JP2002308879A - 5-haloalkylazolopyrimidine compound, production method, and harmful organism control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel azolopyrimidine compound which can become a harmful organism control agent which exhibits sure effects and can be safely used; its production method; and a harmful organism control agent containing the compound. SOLUTION: This azolopyrimidine compound is represented by formula (1) [wherein R1 is H, a halogen, a 1-8C alkyl, a 1-8C haloalkyl, an optionally substituted heterocyclic group, a 1-8C alkylamino group, a 1-8C alkyl(haloalkyl) amino group or the like; R2 is a 1-8C haloalkyl; R3 is H, a 1-4C alkyl or an optionally substituted aryl; L is a halogen, a 1-4C alkyl, a 1-3C haloalkyl, a 1-4C alkoxy or a 1-3C haloalkoxy; n is 0-5; and A is N or CH].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel azolopyrimidine compound, a method for producing the same, and a pesticide containing the compound as an active ingredient.

[0002]

2. Description of the Related Art In the cultivation of agricultural and horticultural crops, many control agents have been used against crop diseases, but their use is insufficient due to insufficient control effect or the emergence of drug-resistant pathogens. From the viewpoint of being restricted, causing phytotoxicity and contamination of plants, and toxicity to humans and livestock and the effects on the environment, there are not a few 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.

[0003] Azolopyrimidine compounds similar to the compounds of the present invention include, for example, WO 99/41255, USP. No. 5,756,590, JP-A-11-03
No. 5581, etc., the triazolopyrimidine compound 5
It is described that a compound whose position is substituted by a methyl group, a chlorine atom or the like is useful as an agricultural and horticultural fungicide.

However, there is no description of a compound having a haloalkyl group at the 5-position of the azolopyrimidine ring as in the present invention. Further, 2-phenyl-4-halogeno-3-oxobutyrate, which is a production intermediate, is a novel compound not described in any literature.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a novel azolopyrimidine compound which can be used as a pesticidal agent which is safe and can be used safely, a method for producing the same, and a pesticidal agent containing these as an active ingredient. The purpose is to do.

[0006]

The present invention provides: 1) a general formula (1)

[0007]

Embedded image

(Wherein R ₁ represents a hydrogen atom, a hydroxy group, a halogen atom, a C _1-8 alkyl group, a C _2-8 alkenyl group, a C _2-8 alkynyl group, a C _3-8 cycloalkyl group, _{A 3-8} cycloalkenyl group, a C _1-8 haloalkyl group, a heterocyclic group optionally having a substituent, an aryl group optionally having a substituent, an amino group, a C _1-8 alkylamino group, C _1-8 haloalkylamino group, C
_1-8 alkyl (haloalkyl) amino group or C _1-8
Represents a dialkylamino group. Here, the heterocyclic group represents a pyridyl group, a pyrrolidinyl group, a piperazinyl group, a morpholinyl group or a piperidyl group. R ₂ represents a C _1-8 haloalkyl group; R ₃ represents a hydrogen atom, a C _1-4 alkyl group or an aryl group which may have a substituent;
Represents a halogen _{atom, C 1-4 alkyl, C 1-3} haloalkyl _{group, C 1-4} alkoxy _group, a _{C 1-3} haloalkoxy group. n represents 0 or an integer of 1 to 5,
Represents N or CH. Azolopyrimidine compound represented by the following formula) or a salt thereof 2) General formula (2)

[0009]

Embedded image

(Wherein, R ₂ , L and n have the same meanings as described above, and R ₄ represents a C _1-4 alkyl group or a phenyl group which may have a substituent). Compound represented by the general formula (3)

[0011]

Embedded image

Wherein A and R ₃ have the same meanings as described above, and are reacted with a compound represented by the general formula (4):

[0013]

Embedded image

Wherein A, R ₂ , R ₃ , L and n have the same meanings as described above, and 3) a general formula (1)

[0015]

