JPH10298011A - Pyridylindole compound and fungicide for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of being profitably synthesized and useful as a fungicide surely effectively and safely used for agriculture and horticulture. SOLUTION: A compound of formula I [X is H, nitro, cyano, a halogen, a 1-6C haloalkyl, a 1-6C alkoxy, etc.; R is H, a metal, a 1-6C alkylcarbonyl(oxymethyl), a 1-6C alkylsulfonyl, etc.; Y is H, nitro, cyano, amino, a halogeno, a 1-6C haloalkyl, a 2-6C alkenyl, etc.; Z is H, cyano, a halogeno; (m), (n) are each 1-4; but a compound wherein X, R, Y and Z are each H is excluded], e.g. 2-(3-fluoro-2-pyridyl)indole. The compound of formula I is obtained e.g. by reacting an acetylpyridine compound of formula II with a phenylhydrazine compound of formula III at -50 to 150 deg.C and subsequently thermally reacting the obtained hydrazone compound of formula IV with an acid such as polyphosphoric acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel pyridylindole compound and a fungicide for agricultural and horticultural use.

[0002]

2. Description of the Related Art In the cultivation of agricultural and horticultural crops, a large number of control agents are used against crop diseases, but their use is insufficient due to insufficient control effect or the emergence of drug-resistant pathogens. Due to their limitations, their potential to cause phytotoxicity and contamination of plants, and their high toxicity to humans, fish and livestock, there are not many satisfactory control agents that are not always satisfactory. Therefore, there is a strong demand for a drug that can be safely used with few such disadvantages. Many pyridyl indole compounds have already been synthesized as compounds similar to the compounds of the present invention. Further, Japanese Patent Application Laid-Open No. 55-15 / 55
No. 1505 describes that the following compound (A) has a bactericidal activity against anthracnose of cucumber. However, Japanese Patent Application Laid-Open No. 55-151505 has no description on gray mold and 2- (2) other than compound (A).
The bactericidal activity of (pyridyl) indole compounds is not yet known.

[0003]

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[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyridylindole compound which can be synthesized industrially advantageously, is a safe and effective fungicide for agricultural and horticultural use.

[0005]

According to the present invention, there is provided a compound represented by the general formula (1):

[0006]

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Wherein X is a hydrogen atom, a nitro group, a cyano group, a halogen atom, a C _1-6 haloalkyl group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, a C _1-6 alkylsulfinyl group Or a C _1-6 alkylsulfonyl group. R represents a hydrogen atom, a metal atom, a C _1-6 alkylcarbonyl group, a C _1-6 alkylcarbonyloxymethyl group,
_1-6 alkylsulfonyl group, benzoyl group (which may be substituted with a halogen atom, C _1-6 alkyl group or C _1-6 alkoxy group), (halogen atom, C _1-6 alkyl group or C _1-6 A benzoyloxymethyl group (optionally substituted with an alkoxy group) or a (halogen atom,
A phenylsulfonyl group which may be substituted by a C _1-6 alkyl group or a C _1-6 alkoxy group). Y is
Hydrogen atom, nitro group, cyano group, amino group, halogen atom, C _1-6 haloalkyl group, C _2-6 alkenyl group, C
_2-6 alkynyl group, C _2-6 haloalkenyl group, C _2-6 haloalkynyl group, di C _1-6 alkylamino group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6
Represents an alkylsulfonyl group, a C _3-8 cycloalkyl group or a C _3-8 cycloalkylmethyl group. Z represents a hydrogen atom, a cyano group or a halogen atom. m and n each independently represent 1, 2, 3, and 4. Where X,
Compounds in which R, Y and Z are all hydrogen atoms are excluded. And a salt thereof, and a general formula (2)

[0008]

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(Wherein, X, R, Z, m, and n have the same meanings as described above, and Y ¹ represents a hydrogen atom, a nitro group, a cyano group,
Amino group, a halogen atom, C _1-6 alkyl, C _1-6 haloalkyl group, C _2-6 alkenyl, C _2-6 alkynyl group, C _2-6 haloalkenyl, C _2-6 haloalkynyl group, Di C _1-6 alkylamino group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 alkoxy group, C _3-8 cycloalkyl group or C _3- Represents an _8- cycloalkylmethyl group. A fungicide for agricultural and horticultural use, particularly a gray mold fungus, comprising as an active ingredient one or more of the pyridylindole compound represented by the formula (1) or a salt thereof.

