JP5442048B2 - Method for producing biphenyl sulfide compound - Google Patents

Description

  The present invention relates to a method for producing a novel biphenyl sulfide compound and a production intermediate for producing the same.

  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 urticae, the activity against citrus mite, which is an important pest of citrus fruits, 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 method for producing a compound having excellent acaricidal activity against citrus mite which is an important pest of citrus fruits.

  In order to develop an insecticide / acaricide having the above-mentioned preferable properties, the present inventors have synthesized various biphenyl sulfide compounds not described in Patent Document 1 and repeatedly studied their insecticide / acaricide activity. It was. As a result, in (4-fluoro-2-methylphenyl) -2,2,2-trifluoroethyl sulfide, 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 mites, and in particular, has excellent acaricidal activity against citrus red mite, thus completing the present invention.

That is, this invention consists of the summary characterized by the following.
( 1 ) Compound represented by the following general formula [III] (wherein L represents a halogen atom or a trifluoromethanesulfonyloxy group, X ¹ represents a hydrogen atom or a halogen atom, X ² represents a halogen atom, X ^{When 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 And a phenyl sulfide compound represented by the following general formula [II-a] in a solvent in the presence of a base and a transition metal catalyst, and a compound represented by the following general formula [Ia] ^{(wherein, X 1, X 2, X} 3, X 4 are the same. the compound represented by the general formula [III]) biphenyl sulfide compound, characterized by the production of Production method.

(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, the (1) A method for producing a biphenyl sulfide compound as described in 1. above.
( 3 ) A compound represented by the following general formula [IV] (wherein 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, X ⁴ represents a halogen atom, and when X ¹ is a halogen atom, X ³ represents a halogen atom and X ⁴ represents a hydrogen atom) and the following general formula [II-b] And a phenyl sulfide compound (wherein L represents a halogen atom or a trifluoromethanesulfonyloxy group) in a solvent in the presence of a base and a transition metal catalyst, the following general formula [Ia compound ^{(wherein, X 1, X 2, X} 3, X 4 are the same. the compound represented by the general formula [IV]) represented by] biphenyl sulfide reduction, characterized in that to produce the Method of manufacturing a thing.

(4) ^{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, the (3) A method for producing a biphenyl sulfide compound as described in 1. above.
(5) the (2) to the following general formula in the production method according to any one of (4) [I-a] a compound represented by (wherein, ^{X 1} is a hydrogen atom or a halogen atom, ^{X 2} is When X ¹ is a hydrogen atom, X ³ is a halogen atom, difluoromethyl group or difluoromethoxy group, X ⁴ is a halogen atom, and when X ¹ is a halogen atom, X ³ is a halogen atom , X ⁴ represents a hydrogen atom.), And then the obtained compound represented by the following general formula [Ia] is reacted with an oxidant in a solvent to obtain the following general formula [Ib]: A method for producing a biphenyl sulfoxide compound, which comprises producing a compound represented by the formula (wherein X ¹ , X ² , X ³ and X ⁴ are the same as the compound represented by the general formula [Ia]).

(6) ^{X 1} is a hydrogen ^atom, X 2, ^{X 3} and ^{X 4} is a fluorine atom, a manufacturing method of biphenyl sulfoxide compound according to (5).
( 7 ) The method for producing a biphenyl sulfoxide compound according to ( 5 ), wherein X ¹ , X ² and X ³ are fluorine atoms.

  According to the present invention, it has a high activity against various insects and / or mites that are harmful in the field of agriculture and horticulture, and in particular has a novel acaricidal activity against citrus mite which is an important pest of citrus fruits. A method for producing a biphenyl sulfide compound and a production intermediate thereof are provided.

The compounds represented by the general formulas [Ia] and [Ib] obtained by the present invention are collectively referred to as compounds represented by the general formula [I] (n represents 0 or 1). Also referred to as compound [I]. Specific examples of the compound represented by the general formula [I] are shown in Table 1. In addition, the compound numbers in Table 1 may be cited in the following description.

