JP2009286780A - Agricultural and horticultural fungicide containing 1,2,3-substituted imidazolium salt as active ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an agricultural and horticultural fungicide having a stable high controlling effect on various disease injuries of vegetable. <P>SOLUTION: This agricultural and horticultural fungicide contains 1,2,3-substituted imidazolium salt expressed by formula (I) [wherein, R<SP>1</SP>, R<SP>3</SP>are each independently H, a substitutable alkyl, a substitutable alkenyl, a substitutable alkynyl or the like; R<SP>2</SP>is H, a substitutable alkyl, a substitutable benzyl, a substitutable phenyl or the like; and X is a halogen atom] as an active ingredient. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an agricultural and horticultural fungicide containing a novel 1,2,3-substituted imidazolium salt having fungicidal activity as an active ingredient.

  In Non-Patent Documents 1 to 3, some of the compounds included in the 1,2,3-substituted imidazolium salts represented by the following formula (I) which are active ingredients of the present invention are used as medical antibacterial agents. It is described as being useful. However, these documents do not describe that the compound represented by the following formula (I) is useful as an agricultural and horticultural fungicide. On the other hand, Patent Documents 1 to 3 describe that substituted imidazolium salt derivatives show a controlling effect on various plant diseases such as tomato plague, pepper gray mold, and the like. This is different from the compound represented by the following formula (I).

JP-A-54-79278 German Published Patent Publication No. 2219845 French Published Patent Publication No. 2486079

Journal of the American Chemical Society (1947), 69, 2269-70 Biosci. Biotechnol. Biochem., 64 (4), 919-923, 2000 Proc. Natl. Acad. Sci. USA, 90, 965-969, 1993

  Many agricultural and horticultural fungicides provided in the past have their characteristics in controlling the phytopathogenic fungi, and some of them have a slightly inferior therapeutic effect or a relatively residual effect compared to the preventive effect. Depending on the application situation, it may show only a practically insufficient control effect against phytopathogenic fungi. Accordingly, there is a demand for the creation of new compounds having a strong phytopathogenic fungi control effect.

  As a result of researches to solve the above-mentioned problems, the present inventors have used various compounds represented by the formula (I) as an active ingredient, thereby causing various diseases, particularly wheat powdery mildew and red rust. Rice blast; rice downy mildew, plague; knowledge that it exhibits excellent control effects against various gray molds, etc. were obtained, and the present invention was completed. That is, the present invention relates to the formula (I):

Wherein R ¹ and R ³ are each independently a hydrogen atom, alkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, phenyl moiety is Q or Z Benzyl which may be substituted, naphthyl moiety in which naphthyl moiety may be substituted with Q or phenyl which may be substituted with Q or Z; R ² is hydrogen atom, alkyl which may be substituted with A, phenyl moiety Is benzyl optionally substituted with Q or Z or phenyl optionally substituted with Q or Z; X is a halogen atom; A is a halogen atom, cycloalkyl, hydroxy, alkoxy, haloalkoxy, phenyl moiety Benzyloxy optionally substituted with Q or Z, phenoxy optionally substituted with Q or Z, alkylthio, alkylsulfur Nyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, benzylthio where the phenyl moiety may be substituted with Q or Z, benzylsulfinyl where the phenyl moiety may be substituted with Q or Z, phenyl moiety with Q or Z Benzylsulfonyl which may be substituted, phenylthio which may be substituted with Q or Z, phenylsulfinyl which may be substituted with Q or Z, or phenylsulfonyl which may be substituted with Q or Z; Z is substituted with Q Phenyl optionally substituted with Q, phenoxy optionally substituted with Q, phenylthio optionally substituted with Q, phenylsulfinyl optionally substituted with Q or phenylsulfonyl optionally substituted with Q; Q is a halogen atom , Alkyl, alkoxy Agricultural and horticultural use containing a 1,2,3-substituted imidazolium salt represented by the following formula: haloalkyl, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, nitro or cyano It relates to an antibacterial agent. The present invention also relates to a method for controlling plant diseases comprising applying a 1,2,3-substituted imidazolium salt represented by the formula (I) to an agricultural or horticultural plant.