In the general formula (1), X is a hydrogen atom,
Nitro group, cyano group, halogen atom such as fluorine, chlorine, bromine, etc., C _1-6 haloalkyl group such as chloromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-C _1-6 alkoxy group such as butoxy, methylthio, ethylthio, propyl, C _1-6 alkylthio groups such as isopropyl thio, methylsulfinyl, ethylsulfinyl, propyl sulfinyl, C _1-6 alkylsulfinyl such as isopropyl sulfinyl And a C _1-6 alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, and butylsulfonyl.

R represents a hydrogen atom, a metal atom such as a transition metal such as nickel, cobalt, manganese, copper, or zinc; a C _1-6 alkylcarbonyl group such as acetoxy, propionyl and isobutyryl; acetoxymethyl, propionyloxymethyl; C _1-6 alkylcarbonyloxymethyl group such as butyryloxymethyl, (halogen atom such as fluorine, chlorine and bromine, C _1-6 alkyl group such as methyl and ethyl, C _1-6 alkoxy group such as methoxy and ethoxy A benzoyl group, which may be substituted with
A benzoyloxymethyl group which may be substituted with a halogen atom such as chlorine or bromine, a C _1-6 alkyl group such as methyl or ethyl, a C _1-6 alkoxy group such as methoxy or ethoxy, or (fluorine, chlorine, bromine) represents a halogen atom, methyl, C _1-6 alkyl groups such as ethyl, methoxy, may be substituted by C _1-6 alkoxy group such as ethoxy) phenyl sulfonyl group, such as.

Y is a hydrogen atom, a nitro group, a cyano group, an amino group, a halogen atom such as fluorine, chlorine and bromine, and a C _1-6 such as trifluoromethyl, trichloromethyl, chloromethyl, dichloromethyl and pentafluoroethyl. C _2-6 alkenyl group such as haloalkyl group, vinyl, 1-propenyl, allyl, crotyl, C _2-6 alkynyl group such as ethynyl, 1-propynyl, propargyl, 1-chlorovinyl, 2-chlorovinyl, 2-fluoro Vinyl, 3
- chloroallyl, C _2-6 haloalkenyl group such as 2-Kurorokurochiru, 2-chloroethynyl, 2-bromo-ethynyl, 3-chloro-2-propynyl, such as 3,3,3-trifluoro-1-propynyl C _{2 -6} haloalkynyl group, di C _1-6 alkylamino group such as dimethylamino, diethylamino, ethylisopropylamino, C _1-6 alkylthio group such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, t-butylthio, methylsulfinyl , Ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, t-butylsulfinyl, and other C _1-6 alkylsulfinyl groups, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl,
C _1-6 such as butylsulfonyl and t-butylsulfonyl
C _3-8 cycloalkyl groups such as alkylsulfonyl group, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; C such as cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl and cyclooctylmethyl
Represents a _3-8 cycloalkylmethyl group.

Z represents a hydrogen atom, a cyano group, or a halogen atom such as fluorine, chlorine, and bromine.

Y ¹ is a hydrogen atom, a nitro group, a cyano group,
Amino group, halogen atom such as fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, s-
C _1-6 alkyl groups such as butyl, t-butyl and hexyl; C such as trifluoromethyl, trichloromethyl, chloromethyl, dichloromethyl and pentafluoroethyl
_1-6 haloalkyl group, C _2-6 alkenyl group such as vinyl, 1-propenyl, allyl, crotyl, ethynyl, 1
- propynyl, C _2-6 alkynyl group such as propargyl, 1-chloro vinyl, 2-chlorovinyl, 2-fluorovinyl, 3-chloroallyl, C _2-6 haloalkenyl group such as 2-Kurorokurochiru, 2-chloro ethynyl, 2-
Bromoethynyl, 3-chloro-2-propynyl, 3,
C _2-6 haloalkynyl groups such as 3,3-trifluoro-1-propynyl, di C _1-6 alkylamino groups such as dimethylamino, diethylamino, ethylisopropylamino, methylthio, ethylthio, propylthio, isopropylthio, butylthio, C _1-6 alkylthio group such as t-butylthio, methylsulfinyl, ethylsulfinyl, propyl sulfinyl, isopropyl sulfinyl, butylsulfinyl, t- butyl sulfinyl C _1-6 alkylsulfinyl group such as Le, methylsulfonyl,
A C _1-6 alkylsulfonyl group such as ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and t-butylsulfonyl; a C _1-6 alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and t-butoxy; represents propyl, cyclopentyl, cyclohexyl, cycloheptyl, C _3-8 cycloalkyl group such as cyclooctyl, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, a C _3-8 cycloalkylmethyl group, such as cyclooctyl methyl .