一般式［Ｉ］で表される化合物は、以下に示す製造法に従って製造することができるが、これらの方法に限定されるものではない。

The compound represented by the general formula [I] can be produced according to the production methods shown below, but is not limited to these methods.

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

（式中、Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は、前記と同じ意味を表し、Ｌはハロゲン原子又はトリフルオロメタンスルホニルオキシ基を表す。）

(Wherein X ¹ , X ² , X ³ and X ⁴ represent 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 general formula [III] with the compound represented by the general formula [II-a] which is the compound of the present invention in a solvent in the presence of a base and a transition metal catalyst, the general formula The compound represented by [Ia] can be produced.

  The amount of the compound represented by the general formula [III] 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 [II-a]. 1.5 moles.

(Process B)
By reacting the compound represented by the general formula [IV] and the compound represented by the general formula [II-b] which is the compound of the present invention in a solvent in the presence of a base and a transition metal catalyst, the general formula The compound represented by [Ia] can be produced.
The amount of the compound represented by the general formula [II-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.

  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 mol, more preferably 0.03, per 1 mol of the compound represented by the general formula [III] or the compound represented by the general formula [II-b]. Use ~ 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; and mixed solvents thereof.

  The usage-amount of the solvent in the above is 0.1-100 liter with respect to 1 mol of compounds represented by the compound represented by general formula [III], or [II-b]. More preferably, it is 1.0-5.0 liters.

  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. Of organic bases.

  The amount of the base used may be 1 to 4 mol per 1 mol of the compound represented by the general formula [III] or the compound represented by [II-b]. More preferably, it is 1.5-2 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 represented by the general formula [Ib] can be produced by a method consisting of the reaction formulas exemplified below.

（式中、Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は、前記と同じ意味を表す。）

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

  A compound represented by [Ib] can be produced by reacting a compound represented by the general formula [Ia] and an oxidizing agent in a solvent in the presence or absence of a catalyst. it can.

  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 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 [Ia].

Examples of the catalyst include sodium tungstate.
Here, the usage-amount of the catalyst to be used is preferably 0.001-1 mol with respect to 1 mol of the compound represented by the general formula [Ia]. More preferably, it is 0.01-0.05 mol.

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

  The amount of the solvent used is preferably 0.1 to 100 liters per 1 mol of the compound represented by [Ia]. More preferably, it is 1.0-5.0 liters.

  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.

Next a specific example of the production intermediates der Ru of compounds of biphenyl sulfide compound in Table 2.

  When using Compound [I] as an active ingredient of an insecticide / acaricide, Compound [I] may be used as it is, but carriers, surfactants, And other supplements, emulsion, suspension, powder, granule, tablet, wettable powder, water solvent, liquid, flowable, granule wettable powder, aerosol, paste, oil, emulsion It can be formulated into various forms such as smoke. These compounding ratios are preferably 0.1 to 90% by mass of the active ingredient and 10 to 99.9% by mass of the agrochemical adjuvant.

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

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

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

  In actual use of these preparations, they can be used as they are or diluted to a predetermined concentration with a diluent such as water. Application of various preparations containing the compound [I], or dilutions thereof, is usually carried out by a commonly used application method, that is, spraying (eg spraying, misting, atomizing, dusting, dusting, water surface application, box Application), soil application (eg, mixing, irrigation, etc.), surface application (eg, application, powder coating, coating, etc.), immersion, poison bait, smoke application, etc. It is also possible to feed the livestock with the active ingredient in a feed to control the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra-high concentration and small quantity spraying method. In this method, it is possible to contain 100% of the active ingredient. The 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.

  Insecticides and acaricides are generally applied at an active ingredient concentration of 0.1 to 5000 ppm when diluted with a diluent. When the preparation is used as it is, the application amount per unit area is preferably 0.1 to 5000 g per 1 ha as an active ingredient compound, but is not limited thereto.