Embedded image

Wherein A, R ₁ , R ₂ , R ₃ , L and n
Has the same meaning as described above. A pest control agent characterized by containing one or more of the azolopyrimidine compound represented by the formula (1) or a salt thereof as an active ingredient.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the general formula (1), R ₁ represents a hydrogen atom; a hydroxy group; a halogen atom such as fluorine, chlorine, bromine, and iodine; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec. A C _1-8 alkyl group such as a -butyl group or a t-butyl group; a C _2-8 alkyl group such as a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group or a 3-butenyl group. Alkenyl group; C _2-8 alkynyl group such as ethynyl group, 1-propynyl group, 1-butynyl group, 2-butynyl group; C _3-8 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group; cyclopentenyl fluoromethyl group; group, C _3-8 cycloalkenyl groups such as cyclohexenyl group
A C _3-8 haloalkyl group such as a difluoromethyl group, a trifluoromethyl group, a difluorochloromethyl group, a chloromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a pentafluoroethyl group; a 1-pyridyl group, Pyridyl group, 3-pyridyl group, 4-pyridyl group, 1-piperazinyl group, 2-piperazinyl group, 4-methyl-1-piperazinyl group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, 1-morpholinyl Group (morpholino group), 2-morpholinyl group, 3-morpholinyl group,
A heterocyclic group which may have a substituent such as a 1-piperidinyl group or a 2-piperinyl group; an aryl group which may have a substituent such as a phenyl group, a 1-naphthyl group or a 2-naphthyl group; Amino group; methylamino group, ethylamino group,
A C _1-8 alkylamino group such as an isopropylamino group;
C _1-8 such as a 2,2,2-trifluoroethylamino group
Haloalkylamino group; C _1-8 alkyl (haloalkyl) amino group such as methyl (2,2,2-trifluoroethyl) amino group and 1-trifluoromethylethylamino group; C ₁ such as dimethylamino group and diethylamino group _-8
Represents a dialkylamino group.

Examples of the substituent for the heterocyclic group and the aryl group include a halogen atom such as fluorine and chlorine; an alkoxy group such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Further, the heterocyclic group and the aryl group may have the same or different substituents at arbitrary positions.

R ₂ is fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, difluorochloromethyl, fluorodichloromethyl, 1-fluoroethyl, 2- Represents a C _1-8 haloalkyl group such as a fluoroethyl group, a 2,2,2-trifluoroethyl group, and a pentafluoroethyl group. R ₃ is a hydrogen atom; a methyl group;
A C _1-4 alkyl group such as an ethyl group; an aryl which may have a substituent such as a phenyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 1-naphthyl group, a 2-naphthyl group; Represents a group. Examples of the substituent of the aryl group include a halogen atom such as fluorine and chlorine; an alkoxy group such as a methoxy group and an ethoxy group; a nitro group; a cyano group; Further, the heterocyclic group and the aryl group may have the same or different substituents at arbitrary positions.

L is a halogen atom such as fluorine, chlorine, bromine or iodine; a C _1-4 alkyl group such as a methyl group or an ethyl group; a C _1-3 haloalkyl group such as a trifluoromethyl group; a methoxy group or an ethoxy group _{C 1-4} alkoxy group and the like; represents a _{C 1-3} haloalkoxy group such as trifluoromethoxy group. n represents 0 or an integer of 1 to 5, and A is
Represents N or CH.

The salts of the present invention include salts of mineral acids such as hydrochloric acid and sulfuric acid, and salts of organic acids such as methanesulfonic acid, acetic acid and oxalic acid.

The compound of the present invention can be produced by the following method. (Production method 1)

[0023]

Embedded image

Wherein A, R ₂ , R ₃ , R ₄ , L and n
Represents the same meaning as described above, R ₁ ′ represents a group represented by R ₁ except for a halogen atom, R ₅ represents a halogen atom, and X represents a hydrogen atom, a halogen atom or a halogen atom substituted. Represents a metal atom such as magnesium, zinc and copper which may be present. )

First, the compound represented by the general formula (2) is
By reacting with the compound represented by the general formula (3),
R₁Is a hydroxy group, a compound represented by the general formula (4)
Get things. Next, the compound represented by the general formula (4) is
By the generation of R, ₁Is a halogen atom
After obtaining the compound (5), the compound is further represented by the general formula (5)
The compound is reacted with the compound represented by the general formula (6).
And by₁Is a halogen atom in the general formula (1-1)
The compounds represented can be prepared.