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced by the following method. (Production method 1)

[0016]

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(In the formula, X, Y, m, and n represent the same meaning as described above.)

That is, the acetylpyridines represented by the general formula (3) and the phenylhydrazines represented by the general formula (4) are mixed with -50 to 1 in a solvent-free or suitable solvent.
By reacting at 50 ° C., hydrazones represented by the general formula (5) are obtained. Examples of the solvent that can be used in this reaction include water, alcohols such as methanol and ethanol, tetrahydrofuran (THF),
Ethers such as dioxane, aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, acetonitrile, N, N-dimethylformamide (DMF)
And the like. Next, the compound represented by the general formula (5) is combined with an acid such as polyphosphoric acid (PPA) by 50 to 20.
By heating to 0 ° C., pyridylindoles represented by the general formula (1-1) can be produced.

(Manufacturing method 2)

[0020]

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(Wherein, X, Y, m, and n have the same meanings as described above, and M represents a divalent metal atom such as zinc or copper.
V ¹ and V ² represent a halogen atom. This production method comprises reacting a 2-metal halide (6) in which the 1-position of the indole ring is protected with a protecting group such as a benzenesulfonyl group with a 2-halogenated pyridine (7) in the presence of a zero-valent palladium catalyst. ), The protective group at the 1-position is removed under alkaline conditions to produce a pyridylindole represented by the general formula (1-1). Examples of the palladium catalyst that can be used in this reaction include tetrakistriphenylphosphine palladium, and the like. Examples of the solvent that can be used include-. The reaction is
It proceeds smoothly at ℃ ~ ℃.

(Production method 3)

[0023]

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(Wherein X and m represent the same meaning as described above,
V ³ represents a halogen atom. R ¹ and R ² are C _1-6
Represents an alkyl group. )

In the general formula (1) or (2), the compound wherein Y or Y ¹ is a C _1-6 alkoxy group is represented by Y or Y
It can be produced by reacting a compound in which ¹ is a halogen atom with a metal alkoxide such as R ¹ ONa. Similarly, a compound in which Y or Y ¹ is a C _1-6 alkylthio group may be added to a compound in which Y or Y ¹ is a halogen atom in the presence of a mercaptan salt such as R ² SNa or a suitable base. it can be prepared by the action of a mercaptan represented by ² SH. Examples of the solvent that can be used in these reactions include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and diethyl ether, and aromatic hydrocarbons such as benzene and toluene.

(Production method 4)

[0027]

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(Where X and m represent the same meaning as described above,
V ⁴ represents a halogen atom. R ³ represents a hydrogen atom or a C _1-4 alkyl group. )

In the general formula (1), a compound in which Y is a C _2-6 alkenyl group or a C _2-6 alkynyl group is produced by reacting a compound in which Y is a halogen atom with an organotin compound in the presence of a catalyst. can do. Examples of the tin compound that can be used for the reaction include alkynyltrialkyltins such as vinyltributyltin, 1-propenyltributyltin, 1-butenyltributyltin, ethynyltrimethyltin, alkynyltrialkyltins such as propynyltrimethyltin, and the like. be able to. Examples of the catalyst include tetrakistriphenylphosphine palladium, dichlorobistriphenylphosphine palladium-copper (I) iodide, and the like.

(Production Example 5)

[0031]

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(Wherein, X, Y, m, and n have the same meaning as described above, and V ⁵ represents a halogen atom.)

In the general formula (1), compounds in which Z is a halogen atom or a cyano group can be produced by a general synthetic chemistry technique. That is, the compound (1-6) wherein Z is a halogen atom by reacting a compound in which Z is a hydrogen atom in the general formula (1) with a halogenating agent such as chlorine, bromine, thionyl chloride, thionyl bromide, and sulfuryl chloride. ) Can be manufactured. The corresponding cyano compound (1-7) can be obtained by reacting chlorosulfonyl isocyanate with a compound in which Z is a hydrogen atom in the presence of a suitable base.

