JP2002201101A - Agricultural and horticultural microbicide composition containing sulfonanilide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agricultural and horticultural microbicide composition containing a sulfonanilide derivative having a slight influence on human beings and beasts, a natural enemy, the environment, fishes and crops, safety and excellently controlling effects on resistant microorganisms. SOLUTION: This agricultural and horticultural microbicide composition comprises a sulfonanilide derivative represented by general formula I or its salt as an active ingredient. 4'-Chloro-2',6'-dinitro-p-toluenesulfonanilide is an example of the general formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an agricultural and horticultural microbicidal composition containing a sulfonanilide derivative.

[0002]

2. Description of the Related Art Conventionally, a large number of compounds having a microbicidal activity have been synthesized and used as a microbicidal composition for agricultural and horticultural use, thereby contributing to a stable supply of agricultural crops. However, it is well known that a large number of compounds in a limited range have been used extensively, which has led to the generation of drug-resistant microorganisms. In addition, the development of safer microbicidal compositions for agricultural and horticultural use has been desired in view of increasing demands for safety of chemical substances and effects on the environment. For this reason, search research for a compound having a novel microbicidal activity has been conducted.
Attention has also been paid to the biological or chemical properties of sulfoneanilide derivatives, and many compounds have been synthesized to date. However, most of them are synthetic intermediates,
Drugs, compounds or reagents synthesized for elucidation of chemical reactions. For benzenesulfonanilides intended for use as agricultural and horticultural microbicidal compositions,
JP-B-44-9304, JP-B-45-6836, JP-B-46-6797, 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-61-197
553, JP-A-61-200959, JP-A-61-2009-
No. 2009960, JP-A-61-205247, JP-A-61-205248, JP-A-61-257960,
JP-A-61-271270, JP-A-62-19010
4, JP-A-63-270658, JP-A-1-156
No. 953, JP-A-1-272566, JP-A-2-72
No. 151, JP-A-2-96560, JP-A-2-212
467, JP-A-2-231465, U.S. Pat. No. 4,497,828, U.S. Pat.
, European Patent No. 193390, German Patent No. 19725447, Japanese Society of Pesticide Science, Vol. 21, No. 1, No. 3
1 to 35 (1996), and Journal of the Japanese Society of Pesticides, Vol. 22, No. 2, pp. 176-184 (1997). However, use of benzylsulfonanilides and styrenesulfonanilides as microbicidal compositions for agricultural and horticultural use has not been reported. 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 a trifluoromethyl group is present at the 3-position of the benzene ring on the benzenesulfonyl side, and aniline It has been reported that compounds having a nitro group or a trifluoromethyl group at the para position of the benzene ring on the side, and a halogen atom or a methyl group at the ortho position show excellent effects on soil diseases such as clubroot. I have. However, in the Journal of the Japanese Society of Pesticides, Vol. 21, No. 31, pages 31-35 (1996), and in the Japanese Journal of Pesticide Science, Vol. 22, No. 2, pages 176-184 (1997), the ortho-position of the benzene ring on the aniline side was changed. Compounds with a nitro group have been reported to lose activity. Compounds having a haloalkyl group, a cyano group or a thiocarbamoyl group at the ortho-position of the benzene ring on the aniline side, except for compounds having a benzenesulfonyl side of 4-trifluoromethylbenzenesulfonyl or 3,5-disubstituted benzenesulfonyl. Not reported. Also, livestock,
The impact on natural enemies, the environment, fish and crops is small and safe.
Sulfonanilide derivatives that have an excellent control effect on resistant microorganisms have not yet been developed.

[0003]

An object of the present invention is to provide a sulfonanilide derivative which has a small effect on humans, livestock, natural enemies, the environment, fish and crops, is safe and has an excellent control effect on resistant microorganisms. An agricultural and horticultural microbicidal composition is provided.

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies for many years to find a compound having an excellent microbicidal activity. It has been found that the anilide derivative or a salt thereof has a surprisingly strong microbicidal action, and has little effect on humans, livestock, natural enemies, environment, fish and crops, and is safe. As a result of further intensive studies based on these findings, the present invention has been completed.

That is, the present invention provides:

Embedded image (Wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom, a C _1-3 alkyl group, a C _1-3 alkoxy group, a halogen atom or a cyano group, and Y represents C _1- Represents a ₃ haloalkyl group, a thiocarbamoyl group, a cyano group or a nitro group, and Z represents a C _1-3 alkyl group, a C _1-3 alkylthio group,
_{1-3 represents an} alkoxy group, a halogen atom, a cyano group or a nitro group, A represents a chemical bond, a methylene group or a vinylene group, and m represents 0, 1, 2, 3 or 4. And (2) the microbicidal composition for agricultural and horticultural use 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 hydrogen atoms, and X ³ is a hydrogen atom or a C _1-3 alkyl group; (5) The microbicidal composition for agricultural and horticultural use according to (3), wherein Y is a nitro group; and (6) The microbicidal composition for agricultural and horticultural use according to (3), wherein Y is a nitro group. (7) Agricultural and horticultural microbicidal composition according to (5), wherein Z is a halogen atom, a methylthio group, a cyano group or a nitro group, and m is 1 or 2. (8) Z is a halogen atom, a methylthio group, a cyano group or a nitro group; (6) agricultural and horticultural microbicidal composition according is 2; (9) sulfonanilide derivative (I) is 4'-chloro -
The agricultural / horticultural microbicidal composition according to the above (7), which is 2 ', 6'-dinitro-p-toluenesulfonanilide; (10) the sulfonanilide derivative (I) is 4'-chloro-2'-nitro-p -The agricultural and horticultural microbicidal composition according to the above (7), which is toluenesulfonanilide; (11) The above (7), wherein the sulfonanilide derivative (I) is 4'-cyano-2'-nitro-p-toluenesulfonanilide. (12) The microbicidal composition for agricultural and horticultural use according to (7) above, wherein the sulfonanilide derivative (I) is 4'-methylthio-2'-nitro-p-toluenesulfonanilide. (13) The sulfonanilide derivative (I) is 2 ′, 4′-
The agricultural and horticultural microbicidal composition according to the above (7), which is dinitro-p-toluenesulfonanilide; (14) the sulfonanilide derivative (I) is 2′-cyano-4′-methylthio-p-toluenesulfonanilide. (15) The agricultural and horticultural microbicidal composition according to the above (8); (15) the agricultural and horticultural use according to the above (8), wherein the sulfonanilide derivative (I) is 2′-cyano-4′-nitro-p-toluenesulfonanilide. And (16) a 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. Things.

[0006]

DETAILED DESCRIPTION OF THE INVENTION Sulfonanilide derivative (I)
May exist as optically active isomers, diastereomers and / or geometric isomers, and the present invention includes each of these isomers and mixtures of these isomers.
X ^1, X ^2, X ³ and methyl groups as C _1-3 alkyl group in X ^4, an ethyl group, a propyl group, and isopropyl group, C _1-3 Examples of the alkoxy group include a methoxy group,
Examples include 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.