It goes without saying that Compound [I] alone is sufficiently effective, but if necessary, other fertilizers and agricultural chemicals such as insecticides, acaricides, nematicides, bactericides, and antiviral agents. These can be used in combination with or in combination with attractants, herbicides, plant growth regulators, etc., and in this case, a more excellent effect may be exhibited.
Here, other pesticides that can be mixed or used together are exemplified below. Chlorfenapyr, abamectin, emamectin, bromopropyrate, bistrifluron, chlorfluazuuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, nobarlon, nobiflumuron, teflubenzuron, triflumuron, aldicarb, Bendiocarb, Benfuracarb, Carbaryl, Carbofuran, Carbosulfan, Ethiophenecarb, Fenobucarb, Formethanate, Furatiocarb, Isoprocarb, Methiocarb, Mesomil, Metorcarb, Oxamyl, Pirimicarb, Propixur, Trimetacarb, XMC, Xylylcarb, Triazamate, Chlorden, Endosulfate Oid, halofenozide, methoxyphenozide, tebufu Nozide, bensultap, cartap, thiocyclam, thiosultap, etiprol, fipronil, phenoxycarb, hydroprene, quinoprene, metoprene, pyriproxyfen, phenazaquin, fenpyroximate, pyridaben, tebufenpyrad, clofentezine, etoxazole, hexathiazox, acetamanidide, tethamiprid Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam, Etofenprox, Halfenprox, Silafluophene, Diethofencarb, Acephate, Azamethiphos, Adinphos-ethyl, Adinphos-methyl, Kazusafos, Chlorethoxyphos, Chlorfenbinphos, Chlorpyrifos, Chlorpyrifos, Chlorpyrifos , Kumaho , Cyanophos, Demeton S. methyl, Diazinone, Dichlorvos, Dicrotophos, Dimethoate, Dimethylvinphos, Disulfoton, EPN, Ethion, Etoprophos, Famflu, Phenamiphos, Fenitrothion, Fention, Phosthiazeto, Heptenophos, Isocarbophos, Isoxathione, Malathione, Carb , Methidathion, mevinphos, monocrotophos, nared, ometoate, oxydimethone methyl, parathion, parathion methyl, phentoate, folate, hosalon, phosmetone, phosphamidone, oxime, pirimiphos methyl, profenofos, propetamphos, prothiophos, pyracrofos, pida Fenthion, quinalphos, sulfotep, tebupyrimfos, temefos, ter Bufos, tetrachlorvinphos, thiomethone, triazophos, trichlorfone, bamidithione, azocyclotin, cyhexatin, fenbutantin oxide, alanicarb, butcarboxyme, butoxycarboxyme, thiodicarb, thiophanox, acrinathrin, allesrin, alpha-cypermethrin, Beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioaresulin, violesmethrin, cycloprotorin, cyfluthrin, cyhalothrin, cypermethrin, ciphenothrin, deltamethrin, empentrin, esfenvalerate, fenpropatoline, fenvalerate, flucitrin, flumethrin , Gamma-cyhalothrin, imiprothrin, lambda-cyhalothrin, methotrin, permethrin Phenothrin, praretrin, resmethrin, taufulvalinate, teflutrin, tetramethrin, tetramethrin, zeta cypermethrin, tralomethrin, transfluthrin, zeta cypermethrin, ZXI-8901, pymetrozine, acequinosyl, acetoprole, imiciafos, indoxocarb , Sanopyrafen, dienochlor, difluvidazine, cyflumethadene, spiromesifen, spirodiclofen, spirotetramat, tolufenpyrad, bifenazate, pyrafluprolol, pyridalyl, pyriprole, fluacrylpyrim, fluazinam, flupirazophos, flubendiamide, flurimphenone, fluprofenzone, fluprofezin , Linaxyl, lepimectin, CL900 67, XDE-175.
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) or publicly known.