In the above-mentioned documents (WO99 / 41255, US Pat. No. 5,756,590), in the compound represented by the general formula (2), R ₂ is a methyl group,
A method is described in which a 5-hydroxy compound is obtained by reacting a compound such as a cyclohexyl group with a compound represented by the general formula (3) (see the following reaction formula).

[0027]

Embedded image

(In the formula, R ₆ represents an alkyl group, R ₇ represents an alkyl group such as a methyl group or a cycloalkyl group such as a cyclohexyl group, and A, R ₃ , L and n have the same meanings as described above. .)

The reaction between the compound represented by the general formula (2) and the compound represented by the general formula (3) is carried out in a solvent or without a solvent at -50 to 200 ° C, preferably 50 to 180 ° C.
C. for 1 to 48 hours. As the solvent used,
For example, amines such as triethylamine and tributylamine; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane; nitriles such as acetonitrile;
Amides such as N, N-dimethylformamide (DMF); dimethylsulfoxide; carboxylic acids such as acetic acid and propionic acid; and the like. Among these, the use of carboxylic acids such as acetic acid is preferred.

The halogenation of the compound represented by the general formula (4) is carried out by adding a halogenating agent to the compound represented by the general formula (4) at -50 to 150 ° C, preferably at 0 to 120 ° C for 1 to 48 hours.
It is performed by reacting for a time. As the halogenating agent, for example, phosphorus oxychloride, phosphorus oxybromide and the like are used.

The compound represented by the general formula (1-1) can be prepared by adding the compound represented by the general formula (5) to a compound at -50 to 150 ° C, preferably 0 ° C to 100
It can be produced by reacting a nucleophilic reagent represented by the general formula (6) at ℃. Examples of the solvent used include aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, THF, and dioxane; nitriles such as acetonitrile; amides such as DMF; dimethyl sulfoxide; Among these, the use of ethers such as THF is preferred.

Examples of the base include inorganic bases such as sodium hydride, potassium carbonate and sodium hydroxide; amines such as triethylamine; and metal salts such as silver carbonate and silver oxide. Among these, the use of amines such as triethylamine is preferred. In addition, as a catalyst,
For example, inorganic salts such as cuprous iodide, lithium chloride, and zinc chloride; tetrakistriphenylphosphine palladium,
Organic metal complexes such as 1,3-bis (diphenylphosphino) propane nickel chloride; and the like.

The compound represented by the general formula (2) as a starting material can be produced, for example, as follows.

[0034]

Embedded image

(Wherein, R ₂ , R ₄ , L and n have the same meanings as described above, and r is a C _1-4 such as a methyl group or an ethyl group.
Represents an alkyl group. That is, by reacting the phenylacetic acid ester compound represented by the general formula (7) with the halogenoacetic acid ester represented by the general formula (8) in the presence of a base, the compound represented by the general formula (2) is obtained. Is obtained.

As the base that can be used in the reaction,
For example, metal hydrides such as sodium hydride and potassium hydride; sodium methoxide, potassium methoxide,
Metal alkoxides such as sodium ethoxide, potassium ethoxide, magnesium ethoxide, potassium t-butoxide; organic metals such as n-butyllithium, sec-butyllithium, t-butyllithium; lithium diisopropylamide, lithium hexamethyldisilazide Alkali metal amides; and the like.

The solvent used in the reaction is not particularly limited as long as it is an inert solvent, but it is preferable to use an inert solvent that can dissolve the reactants. For example, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoric phosphoramide; tetrahydrofuran, 1,2-dimethoxyethane, 1,4
Ether solvents such as dioxane; or mixed solvents of these solvents with hydrocarbon solvents such as benzene, toluene, n-hexane, cyclohexane, and the like.

The reaction proceeds smoothly in a temperature range from -78 ° C to the boiling point of the solvent used. After completion of the reaction, the compound represented by the general formula (2) can be obtained by performing ordinary post-treatment, and can be used as a starting material for producing the compound of the present invention.

In any case, after the reaction is completed, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention is IR, NMR, MAS
It can be determined from the S spectrum or the like.