The C _1-3 haloalkyl group for Y includes, for example, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, chlorofluoromethyl, bromofluoromethyl, chlorodifluoro Methyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-
Examples include a trichloroethyl group, a 1,1,2,2-tetrafluoroethyl group, a pentafluoroethyl group, a 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, a heptafluoropropyl group, and the like.

The C _1-3 alkyl group in Z includes a methyl group, an ethyl group, a propyl group and an isopropyl group, and the C _1-3 alkylthio group includes a methylthio group, an ethylthio group, a propylthio group and an isopropylthio group. The C _1-3 alkoxy group includes 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 each a hydrogen atom or C
_{A 1-3} alkyl group is preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable. 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 nitro group, and m is preferably 1 or 2, and particularly m substituted at the para-position of the aniline moiety of the sulfonanilide.
= 1 is preferred.

The salt of the sulfonanilide derivative (I) may be any salt which is acceptable in agrochemical chemistry. When the sulfonanilide 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 and perchloric acid, for example, formic acid, acetic acid, propionic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid Acids, benzoic acid, picric acid, methanesulfonic acid, salts of organic acids such as p-toluenesulfonic acid, and the like. When the sulfonanilide derivative (I) has acidic properties, for example, alkali metal salts such as lithium, sodium, and potassium; alkaline earth metal salts such as magnesium and calcium; for example, iron, copper, zinc, and manganese Heavy metal salts such as ammonia, methylamine,
Examples thereof include ammonium salts such as dimethylamine, trimethylamine, triethylamine, ethylenediamine, TMEDA (tetramethylethylenediamine), aniline, N, N-dimethylaniline, pyridine, lutidine, collidine, and hydrazine, and salts with urea, guanidine and the like.

When the above-mentioned sulfonanilide derivative (I) or a salt thereof is used as a microbicide composition, it is used as a known form of a general agricultural chemical composition. That is, one or more (preferably 1 to 3) sulfonanilide derivatives (I) or salts thereof are mixed or dispersed as an active ingredient with an appropriate liquid carrier depending on the purpose of use, or an appropriate solid carrier is used. Emulsions, oils, aqueous suspensions, emulsions, liquids, ULVs, wettable powders, powders, DL (driftless) powders, granules, fine granules, fine granules F, flowables, dry Flowables, tablets, jumbo, sprays, ointments,
It is used as a paste, foam, aerosol, microcapsule, seed coating, smoking agent, and stick for crop irrigation. These preparations may be used if necessary, for example, emulsifiers, suspending agents, spreading agents, penetrants, wetting agents, dispersing agents, mucilage agents, stabilizers, binders, flow aids, anti-caking agents, flocculants,
Antioxidants, suspending agents, antifoaming agents, antifreezing agents, preservatives, moisture removing agents, ultraviolet absorbers, ultraviolet scattering agents, coloring agents, suspension stabilizers and the like may be added, and in a manner known per se Can be prepared. That is, it can be produced by uniformly mixing the sulfonanilide derivative (I) or a salt thereof, a liquid carrier or a solid carrier, the above-mentioned various additives, and other agricultural chemical components as necessary.

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 and water dispersible granules are prepared 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. Can be manufactured. For example, powders, DL powders and the like include sulfonanilide derivatives (I) or salts thereof, bulking agents (or solid carriers).
Can be produced by uniformly mixing and pulverizing them. 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 sulfonanilide 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, and the like may be used in a water-soluble film packaged in a unit of 20 to 200 g for easy application. Examples of the water-soluble film include polyvinyl alcohol, carboxymethyl cellulose, starch, gelatin, polyvinyl pyrrolidone, 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 Daiichi Kogyo Seiyaku Co., Ltd.).

As the liquid carrier (solvent) to be used, for example, water, methanol, ethanol, propanol, isopropanol, alcohols such as ethylene glycol, ketones such as acetone and methyl ethyl ketone, for example, 1,4-dioxane, tetrahydrofuran, ethylene glycol Ethers such as monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc., for example, kerosene, kerosene, fuel oil, machine oil, edible oil, etc., aliphatic hydrocarbons, for example, benzene, toluene, xylene, solvent naphtha, methyl naphthalene, etc. Aromatic hydrocarbons, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like, for example, N, N-dimethylformamide, N, N-dimethylacetamide Acid amides, such as ethyl acetate, esters of butyl acetate, fatty acid glycerol esters such as, for example acetonitrile, a solvent such as nitriles such as propionitrile is is appropriate, they are one or
At least one kind (preferably 1 to 3 kinds) can be mixed at an appropriate ratio and used as appropriate.

As solid carriers (diluents, extenders), for example,
Vegetable powder such as soybean flour, tobacco flour, flour, wood flour, etc.
For example, clays such as kaolin, bentonite, and acid clay,
For example, talc such as talc powder, waxite powder, for example, diatomaceous earth,
Mineral powders such as silica such as mica powder, calcium carbonate,
Lumina, sulfur powder, activated carbon, etc. are used.
Or two or more (preferably 1 to 3) at an appropriate ratio
They can be mixed and used as appropriate. Ointment base
For example, polyethylene glycol, pectin, for example
Higher fatty acids such as glyceryl monostearate
Polyhydric alcohol esters such as methylcellulose
Cellulose derivatives, sodium alginate, bentona
Polyhydric alcohol such as citrate, higher alcohol such as glycerin
Cole, petrolatum, white petrolatum, liquid paraffin, pork
Fats, various vegetable oils, lanolin, dehydrated lanolin, hardened oil, trees
One or more kinds of fats and the like (preferably 1 to 3 kinds),
Alternatively, various surfactants shown below were added thereto.
What is used suitably. Emulsifier, spreading agent, penetrant, minute
Surfactants used as powders, if necessary
Soaps, polyoxyethylene alkyl arylates
Class [eg, Neugen ^TM(TM indicates a registered trademark
You. ), EA 142 (EA 142)^TM);
Nonar, manufactured by Nippon Seiyaku Co., Ltd.^TMManufactured by Toho Chemical Co., Ltd.]
Alkyl sulfates [eg, Emar 10^TM, Emar 4
0^TMKao Corporation], alkyl sulfonates [eg,
Neogen^TM, Neogen T^TM; Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
OPEREX; manufactured by Kao Corporation], polyethylene glycol
Ruethers [eg, Nonipol 85 ^TM, Nonipol 10
0^TM, Nonipol 160^TMManufactured by Sanyo Chemical Co., Ltd.]
Alcohol esters [eg, Tween 20^TM, Tui
80^TMNon-ionic and ani
An on-type surfactant is appropriately used.

Further, the sulfonanilide derivative (I) or a salt thereof is used together with, for example, an insecticide, an acaricide, a nematicide, a phytohormone, a plant growth regulator, a fungicide, a synergist, an attractant, a repellent. , A pigment, a fertilizer, and the like, and 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 pesticidal active ingredients may be contained in the same preparation as the sulfonanilide derivative (I) or a salt thereof. Moreover, after formulating into separate preparations, they may be mixed at the time of use.

