WO2002034049A1 - Microbicide compositions for agricultural and horticultural use containing sulfonanilide derivatives - Google Patents

Abstract

Microbicide compositions for agricultural and horticultural use, containing as the active ingredient sulfonanilide derivatives of the general formula (I) or their salts. The compositions are safe by virtue of their little influence on human beings, domestic animals, natural enemies, the environment, fish, and crops, and exert excellent controlling effects even on resistant microbes.

Description

 Description Microbicidal composition for agricultural and horticultural use containing sulfonalide derivative

 TECHNICAL FIELD The present invention relates to a microbicidal composition for agricultural and horticultural use containing a sulfonulylide derivative. Background art

Conventionally, a large number of compounds having a microbicidal activity have been synthesized and used as agricultural and horticultural microbicidal compositions, thereby contributing to the stable supply of agricultural crops. It is well known that drug-resistant microorganisms have been generated and become a problem due to the extensive use of compounds in a limited range. 'In addition, with the increasing demand for the safety of chemical substances and the impact on the environment, there is a need for the development of safer microbicidal compositions for agricultural and horticultural use. For this reason, exploratory research has been conducted on compounds having novel microbicidal activity. Attention has also been paid to the biological or chemical properties of sulfone aeride derivatives, and numerous compounds have been synthesized to date. However, most are synthetic intermediates, pharmaceuticals, compounds or reagents synthesized to elucidate chemical reactions. For benzenesulfonanilides intended for use as microbicidal compositions for agricultural and horticultural use, see JP-B-44-9304, JP-B-45-6836, JP-B-46-6797, and JP-B-46-41638. JP-B-47-15119, JP-A-56-20564, JP-A-57-31655, JP-A-58-118558, JP-A-58-219159, JP-A-61-197553, JP-A-61-200959, JP-A-61-200960, JP-A-61-205247, JP-A-61-205248, JP-A-61-257960, JP-A-61-271270, JP-A-61-271270 62-190104, JP-A-63-270658, JP-A-11-156953, JP-A-11-272566, JP-A-2-72151, JP-A-2-96560, JP-A-2-212467, JP-A-2-231465, U.S. Patent No. 4,497,828, U.S. Patent No. 4,551,478, Patent No. 1933390, Patent No. 193, Patent No. 197, 254, 47, Journal of the Pharmaceutical Society of Japan, Vol. 21 No. 1, No. 31-35 (1 9 9 6)), Journal of the Japanese Agricultural Pharmaceutical Society, Vol. 22, No. 2, pages 176-184 (1997). However, there is no report on the use of penzinoles sulfonides and styrene sulfonides as microbicidal compositions for agricultural and horticultural use.

 In the above-mentioned known patents and literatures, the substituents on the two benzene rings of benzenesulfonanilide have been studied, and a nitro group or trifluoromethyl has been added to the 3-position of the benzene ring on the benzenesulfol side. A compound that has an ethoxy group or a trifluoromethyl group at the para-position of the benzene ring on the arin side and a halogen atom or a methyl group at the ortho-position is resistant to soil diseases such as clubroot. It is reported to have excellent effects. However, Journal of the Japanese Society of Pesticides, Vol. 21, No. 1, pages 31-35 (1996), Journal of the Japanese Society of Pesticide Science, Vol. 22, No. 2, pages 176-184, (199) 7 years), it is reported that a compound having an etro group at the ortho position of the benzene ring on the aniline side loses its activity. Compounds having a haloalkyl group, a cyano group, or a thiocarbamoyl group at the onoleto position of the benzene ring on the phosphorous side are those having a benzenesnolephoeno W rule of 41-triphnoleo-methinolebenzenes / lefonyl, 3,5- It has not been reported except for compounds which are disubstituted benzenesulfonyl.

 In addition, sulfoneride derivatives that have little impact on humans, natural enemies, the environment, fish, and crops, are safe, and have an excellent control effect on resistant microorganisms have not yet been developed. Summary of the Invention

An object of the present invention is to provide an agricultural and horticultural microbicidal composition containing a sulfonanilide derivative, which has a small effect on human animals, natural enemies, the environment, fishes and crops, is safe and has an excellent control effect on resistant microorganisms. In order to solve the above-mentioned problems, the present inventors have conducted intensive studies for many years in order to find a compound having an excellent microbicidal activity, and as a result, have found that a sulfonyllide derivative having a specific structure or a salt thereof Surprisingly have a very strong microbicidal action and It has been found to have little impact on livestock, natural enemies, the environment, fish and crops and is safe. As a result of further intensive studies based on these findings, the present invention has been completed. The present inventors have conducted intensive studies for many years to find a compound having excellent microbicidal activity in order to solve the above-mentioned problems, and as a result, surprisingly, a sulfonuride derivative having a specific structure or a salt thereof was unexpectedly obtained. Have a very strong microbicidal action and have little effect on humans, livestock, natural enemies, the environment, fish, and crops. As a result of further intensive studies based on these findings, the present invention has been completed. That is, the present invention

 (1 set

(Wherein, X ^1, X ^2, X ³ and X ⁴ are each independently a hydrogen atom, an alkyl group, 〇 preparative ₃ alkoxy group, a halogen atom or Shiano group, Y 〇 DOO ₃ Haroa alkyl group, Chio a carbamoyl group, Shiano group or a nitro group, Z is 〇 ₃ §. alkyl group, an alkylthio group, 〇 preparative ₃ alkoxy group, a halogen atom, an Shiano group or a nitro group, a is a chemical bond, methylene group or a vinylene group And m represents 0, 1, 2, 3 or 4.) A microbial biocidal composition for agricultural and horticultural use containing the sulfonanilide derivative (I) or a salt thereof as an active ingredient;

 (2) The agricultural or horticultural microbicidal composition according to the above (1), wherein A is a chemical bond;

(3) The microbicidal composition for agricultural and horticultural use according to the above (2), wherein X ¹ , X ² , and X ⁴ are a hydrogen atom, and X ³ is a hydrogen atom or an _—3 alkyl group;

 (4) The microbicidal composition for agricultural and horticultural use according to the above (2), wherein Y is a nitro group.

 (5) The microbicidal composition for agricultural and horticultural use according to the above (3), wherein Y is a nitro group.

 (6) The microbicidal composition for agricultural and horticultural use according to the above (3), wherein Y is a cyano group.

(7) Z is a halogen atom, methylthio group, cyano group or -toro group, and m is one or more. Or (2) the microbicidal composition for agricultural and horticultural use according to the above (5),

 (8) The microbicidal composition for agricultural and horticultural use according to the above (6), wherein Z is a halogen atom, a methylthio group, a cyano group or a nitro group, and m is 1 or 2.

 (9) The microbicidal composition for agricultural and horticultural use according to the above (7), wherein the sulfonanilide derivative (I) is 4'-chloro-2 ', 6'-dinitro-1p-toluenesulfonarylide;

 (10) The microbicidal composition for agricultural and horticultural use according to the above (7), wherein the sulfonanilide derivative (I) is 4 'monochloro 1 2'-two-row p-toluenesulfonanilide;

(11) The microbicidal composition for agricultural and horticultural use according to the above (7), wherein the sulfonanilide derivative (I) is 4'-l-cyano-1'-nitro-p-toluenesulfonylanilide;

(12) The microbicidal composition for agricultural and horticultural use according to the above (7), wherein the snorehonanilide derivative (I) is 4, -methylthio- 1'-two-tro-p-toluenesulfone alide.