Examples of the alkyl moiety of alkyl, alkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl and haloalkyl in formula (I) include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Tertiary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosanyl, heicosanyl, docosanyl, tricosanyl, tetracosanyl, pentacosanyl, pentacosanyl, hexacosanyl, etc. And linear or branched C _1-26 alkyl. Among these, linear C _1-20 alkyl is desirable.

Examples of alkenyl in the formula (I) include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3-butadienyl, 1-hexenyl, 1-heptenyl, 7-octenyl, 3-nonel, Direct such as 5-decenyl, 10-undecenyl, 7-dodecenyl, 12-tridecenyl, 11-tetradecenyl, 14-pentadecenyl, 11-hexadecenyl, 16-heptadecenyl, 9-octadecenyl, 18-nonadecenyl, 11-icosenyl, 25-hexacocenyl _Examples include chain or branched C 2 _-26 alkenyl. Of these, linear _C2-20 alkenyl is particularly desirable.
Examples of alkynyl in formula (I) include ethynyl, 2-butynyl, 2-pentynyl, 3-methyl-1-butynyl, 2-penten-4-ynyl, 3-hexynyl, 3-nonynyl, 9-decynyl, 10- undecynyl, 11-dodecynyl, 12-tridecynyl, 13-tetradecynyl, 15-hexadecynyl, include straight-chain or branched _{C 2-26} alkynyl such as 25-Hekisakoshiniru. Among these, linear _C2-20 alkynyl is desirable.
The naphthylmethyl in the formula (I) may be either α-naphthylmethyl or β-naphthylmethyl.

The halogen atom in the formula (I) and the halogen atom in haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl and haloalkyl include fluorine, chlorine, bromine or iodine atoms. The number of halogen atoms as a substituent may be 1 or 2 or more, and when 2 or more, each halogen atom may be the same or different. Further, the halogen atom may be substituted at any position.
Examples of cycloalkyl in the formula (I) include C _3-6 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

  The compound represented by the formula (I) exhibits an excellent effect as an active ingredient of agricultural and horticultural fungicides.

The compound represented by the formula (I) can be produced according to the method described in Non-Patent Document 1 or Non-Patent Document 2, and can be produced, for example, by the following Production Method 1 and Production Method 2. The flow will be described in detail below.
Production Method 1 (Intermediate: Production Method of Compound Represented by Formula (IV))

上記フロー中、Ｒ^１及びＲ^２は前述の通りであり；Ｙはハロゲン原子、ＯＳＯ_２Ｒ^４又はＯＰＯ（ＯＲ^５）_２であり；Ｒ^４は、アルキル、ハロアルキル又はアルキル若しくはニトロで置換されてもよいフェニルであり；Ｒ^５はアルキルである。ここでのアルキル及びハロアルキルは前述の通りである。

In the above flow, R ¹ and R ² are as described above; Y is a halogen atom, OSO ₂ R ⁴ or OPO (OR ⁵ ) ₂ ; R ⁴ is substituted with alkyl, haloalkyl or alkyl or nitro. ^May be phenyl; R ⁵ is alkyl. The alkyl and haloalkyl here are as described above.

  The compound represented by the formula (IV) is an intermediate for producing the compound represented by the formula (I), and reacts the compound represented by the formula (II) with the compound represented by the formula (III). Can be manufactured.

  This reaction can usually be performed in the presence of a base. Examples of the base include alkali metal hydrides such as sodium hydride and potassium hydride; alkyllithiums such as n-butyllithium and t-butyllithium; tertiary amines such as triethylamine and diisopropylethylamine; sodium hydroxide and potassium hydroxide. Alkali metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; and the like.