Representative examples of insecticides, acaricides, and nematicides which can be used by mixing with the sulfonanilide derivative (I) or a salt thereof are shown below. Acephate, acetamiprid, acrinatrin
n), alanycarb (alanycarb), aldrin (aldrin),
Allethrin, aluminum phosphide (Aluminiu
m phosphide), amitraz, arsenic acid (Arsenic)
acid), avermectin (avermectin-B), bendiocarb (bendiocarb), benfracarb (benfuracarb), bensultap (bensultap), benzoximate (benzoxim
ate), bifenthrin, bromopropylate, buprofezin, lime nitrogen (Calcium cyanamide), lime sulfur mixture (Calcium po
lysulfide), carbaryl (carbaryl: NAC), carbofuran
(carbofuran), carbosulfan (carbosulfan), cartap (cartap), chlordane (chlordane), chlorfenvinphos (chlorfenvinphos: CVP), chlorfluazuron (chlorfluazuron), chlorfenapyr (chlorphenapy)
r), chlorpyrifos-methyl,
Chromafenozide, Clofenthedine
(clofentezine), clothianidin (clothianidin), cyanophos (cyanophos: CYAP), cycloprotrine (cycloprot
hrin), cyfluthrin (cyfluthrin), cyhalothrin (cyha
lothrin), cypermethrin, cyromazine
(cyromazine), DCIP (dichlorodiisopropylether),
DD (1,3-Dichloropropene), DDT, deltamethrin (deltamethrin), diafenthiuron (diafenthiuro)
n), diazinon, diclofenthion (dic
hlofenthion), dichlorvos (dichlorvos: DDVP), dicofol (dicofol), dieldrin (dieldrin), dienochlor (dienochlor), diflubenzuron (diflubenzuron),
Dimethoate, dimethylvinphos (dimethy
lvinphos), disulfoton, DSP, endosulfan, EPN, esfenvalerate, ethion, ethion, ethofenprox, ethopropho
s), etoxazole, fenbutatin oxide
(fenbutatin oxide), fenitrothion (fenitrothion:
MEP), Fenobucarb, Fenothiocarb
(fenothiocarb), fenoxycarb (fenoxycarb), fenpropathrin (fenpropathrin), fenpyroximate (fenpyroximate), fenvalerate (fenvalerate),
Fipronil, fluazinam,
Flucythrinate, flufenoxuron, flupyrazofos, fluvalinate, formetan
ate), formothion, fosthiazate (fos
thiazate), furathiocarb, halfenprox, hexaflumuron
muron), hexythiazox, hydrogen phosphide
(Hydrogen phosphide), imidacloprid
d), isofenphos, isoprocarb (iso
procarb), isoxathion, malathion (m
alathion), mesulfenfos, metham
Ammonium (metam-ammonium), metham sodium (m
etam-sodium), methidathion (methidathion), methiocarb (methiocarb), methomil (methomyl), methoxychlor (methoxychlor), methoxyphenozide (methoxyfenozi
de), methyl bromide, metolcarb (metocarb)
lcarb: MTMC), milbemycin-A, monocrotophos, nared (naled: BRP), nicotine-sulfate, nicotine-furan (nid
inotefuran), nitenpyram, oxamil
(oxamyl), oxydeprofos (oxydeprofos: ESP), parathion (parathion), permethrin (permethrin), phentoate (phenthoate: PAP), hosalon (phosalone),
Phosmet (PMP), pirimicar (pirimicar)
b), pirimiphos-methyl, potassium oleate (Potassium oleate), profenofos (pro
fenofos), propaphos, propargite (pr
opargite: BPPS), propoxur, prothiofos, protrifenbute
te), pymetrozine, pyraclofos (pyrac
lofos), pyrethrins, pyridaben
en), pyridafenthion, pyrimidifen, pyriproxyf
en), quinalphos, resmethrin (resmethr)
in), salithion (salithion), silafluofen (silaf
luofen), sulfur (Sulfur), sulprofos (sulprofos), tebufenozide (tebufenozide), tebufenpyrad (tebuf
enpyrad), teflubenzuron (teflubenzuron), tefluthrin (tefluthrin), temephos (temephos), tetrachlorvinphos (tetrachlorvinphos), tetradiphone (tetrad
ifon), thiacloprid, thiamethoxam
(thiamethoxam), thiocyclam, thiodicarb, thiometon, tolfenpyrad, tralomethri
n), trichlorfon (DEP), triflumuron, vamidothion, XM
C, acequinocyl, 3-dodecyl-1,4-dihydr
o-1,4-dioxo-2-naphthyl acetate), acetoprole (ac
etoprole, (RS) -1- [5-amino-1- (2,6-dichloro-α, α, α
-trifluoro-p-tolyl) -4- (methylsulfinyl) pyrazol-3-y
l] ethanone), bistrifluron, 1- [2-c
hloro-3,5-bis (trifluoromethyl) phenyl] -3- (2,6-diflu
orobenzoyl) urea), sibutryne (cybutryne, N ² -tert-bu
tyl-N ⁴ -cyclopropyl-6-methylthio-1,3,5-triazine-2,4
-diamine), dinotefuran, (RS) -1-meth
yl-2-nitro-3- (tetrahydro-3-furylmethyl) guanidin
e), ethiprole, 5-amino-1- (2,6-dichlor
o-α, α, α-trifluoro-p-tolyl) -4-ethylsulfinylpyraz
ole-3-carbonitrile), fluacrypyri
m, NA-83, methyl (E) -2- {α- [2-isopropoxy-6- (triflu
oromethyl) pyrimidin-4-yloxy] -o-tolyl} -3-methoxyacr
ylate), flunicoamid (flunicoamid, IKI-220), indoxacarb (indoxacarb, methyl (S) -N- [7-chloro-2,
3,4a, 5-tetrahydro-4a- (methoxycarbonyl) indeno [1,2-
e] [1,3,4] oxadiazin-2-ylcarbonyl] -4 '-(trifluoromet
hoxy carbanilate or methyl (S) -7-chloro-2,3,4
a, 5-tetrahydro-2- [methoxycarbonyl (4-trifluorometho
xyphenyl) carbamoyl] indeno [1,2-e] [1,3,4] oxadiazine-
4a-carboxylate), spinosad, (2R, 3aS, 5a
R, 5bS, 9S, 13S, 14R, 16aS, 16bR) -2- (6-deoxy-2,3,4-tri-O
-methyl-α-L-mannopyranosyloxy) -13- (4-dimethylamin
o-2,3,4,6-tetradeoxy-β-D-erythropyranosyloxy) -9-e
thyl-2,3,3a, 5a, 5b, 6,7,9,10,11,12,13,14,15,16a, 16b-
hexadecahydro-14-methyl-1H-8-oxacyclododeca [b] as-i
ndacene-7,15-dione 50-95%, and (2S, 3aR, 5a
(S, 5bS, 9S, 13S, 14R, 16aS, 16bR) -2- (6-deoxy-2,3,4-tri-O
-methyl-α-L-mannopyranosyloxy) -13- (4-dimethylamin
o-2,3,4,6-tetradeoxy-β-D-erythropyranosyloxy) -9-e
thyl-2,3,3a, 5a, 5b, 6,7,9,10,11,12,13,14,15,16a, 16b-
hexadecahydro-4,14-dimethyl-1H-8-oxacyclododeca [b]
as-indacene-7,15-dione 50-5% mixture), spirodiclofen, 3- (2,4-dichlorophe
nyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl 2,2-dimeth
ylbutyrate), TI-809.