 (13) The microbicidal composition for agricultural and horticultural use according to the above (7), wherein the snorehonanilide derivative (I) is 2 ′, 4 ′ giniro-p-toluene: sulfonic acid auride;

 (14) The microbicidal composition for agricultural and horticultural use according to the above (8), wherein the sulfonanilide derivative (I) is 2, -cyano 4'-methylthio-1p-toluenesulfonide;

 (15) The microbicidal composition for agricultural and horticultural use according to the above (8), wherein the sulfonanilide derivative (I) is 2'-cyano 4'-nitro-p-toluenesulfone alide; and

 (16) The present invention provides the microbicidal composition for agricultural and horticultural use according to any one of the above (1) to (15), which is used for disinfecting clubroot fungi or Aphanomyces spp. On cruciferous crops. Embodiment of the Invention

The sulfonanilide derivative (I) may have optically active, diastereomeric and / or geometric isomers. The present invention includes each of these isomers and a mixture of these isomers. X ^1, X ^2, as the 〇 bets ₃ alkyl group for X ³ and X ⁴ methyl group, Echiru group, a propyl group, and isopropyl group, _ ₃ main DOO alkoxy group as the alkoxy group, an ethoxy group, a propoxy group And an isopropoxy group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the haloalkyl group for Y include, for example, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, chlorofluoromethyl group, bromofluoromethyl group, chlorodifluoromethyl group, Nore, trichloromethyl, tribromomethinole,

2,2,2-Trifnoroleochinole group, 2,2,2-Trichloromethyl group, 1,1,2,2-tetrafluoroethyl group, Pentafluoroethyl group, 2,2 , 2-trifluoro-11- (trifluoromethyl) ethyl group, heptafluoropropyl group and the like. ·

Methyl group as the alkyl group in Z, Echiru group, a propyl group, and isopropyl group, methylthio group as 〇 bets ₃ alkylthio group, Echiruchi O group, propylthio group, and an isopropylthio group, 〇 ₃ alkoxy groups Examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

A is preferably a chemical bond, and X ¹ and X ⁴ are preferably hydrogen atoms. X ² and X ³ are preferably a hydrogen atom or a _—3 alkyl group, particularly preferably a hydrogen atom, a methyl group or an ethyl group. Y is preferably a cyano group or a nitro group, particularly preferably a nitro group. Z is preferably a halogen atom, a methylthio group, a cyano group or a -toro group, and m is preferably 1 or 2, and particularly a compound in which _m = 1 is substituted at the para-position of the adiline portion of the sulfonanilide. preferable. The salt of the sulfonide derivative (I) may be any salt acceptable in agrochemical chemistry. When the sulfonide derivative (I) has basic properties, for example, salts of inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, etc. , For example formic acid, acetic acid, propionic acid, tartaric acid, malic acid, citric acid, Salts of organic acids such as acid, succinic acid, benzoic acid, picric acid, methanesulfonic acid, p-toluenesulfonic acid and the like can be mentioned. When the sulfonanilide derivative (I) has an acidic property, for example, an alkali metal salt such as lithium, sodium, and potassium; an alkaline earth metal salt such as magnesium and calcium; for example, iron, copper, zinc, and manganese; Heavy metal salts such as ammonia, methylamine, dimethylamine, trimethylamine, triethynoleamine, ethylenediamine, TME DA (tetramethylethylenediamine), aniline, N, N-dimethyl / leaniline, pyridin, lutidine, Examples thereof include ammonium salts such as collidine and hydrazine, for example, salts with urea, guanine and the like. (2) When the above sulfonanilide derivative (I) or a salt thereof is used as a microbicide composition, it is used in a form known per se, which can be used for a general agricultural chemical composition. That is, one or more of the sulfonanilide derivative (I) or a salt thereof

(Preferably 1 to 3) as an active ingredient is mixed or dispersed with an appropriate liquid carrier, or mixed or adsorbed with an appropriate solid carrier depending on the purpose of use, as an emulsion, oil, aqueous suspension, Emulsion, liquid, ULV, wettable powder, powder, DL (driftless) powder, granule, fine granule, fine granule F, flowable, drive mouth abs, tablet, jumbo, spray, ointment, paste, Used as a form for foams, aerosols, microforces, seed coatings, smokers, and sticks for plant irrigation. These preparations may be used, if necessary, for example, emulsifiers, suspending agents, spreading agents, penetrants, wetting agents, dispersants, mucilage agents, stabilizers, binders, flow aids, anti-caking agents, flocculants, oxidants Inhibitors, suspending agents, antifoaming agents, antifreezing agents, preservatives, moisture removers, ultraviolet absorbers, ultraviolet scattering agents, coloring agents, suspension stabilizers, etc. may be added, prepared in a manner known per se can do. That is, it can be produced by uniformly mixing the sulfonide derivative (I) or a salt thereof, a liquid carrier or a solid carrier, the above-mentioned various additives as required, and other agricultural chemical components. For example, an emulsion can be produced by uniformly mixing and dissolving a sulfonanilide derivative (I) or a salt thereof, an emulsifier, an organic solvent and the like. For example, granules, wettable powders Can be produced by uniformly mixing and granulating a sulfonanilide derivative (I) or a salt thereof, a dispersant (surfactant), a binder, a bulking agent (or a solid carrier), and the like. For example, powders, DL powders and the like can be produced by uniformly mixing and pulverizing a snorehon-lide derivative (I) or a salt thereof, a bulking agent (or a solid carrier) and the like. For example, a flowable agent is produced by mixing and dispersing components such as a sulfonanilide derivative (I) or a salt thereof and a dispersant using a stirrer, and wet-milling using a dyno mill or the like. For example, a jumbo agent can be produced by uniformly mixing and granulating a sulfonamide derivative (I) or a salt thereof, a dispersant (surfactant), a binder, a suspending agent, a bulking agent (or a solid carrier), and the like. . '

Jumbo powders, powders, granules, wettable powders, wettable powders, etc. may be packaged in water-soluble films in 20 to ²⁰⁰ g units for easy application. Examples of the water-soluble film include polyvinyl alcohol, carboxymethylcellose, starch, gelatin, polypyrrolidone, polyacrylic acid and salts thereof, and pullulan (trade name, sold by Hayashibara Co., Ltd.). And starch-based polysaccharides, and thermoplastic water-soluble polymers such as Paogen (trade name, sold by Dai-ichi Kogyo Seiyaku Co., Ltd.). Examples of the liquid carrier (solvent) used include water, methanol, ethanol, propanol, isopropanol, alcohols such as ethylene glycol, etc., ketones such as acetone, methyl ethyl ketone, etc., for example, 1,4-dioxane, tetrahydrofuran Ethers such as ethylene glycolone monomethyl ether and propylene glycol monomethyl ether; ethylene hydrocarbons such as kerosene, kerosene, fuel oil, machine oils, and edible oils such as benzene and toluene , Xylene, solvent naphtha, methylnaphthalene, etc., aromatic hydrocarbons, such as dichloromethane, chloroform, carbon tetrachloride, etc., halogenated hydrocarbons, such as N, N-dimethylformamide, N, N-dimethyl Solvents such as acid amides such as acetamide, for example, esters such as ethyl acetate, butyl acetate, and fatty acid glycerin ester, and nitriles such as acetonitrile and propionitrile are suitable, and one or two of these are suitable. The above (preferably 1 to 3 types) can be mixed at an appropriate ratio and used as appropriate. Examples of solid carriers (diluents and measuring agents) include vegetable powders such as soybean flour, tobacco flour, flour, and wood flour; clays such as kaolin, bentonite, and acid clay; Talcs, for example, mineral powders such as silicas such as diatomaceous earth and mica powder, calcium carbonate, alumina, sulfur powders, activated carbon and the like are used, and one or more (preferably one to three) of these are suitably used. It can be used as appropriate by mixing in proportions. Examples of ointment bases include, for example, polyethylene glycol, polyethylene, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methylcellulose, sodium alginate, bentonite, higher alcohols, such as glycerin One or more of polyhydric alcohols such as petrolatum, petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hardened oil, resins, etc. (preferably:!: ~ 3 types). Alternatively, those obtained by adding various surfactants shown below to the above or the like are appropriately used. 'Surfactants used as emulsifiers, spreading agents, penetrants, and dispersants include, as necessary' stones, polyoxyethylene alkylaryl ethers [e.g., Neugen

™ (TM indicates that it is a registered trademark), 'A 142 (E · A142) ™; Daiichi Kogyo Seiyaku Co., Ltd., Nonal ^; Toho Chemical Co., Ltd.] , 'Alkyl sulfates [eg, Emar 10 ^™ , Emar 40 ^™ ; manufactured by Kao Corporation], alkyl sulfonates [eg, neogen, Neogen T ^™ ; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neopellets box; manufactured by Kao Corporation], polyethylene glycol ethers [e.g., Nonipol 8 5 ^TM, Nonipol 1 0 0 ^TM, Nonipol 1 6 0 ™; Sanyo Kasei Co., Ltd.], Okaa Le call esters [e.g., Nonionic and anionic surfactants such as Tween 20 ^™ and Tween 80 ^™ ; manufactured by Kao Corporation]. Also, the sulfonanilide derivative (I) or a salt thereof and, for example, an insecticide, an acaricide, a nematicide, a plant hormone, a plant growth regulator, a fungicide, a synergist, an attractant, a repellent, a pigment, a fertilizer. Can be used as appropriate.