(Production Example 6)

[0035]

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(Wherein, X, Y, m and n have the same meanings as described above, and R ⁴ is a C _1-6 alkylcarbonyl group, C _1-6
Represents an alkylcarbonyloxymethyl group, a C _1-6 alkylsulfonyl group, an optionally substituted benzoyl group, an optionally substituted benzoyloxymethyl group or an optionally substituted phenylsulfonyl group. Also,
V ⁶ represents a halogen atom. )

In the general formula (1), R represents a C _1-6 alkylcarbonyl group, a C _1-6 alkylcarbonyloxymethyl group, a C _1-6 alkylsulfonyl group, an optionally substituted benzoyl group, The compound of a benzoyloxymethyl group or a phenylsulfonyl group which may be substituted may be a compound represented by the general formula (1-1) and a halide represented by R ⁴ V ⁶ in the presence of a base. It can be produced by reacting at -50 to 150C below. Bases used in this reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide, sodium methylate, t
Metal alkoxides such as potassium butoxy, and organic bases such as triethylamine and pyridine. Examples of the solvent that can be used include aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, ethers such as diethyl ether and THF, halogenated hydrocarbons such as chloroform, acetonitrile, dimethyl sulfoxide ( DMSO), DMF
And the like. The amount of the halogen compound to be used is preferably 0.5 to 3 equivalents and the base is preferably 0.5 to 3 equivalents to 1 equivalent of the compound represented by the general formula (1-1).

In any of X and Y, C _1-6
The compound having an alkylsulfinyl group or a C _1-6 alkylsulfonyl group can be produced by oxidizing the corresponding compound having a C _1-6 alkylthio group.

(Production Method 7) Among the compounds represented by the general formula (1), the compounds in which R is a metal atom are represented by a general synthetic chemistry method, for example, represented by the general formula (1-1) The compound can be produced by dissolving the compound in an organic solvent such as acetone and ethanol, and adding an aqueous solution of a metal salt such as a metal chloride or an ethanol solution to the solution.

In the present invention, the target product can be obtained by performing ordinary post-treatments after completion of any of the reactions. The structure of the compound of the present invention is IR,
Determined from NMR, MS, etc.

[Bactericide] The compound of the present invention has excellent bactericidal activity against a wide variety of filamentous fungi, so that it can control various diseases which occur during the cultivation of agricultural and horticultural crops including flowers, turf and pasture. Can be used for For example, rice blast disease (Pyricularia oryzae) Sheath Blight (Rhizoctonia solani) bakanae (Gibberella fujikuroi) Gomaha blight (Cochliobolus miyabeanus) barley brownish ear disease (Ustilago nuda) Wheat Fusarium head blight (Gibberella zeae) brown rust ( Puccinia recondita) Memonbyo (Pseudocercosporella herpotrichoides) glume blotch (Leptosphaeria nodorum) powdery mildew (Erysiphe graminis f. sp. tritici ) pink snow mold disease (Micronectriella nivalis) potato late blight (Phytophthora infestans) peanut brown spot disease (Mycosphaerella arachidis ) sugar beet brown spot disease (Cercospora beticola) cucumber powdery mildew (Sphaerotheca fuliginea) rot (Sclerotinia sclerotiorum) gray mold (Botrytis cinerea) downy mildew (Pseudoperonospora cubensis) tomato leaf blight (Cladosporium fulvum) plague (Pytophthora infestans ) Eggplant Black blight ( Corynespora melongenae ) Onion Gray rot ( Botrytis al lii) Strawberry powdery mildew ( Sohaerotheca humuli ) Apple powdery mildew ( Podosphaera leucotricha) Black scab ( Venturia inaequalis ) Moniliania disease ( Monilinia mali ) Oyster anthracnose ( Gloeosporium kaki ) Peach leaf rot ( Monilinia fructicola ) ( Uncinula necator) Downy mildew ( Plasmopara viticola ) Pear Red scab ( Gymnosporangium asiaticum) Black spot ( Alternaria kikuchiana ) Tea Ring spot ( Pestalotia theae) Anthracnose ( Colletotrichum theae-sinensis ) Citrus scab ( Elisinoe fawcetti ) It can be used to control blue mold ( Pennisillium italicum ), western grass, snow rot, and Sclerotinia borealis .

In recent years, various pathogens have developed resistance to benzimidazole agents, dicarboximide agents, and acylalanine agents, resulting in insufficient efficacy of these agents. Is desired. The compound of the present invention is a drug having an excellent bactericidal effect not only on sensitive strains but also on pathogens resistant to benzimidazole agents, dicarboximide agents and acylalanine agents. Diseases which are more preferably applied include wheat powdery mildew, apple scab, gray mold of cucumber, downy mildew of grape, and the like.

The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater objects such as ship bottoms and fish nets. Also, by mixing the compound of the present invention into paints, fibers, and the like, it can be used as an antibacterial and fungicide for walls and bathtubs, shoes and clothes. Some of the compounds of the present invention exhibit insecticidal, acaricidal and herbicidal activities.