Representative examples of fungicides which can be used in admixture with the sulfonanilide derivative (I) or a salt thereof are shown below.
For example, acetic acid (acetic acid), acibenzolar S-methyl (acibenzolar-S-methyl), ambam (amobam), anilazine (anilazine), azoxystrobin (azoxystrobi)
n), benomyl, benthiazol
e), bitertanol, blasticidin
S (blasticidin-S), Bordeaux mixture (Bordeaux mixture),
Bromuconazole, butiobate (buth
iobate), calcium hypochlorit
e), lime sulfur mixture (Calcium polysulfide), captan
(captan), carbendazol, carpropamid, IKF-916 (4-chloro-2-cya
no-N, N-dimethyl-5-p-tolylimidazole-1-sulfonamid
e), chloroneb, chloropicrin
crin), chlorothalonil (TPN), cinnamaldehyde (Cinnamaldehyde), RH-7281 (3,5-dichl
oro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl) 4-met
hylbenzamide), CNA (2,6-Dichloro-4-nitroanilin)
e), cupric hydroxide, copper sulfate (Copper
sulfate), AC382042 (N- (1-cyano-1,2-dimethyl
propyl) -2- (2,4-dichlorophenoxy) propionamide (R, S) -a
nd (R, R) -and (S, R) -and (S, S)), cymoxani
l), cyproconazole, cyprodinil
(cyprodinil), dazomet (dazomet), dichlofluanid (dichlofluanid), DD (1,3-Dichloropropene), diclosymet (diclocymet), diclomezin (diclomezin
e), dietofencarb, difenoconazole, diflumetrim
rim), dimethirimol (dimethirimol), dimethomorph (d
imethomorph), diniconazole-M,
Dinocap, nickel dimethyldithiocarbamate, etridiazole, famoxadone, fenarimol, fenbuconazole, fendazoslam
azosulam), fenhexamid, fenoxanil (NNF-9425: fenoxanil), fenpiclonil
clonil), fentiazon, triphenyltin hydroxide, ferimzon
e), fluazinam (fluazinam), fludioxonil (flud
ioxonil), flumetova (RPA-403397: flumetover), fluoroimide, fluquinconazole (fluq
uinconazole), Flusulfamide, Flutolanil, Flucetyl (fosetyl-Al), Fthalide (fthalide), Flamethopyr (Furametpyr), Hexaconazole (Hexaconazole), Hymexazole
l), imazalil, imibenconazole (imibe
nconazole), iminoctadine albesilate (iminoct
adine-albesilate), iminoctadi acetate
ne-triacetate), iodocarb (iodocarb), ipconazole (ipconazole), iprodione (iprodione), isoprothiolane (isoprothiolane), kasugamycin (kasugam)
ycin), kresoxim-methyl, mancozeb, maneb, mepanipyrim (me
panipyrim), mepronil, metalaxyl (met
alaxyl), metalaxyl-M, metal-sodium, metasulfocarb (methasulf
ocarb), methyl bromide, RPA4072
13 ((s) -5-methyl-2-methylthio-5-phenyl-3-phenylam
ino-3,5-dihydroimidazol-4-one), Metominostrobin
(metominostrobin), Mildiomycin (mildiomyci
n), milneb (milneb), microbutanil (myclobutani
l), nabam, oxadixyl, oxolinic acid, oxypoconazole
(oxpoconazole), oxycarboxin (oxycarboxin),
Oxytetracycline, pefurazoate, penconazole,
Pencuron (pencycuron), picoxystrobin (picox)
ystrobin), polycarbamate, polyoxin, potassium bicarbonate (Potassium hydro
gen carbonate), probenazole (probenazole), prochloraz (prochloraz), procymidone (procymidone),
Propamocarb-hydrochloride,
Propiconazole, propineb
b), pyrazophos, pyributicarb (pyributo)
icarb), pyrifenox, pyrimethanil
(pyrimethanil), pyroquilon (pyroquilon), quinoxyfen (quinoxyfen), quintozene (quintozene: PCNB), silthiopharm (MON65500: silthiopham), sipconazole (sipconazole), sodium bicarbonate (Sodium bibarbo)
nate), sodium hypochlorite,
SSF-129 ((E) -2 [2- (2,5-dimethylphenoxymethyl)
phenyl] -2-methoxyimino-N-methylacetamide), streptomycin, sulfur, tebuconazole, tecloftala
m), tetraconazole, thiabendazole, thiuram (TMTD), thifluzamide, thiophanate methyl
nate-methyl), triadimefon, triadimenol, tricyclazole
zole), tridemorph (tridemorph), triflumizole
(triflumizole), trifloxystrobin (trifloxystr
obin), triforine, validamycin (valid
amycin), vinclozolin, zineb (zine
b), ziram, bethoxazin, 3-benz
o [b] thien-2-yl-5,6-dihydro-1,4,2-oxathiazine 4-oxi
de), BJL994, carbendazim, cyfluphenamide (NF-149), epoxyconazole (epoxiconazole, (2RS, 3SR) -1- [3- (2-chloropheny
l) -2,3-epoxy-2- (4-fluorophenyl) propyl] -1H-1,2,4-tr
iazole), ethaboxam (ethaboxam, (RS) -N- (α-cyano-
2-thenyl) -4-ethyl-2- (ethylamino) -1,3-thiazole-5-ca
rboxamide), fenamidone (fenamidone, (S) -1-anilino
-4-methyl -2-methylthio-4-phenylimidazolin-5-on
e), fenpropimorph, flusilazole, fluberidazole,
Iprovalicarb (iprovalicarb, isopropyl 2-methyl-
1-[(1-p-tolylethyl) carbamoyl]-(S) -propylcarbamat
e), picoxystrobin, methyl (E)-
3-methoxy-2- {2- [6- (trifluoromethyl) -2-pyridyloxyme
thyl] phenyl} acrylate), pyraclostrobin (pyraclos
trobin, methyl N- {2- [1- (4-chlorophenyl) -1H-pyrazol
-3-yloxymethyl] phenyl} (N-methoxy) carbamate), simeconazole, (RS) -2- (4-fluorophenyl) -1
-(1H-1,2,4-triazol-1-yl) -3- (trimethylsilyl) propan-
2-ol), spiroxamine (spiroxamine, 8-tert-butyl-1,
4-dioxaspiro [4.5] decan-2-ylmethyl (ethyl) (propyl) am
ine), trifloxystrobin, meth
yl (E) -methoxyimino-{(E) -α- [1- (α, α, α-trifluoro
-m-tolyl) ethylideneaminooxy] -o-tolyl} acetate), zoxamide, (RS) -3,5-dichloro-N- (3-chloro-1
-ethyl-1-methyl-2-oxopropyl) -p-toluamide), benthiavalicarb, thiadini
l), fenoxanil, ethaboxam (ethabo
xam).