That is, the present invention includes an agricultural and horticultural microbicide containing the sulfonanilide derivative (I) or a salt thereof and another pesticidal active ingredient. Other pesticide active ingredients It may be contained in the same preparation as the sulfonide derivative (I) or a salt thereof. Alternatively, they may be mixed at the time of use after being formulated into separate formulations. Representative examples of insecticides, acaricides, and nematicides that can be used by mixing with the sulfonanilide derivative (I) or a salt thereof are shown below. Asefeto (a _Ce phate), Asetamipu di K cetamiprid), Akurina Bok Jin (acrinathrin), Aranikanorebu (alanycarb), aldrin (aldrin), allethrin (allethrin), aluminum phosphide (Aluminum phosphide) amino Torazu (amitraz), arsenite Acid (Arsenic acid), avermectin '(avermectin-B), Benyaku, becaniolev, benfracanoleb

 (benf uracarb), bensultap, benzoximate, bifenthrin, bromopropylate, bromopropylate, buprofezin, calcium cyanamide, calcium-sulfur mixture (Calcium) ■ polysu'lfide), 'power.; / Renjinore (carbaryl: NAC), canolebofuran (carbofmran), canolepo. Sunorejuan (carbosul.fan),' cartap ', cartap, chronoreden (chlordane), ク ロ kuronorefembinphos (Chlorfenvinphos: CVP), chlorfenorezuron

 (chlorfluazuron), chronorefenapinore (chlorphenapyr), chronorepidiphos-methinore (chlorpyrif os—methy 丄), 'ku' romafuenoji r (chromaf enozide), kurofuena ■ gin (clofentezine), clothianidin, cynoanidin

 (cyanophos: CYAP) cycloprothrin

(cyf luthrin) Sinoヽport Bok phosphorus (Cyhalcrthrin), Shiperume Bok phosphorus (cypermethrin), Shiroma, non cyromazine), DCIP (dichlorodiisopropyl ether; Λ D- D (l, 3- Dichloropropene), DDT, Derutame Trinh ( deltamethrin), diafenthiuron, diazinon, diclofenthion

 (dichlofenthion), dichlorvos (DDVP), dicohol (dicofol), dinoredrin (dieldrin), dienochronole (dienochlor), diphnolebenzuron

 (dif lubenzuron), dimethoate, dimethinolevinphos

(dimethylvinphos), disulfoton, DSP, endosulfan, EPN, esfenvalerate, ethion, ethion, ethofenprox, ethoprophos, Ethoxazole, fenbutatin oxide, fenitrothion (MEP), fenobucarb, fenothiocarb, fenothiocarb, fenoxycarb, fenpropathrinヽ Fenpyroximate, fenvalerate, fipronil, fuoreazinam, fluazinam, flucitrinate, flufenoxuron, flupyrazofos, (F luvalinate), honole metalate

(formetanate) honoremothion (formothion), phosthiazate (fosthiazate), furathiocanoleb (furathiocarb), nonorefenprox (haLf enprox), hexafenolemuron (hexaflumuron), hexthithiazox (hexythiazox); Lee Mita ,, Kuropuri de, ltnidacloprid), isofenphos (isofenphos Roh, Isopurokanorebu _(i soprooar b), isoxathion (isoxathion), malathion ■ (malathion) ,, female Norre Fen host (mesulf enfos), metam 'Anmoniumu (metam - ammonium ), Metha-nat-rimu (metam- sodium), methita, ss (.methidathion ;, methiocanoleb (methiocarb), methinoyl (methorayl), methoxycyclonole .nethoxychlor, methoxyphenozide, methoxyfenozide, Methyl bromide), methanolecanoleb (metolcarb: MTMC), Norebe mycin lambda (Milbemycin one A;), monocrotophos _(monocro tophos), naled (naled: BRP), nicotine sulfate

(nicotine- sulfate), nitinotefuran (nidinotefuran

(nitenpyram), oxamyl, oxydeprofos (ESP), ヽ⁰ lathion, parathion, ぺ normethrin perme1: hrin), fentoate

(phenthoate: PAP), hosalon (phosalone), phosmet (phosmet: PMP), pirimicarb (piriraicarb), pirimiphos Methinole (piriraiphos-methyl), potassium oleate (Potassium oleate), profenofos, propaphos

(propaphos) _N- Prono ^ / Regito (propargite: BPPS), Proboxisnore (propoxur), Prothiofos, Protrifenbute, Promefenzine, Pymetrozine, Pyraclofos, Pyrethrin pyrethrins , Pyridaben (pyridaben), pyridafenthion (pyridaf enthion), pyrimidifen, pyrimidifen ヽ hirarif-roxifen (pyriproxyfen), quinanolephos ^ quinalphos ヽ Resmethrin, salithion, silafluofen

(silafluofen), sulfur (Sulfur), sulprofos (sulprofos), tebufenozide (tebufenozide), tebufenpyrad (tebufenpyrad), tefluvenzuron

(tef lubenzuron) _s Tefunore Bok phosphorus (tefluth: rin), temephos (temephos), Te Bok easier Ronorebinhosu (tetrachlorvinphos), tetradifon (tetradifon), Chiakuropuri de (thiacloprid), Chiame Tokisamu (thiamethoxatn), Chioshikuramu (thiocyclara), Chiojikanorebu (Thiodicarb), thiometon, tolfenpyrad

(tolfenpyrad), tralomethrin, trokumethorin

(trichlorfon: DEP), triflumuron (tr lutnuron), nomidthione

(vamidothion) ^ XM C ヽ acequinocyl (acequinocyl, 3-dodecyl_l, 4_dihydro-

1,4-dioxo-2-naphthyl acetate), acetoprole, (RS) -to- [5-amino- 1- (2,6_dich 丄 oro—α, a, a-trifluoro—p—tolyl) Four

methylsulfinyl) pyrazol_3-—yl ”ethanone) ヽ bis rif luron, 1- [2-chloro_3,5-bis (trii 丄 uo: romethyl) phenyl] —3 -— (2,6-difluorobenzoy 丄) urea), Cybutryne (cybutryne, INF-tert-butyl-N ^4- cyclopropyl-6_methyl1: hio-1, 3, 5-triazine-2, 4-diamine), Tinotefuran (.dinotefuran, (RS) _1— methyl-2— nitro-3- (tetirahydro_3— furylraetnyl) guaniame), ethibu n-one, ethip: ro 丄 e, 5-amino-1 (2-, 6-dichloro-hi,, α-trifluoro-p-tolyl)-4- ethylsulf inylpyrazole-3-carbonitrile) _s -funolecripyrim (fluacrypyrira, NA-83, methyl (E) -2 ~ ta ~ [2-isopropoxy-6- (trif luorometnyl) pyrimidin-4- yloxy] -o-tolyl} -3-me thoxyacrylate) ^ flunicoamid, IKI-220, indoxacarb, methyl (S) _N-[7-chloro-2, 3, 4a, 5-tetrahydro- 4a- (methoxycarbonyl) indeno [l, 2- e] [1, 3, 4] oxadiazin-2-ylcarbonyl] -4'- (trif luoromethoxy carbanilate Or methyl (S) -7-chloro-2, 3, 4a, 5-tetrahydro-2- [methoxycarbonyl (4- trif luoromethoxyphenyl) carbamoyl] indeno [1, 2-e] [1, 3, 4] oxadiazine- 4a- carboxylate), spinosad (spinosad,

(2R, 3aS, 5aR, 5bS, 9S, 13S, 14R, 16aS, 16bR)-2-(6-deoxy—2,3,4-tri-1 0-methyl-a_shiichi mannopyranosyloxy) -13- (4 One dimethylaraino-2, 3, 4, 6-tetradeoxy-] 3— D- erythropyranosyloxy) _9_ethyl_

 2, 3, 3a, 5a, 5b, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16a, 16b-hexadecahydro-14-methyl-lH-8-oxacyclododeca [b] as-indacene- 7, 15-dione 5 0 to 95%, and

 (2S, 3aR, 5aS, 5bS, 9S, 13S, 14R, 16aS, 16bR)-2-(6-deoxy-2, 3, 4- tri-0-methyl--mamiQpyranosy 丄 oxy)-13-(4- dimethylamino-2, 3, 4, 6-tetradeoxy- β-D-erythropyranosyloxy) -9-ethyl-

2, 3, 3a, 5a, 5b, 6, 7, 9, 10, 11, 12, 13, 13, 15, 16a, 16b-hexadecahydro-4, 14- dimethyl-lH-8-oxacyclododeca [b] as- indacene-7, 15-dione 50 0-5% mixture), spirodiclofen, 3- (2,4-dichlorophenyl) -2-oxo_l-oxaspiro [4.5] dec-3-en ~ 4-yl 2, 2-dimethylbutyrate), ΊΊ-809. Typical examples of fungicides that can be used in a mixture with the sulfonanilide derivative (I) or a salt thereof are shown below. For example, acetic acid, acetic acid. S ■ Methyl ·· cibenzolar-S-methyl) anamom, a-razine (anilazine); 'azoki' cystrobin (azoxystrobin), benominole, benizazonore