  Compound [I] is a semi-Lepidopterous insect, Lepidoptera insect, Coleoptera insect, Diptera insect, Hymenoptera insect, Straight-eye insect, Termite insect, Thripidae insect, Spider mite, Plant parasitic nematode Excellent control effect against insects and other pests. Examples of such pests include the following pests.

  Hemiptera pests, for example, Riptortus clavatus, Nezara viridula, Lyme sp., Blissus leucopterus, Stephanitis nashi, etc. Heteroptera, leafhoppers (Nephotettix cincticeps), leafhoppers such as Empoasca sp., Erythroneura sp., Circulifer sp. Planthoppers, Psylla sp. And other killer whales, Silver leaf whitefly (Bemisia tabaci), Whitefly whitefly (Trialeurodes vaporariorum) whitefly, Grape aphid (Viteus vitifolii), Peach aphid (Myzus persicae), Aphis aphid pomi), Wataa Aphids such as Aphis gossypii, Aphis fabae, Aphid pea aphid (Rhopalosiphum psedobrassicas), potato aphid (Aulacorthum solani), wheat aphid (Schizaphis graminum), , Scale insects such as Sanho scale insects (Comstockaspis perniciosa), scale insects (Unaspis yanonensis), sand turtles (Rhodnius sp.) And the like.

  Lepidopterous pests, such as Homona magnanima, Adoxophyes orana, Sparganothis pilleriana, Grapholitha molesta, Leguminivora glycinivorella, Spaspanobea , Mosquitoes such as Eupoecillia ambiguella, minoga such as Bambalina sp., Nesting moths (Nemapogon granellus), squirrels (Tinea translucens), and hummingbirds such as lingon moth (Lyonetia prunifoliella) Hosogaga such as Phyllonorycter rigoniella, Pseudomonas such as Phyllocnistis citrella, Suga such as Plutella xylostella, Prays citri, Paranthrene regalis, Synanthedon sp. Pterinophora gossypiella, potato moth (Phthorimaea operculella), Stomopteryx sp. medinalis), Ostrinia nubilalis, Ostrinia furnacalis, Hellula undalis, Honey moth (Galleria mellonella), Elasmopalpus lignosellus, Loxostege sticticalis, etc. Selenaria and other species such as Selenaria, Malacosoma neustria and other species, Manduca sexta and other hawks, Euproctis pseudoconspersa, and Japanese moth (Lymantria dispar) and other species, Hyphantria cunea Hitriggers such as Tobacco Budworm (Heliothis virescens), Ballworm (Helicoverpa zea), Spodoptera exigua, Helicoverpa armigera, Spodoptera litura, Mitostra brassicae (A), Mamestra brassicas Yags such as Pseudaletia separata and Trichoplusia ni.

  Coleopterous insects, for example, Anomala cuprea, Popillia japonica, Scarabae (Anomala rufocuprea), Eutheola rugiceps, etc., wire worms (Agriotes sp.), Connodeus sp. (Epilachna vigintioctopunctata), ladybirds such as green beetle (Epilachnavarivestis), bark beetles such as Tribolium castaneum, Anoplophora malasiaca, Monshames acanthus, Monochamus alternatus, etc. , Weevil weevil (Callosobruchus chinensis), Colorado potato beetle (Leptinotarsa decemlineata), corn root worm (Diabrotica sp.), Rice beetle (Oulema oryzae), tensite biha Potato beetles such as Chaetoccnema concinna, Phaedon cochlearias, Oulema melanopus, Dicladispa armigera, weevil such as Apion godmani, weevil (Lissorhoptrus oryzophilus), ant weevil (Anthonomus grandis) Beetles, bark beetles, cutworms, beetles, etc.

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

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

  Diptera pests such as German cockroaches (Blatella germanica), American cockroaches (Periplaneta americana), Kera (Gryllotalpa africana), grasshoppers (Locusta migratoria migratoriodes), Melanoplus sanguinipes and the like.