Diseases which are controlled by the sulfonanilide derivative (I) or a salt thereof include, for example, blast (Pyricularia oryzae) and sesame leaf blight (Helminthosp).
orium oryzae, Cochliobolus miyabeanus), idiot disease (G
ibberella fujikuroi), seedling blight (Rhizopus oryzae),
Diseases of rice such as sheath blight (Rhizoctonia solani), for example, oats such as crown rust (Puccinia coronata), such as powdery mildew (Erysiphe graminis), and scald (Rhynchsporium)
secalis), spot disease (Cochliobolus sativus), spot leaf disease (Hel
minthosporium gramineum, Pyrenophora gramineum),
Pyrenophra teres, Tilletia cari
es), barley diseases such as smut (Ustilago nuda), for example, powdery mildew (Erysiphe graminis), blight (Leptosphaeri)
a nodorum, Septoria nodorum), yellow rust (Puccinia str
iiformis), Typhulaincarnata, eye spot disease (Ps
eudocercosporella herpotrichoides), red snow rot (Cal
onectria graminicola, Fusarium nivale), black rust (Pu
ccinia graminis), black bacilli (Typhula ishikariensi)
s), Fusarium head blight (Gibberella zeae), Leaf rust (Puccinia r)
econdita, Puccinia triticina), leaf spot disease (Helminthospor
ium gramineum), brown smut (Tilletia caries), leaf blight (Septoria tritici), naked smut (Ustilagotritici) and other wheat diseases, such as seedling damping (Pythium debaryanum) and other corn diseases, such as red Snow rot (Fusarium ni
vale) and other diseases of rye, such as plague (Phytophthora inf
estans) and other potato diseases such as downy mildew (Peronosp.
oratabacina), plague (Phytophthora nicotianae var.
cotianae), scab (Cercospora nicotianae), mosaic disease (tobacco mosaic virus) and other tobacco diseases, brown spot (C
ercospora beticola), seedling blight (Pythium debaryanum, R
hizoctonia solani), damping-off (Pythium aphanidermatum,
Aphanomyces cochilioides) and other sugar beet diseases, for example, gray mold (Botrytis cinerea) and other paprika diseases,
For example, gray mold (Botrytis cinerea), sclerotia (Sclerot
inia sclerotiorum), kidney diseases such as white rot (Corticium rolfsii), such as powdery mildew (Erysiphe polygon)
i, Sphaerotheca fuliginea, rust (Uromyces fabae, U
romyces phaseoli), broad bean diseases such as gray mold (Botrytis cinerea), such as root rot (Aphanomyces euteich)
es) and the like, for example, brown spot (Mycosphaerella
peanut diseases such as arachidicola)
(Rhizoctonia solani) and other cabbage diseases such as powdery mildew (Sphaerotheca fuliginea) and vine disease (Fusarium
oxysporum), vine blight (Mycosphaerella melonis), downy mildew (Pseudoperonospora cubensis), gray mold (Botryti)
s cinerea), sclerotium disease (Sclerotinia sclerotiorum), anthracnose (Colletotrichum lagenarium), seedling blight (Fusarium o
xysporum, Pythium aphanidermatum, Rhizoctonia solan
i), diseases of cucumber such as mosaic disease (Cucumber mosaic virus), for example, black spot (Alternaria brassicicola),
Plasmodiophora brassicae, seedling blight (Aphan
omyces raphani), such as leaf blight (Se
peria apii) and other celery diseases such as chlorosis (Fusariu
oxysporum) and other radish diseases such as wilt (Fusar
oxysporum), plague (Phytophthora infestans), ring blight (Alternaria solani), gray mold (Botrytis cinere)
a), gray plague (Phytophthora capsici), black spot (Alterna
ria tomato), for example, brown rot (Phyt
ophthora capsici), half body wilt (Verticillium albo-at
rum) and other eggplant diseases such as black spot (Alternaria japoni
ca), clubroot disease (Plasmodiophora brassicae), such as Chinese cabbage diseases, such as plague (Phytophthora capsici), gray mold (Botrytis cinerea), etc. For example, citrus diseases such as black spot (Diaporthe citri), for example, scab (Venturia nashicola), black spot (Alternaria kiku)
chiana), pear diseases such as scab (Gymnosporangium haraeanum), such as downy mildew (Plasmopara viticola), gray mold (Botrytis cinerea), and black rot (Elsinoe ampelina)
Grape diseases such as grape disease, leaf blight (Taphrina deformans), peach diseases such as perforation disease (Mycosphaerella cerasella), such as powdery mildew (Podosphaera leucotria), scab (Cladsp
orium carpophilum), gray mold (Botrytis cinerea),
Scab (Venturia inaequalis), Scab (Gymnosporangiu)
m yamadae), white root rot (Rosellinia nectrix), spotted leaf rot (Alternaria mali) and other apple diseases, such as root rot
(Phoma lingam), such as oilseed rape, sunflower, carrot, capsicum, strawberry, melon, kiwifruit, onion, chive, sweet potato, fig, plum, asparagus, oyster, soybean, azuki, watermelon, shungiku, spinach, tea, etc. Diseases of cereal fruits and vegetables.
In particular, it has an excellent control effect on soil diseases such as root-knot disease of plants such as cruciferous plants (for example, canola, turnip, cauliflower, cabbage, komatsuna, rape, Chinese cabbage) and diseases caused by Aphanomyces (Aphanomyces) genus bacteria. .

The agricultural and horticultural microbicide containing the sulfonanilide derivative (I) or its salt 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 by nursery box treatment, foliage application of crops, treatment at the time of irrigation after transplantation, treatment of crop roots, underwater application of paddy fields, seed treatment or soil mixing treatment, direct application to fruit tree trunks, etc. However, a treatment at the time of irrigation after transplantation or a seedling box treatment or transplantation is particularly preferable. 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., but in general, the active ingredient (sulfonanilide derivative (I) or its salt) is from 0.3 g per hectare. 10,000g, preferably 50
g to 5,000 g. When the composition of the present invention is a wettable powder, it may be used after being diluted so that the final concentration of the active ingredient is in the range of 0.1 to 10,000 ppm, preferably 10 to 1,000 ppm. The content of the sulfonanilide derivative (I) or a salt thereof is usually about 0.1 to 8 relative to the total amount of the preparation.
0% by weight, preferably about 1 to 20% by weight. Specifically, emulsions, solutions, wettable powders (eg, wettable powders for granules),
When used in an aqueous suspension preparation, microemulsion or the like, it is generally about 1 to 80% by weight, preferably about 1 to 20% by weight.
A suitable amount is about weight%. When used in oils, powders and the like, it is usually about 0.1 to 50% by weight, preferably about 1 to 2% by weight.
About 0% by weight is appropriate. When used in granules, tablets, jumbo preparations, etc., 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 / or microbicides) incorporated in the composition of the present invention are usually about 1 to 80% by weight, preferably about 1 to 80% by weight, based on the total amount of the preparation. Is about 1
It is used in a range of about 20% by weight. The content of the additives other than the active ingredient is the kind or content of the pesticide active ingredient,
Alternatively, although it depends on the dosage form of the preparation, it is usually 0.00
About 1 to 99.9% by weight, preferably about 1 to 99% by weight
It is about. More specifically, the surfactant is usually added in an amount of about 1 to 20% by weight, preferably about 1 to 20% by weight based on the total amount of the composition.
It is preferable to add about 15% by weight, about 1 to 20% by weight of a flow aid and about 1 to 90% by weight, preferably about 1 to 70% by weight of a carrier. Specifically, in the case of producing a liquid preparation, the surfactant is usually about 1 to 20% by weight, preferably about 1 to 10% by weight, and water is 20 to 90% by weight.
It is preferable to add about weight%. When used, emulsions, wettable powders (eg, wettable powders for granules) 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 sulfonanilide derivative (I) or a salt thereof is produced, for example, by condensation of specific starting compounds shown in the following methods A and B or by nitrating specific starting compounds shown in the method C. be able to.