 (benthiazole), bitertanol, blasticidin. S

(blasticidin-S) Bonoredo liquid (Borde test mixture), Bromconazo monole

(bromuconazole), buthiobate (buthiobate), hypochlorite Kanoreshiumu (Calcium hypochlorite), lime sulfur (Calcium polysulfide), Kiyaputan (Captan), a force Honoré vendor zone Honoré (carbendazol), the force Norepuronoヽ⁰ mi de (Carpropamid ), IKF—9 1 6

(4- ch 丄 or.-2- cyano-N, N-dimethyl-5- p-tolylimidazole-1-sulfonamide) ヽ ク ロ 口 Neb (chloroneb), Chronolepicrin (chloropicrin), Chlorothalinole

(chlorothalonil: TPN), cinnamon aldehyde (Cinnatnaldehyde), RH _ 7 2 8 1 (3, 5-dichloro-N- (3-chloro-l-ethyl-l-methyl-2-oxopropyl 4-methylbenzamide) _N CNA (2, 6-Dichloro_4-nitroaniline), copper hydroxide

(Copper hydroxide), Copper sulfate, AC 3 8 0 4 2 (N- (T cyano-1, 2-dimethylpropyl) -2- (2, 4-dichlorophenoxy) propionamide (R, S) -and (R, R)-and (S, R)-and (S, S)), cymoxanil (cyrao x anil), cyproconazo monole

(cyproconazole) ^ cyprodinil, dazomet, Diklov Dichlof luanid, D—D (1,3-Dichloropropene), diclocymet (diclocymet;), diclomedin (diclomezine), dietofencanoleb

(diethof encarb) _s difenoconazole (difenoconazole), diphnomoletrim (diflumetorim), dimmetrimonole, aimetirimol), dimethomorph (dimethomorph), dinoconazole (M), dinocapate (dinocap), dizomiresin (Etridiazole), famoxadone, fenarimol, fenbuconazole, fenhexazolam, fenhexamid, fenoxanil (NF-9425: fenoxanil), fenpinilil fenpiclonil), fenthiazon (fentiazon), 7 acid disulfide trifenenoles (fentin hydroxide), ferimzone

(ferimzone), fluazinara (fluazinara), fluodioxonil (fludioxonil), flunoremetoba (RPA-403397: flumetover), flunolenoreimide (fluoroimide), funolequin conazo mono (fluquinconazole), funoresnolefamide (f lusatn) . ヽ ノ レ ニ (fl.utolanil), josetil (fosetyl-Al), fthalide (fthalide), flamedovir (furaraetpyr) _s hexanazonole (hexaconazole), hymexazolol (hymexazol), imazalinol ol Nore (imibenconazole), iminoctadine-anolebecinoleate (iminoctadine— albesilate), iminoctadine acetate

 minoctadine-triacetate, yo-kanorebu odocarb), ifconazo-nore

(ipconazole), ipron-one, iprodione), isof-mouth teofon '(isoprotniolane eight kasugamycin (kasuga.mycin), kresoxim. methinole (kresoxim-raethyl), mancozeb (mancozeb), maneb (maneb), menopirim nepaniprim , Mepronil, metalaxylone (metalaxyl), metalaxylone M (metalaxyl-M), 'metam' sodium (metam-sodium), methasulfocarb (methasulfocarb), methyl bromide (methyl bromide), RPA 4 0 7 2 1 3 ((s) -5-methytri 2-methylthio-5-phenyl—3—phenylamino—ύ, 5_dihydroitnidazol—4—one), meth ^ nostrohin

(metominostrobin ^ Noreti old hygromycin (mildiomycin, Minorenebu (mil neb), Mi Kurobutaninore _(myc lobutanil), Nabamu (nabam), Okisajikishinore (oxadixyl), Okisoryukku acid (oxolinic acid), O carboxymethyl Poco Nazo Honoré (oxpoconazole), O key Shikanorepoxin (oxycarboxin oxytetracycline), ぺ Furazoate (pefurazoate), Penconazo mono (penconazole), Pencic mouth (pencycuron), Picoxyst mouth bin (picoxys robin), Polycarbamate

(polycarbamate), polyoxin, potasium hydrogen carbonate (Prozon-pronazole, probenazole), fukurofuzu

(prochloraz), procymidone, propamocalp hydrochloride

 (propamocarb-hydrochloride, propiconaole, propineb, pyrazophos, pyributicarb, pyrifenox, pyrimetanil, pyroquilon

(pyroquilon) _N 'Quinoxifene (qui band yf en), quintozene (quintozene: PCNB), si / retio-off arm (M0N65500: silthiopham), sipconazonole (sipconazole), sodium hydrogencarbonate (sodium bibarbonate), sodium hypochlorite (Sodium hypochlorite), SSF- 12 9 ((E) -2 [2- (2,5- · dlmethyl'phenoxytnethyl) phenyl] 1-2- methoxyimino_N-methylacetamide) Small streptomycin, sulfur , Tebuconazonole (tebuconazole), techoku phtalam (tecloftalam), tetraconazo monole (te raco basket ole eight thiabendazonore (thiabendazole), thiuram (thiram: TMTD), tifunorezamide (thifluzamide), thiophanate methimefion ), Triadimenol (triadimenol), tricyclazole (tricyclazole), tridemolenolef (tridemorph), triflumizole ( tr: if lumizole), trifloxystrobin, JJ holin (triforine), nodidamycin (val idamycin), vinclozolin (vi _nc l _ozo l in), zineb (zineb), ziram (ziratn), besoxazine ( bethoxazin, 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxide ヽ BJL994, carbendazim, cyfluphenamid, NF- 149), epoxyconazole (epoxiconazole, (2RS, 3SR)-1- [3_ (2-chlorophenyl)-2, 3_epoxy- 2--(4-fluoroorophenyl) propyl]-1H-1, Δ, 4-triazole) , Ethaboxam, (RS) _N_ (a-cyano-2-thenyl) —4_ethyl_2— (ethylamino) -1,3-thiazole-5_carboxaraide, fenamidone (fenamidone, (S) -1-ani lino-4 methyl _2- methylthio- 4 phenylimidazolin- 5-one), fenpropimonoref

(f enpropimorph), flusi lazole, fbergignore (fuberidazole), I pro Barika Norev (iprovalicarb, isopropyl 2- methyl- 1 over [(1- p-tolylethyl) carbamoyl ] - (S) -propylcarbamate) s Pikokishisuto opening bottles

(picoxystrobin, methyl (E) -3-methoxy -2-{2-[6-(trif luoromethyl)-2- pyridyloxymethylj phenyl} acrylate), pyraclostrobin, methyl N- (2- (1- (4 -chlorophenyl)-ΙΗ-pyrazol- 3- yloxymetnylj phenyl} (N- methoxy) carbamate) Simeconazole '~ sorecon (simeconazole, (RS) — 2— (4—

fluorophenyl)-1-(1H-1,2,4-triazol-l-yl) -3- (trimethylsilyl) propan ~ 2-ol), spiroxamine (8-tert-butyl-l, 4-dioxaspiro [4 5] decan-2-ylmethyl (ethyl) (propyl) amine), trifloxystrobin, methyl (E) -methoxyimmo- {(^ -α-[1- (a, a _{? A} -trif luoro -m-tolyl) ethylideneaminooxy]-o-tolyl} acetate), zoxamide (zoxamide, (RS)-3, 5-dichloro-N- (3-chloro- 1-ethyl-1-methyl- 2-oxopropyl) p -toluamide), benthiavalicarb (benthiavalicarb), thiazininole (thiadinil), fenoxanil (ethoxanil) ^ ethaboxam (ethaboxam). 'The diseases controlled by the sulfonanilide derivative (I) or its salt are: For example, blast (Pyricularia oryzae), sesame leaf blight +

(Helmmthosporium oryzae _N Cochliooolus miyabeanus) _N stupid ^ 內, Gibberel la fujikuroi), seedling blight (Rhizopus oryzae), sheath blight (Rhizoctonia solani), and other rice diseases such as crown rust (Puccinia coronata) Diseases of barley, for example, udon 內, Erysiphe graminis), Rynchsporium secalis ヽ spot disease