When the compound of the present invention is actually applied, it can be used in a pure form without adding any other components, and can be used in the form of a general pesticide for use as a pesticide, ie, wettable powder, granule , Powders, emulsions, aqueous solvents, suspensions, flowables and the like. When a solid agent is intended as an additive or carrier, a soybean grain, vegetable powder such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay or other mineral fine powder, benzoic acid Organic and inorganic compounds such as soda, urea, and sodium sulfate are used. For liquid dosage form, kerosene,
Petroleum fractions such as xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide,
Dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. are used as solvents. In order to obtain a uniform and stable form in these preparations, a surfactant may be added, if necessary.

The wettable powders, emulsions and flowables are used by diluting them to a predetermined concentration with water to prepare suspensions or emulsions.

Although the compound of the present invention exerts a sufficient effect even when used alone, it can be used in combination with one or more kinds of various fungicides, insecticides, acaricides or synergists. Fungicides, insecticides, acaricides, nematicides, and plant growth regulators that can be used in combination with the compound of the present invention include the following.

(Disinfectant) Copper agent: basic copper chloride, basic copper sulfate, etc. Sulfur agent: thiuram, maneb, mancozeb, polycarbamate, propineb, ziram, zineb, etc. Polyhaloalkylthio agent: captan, dichlorfluanide, Folpet, etc. Organic chlorine agents: chlorothalonil, fthalide, etc. Organic phosphorus agents: IBP, EDDP, tolclofosmethyl,
Pyrazophos, fosetyl, etc. Benzimidazole agents: thiophanate methyl, benomyl, carbendazim, thiabendazole, etc. Dicarboxyimide agents: iprodione, vinclozolin, procymidone, fluoroimide, etc.

Carboxamide agents: oxycarboxin, mepronil, flutranyl, teclophthalam, triclamide, pencyclon, etc. Acylalanine agents: metalaxyl, oxadixyl, furalaxyl, etc. SBI agents: triadimefon, triadimenol, bitertanol, microbutanil, hexaconazole, propicon Nazole, trifumizole, prochloraz, pefurazoate, fenarimol, pyrifenox, triforine, flusilazole, etaconazole, diclobutrazol, fluotrimazole, flutriafen, penconazole, diniconazole, cyproconazole, imazalil, tridemorph, fenpropimorph, butiobate, etc. Antibiotics: polyoxin, blasticidin S, kasugamycin, validamycin, Acid dihydrostreptomycin, etc. Others: propamocarb hydrochloride, quintozene, hydroxy isoxazole, methasulfocarb, Anirajin,
Isoprothiolane, probenazole, quinomethionate, dithianone, dinocab, diclomedine, mepanipyrim, ferimzone, fluazinam, pyroquilon, tricyclazole, oxolinic acid, dithianone, iminoctadine acetate, simoxanil, pyrrolnitrin, metasulfocarb, dietofencaribine, citapfencarburinabine , Dozine, dimethomorph, phenazine oxide, etc.

(Insecticide / Acaricide) Organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formotion, marathon, trichlorfon, thiomethon,
Hosmet, dichlorvos, acephate, EPBP,
Methyl parathion, oxydimetone methyl, ethion,
Salithione, cyanophos, isoxathion, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenophos, pyraclophos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, carbosulfan, benfracarb, flatiocarb, propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, ethiophencarb, phenoxycarb and the like.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, ethion Fenprox, cycloprothrin, trolametrin, silafluofen, brofenprox, acrinasuri, etc. Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, cartap, thiocyclam, bensultap, benzoepin, Diafenthiuron, acetamiprid, nitenpyram, imidacloprid, fipronil, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses, and the like. Nematicides: fenamiphos, phosthiazate and the like. Acaricides: chlorbenzilate, phenisobromolate, dicophor, amitraz, BPPS, benzomate,
Hexitiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cyhexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like. (Plant growth regulator) gibberellins (eg gibberellin A
_3, gibberellin A _4, gibberellin A ₇₎ IAA, NA
A.

[0051]

The compounds of the present invention will be described more specifically with reference to Examples and Reference Examples.