The compounds of the present invention obtained as described above are shown in Table 1. The abbreviations in Table 1 represent the following meanings. Me: methyl group, Et: ethyl group, Pr: propyl group,
Bu: butyl group, Hex: hexyl group, MeAl: methylallyl group, Mor: morpholino group, Pyr: 2-pyridyl group, Pip: 1-piperidinyl group, n: normal,
i: iso, c: cyclo In Table ₁ , R ₁ , R ₂ , L and n correspond to the following compounds, respectively.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

[Table 6]

[0047]

[Table 7]

[0048]

[Table 8]

[0049]

[Table 9]

[0050]

[Table 10]

[0051]

[Table 11]

[0052]

[Table 12]

[0053]

[Table 13]

[0054]

[Table 14]

[0055]

[Table 15]

[0056]

[Table 16]

[0057]

[Table 17]

[0058]

[Table 18]

[0059]

[Table 19]

[0060]

[Table 20]

[0061]

[Table 21]

[0062]

[Table 22]

[0063]

[Table 23]

(Agricultural and horticultural fungicides) The compounds of the present invention can be used in a wide variety of fungi, for example, algae (Oomycete).
s), Ascomycetes,
It has an excellent bactericidal activity against bacteria belonging to Deuteromycetes and Basidiomycetes. The composition containing the compound of the present invention as an active ingredient is used for controlling various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf, grass, seed treatment, foliage spraying,
It can be used by soil application or water surface application.

- 0065] For example, sugar beet Cercospora leaf spot disease (Cercospora beticola) Groundnut brown spot disease (Mycosphaerella arachidis) Black astringency disease (Mycosphaerella berkeleyi) cucumber powdery mildew (Sphaerotheca fuliginea) stem blight (Mycosphaerella melonis) Sclerotinia rot (Sclerotinia sclerotiorum) Botrytis (Botrytis cinerea) scab (Cladosporium cucumerinum) tomatoes Botrytis (Botrytis cinerea) leaf blight (Cladosporium fulvum) eggplant gray mold (Botrytis cinerea) black blight (Cory espora melongenae) powdery mildew (Erysiphe cichoracearum) strawberry gray mold (Botrytis cinerea) Powdery mildew (Sohaerothecahumuli) Onion gray rot (Botrytis allii) gray mold (Botrytis cinerea) beans rot (Sclerotinia sclerotiorum) Gray mold disease (Botrytis cinerea) apple powdery mildew (Podosphaera leucotricha) scab (Venturia inaequalis) blossom disease (Monilinia mali) oysters powdery mildew (Phyllactinia kakicola) anthracnose (Gloeosporium aki) corner spots deciduous disease (Cercospora kaki) Peach, cherry Haihoshibyo (Monilinia fructicola)

[0066] grape Botrytis (Botrytis cinerea) Powdery mildew (Uncinula necator) ripe rot (Glomerella cingulata) pear scab (Venturia nashicola) gymnosporangium (Gymnosporangium asiaticum) black spot disease (Alternaria kikuchiana) tea Wamadarabyo ( Pestalotia theae) and anthracnose (Colletotrichum theae-sinen sis) citrus scab (Elsinoe fawcetti) blue mold disease (Penicillium italicum) green mold disease (Penicillium digitatum) gray mold (Botrytis cinerea) barley noodles This disease (Erysiphe graminis f.sp.ho rdei) loose smut (Ustilago nuda) Wheat Fusarium head blight (Gibberella zeae) leaf rust (Puccinia recondita) leaf spot (Cochliobolus sativus) Memonbyo (Pseudocercosporella herpot richoides) Fu Blight disease (Leptosphaeria nodorum) powdery mildew (Erysiphe graminis f.sp.t ritici) pink snow mold disease (Micronectriella nivalis)

[0067] rice blast (Pyricularia oryzae) Sheath Blight (Rhizoctonia solani) bakanae (Gibberella fujikuroi) Gomaha blight (Cochliobolus niyabeanus) tobacco rot (Sclerotinia sclerotiorum) Powdery mildew (Erysiphe cichoracearum) Tulip gray mold disease (Botrytis cinerea) bentgrass snow mold large-Rot (Sclerotinia borealis) Orchard grass powdery mildew (Erysiphe graminis) soybean purpura (Cercospora kikuchii) potato tomato late blight (Phytophthora infest ns) cucumber downy mildew (Pseudoperonospora cubensis) Grape downy mildew (which can be used to Plasmopara viticola) control of such.