  In the production method 1, the compound represented by the formula (IV) can be produced by directly reacting the compound represented by the formula (II) and the compound represented by the formula (III), but the reaction is carried out in the presence of a solvent. It is desirable to let them. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane; ethyl formate, acetic acid Carboxylates such as methyl, ethyl acetate, ethyl propionate; aromatic hydrocarbons such as benzene, toluene, xylene; polar aprotic solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide; and These mixed solvents can be used.

The reaction temperature of Production Method 1 is 40 ° C to 150 ° C, preferably 60 ° C to 120 ° C. The reaction time is 1 hour to 48 hours, preferably 2 hours to 24 hours. For the reaction of the production method 1, it is also effective to carry out the reaction under pressure using, for example, an autoclave or the like in order to rapidly advance the reaction.
Production Method 2 (Production Method of Compound Represented by Formula (I))

In the above flow, R ¹ , R ² , R ³ and X are as described above.
The compound represented by the formula (I) can be produced by reacting the compound represented by the formula (IV) obtained by the production method 1 with the compound represented by the formula (V). In order to rapidly advance the reaction, the compound represented by the formula (V) is often used in a ratio of 1 mol or more with respect to 1 mol of the compound represented by the formula (IV).

  In production method 2, the compound represented by the formula (I) can be produced by directly reacting the compound represented by the formula (IV) and the compound represented by the formula (V). It is desirable to let them. The solvent is not particularly limited as long as it does not adversely affect the reaction. For example, the same solvents as those used in the production method 1 can be used.

  The reaction temperature of production method 2 is 50 ° C to 130 ° C, preferably 60 ° C to 110 ° C. The reaction time is 4 hours to 48 hours, preferably 6 hours to 24 hours. It is also effective to carry out the reaction under pressure using, for example, an autoclave or the like in order to advance the reaction quickly.

  The compound represented by the formula (I) (hereinafter abbreviated as the compound of the present invention) is useful as an active ingredient of agricultural and horticultural fungicides, such as rice blast, sesame leaf blight, coat blight; wheat Powdery mildew, red mold, rust, snow rot, naked scab, eye spot, leaf blight, dry blight; citrus black spot, common scab; apple moniliosis, powdery mildew, Spot deciduous disease, black spot disease; pear black star disease, black spot disease; peach ash star disease, black star disease, fomoposis rot disease; grape black rot, late rot, powdery mildew, mildew; oyster charcoal Downy mildew, decoction of cucurbits, powdery mildew, vine blight, downy mildew; tomato ring-rot, leaf mold, plague; black spot of cruciferous vegetables; summer plague of potato Strawberry powdery mildew; effective in controlling various crops such as gray mold and mycorrhizal diseases, but especially wheat and vegetable powdery mildew And it shows an excellent control effect on rice blast. It is also effective for controlling soil diseases caused by phytopathogenic fungi such as Fusarium, Psium, Rhizoctonia, Verticillium, and Plasmodiohora.

  The compound of the present invention is usually prepared by mixing the compound with various agricultural adjuvants, powders, granules, granule wettable powders, wettable powders, aqueous suspensions, oily suspensions, aqueous solvents, emulsions, It can be formulated into various forms such as liquids, pastes, aerosols, microdispersions, etc., but can be made into any conventional form used in the art as long as it meets the purpose of the present invention. it can. Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch, etc .; water , Toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, alcohol, etc. Solvent; fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester, alkyl aryl phosphate, styryl Aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate Salts, anionic surfactants such as salt of naphthalene sulfonic acid formalin condensate; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fat Acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyoxyethylene fatty acid ester, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm oil, palm oil, palm Oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, cutting oil, liquid paraffin, etc. Examples include vegetable oil and mineral oil. As long as it does not deviate from the object of the present invention, one or two or more kinds of auxiliary components can be appropriately selected and used. Further, in addition to the above-mentioned adjuvants, it can also be used by appropriately selecting from those known in the art, a bulking agent, a thickener, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a safener, Various commonly used adjuvants such as antifungal agents can also be used. The compounding ratio of the compound of the present invention and various adjuvants is generally 0.005: 99.995 to 95: 5, preferably 0.2: 99.8 to 90:10. In actual use of these preparations, use them as they are, or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.