Example 1 Synthesis of 2- (3-fluoro-2-pyridyl) indole (Compound No. 27)

[0053]

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2-acetyl-3-fluoropyridine 2.0
g (14.4 mmol) in ethyl alcohol 3.0 ml
To the mixture was added 1.6 g (14.8 mmol) of phenylhydrazine, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain about 3.2 g of crude 1- (3-fluoro-2-pyridyl) -1-ethanonephenylhydrazone. To this, 16 g of polyphosphoric acid (PPA) was added, and
Stirred for hours. After completion of the reaction, 200 ml of water was added to the reaction solution, and a 20% aqueous sodium hydroxide solution was added thereto under cooling to make the solution alkaline, followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was washed with methyl alcohol to obtain 2.3 g of the desired compound. 75% through two steps,
mp. 164-165 ° C

Example 2 Synthesis of 2- (3-methoxy-2-pyridyl) indole (Compound No. 32)

[0056]

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2- (3-fluoro-2) was added to 10 ml of DMF.
-Pyridyl) indole 0.5 g (2.36 mmol) and sodium methoxide in 28% methyl alcohol 2.3
g (11.8 mmol) was added and heated at 120 ° C. for 3 hours. The reaction solution was poured into ice water, extracted with ether, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with n-hexane to obtain 0.3 g of the desired compound. Yield 57%, mp. 146-147 ° C

Example 3 Synthesis of 2- (3-methylthio-2-pyridyl) indole (Compound No. 31)

[0059]

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0.5 g (2.36 mmol) of 2- (3-fluoro-2-pyridyl) indole and 5.5 g (11.8 mmol) of a 15% aqueous solution of sodium salt of methyl mercaptan
l) was added to 10 ml of DMF and heated at 100 ° C. for 2 hours. The reaction solution was poured into ice water, extracted with ether, washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to give the desired compound 0.35.
g was obtained. Yield 62%, mp. 101-102 ° C

Reference Example 1 Synthesis of 2- (3-bromo-2-pyridyl) -1- (1-ethoxyethyl) indole

[0062]

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1.1 g of sodium hydride (2%
7.0 mmol) was suspended in 30 ml of DMF, and 2- (3
-Bromo-2-pyridyl) indole 6.7 g (24.5 m)
mol) and 20 ml of DMF were added dropwise under ice cooling.
The mixture was further stirred at room temperature for 1 hour. Next, 2.9 g (27.0 mmol) of 1-chloroethyl ethyl ether was added to the mixture.
l) was added dropwise under ice-cooling, and the mixture was further stirred at 50 to 60 ° C for 2 hours. The reaction mixture is poured into water, extracted with ether,
After washing with water, the solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to give 7.2 g of the desired compound.
I got 85% yield

Reference Example 2 Synthesis of 1- (1-ethoxyethyl) -2- [3- (2-trimethylsilyl) ethynyl-2-pyridyl] indole

[0065]

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2.0 g of the oil obtained in Reference Example 1 (5.80
was dissolved in 20 ml of triethylamine, and 1.1 g (11.6 mmol) of trimethylsilylacetylene was added. Further, 0.2 g (0.29 mmol) of dichlorobistriphenylphosphinepalladium (II) and primary iodide were dissolved.
0.11 g (0.58 mmol) of copper was added, and the mixture was heated under reflux for 3 hours. 5 ml of a saturated aqueous solution of sodium carbonate was added to the reaction solution, the mixture was concentrated under reduced pressure, water, chloroform and celite were added, and the mixture was filtered and separated. The chloroform layer was washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 2.0 g of the desired compound. 95% yield

Reference Example 3 1- (1-ethoxyethyl) -2- (3-ethynyl-2)
Synthesis of (pyridyl) indole

[0068]

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The oily substance obtained in Reference Example 2 (2.0 g, 5.50)
mmol) was dissolved in 20 ml of methanol, and 1.1 g (7.97 mmol) of potassium carbonate was added, followed by stirring at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, water, chloroform and celite were added, and the mixture was filtered and separated. The chloroform layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 1.7 g of the desired compound.

Example 4 Synthesis of 2- (3-ethynyl-2-pyridyl) indole (Compound No. 24)

[0071]

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1.7 g of the crude oil obtained in Reference Example 3 was dissolved in 15 ml of methanol, 2 ml of 2N hydrochloric acid was added, and the mixture was heated at 60 ° C. for 20 minutes. The reaction mixture was concentrated under reduced pressure, dissolved in chloroform, washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue obtained was purified by silica gel column chromatography to obtain 0.6 g of the desired compound. Obtained. Yield 34%, mp. 119-120
° C

Example 5 Synthesis of 2- (3-chloro-2-pyridyl) -1-phenylsulfonylindole (Compound No. 66)

[0074]