[Method A]

Embedded image (In the formula, X ¹ , X ² , X ³ , X ⁴ , A, Y, Z and m are as defined above, and L represents a leaving group.)

[Method B]

Embedded image (Wherein X ¹ , X ² , X ³ , X ⁴ , A, Y, Z and m have the same meanings as described above, and L ′ represents a leaving group.)

[0022]

[Method C] (Wherein, X ¹ , X ² , X ³ , X ⁴ and A have the same meanings as described above; when Y represents a newly introduced nitro group, Y ⁰ represents a hydrogen atom; Z ⁰ and n Is the above Z
And m have the same meaning. When at least one of Z represents a newly introduced nitro group, Y ⁰ and Z ⁰ each have the same meaning as Y and Z described above, and n is 1,
Represents 2, 3 or 4. )

In the method A, as the leaving group L, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, for example, a benzenesulfonyloxy group, a p-
It represents an aromatic sulfonyloxy group such as a toluenesulfonyloxy group and a 4-chlorobenzenesulfonyloxy group.

In the method B, the leaving group L 'includes, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, for example, a C _1-3 alkoxy group such as a methoxy group, an ethoxy group and a propoxy group; For example, a methylthio group,
Ethylthio, C _1-3 alkylthio group such as a propylthio group, such as methane sulfinyl group, ethanesulfinyl group, C _1-3 alkylsulfinyl group such as propane sulfinyl group, for example, methanesulfonyl group, ethanesulfonyl group, a propane-sulfonyl group C _1-3 alkanesulfonyl groups, for example, aromatic sulfonyl groups such as benzenesulfonyl group, p-toluenesulfonyl group and 4-nitrobenzenesulfonyl group, for example, C _1- such as methanesulfonyloxy, ethanesulfonyloxy group, propanesulfonyloxy group ₃ Alkanesulfonyloxy groups, for example, aromatic sulfonyloxy groups such as benzenesulfonyloxy group, p-toluenesulfonyloxy group, 4-nitrobenzenesulfonyloxy group, and phenoxy groups.

The reaction of the method A or the method B is usually carried out in a solvent or without a solvent. When the solvent is used in a solvent, for example, petroleum ether, pentane, hexane,
Hydrocarbons such as cyclohexane, benzene, toluene and xylene, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethylene and chlorobenzene, for example, diethyl ether, diisopropyl Ethers such as ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, ethylene glycol monomethyl ether and diethylene glycol dimethyl ether; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone such as acetonitrile and propio Nitriles such as nitriles such as N, N-dimethylformamide, N, N
N-dimethylacetamide, amides such as N-methylpyrrolidone, sulfoxides such as dimethylsulfoxide, sulfones such as sulfolane, nitro compounds such as nitromethane, nitrobenzene, etc., such as methanol, ethanol, isopropanol, 1-butanol, Examples thereof include alcohols such as ethylene glycol, carbon disulfide, and water.

The reaction is carried out at a temperature of -100 to 300 ° C., preferably at -50 to 200 ° C., for a reaction time of 1 minute to 1 week, preferably 5 minutes to 24 hours. An acid or a base may be added to promote the reaction. Examples of such an acid include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid, nitric acid, and 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, p-toluenesulfonic acid, trifluoromethane Organic acids such as sulfonic acid and the like, and as the base, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, metal hydroxides such as calcium hydroxide, for example, sodium carbonate, potassium carbonate,
Metal carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, for example, metal hydrides such as sodium hydride, potassium hydride, calcium hydride, and the like, metal amides such as lithium diisopropylamide, sodium amide, potassium amide, for example, methyllithium , N-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium and other organic lithium reagents such as methylmagnesium bromide and ethylmagnesium chloride (Grignard reagent) such as metallic lithium and metallic sodium , Metals such as potassium, for example, trimethylamine, triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, lutidine, collidine, DMAP
Organic bases such as (4-dimethylaminopyridine), TMEDA (tetramethylethylenediamine), and DBU (1,8-diazabicyclo [5.4.0] undes-7-ene). In order to promote the reaction, for example, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, tungsten, platinum, gold, mercury (E.g., oxides, fluorides, chlorides, bromides, iodides, sulfides, sulfates, nitrates, phosphates, perchlorates, etc.) or a simple metal as a catalyst in an amount of 0.000001 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. As the nitrating agent in the method C, 30 to 100% nitric acid or fuming nitric acid is generally used. For example, alkali metal nitrates such as sodium nitrate and potassium nitrate; alkyl nitrates such as ethyl nitrate and amyl nitrate; Using borate (NO ₂ BF ₄ ), nitronium trifluoromethanesulfonate (NO ₂ CF ₃ SO ₃ ), nitrogen oxides (eg, NO ₂ , N ₂ O ₃ , N ₂ O ₄ , N ₂ O ₅ ) You may. Particularly, 50 to 100% nitric acid is preferable. The nitrating agent can be used in an amount of about 1.0 to 20 equivalents with respect to the raw material (VI).
It is 0 equivalent. When 90% or more of nitric acid is used, about 1.0 to 3.0 equivalents are 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, trifluoroacetic anhydride and trifluoromethanesulfonic acid. If desired, a solvent which does not adversely influence the reaction or a mixture thereof may be used. As such a solvent, in addition to the above-mentioned acidic solvent, the method A or the method B
And the same solvents as those described in the above. These solvents can be used alone or, if necessary,
Species or more (preferably, two or three) may be mixed and used at an appropriate ratio, for example, a ratio of about 1: 1 to 1:10 (volume ratio). When the reaction solvent is not homogeneous, for example, triethylbenzylammonium chloride, tri-n-
The reaction may be carried out in the presence of a quaternary ammonium salt such as octylmethylammonium chloride, trimethyldecylammonium chloride, tetramethylammonium bromide or cetylpyridinium bromide, or a phase transfer catalyst such as crown ethers. Particularly preferred solvents are acetic acid and acetic anhydride. The reaction temperature is usually about -50 to 200 ° C,
Preferably it is in the range of about -20 to 130 ° C. Reaction times range from about 1 minute to 48 hours, preferably from about 15 minutes to 10 hours.