  The concentration of the compound of the present invention varies depending on the target crop, method of use, formulation form, application rate, etc., and cannot be generally defined, but in the case of foliage treatment, it is usually 0.1 to 10,000 ppm, preferably 1 to 2,000 ppm. In the case of soil treatment, it is usually 10 to 100,000 g / ha, preferably 200 to 20,000 g / ha.

  The compound of the present invention is generally applied for application of its various preparations or dilutions thereof, that is, spraying (eg spraying, spraying, misting, atomizing, dusting, water surface application, etc.), soil application (Mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.) can be performed. It can also be applied by the so-called ultra low volume application method (ultra low volume). In this method, it is possible to contain 100% of the active ingredient.

  The compound of the present invention may contain other agricultural chemicals as necessary, such as fungicides, insecticides, acaricides, nematicides, soil insecticides, antiviral agents, attractants, herbicides, plant growth preparations, etc. Can be mixed and used together. In this case, a more excellent effect may be exhibited.

In the above-mentioned other pesticides, as an active ingredient compound (generic name; including partial application or Japanese Plant Protection Association test code), for example, mepanipyrim, pyrimethanil, cyprodinil ), Anilinopyrimidinamine compounds such as ferimzone;
Tria like 5-chloro-6- (2,4,6-trifluorophenyl) -7- (4-methylpiperidin-1-yl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds;
Pyridinamine compounds such as fluazinam;
Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, o Oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole , Fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, cimeconazole, pefurazoate, ipconazole, ipconazole ), Azole compounds such as imibenconazole;
Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, quintozene;
Imidazole compounds such as benomyl, thiophanate-methyl, carbendazim, thiabendazole, fuberiazole, cyazofamid;
Cyanoacetamide compounds such as cymoxanil;
Metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as kiralaxyl, chiax ), Phenylamide compounds such as furalaxyl, cyprofuram;
Sulfenic acid compounds such as dichlofluanid;
Copper-based compounds such as cupric hydroxide and oxine copper;
Isoxazole compounds such as hymexazol;
Fosetyl aluminum (fosetyl-Al), tolclofos-Methyl, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate, edifenphos, iprobenphos Organophosphorus compounds such as (iprobenfos);
N-halogenothioalkyl compounds such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil, mepronil, zoxamide, tiadinil;
Carboxin, oxycarboxin, thifluzamide, penthiopyrad, boscalid, bixafen, fluopyram, isothianil, 3- (difluoromethyl) -1 -Methyl-N-[(1RS, 4SR, 9RS) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl] pyrazole-4-carboxamide and 3- (difluoromethyl) A mixture of -1-methyl-N-[(1RS, 4SR, 9SR) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl] pyrazole-4-carboxamide (isopyrazam Anilide compounds such as (isopyrazam));
Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox;
Carbinol compounds such as fenarimol, flutriafol;
Piperidine compounds such as fenpropidin;
Morpholine compounds such as fenpropimorph, spiroxamine, and triridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph and flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-methyl, metominofen, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin , Strobilurin compounds such as pyraclostrobin, fluoxastrobin;
Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Silylamide compounds such as silthiopham;
Iprovalicarb, Benthiavalicarb-isopropyl, methyl [S- (R, S)]-[3- (N-isopropoxycarbonylvalinyl) -amino] -3- (4-chloro -Amino acid amide carbamate compounds such as -phenyl) propionate (valiphenal);
Imidazolidine compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamid;
Benzenesulfonamide compounds such as flusulfamid;
Oxime ether compounds such as cyflufenamid;
Phenoxyamide compounds such as fenoxanil;
Atraquinone compounds;
Crotonic acid compounds;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadine and dodine;
4-quinolinol derivative compounds such as 2,3-dimethyl-6-t-butyl-8-fluoro-4-acetylquinoline;
Cyanomethylene compounds such as 2- (2-fluoro-5- (trifluoromethyl) phenylthio) -2- (3- (2-methoxyphenyl) thiazolidine-2-ylidene) acetonitrile;
Other compounds include pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, and sodium metam Metam-sodium, nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom; also known as amibromdole, fluicolide, fluicolide , Carpropamid, meptyldinocap and the like.