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1.26 g of diisopropylamine (12.5 m
mol) was dissolved in 10 ml of dry THF, and the mixture was dissolved in a stream of nitrogen.
At 0 ° C., 7.81 ml of 1.6 M n-butyllithium was added dropwise, and the mixture was stirred for 30 minutes. To this, a solution of 3.00 g (11.7 mmol) of 1-phenylsulfonylindole in 12 ml of dry THF was added dropwise under ice-cooling, and the mixture was further stirred for 30 minutes. To this was added 1.70 g (12.5 mmol) of zinc chloride, and the mixture was stirred for 1 hour under ice-cooling.
A solution of the compound into which Cl was introduced was obtained. Meanwhile, in another flask, 0.17 g (0.24 mmol) of dichlorobis (triphenylphosphine) palladium (II) was charged,
1.5M diisobutylaluminum hydride in a nitrogen stream
0.15 ml of a toluene solution was added, and the mixture was stirred at room temperature for 20 minutes. To this, 1.16 g of 2,3-dichloropyridine (7.8 m
mol) and a solution containing the previously synthesized indole 2-ZnCl, and the mixture was heated and refluxed for 4 hours under a nitrogen stream. The reaction mixture was allowed to cool, water and ethyl acetate were added, and the layers were separated. The residue obtained by dehydrating and concentrating the organic layer was purified by silica gel column chromatography, and 2.78 g of the desired compound was obtained.
I got Yield 96%, mp. 38-40 ° C

Example 6 Synthesis of 2- (3-chloro-2-pyridyl) indole (Compound No. 1)

[0077]

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2- (3-chloro-2-pyridyl) -1-
Phenylsulfonyl indole 2.51 g (6.8 mmol
l) was dissolved in 60 ml of dioxane, and 40 ml of a 5N aqueous sodium hydroxide solution was added dropwise while stirring at room temperature.
Next, 20 ml of methanol was added to make a uniform solution, and the mixture was heated under reflux for 3 hours. After the reaction solution was concentrated under reduced pressure, water and ethyl acetate were added, and the mixture was separated. The organic layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure, and the obtained residue was washed with a mixed solvent of hexane-ether = 2: 1 to obtain 1.14 g of the desired compound. Yield 73%, mp. 167-169
° C

Example 7 Synthesis of 3-cyano-2- (5-ethyl-2-pyridyl) indole (Compound No. 34)

[0080]

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0.5 g (2.3 mmol) of 2- (5-ethyl-2-pyridyl) indole was dissolved in 20 ml of dry acetonitrile, and 0.32 g (2.3 mmol) of chlorosulfonyl isocyanate was added dropwise under ice cooling. . After stirring for 30 minutes as it is, 0.5 ml of DMF was added dropwise, and the mixture was added at room temperature for 3 minutes.
Stirred for hours. Water and ethyl acetate were added to the reaction solution, the layers were separated, the organic layer was dehydrated and concentrated under reduced pressure. The residue obtained was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to give the target compound. 0.25 g was obtained. Yield 45%, mp. 74-76 ° C

Table 1 shows typical examples of the compounds of the present invention, including the above Examples.

[0083]

[Table 101]

[0084]

[Table 102]

[0085]

[Table 103]

[0086]

[Table 104]

Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratios are not limited to these examples, but can be changed in a wide range. Parts in Formulation Examples are parts by weight.

Example 8 Water-dispersible powder 40 parts of the compound of the present invention 53 parts of diatomaceous earth 4 parts of higher alcohol sulfate ester 3 parts of alkylnaphthalene sulfonate If the above are uniformly mixed and finely pulverized, the active ingredient 40
% Wettable powder.

Example 9 Emulsion 30 parts of the compound of the present invention 33 parts of xylene 30 parts of dimethylformamide 7 parts of polyoxyethylene alkyl allyl ether By mixing and dissolving the above, an emulsion having an active ingredient of 30% is obtained.

Example 10 Suspension The compound of the present invention 10 parts Sodium ligninsulfonate 4 parts Sodium dodecylbenzenesulfonate 1 part Xanthan gum 0.2 part Water 84.8 parts The above components are mixed until the particle size becomes 1 micron or less. If wet milled, a 10% active ingredient suspension is obtained.

[0091]

Next, Test Examples show that the compounds of the present invention are useful as effective components of various plant disease controlling agents. The control effect was determined by visually observing the growth of lesions and flora that appeared on leaves, stems and the like at the time of the survey, and calculating the control effect.