Diseases of barley such as (Cochliobolus sativus, ¾ ¾5¾ (Helmmthosporium grammeum, Pyrenophora grand m), net spot disease (Pyrenophra teres), net smut (Til letia caries), naked smut (Ustilago nuda), for example, powdery mildew (Erysiphe graminis), Leptosphaeria nodorum, ^ eptoria nodorum) // Hei (JPuccirda stri iformis) _s Brown small-grained bacteria (Typhula incarnata), Psudocercosporel la herpotrichoides, Red snow rot ( Calonectria graminicola, Fusarium nivale), black rust (Puccinia graminis), black blast (Typhula ishikariensis), red mold (Gibberel la zeae), red rust (Puccinia recondita, Puccinia triticina) f (Helminthosporium gramineum) Aphid H¾ disease (Til let ia caries), leaf blight

Wheat diseases such as (Septoria tritici) and naked smut (Ustilago tritici), for example, maize diseases such as seedling blight (Pythium debaryanum), for example, red snow rot

 Diseases of rye such as (Fusarium ni vale), for example, potato such as plague (Phytophthora infestans), for example, downy mildew (Peronospora tabacina), plague

 Phytophthora nicotianae var. Inside

 (Pythium aphanidermatum, Aphanomyces cochilioides) and other Anthe's;) reports, for example, diseases of paprika such as Botrytis cinerea, for example, Gray mold

(Botrytis cinerea), nucleus;) ¾ (clerotinia sclerotiorum), kidney diseases such as white bei (orticium rolfsii), such as powdery mildew (Erysiphe · 'pol'ygon'i, Sphaerotheca' fuliginea) ヽ rust f? F (Uromyces fabae, Uromyces 'phaseoli), Broad bean diseases such as Botrytis cinerea', Endo diseases such as root rot (Aphanomyces euteiches), and laccasei such as brown spot (Mycosphaerella arachidicola) Diseases, for example, cabbage diseases such as seedling wilt (Rhizoctonia solani), such as powdery mildew (Sphaerotheca fuliginea), vine disease

_(Fusarium oxysporum) Λ vine blight (Mycosphaerella melonis) base and ■;)內

 (Pseudoperonospora cubensis), Gray force, Blight (Botrytis cinerea), Sclerotia

(Sclerotinia sclerotiorum) Te (Colletotrichum lagenarium) ^

(Fusarium oxysporum, Pythium aphanidermatum, Rhizoctonia solani), Cucumber mosaic virus, etc. Disease of komatsuna, for example, celery disease such as leaf blight (Septoria apii), for example, radish disease such as chlorosis (Fusarium oxysporum), for example, wilt

(Fusarium oxysporum), projecting disease (Phytophthora infestans) _lambda Wamon炳(Alternaria solani), gray force, Pi's disease (Botrytis cinerea), gray blight (Phytophthora capsici), black spot disease (Alternaria tomato) tomato diseases such as, For example, eggplant diseases such as brown rot (Phytophthora capsici) and half body wilt (Vert ici Ilium albo-atrum), for example, black spots Diseases (Altemaria japonica) _s Diseases of Japanese cabbage such as root-knot disease (Plasmodiophora brassicae) such as plague (Phytophthora capsici) and peppers such as gray blight (Botrytis cinerea) such as Botrytis cinerea Diseases of lettuce, for example, diseases of citrus such as black spot (Diaporthe citri), for example, diseases of pear such as scab (Venturis nashicola) _s black spot; / Hei (Alternaria kikuchiana) _s Red scab (Gymno sporangium haraeanutn), For example, grape diseases such as downy mildew (Plasmopara viticola), gray mold (Botrytis cinerea), and black rot (Elsinoe ampelina); peaches such as wilt (Taphrina deformans) and perforated U¾ (Mycosphaerella cerasella); Notice, f row ■ Hatton powder hei '(Podosphaera leucotria), stiffness, disease (Cladsporium carpophilum), gray rickby (Botrytis cinerea) (Venturia inaequalis) _s Akahoshi

 (Gymnosporangium yamadae Diseases of apples such as white root rot (Rosellinia nectrix) and spot spots (Alternaria mali) such as oilseed rape such as radish (Phoma lingara), castor, carrot, capsicum, strawberry, melon Diseases of cereal fruits and vegetables such as kiwi fuorinetto, onion, yura, sardine, fig, plum, asparagus, oyster, soybean, azuki, watermelon, shiyuniku, spinach, tea, etc. Particularly, cruciferous plants (for example, , Canola, turnip, cauliflower, cabbage, komatsuna, rapeseed, Chinese cabbage)

It has an excellent control effect against soil diseases such as those caused by bacteria of the genus (Aphanomyces). The agricultural and horticultural microbicide containing the sulfonanilide derivative (I) or a salt thereof of the present invention as an active ingredient can be used in the same manner as a conventional microbicide. For example, it can be used for nursery box treatment, crop foliage application, post-transplant irrigation treatment, crop plant treatment, paddy water application, seed treatment or soil mixing treatment, direct application to fruit tree trunks, etc. Although it is possible to do so, it is particularly preferable to use a soil mixing treatment, a nursery box treatment or a treatment at the time of irrigation after transplantation.

The amount of application can be varied over a wide range according to the time of application, the place of application, the method of application, etc. In general, the amount of active ingredient (sulfoneuride derivative (I) or its salt) per hectare is zero. 3 g ~: LO, 00 g, preferably 50 g ~ 5, It is desirable that the application be made to be 0 0 g. When the composition of the present invention is a wettable powder, the composition is diluted so that the final concentration of the active ingredient is in the range of 0.1 to 10 ppm, preferably 10 to 10 ppm. And use it. The content of the sulfonide derivative (I) or a salt thereof is usually about 0.1 to 80% by weight, preferably about 1 to 20% by weight, based on the whole preparation. Specifically, when used in emulsions, solutions, wettable powders (eg, water-dispersible granules), aqueous suspension preparations, microemulsions, etc., they are usually about 1 to 80% by weight, preferably about 1 to 80% by weight. About 20% by weight is appropriate. When used in oils, powders and the like, the amount is usually about 0.1 to 50% by weight, preferably about 1 to 20% by weight. When used in granules, tablets, jumbo preparations and the like, the amount is usually about 5 to 50% by weight, preferably about 1 to 20% by weight. Other pesticidal active ingredients (eg, insecticides, acaricides, herbicides and Z or microbicides) incorporated in the composition of the present invention are usually about 1 to 80% by weight based on the total amount of the preparation. The preferred is about 1 to 20 weight. /. Used in a range of degrees. The content of additives other than the above-mentioned active ingredients varies depending on the type or content of the pesticidal active ingredient or the dosage form of the preparation, but is usually about 0.001 to 99.9% by weight, preferably about 1%. ~ 9.9 weight ° / ₀ . More specifically, the surfactant is usually about 1 to 20% by weight, preferably about 1 to 15% by weight, and the flow aid is about 1 to 20% by weight based on the total amount of the composition. It is preferable to add about 1 to 90% by weight, preferably about 1 to 70% by weight, of the carrier. Specifically, when a liquid preparation is produced, a surfactant is usually added in an amount of about 1 to 20% by weight, preferably about 1 to 10% by weight, and water is added in an amount of about 20 to 90% by weight. Is preferred. When used, the emulsion, water-dispersible powder (eg, water-dispersible granule) and the like are preferably diluted with water or the like and increased in volume (for example, about 100 to 5,000 times) before spraying. The sulfonide derivative (I) or a salt thereof can be prepared, for example, by condensing a specific raw material compound shown in the following method A and method B, or by converting a specific raw material compound shown in the method C into two or more. Can be manufactured.

[Method A]

(In the formula, X ¹ , X ² , XX ⁴ , A, Y, Z and m have the same meanings as described above, and L represents a leaving group.)

[Method B]

(In the formula, X ¹ , X ² , X ³ , X ⁴ , A, Y, ', and m have the same meanings as described above, and L ′ represents a leaving group.)