In the other pesticides, as an insecticide, acaricide, nematicide or soil pesticide, that is, an active ingredient compound of a pesticide (generic name; including some pending applications or test codes), For example, profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephatethio, prothiophos , Fosthiazate, cadusafos, dislufoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate (dimethoate) dimethoate), sulprofos, thiome Thiometon, bamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorbin Phosphine (tetrachlovinphos), chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, adinphos-methyl, fenthion, heptenophos ), Methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, metamidophos, imicyafos, parathion-methyl ( parathion-methyl), terbufos Organophosphate compounds such as (terbufos), phosphamidon, phosmet, phorate;
Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, fenobucarb Carbamates such as carbosulfan, benfuracarb, bendiocarb, furathiocab, isoprocarb, metolcarb, xylylcarb, XMC, fenothiocarb Compound;
Nereistoxin derivatives such as cartap, thiocyclam, bensultap, sodium thiosultap-sodium;
Organochlorine compounds such as dicophor, tetradifon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;
Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, cyfluthrin , Fenpropathrin, flucytrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin, esfenvalerate, Tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermeline (alpha-cyperme) thrin), allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-cypermethrin ( pyrethroid compounds such as beta-cypermethrin), beta-cyfluthrin, mettofluthrin, phenothrin, imidate, flumethrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron, novaluron, novaluron, ), Bistrifluron, benzoylurea compounds such as fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, fenoxycarb, diofenolan;
Pyridazinone compounds such as pyridaben;
Pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole, pyriprole;
Imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuranoid, dinotefuranoid, etc.
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
Pyridine compounds such as Pyridaryl, flonicamid and the like;
Tetronic acid compounds such as spirodiclofen;
Strobilurin compounds such as fluacrypyrin;
Pyridinamine compounds such as flufenerim;
Dinitro compounds; organic sulfur compounds; urea compounds; triazine compounds; hydrazone compounds;
Other compounds include buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen, triazamate, pymetrozine, pyrimidifen, and pyrimidifen. ), Indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene, diafenthiuron, benclothiaz , Bifenazate, spiromesifen, spirotetramat, propargite, clofentezine, metaflumizone, fulvenge Flubendiamide, cyflumetofen, chlorantraniliprole, cyenopyrafen, pyrifluquinazone, phenazaquin, pyridaben, pyridoben, amidoflumet, chlorobenzoate Sulfluramid, hydramethylnon, metaldehyde, HGW-86, ryanodine, flufenerim, pyridalalyl, verbutin, thiazolylcinnanonitrile And compounds such as amidoflumet; AKD-1022, IKA-2000 and the like. Furthermore, Bacillus thuringienses aizawai, Bacillus thuringienses kurstaki, Bacillus thuringienses israelensis, Bacillus thuringienses japonensis, Bacillus thuringienses tenebrionis, crystalline protein toxins produced by Bacillus thuringienses; Microbial pesticides such as: avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin ), Antibiotics such as emamectin, spinetoram and semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet; And mixed use It can also be used in combination.

  Next, examples of the present invention will be described, but the present invention is not limited thereto. First, the synthesis example of this invention compound is described.