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

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

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

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

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

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

  Next, an example is given and the present invention is explained concretely. In addition, the manufacturing method of the manufacturing intermediate which is this invention compound is also described collectively.

Example 1
Preparation of [4-fluoro-2-methyl-5- (3,4,5-trichlorophenyl) phenyl] -2,2,2-trifluoroethyl sulfide (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 (triphenylphosphine) palladium 0.13 g, tetrahydrofuran 50 ml, 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) to obtain 0.85 g of oily [4-fluoro-2-methyl-5- (3,4,5-trichlorophenyl) phenyl] -2,2,2-trifluoroethyl sulfide ( Yield 94%).
1H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.53 (3H, s), 3.33 (2H, q), 7.08 (1H, d), 7.53 (2H, s), 7.58 (1H, d)

Example 2
Preparation of [5- (4-difluoromethoxy-3,5-dichlorophenyl) -4-fluoro-2-methylphenyl] -2,2,2-trifluoroethyl sulfide (Compound No. I-2):
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 A mixture of 0.5 g, 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) to obtain 0.82 g of oily [5- (4-difluoromethoxy-3,5-dichlorophenyl) -4-fluoro-2-methylphenyl] -2,2,2-trifluoroethyl sulfide. (Yield 91%).
1H-NMR data (CDCl ₃ / TMS δ (ppm) value)
2.53 (3H, s), 3.34 (2H, q), 6.64 (1H, t), 7.08 (1H, d), 7.52 (2H, s), 7.57 (1H, d)

Example 3
Preparation of [4-fluoro-2-methyl-5- (3,4,5-trifluorophenyl) phenyl] -2,2,2-trifluoroethyl sulfide (Compound No. I-3):
1.0 g 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid, 0.72 g 1-bromo-3,4,5-trifluorobenzene, sodium carbonate 0. A mixture of 80 g, tetrakis (triphenylphosphine) palladium 0.2 g, tetrahydrofuran 50 ml 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) to obtain 1.1 g of oily [4-fluoro-2-methyl-5- (3,4,5-trifluorophenyl) phenyl] -2,2,2-trifluoroethyl sulfide. (Yield 85%)

Example 4
Preparation of [4-fluoro-2-methyl-5- (3,4,5-trifluorophenyl) phenyl] -2,2,2-trifluoroethyl sulfoxide (Compound No. I-5):
0.54 g of [4-fluoro-2-methyl-5- (3,4,5-trifluorophenyl) phenyl] -2,2,2-trifluoroethyl sulfide synthesized by the method of Example 3 was added to 20 ml of chloroform. After dissolution, 0.27 g of m-chloroperbenzoic acid was added over 15 minutes at room temperature, and the mixture was further reacted for 1 hour. The reaction mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to give [4-fluoro-2-methyl-5- (3,4,5-trifluoro). Phenyl) phenyl] -2,2,2-trifluoroethyl sulfoxide was obtained (yield 97%).

Example 5
Production of [4-fluoro-2-methyl-5- (2,3,4-trifluorophenyl) phenyl] -2,2,2-trifluoroethyl sulfide (Compound No. (I-4)):
1.0 g 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid, 0.72 g 1-bromo-2,3,4-trifluorobenzene, sodium carbonate 0. A mixture of 80 g, tetrakis (triphenylphosphine) palladium 0.2 g, tetrahydrofuran 50 ml 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) to obtain 0.95 g of oily [4-fluoro-2-methyl-5- (2,3,4-trifluorophenyl) phenyl] -2,2,2-trifluoroethyl sulfide. (Yield 73%).