(In the formula, X ¹ , X ² , X ³ , and XA have the same meanings as above, and when Y represents a newly introduced nitro group, Y ° represents a hydrogen atom; Ζ ° and η each represent Represents the same meaning as と and m described above When at least one of Z represents a newly introduced nitro group, Y ° and Z ° represent the same meaning as Y and Z described above, respectively, and n represents Represents 1, 2, 3 or 4.) In method A, the leaving group L is, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, for example, a benzenesulfo-loxy group, a p-toluenesulfo -Represents an aromatic sulfonyloxy group such as a 4-hydroxyl-benzenebenzenesulfonyloxy group. In method B, submitted leaving group L, as, for example fluorine atom, chlorine atom, bromine atom, a halogen atom such as iodine atom, for example, main butoxy group, an ethoxy group, 〇 preparative ₃ alkoxy group such as a propoxy group, for example methylthio group, Echiruchio group, 〇 preparative ₃ alkylthio group such as a propylthio group, e.g. methane sulfide El group, Etansurufuie group, such as propane sulfide El group. C _{3 s-} alkane sulfonyl groups such as methans / lefonyl groups, ethanes-no-lefonyl groups, propanesulfonyl groups, etc. Aromatic sulfonyl groups such as benzene sulfoninole group and 4-nitrobenzene sulfoninole group; alkane sulfooxy groups such as methanesulfonyloxy, ethanesulfuroxy and propanesulfonyloxy groups; and benzenesulfonylo Aromatic sulfooxy groups such as xy group, p-toluenesulfonyloxy group, 4-nitrobenzenesulfonyloxy group, phenoxy group and the like. 'The reaction of Method A or Method B is usually performed in a solvent or without a solvent. Solvents used in a solvent include, for example, petroleum ether, pentane, hexane, and cyclohexane, hydrocarbons such as hexane, benzene, toluene, and xylene, for example, dichloromethane, chlorohonolem, and tetrahydrocarbon. Halogenated hydrocarbons such as 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethylene, and benzene, for example, dimethyl ether, diisopropylether, tetrahydrofuran, 1,4-dioxane, dimethoxetane, ethylene glycolone Aethenoles such as monomethinole ether and diethylene glycol dimethyl ether; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; and nitrinoles such as acetonitrile and propionitrile For example, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methinolepyrrolidone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; Examples of such compounds include benzene and other two-port compounds, for example, methanol such as methanol, ethanol, isopropanol, 1-butanol, alcohols such as ethylene glycol, carbon disulfide, and water. The reaction is carried out at a temperature of 100 to 300 ° C, preferably at 150 to 200 ° C, and a reaction time of 1 minute to 1 week, preferably 5 minutes to 24 hours.

Acids or bases may be added to promote the reaction, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid Inorganic acids such as acids, for example, formic acid, acetic acid, propionic acid, trifluoroacetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric acid, methanesulfonic acid, -toluenesulfonic acid, trifluorosulfonic acid Examples of the base include organic acids such as methanesulfonic acid and the like. Examples of the base include metal hydroxides such as lithium hydroxide, sodium hydroxide, hydroxy potassium and hydroxy calcium hydroxide, for example, sodium carbonate, potassium carbonate, and the like. Metal carbonates such as sodium bicarbonate and hydrogen bicarbonate, metal water such as sodium hydride, hydrogen hydride and calcium hydride Metal amides such as lithium disopropylamide, sodium amide and potassium amide; organic lithium reagents such as methyllithium, n_butyllithium, sec-butyllithium, tert-butyllithium and phenyllithium , For example, organic magnesium reagents (Grignard reagents) such as methylmagnesium bromide and ethylmagnesium chloride, and metals such as lithium metal, sodium metal, metal spheres, and the like, for example, trimethylamine, triethylamine, disodium Propylethylamine, N, N-dimethylaniline, pyridine, lutidine, coliidine, DMAP (4-dimethylaminopyridine), TME DA (tetramethylethylenediamine), DBU (1,8-diazabicyclo [5.4] . 0] Organic salts such as And the like. In order to promote the reaction, for example, titanium, vanadium, chromium, manganese, iron, konore, eckel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, force-donium, tungsten , Platinum, gold, mercury and other metal salts (eg oxides, fluorides, chlorides, bromides, iodides, sulfides, sulphates, nitrates, phosphates, perchlorates, etc.) or simple metals May be added as a catalyst in an amount of 0.001 to 1000 equivalents, preferably 0.001 to 10 equivalents. In the method C, the raw material represented by the formula (VI) can be produced by a method similar to the method A or the method B or a method analogous thereto.

The method used in Method C is 30 to 30%; LOO% nitric acid and fuming nitric acid are commonly used, for example, alkali metal nitrates such as sodium nitrate and potassium nitrate, and alkyl nitrates such as ethyl nitrate and amyl nitrate. , nitro Yu arm tetrafluoropropoxy O b Poreto (N 0 ₂ BF _4), nitro E © beam triflate Ruo b methanesulfonate _{(N 0 2 CF 3 S 0} 3), nitrogen oxides (e.g., N_〇 _2, N ₂ 0 ₃ it may be used N ₂ 0 There N ₂ 0 ₅₎ or the like. Particularly preferred is 50 to 100% nitric acid. The nitrating agent can be used in an amount of about 1.0 to 20 equivalents based on the raw material (VI), but is preferably 1.0 to 10 equivalents when nitric acid is used. Further, when using 90% or more of nitric acid, about 1.0 to 3.0 equivalent is preferable. '' The nitration reaction may be carried out without solvent, but is usually carried out in the presence of an acidic solvent such as sulfuric acid, acetic acid, acetic anhydride, anhydrous trifluoroacetic acid, and trifluorosulfonic acid. If desired, a solvent which does not adversely influence the reaction or a mixture thereof may be used. Examples of such a solvent include the same solvents as those described in Method A or Method B, in addition to the acidic solvents described above. These solvents can be used alone, or, if necessary, two or more (preferably two to three) in an appropriate ratio, for example, about 1: 1 to 1:10 (by volume) ) May be used as a mixture. If the reaction solvent is not homogeneous, for example, triethylbenzylammonium chloride, tri-n-octylmethylammonium chloride, trimethyldecylammonium chloride, tetramethylammonium-bromobromide, cetyl The reaction may be carried out in the presence of a quaternary ammonium salt such as pyridinium bromide or a phase transfer catalyst such as crown ethers. Particularly preferred solvents are acetic acid and acetic anhydride. The temperature of this reaction is usually in the range of about 150 to 200 ° C, preferably about 120 to: L30 ° C. Reaction times range from about 1 minute to 48 hours, preferably from about 15 minutes to 10 hours. Hereinafter, the present invention will be described in more detail with reference to Reference Examples, Examples, Formulation Examples, and Test Examples, which should not be construed as limiting. Silica gel / Recala for reference examples The elution in the column chromatography was performed under observation by TLC (Thin Layer Chromatograph, thin layer chromatography). In the TLC observation, Kieselgel 60 F254 (70-230 mesh) manufactured by Merck was used as the TLC plate, and the solvent used as the elution solvent in the column chromatography was used as the developing solvent. A UV detector or an iodine coloring method was adopted as a detection method. For the silica gel for the column, Kieselgel 60 (70 to 230 mesh) manufactured by Merck was used. When a mixed solvent is used as the developing solvent, the figures in parentheses indicate the volume mixing ratio of each solvent. The NMR (nuclear magnetic resonance) spectrum indicates proton NMR, which was measured with a Bruker AC-200P (200 MHz) spectrometer using tetramethylsilane as the internal standard. Values are given in ppm. The abbreviations used in the following Reference Examples, Examples and Tables have the following meanings. s: singlet, d: doublet, t: triplet, q: quinolette, m: manolet, dd: double doublet, dt: double triplet, dq: double quartet, septet: septet (sevenfold line), br: broad (wide) , Brs: Broad-Single grating, ddd: Double-double doublet, ddt: Double-double triplet, brd: Broad doublet, brq: Broad quartet, J: Force coupling constant, J _HF : Between hydrogen atom and fluorine atom force Ppuringu constant, Hz: to Noretsu, Me: methyl group, Et: Echinore group, Pr: propyl group, CDC1 _3: heavy chloroform, DMSO-d _6: heavy dimethyl sulfoxide, DMF: N, N-dimethylcarbamoyl Honoré formamide, %: Weight ⁰ /. Mp: melting point, room temperature means 15 to 25 ° C. Reference Example 14 Synthesis of 4, -chloro-4-fluorobenzenesulfonanilide 4-55-chloroaniline (2.55 g, 20.Omraol) was dissolved in 10.0 ml of pyridine, and the mixture was stirred at room temperature with stirring to obtain 4-fluorochlorobenzene. 4.00 g (20.6 mmol) of robenzenesulfonyl were added. After stirring at room temperature for 4 hours, 100. Oml of water was added and the mixture was stirred for 30 minutes. The precipitated crystals were collected by filtration and washed with water to give 5.68 g (99%) of the title compound as pale yellow crystals.