Synthesis Example 1 (Synthesis of 1-dodecyl-2-methylimidazole (Intermediate No. IV-1))
After adding 6 g of 2-methylimidazole and 9.1 g of dodecyl bromide to 150 ml of chloroform, the mixture was heated and stirred for 24 hours under reflux. Next, after cooling the reaction solution to room temperature, chloroform was distilled off under reduced pressure. Water was added to the residue, neutralized with 1N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed twice with water, dried over anhydrous magnesium sulfate, and the residue after evaporation of the solvent was purified by silica gel column chromatography (eluent: chloroform / methanol = 15/1) to obtain the target compound 1- 3.89 g of dodecyl-2-methylimidazole was obtained as an oil.

Synthesis Example 2 (Synthesis of 1-benzyl-3-dodecyl-2-methylimidazolium iodide (Compound No. I-33))
After adding 1.03 g of benzyl bromide and 2.49 g of potassium iodide to 100 ml of chloroform, the mixture was heated and stirred for 1 hour under reflux. To this reaction solution, 0.75 g of 1-dodecyl-2-methylimidazole obtained in Synthesis Example 1 was added, and the mixture was further heated and stirred under reflux for 8 hours. Next, the reaction solution is cooled to room temperature, insolubles are filtered off, the solvent is distilled off under reduced pressure, and the resulting residue is subjected to silica gel column chromatography (eluent: chloroform / methanol = 5/1). Thereafter, ethyl acetate was added to the obtained crude product to solidify it, and 0.65 g of 1-benzyl-3-dodecyl-2-methylimidazolium iodide as a target product was obtained as a white powder.

Representative examples of the compound represented by the formula (I) are listed in Table 1. In addition, Table 2 lists compounds represented by the formula (IV) which are intermediates for production. These compounds were synthesized based on the above-mentioned synthesis example, Experimental on Non-patent Document 1, page 2270, Production Method described on Non-patent Document 2, pages 919 to 920, Production Method 1 and Production Method 2 described above. Compound No. I-20 in Table 1 is compound comp. No. 24 described in Non-Patent Document 1. Further, compounds Nos. IV-1 and IV-2 in Table 2 are the compounds NH117 and NH115 described in Non-Patent Document 2, respectively. In each table, No. indicates the compound No., Me is methyl, Et is ethyl, Pr (i) is isopropyl, Bu (n) is normal butyl, Bu (t) is tertiary butyl, Ph Represents phenyl, and the temperature indicated as a physical property is the melting point.
The compounds represented by formula (I) whose ¹ H-NMR was measured are shown in Table 3, Table 4 or Table 5. On the other hand, the compounds represented by formula (IV) whose ¹ H-NMR was measured are shown in Tables 6 and 7.

Below, the test example regarding the fungicide for agriculture and horticulture which contains the compound represented by the compound represented by Formula (I) or Formula (IV) as an active ingredient is described.
Test Example 1 (Spore germination inhibition test)
Using a 96-well microplate, the spore germination inhibition rate (0 to 100%) was evaluated under a microscope after 1 day or 3 days in a predetermined concentration of drug solution. Table 8 shows the lowest effective concentration (ppm) that was found to be effective at 70% or more. In addition,> 100 or> 30 indicates that the lowest effective concentration is 100 ppm or more or 30 ppm or more, respectively.

Test Example 2 (Spore germination / hyphal elongation inhibition test)
Using a 96-well microplate, the spore on the agar medium was treated with a predetermined concentration of the chemical solution, and the subsequent spore germination / hyphal elongation inhibition (0-100%) was visually confirmed under a microscope. Table 8 shows the lowest effective concentration (ppm) that was found to be effective at 70% or more. In addition,> 100 or> 30 indicates that the lowest effective concentration is 100 ppm or more or 30 ppm or more, respectively.

In each test of the following Test Examples 3 to 6, the control index was in accordance with the following criteria.
[Control index] [Disease severity: Visual observation]
5: No lesion or sporulation is observed.
4: The lesion area, the number of lesions, or the spore formation area is less than 10% of the untreated area.
3: The lesion area, the number of lesions, or the sporulation area is less than 40% of the untreated area.
2: The lesion area, the number of lesions, or the sporulation area is less than 70% of the untreated area.
1: The lesion area, the number of lesions, or the spore formation area is 70% or more of the untreated area.