In recent years, various pathogens have developed resistance to benzimidazole fungicides, dicarboximide fungicides, and the like, resulting in a lack of efficacy of these agents. ing. The compound of the present invention is a drug having an excellent bactericidal effect not only on pathogenic bacteria sensitive to such drugs but also on resistant bacteria. For example, gray mold fungus ( Botrytis cinerea ) and sugar beet brown spot fungus ( Cercospora beticol ) showing resistance to benzimidazole fungicides such as thiophanate methyl, benomyl, and carbendazim.
a ), Apple scab ( Venturia inaeq)
ualis ), pear scab ( Venturia na)
The compounds of the present invention are also effective against Shicola ) as well as the susceptible bacteria.

Further, dicarboximide fungicides (for example, vinclozolin, procymidone, iprodione)
Botrytis cin which is resistant to
The compounds of the present invention are also effective against e .

Diseases more preferably applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple scab, gray mold on cucumber, and brown spot on peanut.

The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contacts such as ship bottoms and fish nets. Some of the compounds of the present invention exhibit insecticidal / miticidal activity.

The fungicide of the present invention comprises one or more compounds of the present invention.
Contains more than one species as active ingredients. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be in the form of a general pesticide for the purpose of using it as a pesticide, that is, wettable powder, granule, powder, It can also be used in the form of emulsions, aqueous solvents, suspensions, wettable powders and the like.

As the additives and carriers that can be added to the pesticide preparation, when a solid agent is intended, plant powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum,
Mineral fine powders such as talc, bentonite, pyrophyllite and clay, and organic and inorganic compounds such as sodium benzoate, urea and sodium sulfate are used.

When a liquid dosage form is intended, kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide,
Dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water and the like can be used as the solvent. further,
In order to obtain a uniform and stable form in these preparations, a surfactant may be added as necessary. The surfactant that can be added is not particularly limited, and examples thereof include an alkylphenyl ether to which polyoxyethylene is added, an alkyl ether to which polyoxyethylene is added, a higher fatty acid ester to which polyoxyethylene is added, and polyoxyethylene. Non-ionic surfactants such as sorbitan higher fatty acid esters to which polyoxyethylene is added, tristyryl phenyl ether to which polyoxyethylene is added,
Polyoxyethylene-added alkyl phenyl ether sulfate, alkyl benzene sulfonate,
Examples thereof include sulfates of higher alcohols, alkylnaphthalenesulfonates, polycarboxylates, ligninsulfonates, formaldehyde condensates of alkylnaphthalenesulfonates, and copolymers of isobutylene-maleic anhydride.

The obtained wettable powder, emulsion, flowable, aqueous solvent, and granular wettable powder are diluted with water to a predetermined concentration, and then dissolved,
Powders and granules are used as a suspension or emulsion by spraying them on plants. In addition, the amount of the active ingredient is usually preferably 0.01 to
It is 90% by weight, more preferably 0.05 to 85% by weight.

The formulated fungicidal composition of the present invention is applied to a plant, a seed, a water surface or soil as it is or after being diluted with water or the like. The application amount varies depending on weather conditions, formulation form, application magnetism, application method, application place, target disease to be controlled, target crop, etc., but it is usually 1 to 1,000 g, preferably 10 to 10 g, in terms of the amount of the active compound per hectare.
１００100 g.

When a wettable powder, an emulsion, a suspension, a water solvent, a granule wettable powder or the like is diluted with water and applied, its application concentration is 1 to 3.
It is 1000 ppm, preferably 10 to 250 ppm. In the case of granules, dusts, etc., they are applied without dilution. It goes without saying that the compound of the present invention is effective alone, but it can also be used in combination with one or more of various fungicides, insecticides / miticidal agents, or synergists.

Representative examples of fungicides, insecticides, acaricides, and plant growth regulators which can be used by mixing with the compound of the present invention are shown below.