 Melting point: 148.0-150.0. C

_{NMR (CDC1 3) δ: 6.} 80 (1Η, s), 7. 01 (. 2H, d, J = 8 8Hz),

7.13 (2H, dd, J = 8.8Hz, J _HF = 8.2Hz), 7.23 (2H, d, J = 8.8Hz), 7.77 (2H, dd, J = 8.8 Hz, J _HF = 5.0 Hz) Reference Example 2 Synthesis of N— (4-chlorophenyl) benzylsulfonamide 4.1-Chloroerin 2.55 g (20.0 g) ol) was dissolved in 15.0 ml of acetonitrile, and 3.82 g (20. Ommol) of benzylsulfonyl chloride was added with stirring under ice cooling. Under ice cooling, 1.70 ml (21. Ommol) of pyridine was added dropwise, and the mixture was returned to room temperature and stirred for 18 hours. After concentration under reduced pressure, 100.0 ml of water was added, and the mixture was acidified with dilute hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1: 3) to give 4.58 g (81%) of the title compound as white crystals.

 Melting point: 112. 0- 113.5 ° C

Employment _{R (CDC1 3) 5: 4.} 32 (2Η, s), 6. 44 (1H, s), 7. 06 (. 2H, d, J = 8 9Hz), 7. 15- 7, 45 (7H , m) · The starting compound of the formula (VI) shown in Table 1 was produced by the same method as in Reference Example 1 or 2, or a method analogous thereto.

Table 1. Starting compounds (intermediates)

Intermediate No. χ ¹ χ ² χ ³ X ⁴ AY ° Z ° n Melting point (° C)

 1 _ 1 υ U TJ 1 ΛΟ Λ_1 Λ Λ

 η η Θ n U, U U

1 丄 ο ζ ι ητ η Me H n j_CF ₃ rn no

 1 ιτ τ

丄 ー 3 ο η ητ Men ri 4_CF ₃ 1 i Πy. 1/1 1 n

 t) ー 丄 4 丄 《U

1 1 1 4 A π υ π υ Menu 11b, (J—lib.

O b b τ ητ τ ητ Men 4_N0 ₂ 194.b-ly .o

 υ

 ー η υ η Me u n n 4-1 / r * 7Π

 (O. ~ ί,

 1-8 ττ TT

 JN H 4

 1-9 ττ Η CN H H

 τ

 1 1 10 Η Η H H H 4-CI 89.5-90.5

 I-11 Η Η-Me H H 4-CI

1-12 Η Η HH CH ₂ H 4 CI 112.0-113.5

 1 ー 丄 3 Η Η H H Cn-CH H 4 CI 110.o-ill. 5

 1 14 14 ττ ττ

 ht H Jl 4 丄 119. '5-121. 5

 1 1

 One 15 Η ττ OMe H H 4 One CI

 1— 1 η η h 4 丄 148. ϋ 15 U. U

 1-1 (υ

 Shu n TT

 h 4

 1 "1ο τ ητ 丄 n H 4 丄 <

 1-19 η 4 t 1 /

 SH H ISHI 144.o-415.5

 1 20 1 I H H 4 1 CI

 1 1 21 H

 1-22 Η Η Me H H 3-C1

1-23 Η Η Me HH 3, 4-Cl ₂ 144. 5-146. 5

 1-24 Η Η Me H H 4- Br 149. 0-150. 0

 1-25 Η Η Me H H 4-SMe 113. 0-114.5

 1-26 Η Η Me H CN 134.5-136.5

 1-27 Η Η Me H H 3-CN 107. 0-108.5

 1-28 Η Η Me H H 4-CN 182.0-184.0

 1-29 Η Η CI H H 4-CN 182.5-184.0

 In the table,-represents a chemical bond. Example 14 Synthesis of 4,2-chloro-2'-trinoroleolomethinole p-tonolenes / lejonanilide (Compound No. 2-2)

2-Amino-1-benzo-benztrifluoride 3.91 g (20. Oramol) is mixed with 10.0 ml of pyridine, and stirred at room temperature while stirring. 4. OOg (21. Omraol) was added. After stirring at room temperature for 15 hours, 100.0 ml of water was added and stirring was continued for 30 minutes. The precipitated crystals were filtered, washed with water, and recrystallized from cold ethyl acetate monoether to give 6.23 g (89%) of the title compound as white crystals.

 Melting point: 105.0-106.0. C

_{NMR (CDC1 3) 6: 2.} 39 (3Η, s), 6. 81 (1H, brs), 7. 24 (. 2Η, d, J = 8 4),

 7.46 (1H, d, J = 2.4Hz), 7.48 (1H, dd, J = 9.7 & 2.4Hz), 7.64 (2H, d, J = 8.4Hz),

7.80 (1H, d, J = 9.7 Hz) Example 24 Synthesis of 4,1-chloro-2'-nitro-p-toluenesulfonanilide (Compound No. 2-14)

 3.00 g (17.4 mol) of 2-chloroaniline was mixed with 9.0 ml of pyridine, and while stirring at room temperature, 3.55 g (18.6 mmol) of shiridani p-toluenesulfonyl was added. Was. After stirring at room temperature for 18 hours, 80.0 ml of water was added and stirring was continued for 1 hour. 'The precipitated crystals were collected by filtration, washed with water, dissolved in ether, and extracted with a 1% aqueous sodium hydroxide solution. The aqueous layer was washed with ether, made acidic with hydrochloric acid, and extracted with chloroform. The dried mouth layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2.65 g (47%) of the title compound as yellow crystals.

 Melting point: 110. 0-111. 0 ° C

^{NMR (CDCI3) δ:. 2} 40 (3Η, s), 7. 27 (. 2H, d, J = 8 4Hz), 7. 54 (1H, dd, J co 9. 0 & 2. 4Hz), 7 71 (2H, d, J = 8.4 Hz), 7.83 (1H, d, J = 9.0 Hz), 8.09 (1H, d, J = 2.4 Hz),

9. 72 (1H, s) Example 3 2 ′, 4′—Dinitro—! Synthesis of mono-toluenesulfonanilide (Compound No. 2-8)

60 ° /. 4.56 g (50. Omraol) of p-toluenesulfonamide was added thereto while suspending 4.Og (100 mmol) of sodium hydride in 20.0 ml of DMF and stirring under ice-cooling. After stirring for 30 minutes under water cooling, 10.1 g (50. Ommol) of 1-chloro-2,4-dinitrobenzene was added, and the mixture was stirred for 1 hour under ice cooling and for 2 hours at room temperature. 200.0 ml of water was poured, and the precipitated crystals were filtered, washed with water, suspended in 12.1 ml of ethanol, and stirred at room temperature for 1 hour. Filter the crystals After recrystallization from ethyl acetate, the title compound was obtained as pale yellow crystals (10 lg, 60%). '

 Melting point: 161.0-163.0 ° C

Keio _{R (CDC1 3) δ: 2.} 42 (3Η, s), 7. 34 (. 2Η, d, J = 8 5Hz), 7. 84 (. 2H, d, J = 8 5Hz),

8.00 (1H, d, J = 9.3Hz), 8.39 (1H, dd, J = 9.3 & 2.6Hz), 9.06 (1H, d, J = 2.6Hz),

10.35 (1H, s) Example 4 Synthesis of N- (4-chloro-2-nitrophenone)-(trans) -β-styrenesulfonamide (Compound οο.2-16)

 Ν— (4—Fenora) I (Trans) I i3—Styrene snolehonamide

2.0 g (6.81 mraol) was suspended in 7.0 ml of acetic acid, and 0.30 ml (7. G2raraol) of 97% fuming nitric acid was added dropwise with stirring at room temperature. After stirring at 50 ° C for 30 minutes, 100.0 ml of water was poured to precipitate crystals. Filtering the crystals, by washing with water, the title compound as a yellow crystal 2. 04g (89 _^0/0) were obtained.

 Melting point: 102, 5-103. 5 ° C

_{NMR (CDC1 3) δ:.} . 6. 81 (. LH, d, J = 15 3Hz), 7. 35-7 55 (5H, m), 7. 59 (1H, dd, J = 9 0 & 2 .5Hz), 7.64 (1H, d, J = 15.3Hz), 7.83 (1H, d, J = 9.0Hz), 8.21 (1H, d, J = 2.5Hz), 9 76 (1H, brs) Example 5 Synthesis of 4-Chloro-4,1-cyano1-2'-one-to-mouth benzenesulfonanilide (Compound No. 2-29)

4 1.0 g _ 4, 1, cyanobenzenesulfonide 4.03 g (13.8.1) is suspended in 15.0 ml of acetic anhydride, and stirred at room temperature, and 0.61 ml of 97% fuming nitric acid is stirred. 14.3mraol) was dropped. After stirring at 50 ° C for 1 hour, the mixture was allowed to cool to room temperature, added with 100.0 ml of water, and stirred for 30 minutes. Precipitated crystal was filtered by washing with water, 4. give 30g ⁽⁹ 3%) of the title compound as pale yellow crystals.

