Table 3.

 The comparative compounds (a), (b), (c), (d), and (e) used were the compound numbers [1-356] exemplified in JP-A-2000-198768, respectively. ], [1-358], [1-361], [I 414] and [I 599].

 [0081] [Chemical 5]

[0082] [Equation 1] Number of surveyed adults in treatment area

 Death rate (%) =

Number of pre-treatment adults in treatment area

[0083] [Table 3] Compound number Concentration (ppm) Mortality (%)

 6.25 100

 I one 1

 1.56 100

 6.25 95

 I 1 2

 1.56 86

 6.25 96

 I one 5

 1.56 82

 6.25 97

 I one 6

 1.56 91

 6.25 100

 I 1 7

 1.56 93

 6.25 93

 I 1 8

 1.56 87

 6.25 95

 Comparative compound a

 1.56 25

 6.25 20

 Comparative compound b

 1.56 0

 6.25 53

 Comparative compound c

 1.56 8

 6.25 0

 Comparative compound d

 1.56 0

 6.25 31

 Comparative compound e

 1.56 19

[0084] Test Example 2 Namihada two control test (immersion treatment)

 A wettable powder prepared according to Formulation Example 2 was diluted with water to a predetermined concentration. Soybean seedlings previously inoculated with Namihada-adult were dipped in the chemical and air-dried. The treated soybean seedlings were placed in a thermostatic chamber at 25 ° C, and after 13 days, the number of surviving insects was examined, and the control value was calculated by the formula of formula 2. The test was conducted in a single run. The results of this test are shown in Table 4.

 [Equation 2]

[0085] [Table 4] Compound number Concentration (ppm) Control value

 I 1 1 500 100

 I-2 500 100

 I one 5 500 100

 I 1 6 500 100

 I one 7 500 100

 I 1 8 500 100

 I 1 9 500 100

 Comparative compound a 500 100

 Comparative compound b 500 100

 Comparative compound c 500 100

 Comparative compound d 500 100

 Comparative compound e 500 100

[0086] Test Example 3 Tobiroronka insecticidal test

 A wettable powder prepared according to Formulation Example 2 was diluted with water to a predetermined concentration. Rice buds and rice bran were immersed in the chemical solution and placed in a plastic cup with a capacity of 60 ml. To this, 10 3rd-instar larvae were released, covered and placed in a constant temperature room at 25 ° C. Six days later, the number of surviving insects was counted, and the dead insect rate was determined by the formula of Formula 3. The test was conducted on a continuous basis. The results of this test are shown in Table 5.

[0087] [Equation 3] Ishi-. _{I l} , 10 — Number of living insects in the treatment area

 Mortality (%) = X 100

[0088] [Table 5] Compound number Degree ψρπυ Mortality (%)

 I one 5 500 100

 I 1 6 500 100

 I 1 9 500 100

 Comparative compound a 500 90

 Comparative compound b 500 100

 Comparative compound e 500 100 Industrial applicability

 The novel bifusulsulfide compound of the present invention has high activity against various harmful insects and moths or mites, and in particular, has excellent acaricidal activity against citrus mite mite, which is an important citrus pest. It is widely used in the field of agriculture and horticulture as an active ingredient of insecticides. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application 2005-273483 filed on September 21, 2005 are cited here as disclosure of the specification of the present invention. Incorporated.

Claims

Claim General Formula [I]

 [Chemical 1]

(n represents 0 or 1,

X ¹ represents a hydrogen atom or a halogen atom, X ² represents a halogen atom, and when X ¹ is a hydrogen atom, X ³ represents a halogen atom, a difluoromethyl group or a difluoromethoxy group, and X ⁴ represents a halogen atom. When X ¹ is a halogen atom, X ³ is a halogen atom and X ⁴ is a hydrogen atom. ) Bisulfursulfide compound represented by

[2] X ¹ is a hydrogen atom, X ² is a chlorine atom, X ³ is a chlorine atom, a difluoromethyl group or a difluoromethoxy group, X ⁴ is a fluorine atom or a chlorine atom, and n force The bisulfur-sulfide compound according to claim 1, which is ^.

[3] The bisulfursulfide compound according to claim 1, wherein X ¹ is a hydrogen atom, X ² , X ³ and X ⁴ are fluorine atoms, and n is 1.

[4] The bisulfide compound according to claim ¹ , wherein X ¹ , X ² and X ³ are fluorine atoms, and n is 1.

[5] of claims 1 to 4, according to whether the deviation Bifuwe - Formula a production intermediate of Rusurufuido Compound [[pi] (wherein, X ⁵ is - B (OH), halogen atom or triflate Ruo b methanesulfonyl -Le

 2

 A phenylsulfide compound represented by the formula:

[Chemical 2]

[6] An insecticide / acaricide containing the biphenylsulfide compound according to any one of claims 1 to 4 as an active ingredient.

 [7] Applying an effective amount of the bisulfursulfide compound according to any one of claims 1 to 4.

A method for controlling harmful insects, mites and Z or nematodes in the field of agriculture and horticulture.

[8] The method for controlling according to claim 7, wherein the mites are mandarin oranges and mites.