Test Example 1 Cucumber Gray Mold Control Test Cucumber cultivated in an unglazed pot (variety "Sagami Hanshiro")
An emulsion of the compound of the present invention was sprayed on the seedlings at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, a spore suspension (containing glucose and yeast extract) of cucumber gray mold fungus ( Botrytis cinerea ) is inoculated dropwise onto cucumber cotyledons, and a high humidity, constant temperature room (20
C) for 4 days. The lesion diameter on the cotyledon was compared with that of untreated, and the control effect was determined.
% Or more. 1, 2, 8, 10,
17, 18, 19, 24, 25, 27, 31, 32, 3
3, 35, 42, 75.

Test Example 2 Wheat Powdery Mildew Control Test Wheat seedlings (variety "Chihoku", cultivated in unglazed pots)
(0.1-1.2 leaf stage), the emulsion of the compound of the present invention was sprayed at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, and wheat powdery mildew ( Erysiphe gram)
inia f. sp. tritici ) were shaken off and inoculated and kept in a greenhouse at 22-25 ° C. for 7 days.
The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. 1, 8, 19, 24, 27, 32, 33,
75.

Test Example 3 Test for Control of Grape Downy Mildew Leaves of leaves of openly planted grapes (variety “Kaiji”, 3rd grade) were punched into a disc having a diameter of 30 mm, and an emulsion of the compound of the present invention was dissolved in a chemical solution having a concentration of 200 ppm of the active ingredient. Dipped. After immersion, air-dry at room temperature, grape downy mildew ( Plasmopar)
a viticola) a zoosporangia suspension is spray inoculation was held for 10 days in a constant temperature chamber under illumination (20 ° C.). The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. 34.

Test Example 4 Apple Scab Control Test Apple seedlings (cultivar “Kunimitsu”, 3
~ 4 leaf stage), the emulsion of the compound of the present invention
Sprayed at a concentration of pm. After spraying, air-dry at room temperature and scab of apple ( Venturia inaequali)
The conidia of s ) were inoculated and kept in a high humidity constant temperature room (20 ° C.) where light and dark were repeated every 12 hours for 2 weeks. The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. 1, 19, 24, 25, 27, 36, 75.

[Table 105]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinsuke Sano 345 Takada, Odawara-shi, Kanagawa Japan Nippon Soda Co., Ltd.Odawara Research Institute Co., Ltd.

Claims (3)

[Claims] 1. A compound of the general formula (1) [Wherein X represents a hydrogen atom, a nitro group, a cyano group, a halogen atom, a C _1-6 haloalkyl group, a C _1-6 alkoxy group,
Represents a C _1-6 alkylthio group, a C _1-6 alkylsulfinyl group or a C _1-6 alkylsulfonyl group. R represents a hydrogen atom, a metal atom, a C _1-6 alkylcarbonyl group, C _1-6
Alkylcarbonyloxymethyl group, C _1-6 alkylsulfonyl group, benzoyl group (optionally substituted with a halogen atom, C _1-6 alkyl group or C _1-6 alkoxy group), (halogen atom, C _1-6 Alkyl group or C
_A benzoyloxymethyl group (which may be substituted with a _1-6 alkoxy group) or a phenylsulfonyl group (which may be substituted with a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group). Y represents a hydrogen atom, a nitro group, a cyano group, an amino group, a halogen atom, a C _1-6 haloalkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _2-6 haloalkenyl group, a C _{2- 6} haloalkynyl, di C _1-6 alkylamino, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, C _3-8 cycloalkyl or C _3-8 cycloalkyl Represents an alkylmethyl group. Z represents a hydrogen atom, a cyano group or a halogen atom. m and n each independently represent 1, 2, 3, and 4. However, compounds in which X, R, Y, and Z are all hydrogen atoms are excluded. Or a salt thereof. 2. A compound of the general formula (2) (Wherein, X, R, Z, m, and n represent the same meaning as described above,
Y ¹ is a hydrogen atom, nitro group, cyano group, amino group, halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _{2- 6}
Haloalkenyl group, C _2-6 haloalkynyl group, di C _1-6
Alkylamino group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C
_1-6 alkoxy group, C _3-8 cycloalkyl group or C
Represents a _3-8 cycloalkylmethyl group. Where X, R, Y
Compounds in which ¹ and Z are both hydrogen atoms are excluded. A fungicide for agricultural and horticultural use, characterized by containing one or more of the pyridylindole compound represented by the formula (1) or a salt thereof as an active ingredient. 3. A compound of the general formula (2) (Wherein, X, R, Y ¹ , Z, m, and n represent the same meaning as described above), which contains one or more of a pyridylindole compound or a salt thereof as an active ingredient. Characteristic gray mold control agent.