Example 6
Production of [4-fluoro-2-methyl-5- (2,3,4-trifluorophenyl) phenyl] -2,2,2-trifluoroethyl sulfoxide (Compound No. (I-6)):
Dissolve 0.51 g of [4-fluoro-2-methyl-5- (2,3,4-trifluorophenyl) phenyl] 2,2,2-trifluoroethyl sulfide synthesized by the method of Example 5 in 20 ml of chloroform. Then, 0.25 g of m-chloroperbenzoic acid was added over 15 minutes at room temperature, 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 then the solvent was distilled off under reduced pressure to give [4-fluoro-2-methyl-5- (2,3,4-trifluoro). Phenyl) phenyl] -2,2,2-trifluoroethyl sulfoxide was obtained (yield 94%).

Example 7
Preparation of [4-fluoro-2-methyl-5- (3-chloro-4-difluoromethyl-5-fluoro) phenyl] -2,2,2-trifluoroethyl sulfide (Compound No. I-7):
To 69 g of fuming nitric acid, 30.9 g of 2-chloro-6-fluorobenzaldehyde was added at 0 ° C. over 15 minutes, and the mixture was stirred 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-6-fluoro-3-nitrobenzaldehyde.
2-chloro-6-fluoro-3-nitrobenzaldehyde (23.2 g) was dissolved in methanol (300 ml), tin (40.6 g) was added, and concentrated hydrochloric acid (100 ml) was added dropwise over 30 minutes. After cooling to room temperature, the reaction mixture was neutralized with 25% aqueous sodium hydroxide and insolubles were filtered off. The filtrate was 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 20.2 g of 3-amino-2-chloro-6-fluorobenzaldehyde dimethyl acetal.
It was dissolved in 20.2 g of 3-amino-2-chloro-6-fluorobenzaldehyde dimethyl acetal and 100 ml of N, N-dimethylformamide, 16.4 g of N-bromosuccinimide was added, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture 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 give 3-amino-4-bromo-2-chloro-6-fluoro. 25.8 g of benzaldehyde dimethyl acetal was obtained.
2-amino-4-bromo-2-chloro-6-fluorobenzaldehyde dimethyl acetal (25.8 g) was dissolved in N, N-dimethylformamide (90 ml), and t-butyl nitrite (12.0 g) was added dropwise at 50 ° C. over 15 minutes. The mixture was further stirred for 30 minutes. The reaction mixture was poured into water, extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and 4-bromo-2-chloro-6-fluorobenzaldehyde dimethyl acetal 8 0.7 g was obtained.
A mixture of 8.7 g of 4-bromo-2-chloro-6-fluorobenzaldehyde dimethyl acetal, 20 ml of ethanol and 5 ml of concentrated hydrochloric acid was heated to reflux for 6 hours. After cooling at room temperature, water was added and the mixture was 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 to obtain 4.7 g of 4-bromo-2-chloro-6-fluorobenzaldehyde.
4-Bromo-2-chloro-6-fluorobenzaldehyde (4.7 g) was dissolved in dichloromethane (50 ml), diethylaminosulfur trifluoride (3.9 g) was added over 15 minutes at room temperature, and the mixture was further 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 obtained residue was purified by silica gel column chromatography to obtain 4.1 g of 5-bromo-1-chloro-2-difluoromethyl-3-fluorobenzene.
0.78 g of 5-bromo-1-chloro-2-difluoromethyl-3-fluorobenzene, 0.80 g of 2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid, A mixture of 0.31 g of tetrakis (triphenylphosphine) palladium, 0.64 g of sodium carbonate, 50 ml of tetrahydrofuran and 50 ml of water was heated to reflux for 3 hours. After cooling to room temperature, 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 (elution solvent: n-hexane), [4- 1.0 g (84% yield) of fluoro-2-methyl-5- (3-chloro-4-difluoromethyl-5-fluorophenyl) phenyl] 2,2,2-trifluoroethyl sulfide was obtained.
1H-NMR data (CDCl ₃ / TMS δ (ppm) value) is shown below.
2.54 (3H, s), 3.34 (2H, q), 7.09 (1H, t), 7.10 (1H, d), 7,25 (1H, d), 7.40 (1H, d), 7.60 (1H, d)