Fungicides: captan, folpet, thiuram, ziram, zineb, maneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintosen, captaphor, iprodione, prosimidon, vinclozolin, fluoroimide, thymoxanil, mepronil, flutranil, pencyclon, oxy Carboxin, fosetyl aluminum, propamocarb, triadimefon, triadimenol, propiconazole, diclobutrazole, bitertanol, hexaconazole,
Microbutanil, flusilazole, metconazole,
Etaconazole, Fluotrimazole, Cyproconazole, Epoxyconazole, Flutriafen, Benconazole, Diniconazole, Cyproconazoles, Fenarimol, Triflumizole, Prochloraz, Imazalil, Pefurazoate, Tridemorph, Fenpropimorph, Triforin, Butiobate, Pyri Phenox, anilazine, polyoxin, metalaxyl, oxadixyl, furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate methyl, himexazole, basic copper chloride, basic Copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencarb, metas Hocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenphos, mepanipyrim, fermzone, triclamide, metasulfocarb, fluazinam, ethoxyquinolate, dimethomorphone, pilomorphone Phenazine oxide, thiabendazole, tricyclazole, vinclozolin, simoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, hydroxyisoxazole, iminoctazine acetate and the like.

Insecticides and miticides: Organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidione, fentoate, dimethoate, formotion, marathon, trichlorfon, thiometon, phosmet, dichlorvos, acephate, EPBP, methyl parathion. , Oxydimetone methyl, ethion, salithion, cyanophos, isoxathion, pyridafenthion, hosalon,
Methidathion, sulprophos, chlorfenvinphos,
Tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiomethone, propenophos, pyraclofos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, carbofuran, carbosulfan, benfracarb, fratiothiocarb, propoxur, BPMC, MTMC, MIP
C, carbaryl, pirimicarb, ethiophenecarb,
Phenoxycarb, EDDP and the like.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propmethrin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, ethitol Fenprox, cycloprothrin, trolametrin, silafluofen, brofenprox, acrinasulin and the like.

Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzoepin, diafenthiu Ron, acetamiprid, imidacloprid, nitenpyram, fipronil, cartap, thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.

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 A3, gibberellin A4, gibberellin A7) IA
A, NAA.

[0085]

The compounds of the present invention will be described in more detail with reference to the following examples. Example 1 7-chloro-6- (2-chloro-6-fluorophenyl) -5-trifluoromethyl-1,2,4
Of triazolo [1,5-a] pyrimidine 1) Production of ethyl 2- (2-chloro-6-fluorophenyl) -4,4,4-trifluoro-3-oxobutyrate

[0086]

Embedded image

To a solution of 43.3 g of ethyl 2-chloro-6-fluorophenyl acetate in 100 ml of DMF was added 85.2 g of ethyl trifluoroacetate.
At room temperature, 8 g of sodium hydride was added little by little. The reaction mixture was heated to 70 ° C. and stirred until no more hydrogen was generated. After cooling, the reaction mixture was poured into 1N-hydrochloric acid and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and then purified by silica gel silica gel column chromatography (eluent: n-hexane) to obtain 12 g of the desired product. Yield 20% n _D ^22.4 = 1.4773

2) 6- (2-chloro-6-fluorophenyl) -7-hydroxy-5-trifluoromethyl-
Production of 1,2,4-triazolo [1,5-a] pyrimidine

[0089]

Embedded image

Ethyl 2- (2-chloro-6-fluorophenyl) -4,4,4-trifluoro-3-oxobutyrate 3.13 g, 3-amino-1H-1,2,4-
Mix triazole and 3 ml of acetic acid and mix the mixture with 10
Stirred at 0 ° C. for 4 hours. The reaction was cooled to room temperature,
Crystallized crystals were collected by filtration. The crystallized crystals were washed with diethyl ether and dried to obtain 0.7 g of the desired product. Yield 21% Melting point: 220 ° C up

3) 7-chloro-6- (2-chloro-6-
Fluorophenyl) -5-trifluoromethyl-1,
Production of 2,4-triazolo [1,5-a] pyrimidine

[0092]