Test Example 3 (Wheat powdery mildew prevention effect test)
Growing wheat (variety: Norin 61) in a 7.5cm diameter plastic pot, and when the 1.5 leaf stage is reached, 10ml of chemical solution adjusted to the prescribed concentration of the compound represented by formula (I) is applied to the spray gun. And sprayed. After the chemical solution was dried (on the day of treatment), conidial spores of powdery mildew (Erysiphe graminis) were sprinkled and inoculated and kept in a constant temperature room at 20 ° C. The spore formation area was investigated 6 to 7 days after the inoculation, and the control index was determined according to the above evaluation criteria. Compound Nos. I-16, I-17, I-18, I-40, I-42, I-46, I-47, I-50, I-51, I-52, I-56, I- When tested for 58, I-60, I-61, I-62 and I-69, it showed an effect with a control index of 4 or more at 400 ppm.

Test example 4 (wheat wheat blight prevention test)
Wheat (variety: Norin 61) is cultivated in a 7.5cm diameter plastic pot, and when the 1.5 leaf stage is reached, the compound represented by formula (I) or the compound represented by formula (IV) is predetermined. 10 ml of chemical solution adjusted to the concentration was sprayed with a spray gun. After the chemical solution was dried (on the day of treatment), a conidial spore suspension of a blight fungus (Septoria nodorum) was spray-inoculated, and kept in an inoculation box at 20 ° C. for 72 hours, and then kept in a constant temperature room at 20 ° C. Six to seven days after the inoculation, the number of lesions was examined, and a control index was determined according to the above evaluation criteria. Compound Nos. I-5, I-17, I-18, I-19, I-20, I-21, I-27, I-28, I-29, I-31, I-32, I- 33, I-38, I-39, I-40, I-41, I-43, I-44, I-46, I-48, I-52, I-53, I-54, I-59, I-60, I-61, I-62, I-64, I-66, I-67, I-68, I-70, and IV-2 were tested and showed an effect of controlling index 4 or more at 400 ppm. It was.

Test Example 5 (wheat red rust prevention effect test)
Wheat (variety: Norin 61) is cultivated in a 7.5cm diameter plastic pot, and when the 1.5 leaf stage is reached, the compound represented by formula (I) or the compound represented by formula (IV) is predetermined. 10 ml of chemical solution adjusted to the concentration was sprayed with a spray gun. After the chemical solution was dried (on the day of treatment), it was inoculated with summer spores of Puccinia recondita and kept in a constant temperature room at 20 ° C. The spore formation area was investigated 6 to 7 days after the inoculation, and the control index was determined according to the above evaluation criteria. When the compounds No. I-3, I-4, I-21, I-32, I-33, I-34 and IV-2 were tested, they showed an effect of a control index of 4 or more at 200 ppm.

Test Example 6 (Tomato plague prevention effect test)
Tomato (variety: yellow pair) was cultivated in a 7.5 cm diameter plastic pot, and when reaching the third leaf stage, 10 ml of a chemical solution adjusted to a predetermined concentration with the compound represented by formula (I) was sprayed with a spray gun. . After the drug solution was dried (the day after the treatment), a zoospore suspension of Phytophthora infestans was spray-inoculated and kept in a 20 ° C. inoculation box for 18 hours, and then kept in a constant temperature room at 20 ° C. Three days after the inoculation, the lesion area was examined, and the control index was determined according to the evaluation criteria. The compounds No. I-29, I-38, I-39, I-40, I-41 and I-70 were tested and showed an effect of a control index of 4 or more at 400 ppm.

Formulation Example 1
(1) Compound of the present invention 20 parts by weight (2) 72 parts by weight of clay (3) Sodium lignin sulfonate 8 parts by weight or more is uniformly mixed to obtain a wettable powder.