Example 8
Preparation of (5-bromo-4-fluoro-2-methylphenyl) -2,2,2-trifluoroethyl sulfide (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, the solvent was distilled off under reduced pressure, and 5-bromo-4-fluoro-2-methylbenzenesulfonyl chloride 29 g
Got. To the obtained sulfonyl chloride, 300 ml of acetic acid was added, 6.3 g of red phosphorus and 0.5 g of iodine were added, and the mixture was heated to reflux for 2 hours. After cooling to room temperature, the solid was filtered off and the solvent was distilled off under reduced pressure. The residue was extracted with ethyl acetate, washed with saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and 5-bromo-4-fluoro-2-methyl-1- 26.6 g of acetylthiobenzene 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 13.6 g of potassium carbonate, 28 g of 2,2,2-trifluoro-1-iodoethane, and 3.2 g of Rongalite were added 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: n -Hexane) to obtain 25.1 g of (5-bromo-4-fluoro-2-methylphenyl) -2,2,2-trifluoroethyl sulfide (yield 93%).
1H-NMR data (CDCl ₃ / TMS δ (ppm) value) is shown below.
2.44 (3H, s), 3.33 (2H, q), 7.02 (1H, d), 7.70 (1H, d)

Example 9
2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) benzeneboronic acid (Intermediate Compound No. II-2):
Under a nitrogen stream, 350 ml of dry ether was added to 25.1 g of 5-bromo-4-fluoro-2-methylphenyl 2,2,2-trifluoroethyl sulfide synthesized by the method of Example 8 and cooled to -60 ° C. did. Under a nitrogen stream, 53.8 ml of n-butyllithium (n-hexane solution, 1.54 mol / L) was added dropwise to the mixture over 15 minutes. After 5 minutes, an 8.6 g / 50 ml ether solution of trimethoxyborane was further added dropwise over 10 minutes. The temperature was raised, and a 16 g / 100 g aqueous solution of sulfuric acid was added dropwise at around -20 ° C. and 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 to give 2-fluoro-4-methyl-5- (2 , 2,2-trifluoroethylthio) benzeneboronic acid 18.0 g (81% yield).

  Next, the formulation method will be specifically described with reference to typical formulation examples. The kind and compounding ratio of a compound and an adjuvant are not limited only to this, It can change in the wide range. In the following description, “part” means part by mass.

Example 10
Formulation Example 1 Emulsion Compound No. (I-1) 30 parts Cyclohexanone 20 parts Polyoxyethylene alkyl aryl ether 11 parts Calcium alkylbenzenesulfonate 4 parts Methyl naphthalene 35 parts Moreover, it can replace with a compound number (I-1) and can obtain an emulsion similarly using each compound of Table 1.

Example 11
Formulation Example 2 Wetting agent Compound of compound number (I-1) 10 parts Naphthalenesulfonic acid formalin condensate sodium salt 0.5 part Polyoxyethylene alkylaryl ether 0.5 part Diatomaceous earth 24 parts Clay 65 parts Uniform mixing This was pulverized into a wettable powder. In addition, a wettable powder can be similarly obtained using each of the compounds shown in Table 1 instead of the compound number (I-1).

Example 12
Formulation Example 3 Dust Compound of Compound No. (I-3) 2 parts Diatomaceous earth 5 parts Clay 93 parts The above was mixed and ground uniformly to obtain a powder. Moreover, it can replace with compound number (I-3) and can obtain a powder similarly using each compound of Table 1.

Example 13
Formulation Example 4 Granules Compound of compound number (I-3) 5 parts Sodium salt of lauryl alcohol sulfate 2 parts Sodium lignin sulfonate 5 parts Carboxymethylcellulose 2 parts Clay 86 parts The above was mixed and ground uniformly. 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 compound number (I-3) and can obtain a granule similarly using each compound of Table 1.

  Next, the effect of the insecticide / acaricide containing compound [I] as an active ingredient will be described with reference to test examples.