[0029]

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 the invention. Elution in silica gel column chromatography such as Reference Example is performed by TLC (Thin L
ayer Chromatograph (thin layer chromatography). In TLC observation, Kieselgel 60F2 manufactured by Merck was used as a TLC plate.
As a developing solvent, a solvent used as an elution solvent in column chromatography was used as a developing solvent, and a UV detector or an iodine coloring method was used as a detection method. As the silica gel for the column, Kieselgel 60 (70 to 230 mesh) manufactured by Merck was used. When a mixed solvent is used as a developing solvent, the numerical values shown in parentheses are the volume mixing ratios of the respective solvents. The NMR (nuclear magnetic resonance) spectrum shows proton NMR, using Bruker AC-20 using tetramethylsilane as internal standard.
It was measured with a 0P (200 MHz) spectrometer, and all δ values were shown in ppm. The abbreviations used in the following Reference Examples, Examples and Tables have the following meanings. s: singlet,
d: doublet, t: triplet, q: quartet,
m: multiplet, dd: double doublet, dt: double triplet, dq: double quartet, septet: septet (sevenfold line), br: broad (wide), brs:
Broad singlet, ddd: Double double doublet, ddt: Double double triplet, brd: Broad doublet, brq: Broad quartet, J: Coupling constant, _{JH F} : Coupling constant between hydrogen atom and fluorine atom, Hz: Hertz, Me: methyl group, Et: ethyl group, Pr:
Propyl group, CDCl _3: deuterated chloroform, DMSO-d _6: heavy dimethyl sulfoxide, DMF: N, N-dimethylformamide,%: wt%, mp: melting point, also Room temperature is 15
Means ~ 25 ° C.

Reference Example 1 Synthesis of 4'-chloro-4-fluorobenzenesulfonanilide 2.55 g (20.0 mmol) of 4-chloroaniline was added to 10.0 ml of pyridine.
And 4.00 g (20.6 mmol) of 4-fluorobenzenesulfonyl chloride was added with stirring at room temperature. After stirring at room temperature for 4 hours, 100.0 ml 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 the title compound (5.68 g, 99%) as pale-yellow crystals. Melting point: 148.0-150.0 ° C NMR (CDCl ₃ ) δ: 6.80 (1H, s), 7.01 (2H, d, J = 8.8 Hz), 7.13
(2H, dd, J = 8.8Hz, J _HF = 8.2Hz), 7.23 (2H, d, J = 8.8Hz), 7.7
7 (2H, dd, J = 8.8Hz, J _HF = 5.0Hz)

Reference Example 2 Synthesis of N- (4-chlorophenyl) benzylsulfonamide 2.55 g (20.0 mmol) of 4-chloroaniline was treated with acetonitrile 1
The solution was dissolved in 5.0 ml, and 3.82 g (20.0 mmol) of benzylsulfonyl chloride was added with stirring under ice cooling. Pyridine 1.70m under ice cooling
After l (21.0 mmol) was added dropwise, the mixture was returned to room temperature and stirred for 18 hours. After concentration under reduced pressure, 100.0 ml of water was added, 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 NMR (CDCl ₃ ) δ: 4.32 (2H, s), 6.44 (1H, s), 7.06 (2H, d, J =
8.9Hz), 7.15-7.45 (7H, m)

By the same method as in Reference Example 1 or 2, or a method analogous thereto, the starting compounds of the formula (VI) shown in Table 1 were produced.

Embedded image

[0033]

[Table 1]

Example 1 4'-chloro-2'-trifluoromethyl-p-toluenesulfonanilide (compound N
o. Synthesis of 2-2) 2-amino-5-chlorobenztrifluoride 3.91 g (2
0.0 mmol) was mixed with 10.0 ml of pyridine, and 4.00 g (21.0 mmol) of p-toluenesulfonyl chloride was added with stirring at room temperature. 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-ether to give 6.23 g (89%) of the title compound as white crystals. _{Mp: 105.0-106.0 ℃ NMR (CDCl 3)} δ: 2.39 (3H, s), 6.81 (1H, brs), 7.24 (2H, d,
J = 8.4), 7.46 (1H, d, J = 2.4Hz), 7.48 (1H, dd, J = 9.7 & 2.4
Hz), 7.64 (2H, d, J = 8.4Hz), 7.80 (1H, d, J = 9.7Hz)

Example 2 4'-chloro-2'-nitro-
Synthesis of p-toluenesulfonanilide (Compound No. 2-14) 3.00 g (17.4 mmol) of 4-chloro-2-nitroaniline was mixed with 9.0 ml of pyridine and, while stirring at room temperature, 3.55 g of p-toluenesulfonyl chloride ( 18.6 mmol) was added. 18 at room temperature
After stirring for an hour, 80.0 ml of water was added and stirring was continued for 1 hour.
The precipitated crystals were filtered, washed with water, and dissolved in ether 1%
Extracted with aqueous sodium hydroxide. The aqueous layer was washed with ether, acidified with hydrochloric acid, and extracted with chloroform. The chloroform compound was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give the title compound as yellow crystals.
2.65 g (47%) were obtained. Melting point: 110.0-111.0 ° C NMR (CDCl ₃ ) δ: 2.40 (3H, s), 7.27 (2H, d, J = 8.4 Hz), 7.54
(1H, dd, J = 9.0 & 2.4Hz), 7.71 (2H, d, J = 8.4Hz), 7.83 (1
H, d, J = 9.0Hz), 8.09 (1H, d, J = 2.4Hz), 9.72 (1H, s)

Example 3 Synthesis of 2 ', 4'-dinitro-p-toluenesulfonanilide (Compound No. 2-8) 4.0 g (100 mmol) of 60% sodium hydride was suspended in 20.0 ml of DMF and cooled with ice. While stirring, 8.56 g (50.0 mmol) of p-toluenesulfonamide was added. After stirring for 30 minutes under ice cooling, 10.1 g of 1-chloro-2,4-dinitrobenzene (50.0 g) was added.
mmol) and the mixture was stirred for 1 hour under ice cooling and for 2 hours at room temperature.
After pouring 200.0 ml of water, filtering the precipitated crystals, washing with water,
The suspension was suspended in 12.0 ml of ethanol and stirred at room temperature for 1 hour.
The crystals were collected by filtration and recrystallized from ethyl acetate to give 10.1 g (60%) of the title compound as pale yellow crystals. Melting point: 161.0-163.0 ° C NMR (CDCl ₃ ) δ: 2.42 (3H, s), 7.34 (2H, d, J = 8.5 Hz), 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-nitrophenyl)-(trans) -β-styrenesulfonamide (Compound No. 2-16) N- (4-chlorophenyl)-(trans)- 2.00 g (6.81 mmol) of β-styrene sulfonamide was suspended in 7.0 ml of acetic acid, and stirred at room temperature while stirring 0.3% of 97% fuming nitric acid (7.02 mmo).
l) was added dropwise. After stirring at 50 ° C for 30 minutes, 100.0 ml of water was poured to precipitate crystals. The crystals were filtered and washed with water to give 2.04 g (89%) of the title compound as yellow crystals. Melting point: 102.5-103.5 ° C NMR (CDCl ₃ ) δ: 6.81 (1H, d, J = 15.3 Hz), 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, b
rs)