 Melting point: 193.0-195.0 ° C

Employment _{R (CDC1 3) δ: 7.} 53 (. 2H, d, J = 8 8Hz), 7. 81 (. 1H, dd, J = 8 8 & L 9Hz),

7.88 (2H, d, J = 8.8Hz), 7.95 (1H, d, J = 8.8Hz), 8.50 (1H, d, J = l.9Hz), 10.28 (1H, brs) Further, the sulfonanilide derivative (I) shown in Table 2 was produced by the same method as in the above example or a method analogous thereto. The symbol A in the production method column indicates that it was produced by the same method as in Example 1 or Example 2 or a method analogous thereto, and the symbol B indicates that it was produced by the same method as Example 3 or a method analogous thereto. And the symbol C indicate that the compound was produced by the same method as in Example 4 or Example 5, or a method analogous thereto, but the method for producing each compound is limited to the method described in Table 2. It should not be. +

(The symbols in the formula are as defined above.)

90

: —

D = i li I! O CJ

 ΰ> Ή

 :

ε-ss¾ -Re Formulation Example 1

Compound No. 2-8 (0. 33 wt%), NEWKALGEN NV- 1203 (1. 0 wt _^0/0), and a dust was mixed well clay (98.67 wt%). Formulation Example 2

Compound was pulverized by a jet mill No. 2 - 14 (1 1. 0 wt _^0/0), Sonoreponore 5 11 5 (5.0 wt _^0/0), NEWKALGEN WG- 4 (5.0 wt _^0/0) After lactose (79.0% by weight) was uniformly mixed, a small amount of water was added and the mixture was kneaded with stirring, kneaded, granulated by an extrusion granulator, and dried to obtain a dry flowable agent. Formulation Example 3

Compound No. 2-27, PCNB, rig (0.5 weight ⁰ /.) (0.5 Weight ⁰ /.) - Sodium Nsu sulfonic acid (5 weight _^0/0), clay (94 weight _^0/0) Was thoroughly pulverized and mixed, water was added and kneaded well, and the mixture was granulated and dried to obtain granules. Formulation Example 4

Compound No. 2-28, I KF-916 ( 8 wt%), xylene (8 5 weight _^0/0), O carboxymethyl ethylene glycol ether (2 weight ⁰ /.) (Bruno - Paul 85 ^TM) (5 by weight %) To obtain an emulsion. Formulation Example 5

Compound No. 2-34 (0. 5 wt _^0/0), Kurorota port El (1 wt _^0/0), white carbon (3 wt _^0/0), and mixing well clay (95, 5 wt%) It was a powder. Formulation Example 6

Compound No. 2-16 (0. 15 weight ⁰ / o), Furusurufuamido (◦. 15 weight _^0/0), Yuyukarugen NV- 1203 (1. 0 wt _^0/0), clay (98.7 wt _^0/0 ) Was mixed well to make a powder. Formulation Example 7

Compound No. 2-29 (0. 1 wt _^0/0), fluazinam (0.4 wt _^0/0), NEWKALGEN NV- 1 203 (1. 0 wt _^0/0), clay (98.5 wt ⁰ / ₀ ) was mixed well to obtain a powder. Formulation Example 8

Compound No. 2-7 (0. 5 wt%), cartap hydrochloride (2 wt _^0/0), white Tokabon (3 wt _^0/0), thoroughly mixed clay (94.5 wt _^0/0) Powder. Formulation Example 9

Compound No. 2-14 (0. 5 wt _^0/0), the two Tenbiramu (0.3 wt _^0/0), white Tokabon '(3 wt _^0/0)., Clay (96.2 wt _^0/0) Was mixed to obtain a powder. Formulation Example 10

Compound No. 2-34 (0. 5 wt%), Kurochia two Jin (0.3 wt _^0/0), sodium rig Ninsuruhon acid (5 wt _^0/0), clay (94.2 wt _^0/0) After mixing well, adding water and kneading well, granulated and dried to obtain granules. Control test test compound to the test example 1 komatsuna clubroot (Plasmodiophora brassicae) and (. Indicated compounds shown in Table 2 N o.) Was dissolved in dimethylformamide (final concentration 1 wt _^0/0), and further, xylene (final concentration 0.02 wt _^0/0), and diluted with Tween 20 (trade name) (final concentration ◦. 0 2 wt%) by adding water. The prepared drug solution was irrigated into soil contaminated with clubroot so that the active ingredient was 353.7 mg / m ² , mixed well, and then seeded with Komatsuna. After cultivation in a greenhouse for 4 to 6 weeks, the roots of Komatsuna were washed out and examined for disease severity, and the results were expressed using the following control values.

 Control value 3: Disease severity 30% or less

Control value 2: Disease severity 31-40% Control value 1: Disease severity 41 to 50%

 Control value 0: Disease incidence 5 1% or more Table 3 · Control test results

産業上の利用の可能性

Industrial applicability

 The sulfonanilide derivative (I) or a salt thereof has a microbicidal action, has a small effect on human animals, natural enemies, the environment, fish, and crops, is safe, and has an excellent control effect on drug-resistant microorganisms. Therefore, it is useful as an excellent agricultural and horticultural microbicide. In particular, it has an excellent control effect on soil diseases such as root-knot disease of cruciferous plants (for example, canola, potato, cauliflower, cabbage, komatsuna, rapeseed, Chinese cabbage) and diseases caused by Aphanomyces genus bacteria. Have.

Claims

Scope of claim

(Wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom, a C ^ s alkynole group, an alkoxy group, a halogen atom or a cyano group, Ύ represents a halalkyl group, a thiocarbamoyl group, It represents Shiano group or a nitro group, Z is a C Bok ₃ § alkyl group, ₃ alkylthio group, C ^ ₃ alkoxy group, a halogen atom, Shiano group or a nitro group, a represents a chemical bond, methylene group or a vinylene group And m represents 0, 1, 2, 3, or 4.) A microbial biocidal composition for agricultural and horticultural use, comprising as an active ingredient the sulfonyllide derivative (I) or a salt thereof. 2. The microbicidal composition for agricultural and horticultural use according to claim 1, wherein A is a chemical bond. 3. The microbicidal composition for agricultural and horticultural use according to claim ² , wherein X ¹ , X ² and X ⁴ are a hydrogen atom, and X ³ is a hydrogen atom or an alkyl group.  4. The microbicidal composition according to claim 2, wherein Y is a nitro group. 5. The microbicidal composition for agricultural and horticultural use according to claim 3, wherein Y is a nitro group.  6. The microbicidal composition for agricultural and horticultural use according to claim 3, wherein Y is a cyano group.  7. The agricultural and horticultural microbicidal composition according to claim 5, wherein Z is a halogen atom, a methylthio group, a cyano group or a nitro group, and m is 1 or 2.  8. The microbicidal composition for agricultural and horticultural use according to claim 6, wherein Z is a halogen atom, a methylthio group, a cyano group or a nitro group, and m is 1 or 2.  9. The Snorrehonanilide derivative (I) is 4 ', 1', 6, and dinitro! 8. The microbicidal composition for agricultural and horticultural use according to claim 7, which is a monotoluene sulfonyl halide. 10. The microbicidal composition for agricultural and horticultural use according to claim 7, wherein the sulfone halide derivative (I) is 4,1-chloro-2'-nitro-1p-toluenesulfonanilide. 11. The sulfonanilide derivative (I) is 4'-one-cyano-one'-nitro-one; p-toluene 8. The microbicidal composition for agricultural and horticultural use according to claim 7, which is ensulfonide.  12. The sulfonanilide derivative (I) is 4'-methylthio-1,2-nitro! 8. The microbicidal composition for agricultural and horticultural use according to claim 7, which is toluenesulfonide. 13. The microbicidal composition for agricultural and horticultural use according to claim 7, wherein the sulfonide derivative (I) is 2 ', 4'dinitro_p-toluenesulfuryulide.  14. The microbicidal composition for agricultural and horticultural use according to claim 8, wherein the sulfonanilide derivative (I) is 2'-cyano-14'-methylthio-1p_toluenesulfonide. 15. The microbicidal composition for agricultural and horticultural use according to claim 8, wherein the sulfonide derivative (I) is 2, -cyano_4, · 12thro_p-toluenesulfonanilide.  16. The microbicidal composition for agricultural and horticultural use according to any one of claims 1 to 15, which is used for disinfecting clubroot fungi or Aphanomyces spp. On cruciferous crops.