Formulation Example 2
(1) Compound of the present invention 5 parts by weight (2) Talc 95 parts by weight or more is uniformly mixed to obtain a powder.

Formulation Example 3
(1) Compound of the present invention 20 parts by weight (2) N, N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene alkylphenyl ether 10 parts by weight (4) Xylene 50 parts by weight or more are uniformly mixed and dissolved. To make an emulsion.

Formulation Example 4
(1) Clay 68 parts by weight (2) Lignin sulfonic acid soda 2 parts by weight (3) Polyoxyethylene alkylaryl ether sulfate 5 parts by weight (4) Fine powder silica A mixture of each component of 25 parts by weight or more and the compound of the present invention Are mixed at a weight ratio of 4: 1 to obtain a wettable powder.

Formulation Example 5
(1) Compound of the present invention 50 parts by weight (2) Oxidated polyalkylphenyl phosphate triethanolamine 2 parts by weight (3) Silicone 0.2 parts by weight (4) Water 47.8 parts by weight or more uniformly (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are further added to the mixed and pulverized stock solution, and the mixture is uniformly mixed, granulated and dried to obtain a granulated wettable powder.

Formulation Example 6
(1) Compound of the present invention 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene phosphate ester 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight (1)- (3) is uniformly mixed in advance and diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove the acetone and form granules.

Formulation Example 7
(1) Compound of the present invention 2.5 parts by weight (2) N-methyl-2-pyrrolidone 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to give a trace amount of spray. (ultra low volume formulation).

Formulation Example 8
(1) Compound of the present invention 20 parts by weight (2) Oxidated polyalkylphenyl phosphate triethanolamine 2 parts by weight (3) Silicone 0.2 part by weight (4) Xanthan gum 0.1 part by weight (5) Ethylene glycol 5 Part by weight (6) Water 72.7 parts by weight or more are uniformly mixed and pulverized to obtain an aqueous suspension.

    The compound represented by the formula (I) exhibits an excellent effect as an active ingredient of agricultural and horticultural fungicides.

Claims (2)

Formula (I):

Wherein R ¹ and R ³ are each independently a hydrogen atom, alkyl optionally substituted with A, alkenyl optionally substituted with A, alkynyl optionally substituted with A, phenyl moiety is Q or Z Benzyl which may be substituted, naphthyl moiety in which naphthyl moiety may be substituted with Q or phenyl which may be substituted with Q or Z; R ² is hydrogen atom, alkyl which may be substituted with A, phenyl moiety Is benzyl optionally substituted with Q or Z or phenyl optionally substituted with Q or Z; X is a halogen atom; A is a halogen atom, cycloalkyl, hydroxy, alkoxy, haloalkoxy, phenyl moiety Benzyloxy optionally substituted with Q or Z, phenoxy optionally substituted with Q or Z, alkylthio, alkylsulfi Nyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, benzylthio where the phenyl moiety may be substituted with Q or Z, benzylsulfinyl where the phenyl moiety may be substituted with Q or Z, phenyl moiety with Q or Z Benzylsulfonyl which may be substituted, phenylthio which may be substituted with Q or Z, phenylsulfinyl which may be substituted with Q or Z, or phenylsulfonyl which may be substituted with Q or Z; Z is substituted with Q Phenyl optionally substituted with Q, phenoxy optionally substituted with Q, phenylthio optionally substituted with Q, phenylsulfinyl optionally substituted with Q or phenylsulfonyl optionally substituted with Q; Q is a halogen atom , Alkyl, alkoxy, Aroalkyl, haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, nitro or cyano]], 1,2 and 3-substituted imidazolium salts represented by Disinfectant. A method for controlling plant diseases, comprising applying the 1,2,3-substituted imidazolium salt represented by the formula (I) according to claim 1 to an agricultural or horticultural plant.