Test Example 1 Citrus spider mite killing insect test A Citrus leaf mite female adult was inoculated into a citrus leaf disc on an agar medium. 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 ). It was placed in a thermostatic chamber at 25 ° C. for 2 days after the treatment, the number of live insects was examined, and the death rate was determined by the formula of Formula 1. The test was conducted in a single run. The results of this test are shown in Table 3.
In addition, the comparative compounds (a), (b), (c), (d) and (e) used are compound numbers [I-356] and [I] illustrated in JP-A-2000-198768, respectively. I-358], [I-361], [I-414] and [I-599].

Test Example 2 Spider mite 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 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. The results of this test are shown in Table 4.

Test Example 3 Brown planthopper 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 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 (3). The test was conducted in a single run. The results in this test are shown in Table 5.

The novel biphenyl sulfide compound obtained by the present invention has high activity against various harmful insects and / or mites, and particularly has excellent acaricidal activity against citrus mite which is an important pest of citrus fruits. It is widely used in the field of agriculture and horticulture as an active ingredient of insecticides and acaricides.
It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2005-27383 filed on September 21, 2005 are cited herein as disclosure of the specification of the present invention. Incorporated.

Claims (7)

Compound represented by the following general formula [III] (wherein L represents a halogen atom or a trifluoromethanesulfonyloxy group, X ¹ represents a hydrogen atom or a halogen atom, X ² represents a halogen atom, and X ¹ represents a hydrogen atom) In the case of an atom, X ³ represents a halogen atom, a difluoromethyl group or a difluoromethoxy group, X ⁴ represents a halogen atom, and when X ¹ is a halogen atom, X ³ represents a halogen atom and X ⁴ represents a hydrogen atom. ) And a phenyl sulfide compound represented by the following general formula [II-a] in a solvent in the presence of a base and a transition metal catalyst, a compound represented by the following general formula [Ia] (wherein the method of ^{X 1, X 2, X 3} , X 4 is biphenyl sulfide compound, characterized in that for manufacturing the same.) the compound represented by the general formula [III]

^2. The biphenyl according to claim 1 , wherein 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, and X ⁴ is a fluorine atom or a chlorine atom. A method for producing a sulfide compound. A compound represented by the following general formula [IV] (wherein 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 or difluoromethyl) Group or difluoromethoxy group, X ⁴ represents a halogen atom, and when X ¹ is a halogen atom, X ³ represents a halogen atom and X ⁴ represents a hydrogen atom.) And the following general formula [II-b] A phenyl sulfide compound (wherein L represents a halogen atom or a trifluoromethanesulfonyloxy group) is reacted in a solvent in the presence of a base and a transition metal catalyst, and is represented by the following general formula [Ia]. compound ^{(wherein, X 1, X 2, X} 3, X 4 are the same. the compound represented by the general formula [IV]) manufactured biphenyl sulfide compound, characterized by the production of Method.

The biphenyl according to claim 3 , wherein 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, and X ⁴ is a fluorine atom or a chlorine atom. A method for producing a sulfide compound. Claim 2 following general formula in the production method according to any one of the 4 [I-a] a compound represented by (wherein, X ¹ is a hydrogen atom or a halogen atom, X ² represents a halogen atom, X ^{When 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 The compound represented by the following general formula [Ib] and the resulting compound represented by the following general formula [Ia] are reacted with an oxidizing agent in a solvent to obtain a compound represented by the following general formula [Ib] (wherein , X ¹ , X ² , X ³ , and X ⁴ are the same as the compound represented by the general formula [Ia].), A method for producing a biphenyl sulfoxide compound.

The method for producing a biphenyl sulfoxide compound according to claim 5 , wherein X ¹ is a hydrogen atom, and X ² , X ^3, and X ⁴ are fluorine atoms. The method for producing a biphenyl sulfoxide compound according to claim 5 , wherein X ¹ , X ² and X ³ are fluorine atoms.