Example 5 4-Chloro-4'-cyano-
2'-nitrobenzenesulfonanilide (Compound No.
Synthesis of 2-29) 4-chloro-4'-cyanobenzenesulfonanilide 4.
03 g (13.8 mmol) was suspended in 15.0 ml of acetic anhydride, and 0.61 ml (14.3 mmol) of 97% fuming nitric acid was added dropwise with stirring at room temperature. Five
After stirring at 0 ° C. for 1 hour, the mixture was allowed to cool to room temperature, 100.0 ml 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 4.30 g (93%) of the title compound as pale yellow crystals. Melting point: 193.0-195.0 ° C NMR (CDCl ₃ ) δ: 7.53 (2H, d, J = 8.8 Hz), 7.81 (1H, dd, J = 8.8)
& 1.9Hz), 7.88 (2H, d, J = 8.8Hz), 7.95 (1H, d, J = 8.8Hz),
8.50 (1H, d, J = 1.9Hz), 10.28 (1H, brs)

Further, sulfonanilide derivatives (I) shown in Table 2 were produced in the same manner as in the above-mentioned Examples or in a manner 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 production method of each compound should not be limited to only the method described in Table 2. .

[0040]

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

[Table 2]

Formulation Example 1 Compound No. 2-8 (0.33% by weight), Newcalgen NV-1203 (1.0% by weight), clay (98.67%)
% By weight) to give a powder.

Formulation Example 2 Compound No. crushed by a jet mill 2-14 (11.0% by weight), Solpol 5115 (5.0% by weight), Newcargen WG-4 (5.0% by weight), lactose for industrial use (79.
(0% by weight), and a small amount of water was added thereto, followed by stirring, mixing and kneading, granulation by an extrusion granulator, and drying to obtain a dry flowable agent.

Formulation Example 3 Compound No. 2-27 (0.5% by weight), PCNB (0.5% by weight)
% By weight), sodium ligninsulfonate (5% by weight), and clay (94% by weight) were 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. An emulsion was prepared by mixing 2-28 (2% by weight), IKF-916 (8% by weight), xylene (85% by weight), and oxyethylene glycol ether (Nonipol 85 ^™ ) (5% by weight).

Formulation Example 5 Compound no. 2-34 (0.5% by weight), chlorothalonil (1% by weight), white carbon (3% by weight), and clay (95.5% by weight) were mixed well to form a powder.

Formulation Example 6 Compound no. 2-16 (0.15% by weight), Flusulfamide (0.15% by weight), Newcargen NV-1203
(1.0% by weight) and clay (98.7% by weight) were mixed well to form a powder.

Formulation Example 7 Compound No. 2-29 (0.1% by weight), fluazinam (0.4% by weight), Newcalgen NV-1203
(1.0% by weight) and clay (98.5% by weight) were mixed well to obtain a powder.

Formulation Example 8 Compound No. 2-7 (0.5% by weight), cartap hydrochloride (2% by weight), white carbon (3% by weight), and clay (94.5% by weight) were mixed well to prepare a powder.

Formulation Example 9 Compound No. 2-14 (0.5% by weight), nitenpyram (0.3% by weight), white carbon (3% by weight), and clay (96.2% by weight) were mixed well to form a powder.

Formulation Example 10 Compound No. 2-34 (0.5% by weight), clothianidin (0.3% by weight), sodium ligninsulfonate (5%)
% By weight) and clay (94.2% by weight) were thoroughly pulverized and mixed, water was added and kneaded well, and the mixture was granulated and dried to obtain granules.

Test Example 1 Komatsuna Clubroot (Plasmodioph)
ora brassicae) A test compound (compound No. shown in Table 2 above) was dissolved in dimethylformamide (final concentration 1% by weight).
Further, xylene (final concentration: 0.02% by weight) and Tween 20 (trade name) (final concentration: 0.02% by weight) were added, followed by dilution with 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 to 40% Control value 1: Disease severity 41 to 50% Control value 0: Disease severity 51% or more

[0052]

[Table 3]

[0053]

Industrial Applicability The sulfonanilide derivative (I) or a salt thereof has a microbicidal action, has a small effect on humans, livestock, natural enemies, the environment, fishes and crops, is safe, and has excellent control against drug-resistant microorganisms. Since it is a sulfonanilide derivative having an effect, it is useful as an excellent agricultural and horticultural microbicide. In particular, cruciferous plants (eg, canola,
Turnip disease and Aphanomyces of turnip, cauliflower, cabbage, komatsuna, rape, Chinese cabbage
It has an excellent control effect on soil diseases such as diseases caused by genera.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AA03 AB03 4H011 AA01 BA01 BB07 BC01 BC07 BC18 BC20 DA02 DA15 DA16 DH03

Claims (16)

[Claims] (1) Formula (1) (Wherein X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom, a C _1-3 alkyl group, a C _1-3 alkoxy group, a halogen atom or a cyano group, and Y represents C _1- Represents a ₃ haloalkyl group, a thiocarbamoyl group, a cyano group or a nitro group, and Z represents a C _1-3 alkyl group, a C _1-3 alkylthio group,
_{1-3 represents an} alkoxy group, a halogen atom, a cyano group or a nitro group, A represents a chemical bond, a methylene group or a vinylene group, and m represents 0, 1, 2, 3 or 4. ) A microbicidal composition for agricultural and horticultural use containing the sulfonanilide derivative (I) or a salt thereof as an active ingredient. 2. The agricultural and horticultural microbicidal composition according to claim 1, wherein A is a chemical bond. 3. The agricultural and horticultural microbicidal composition according to claim ² , wherein X ¹ , X ² and X ⁴ are hydrogen atoms, and X ³ is a hydrogen atom or a C _1-3 alkyl group. 4. The agricultural and horticultural 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 agricultural and horticultural microbicidal composition 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 method according to claim 9, wherein the sulfonanilide derivative (I) is 4′-
The agricultural / horticultural microbicidal composition according to claim 7, which is chloro-2 ', 6'-dinitro-p-toluenesulfonanilide. 10. The sulfonanilide derivative (I) is 4 ′
The agricultural / horticultural microbicidal composition according to claim 7, which is -chloro-2'-nitro-p-toluenesulfonanilide. 11. The sulfonanilide derivative (I) is 4 ′
The microbicidal composition for agricultural and horticultural use according to claim 7, which is -cyano-2'-nitro-p-toluenesulfonanilide. 12. The sulfonanilide derivative (I) is 4 ′
The agricultural / horticultural microbicidal composition according to claim 7, which is -methylthio-2'-nitro-p-toluenesulfonanilide. 13. The microbicidal composition for agricultural and horticultural use according to claim 7, wherein the sulfonanilide derivative (I) is 2 ′, 4′-dinitro-p-toluenesulfonanilide. 14. The sulfonanilide derivative (I) is 2 ′
The microbicidal composition for agricultural and horticultural use according to claim 8, which is -cyano-4'-methylthio-p-toluenesulfonanilide. 15. The sulfonanilide derivative (I) is 2 ′
The microbicidal composition for agricultural and horticultural use according to claim 8, which is -cyano-4'-nitro-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 sp. On cruciferous crops.