Embedded image

7-hydroxy-6- (2-chloro-6-
Fluorophenyl) -5-trifluoromethyl-1,
0.6 g of 2,4-triazolo [1,5-a] pyrimidine
And 10 ml of phosphorus oxychloride were mixed, and the mixture was heated under reflux for 4 hours. The reaction mixture was concentrated, 2 ml of a saturated aqueous solution of sodium bicarbonate, 10 ml of water and ethyl acetate were added and stirred. The organic layer was separated, dried over anhydrous magnesium sulfate, concentrated, and then purified by silica gel column chromatography (developing solvent, n-hexane: ethyl acetate = 5: 1) to obtain 0.65 g of the desired product. . 52% yield, amorphous

Example 2 6- (2-Chloro-6-fluorophenyl) -7- (4
-Methylpiperidino) -5-trifluoromethyl-1,
Production of 2,4-triazolo [1,5-a] pyrimidine

[0095]

Embedded image

7-chloro-6- (2-chloro-6-fluorophenyl) -5-trifluoromethyl-1,2,4
0.1 g of triazolo [1,5-a] pyrimidine in TH
0.04 g of triethylamine and 4-
0.04 g of pipecoline was added, and the mixture was stirred at room temperature for one day.
After concentrating the reaction mixture, silica gel column chromatography (developing solvent; n-hexane: ethyl acetate = 5:
Purification in 1) gave 0.1 g of the desired product. Yield 85% Melting point: 165-166 ° C

Example 3 6- (2-Chloro-6-fluorophenyl) -7-cyclohexyl-5-trifluoromethyl-1,2,4-triazolo [1,5-a] pyrimidine (Compound No. 2) )Manufacturing of

[0098]

Embedded image

6- (2-chloro-6-fluorophenyl) -7-chloro-5-trifluoromethyl-1,2,2
0.57 g of 4-triazolo [1,5-a] pyrimidine,
0.08 g of 1,3-bis (diphenylphosphino) propane nickel chloride and 10 ml of THF were mixed,
Under a nitrogen stream, 2 ml of a 1 M cyclohexylmagnesium bromide THF solution was added dropwise at room temperature, and the mixture was stirred overnight. After evaporating the solvent from the reaction mixture under reduced pressure, ethyl acetate and saturated saline were added and the mixture was stirred. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue obtained was purified by silica gel column chromatography (developing solvent; n-hexane: ethyl acetate = 10: 1) to obtain 0.15 g of the desired product. Was. Yield 25% Melting point: 162-163 ° C

Table 2 shows typical examples of the compounds of the present invention including the above examples. The abbreviations have the same meaning as in Table 1.

[0101]

[Table 24]

[0102] Compound No. ¹ of the second compound H-NMR data _{(CDCl 3, δppm); 7.22} (1H,
t), 7.46 (1H, t), 7.55 (1H, d
t), 8.80 (1H, s)

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

Example 4 Wetting agent 40 parts of the compound of the present invention 48 parts of clay 48 parts of sodium salt of dioctyl sulfosuccinate 4 parts of sodium salt of lignin sulfonic acid 8 parts If the above are uniformly mixed and finely pulverized, the active ingredient 40 will be obtained.
% Wettable powder.

Example 5 Emulsion 10 parts of the compound of the present invention 53 parts of Solvesso 200 53 parts of cyclohexanone 26 parts of calcium dodecylbenzenesulfonate 1 part of polyoxyethylene alkyl allyl ether 10 parts The above ingredients are mixed and dissolved to obtain an emulsion having an active ingredient of 10%.

Example 6 Dusts 10 parts of the compound of the present invention 90 parts of clay If the above components were uniformly mixed and finely pulverized, the active ingredient 10
% Powder.

Example 7 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Potassium phosphate 1 part The above components were well pulverized and mixed, and water was added and kneaded well.
The granules are dried by granulation to obtain granules having an active ingredient of 5%.

Example 8 Suspension The compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts Wet milling down to submicron yields a 10% active ingredient suspension.

Example 9 Water-dispersible granules 40 parts of the present compound 40 parts of clay 36 parts of potassium chloride 10 parts of sodium alkylbenzenesulfonate 1 part of sodium ligninsulfonate 8 parts of formaldehyde condensate of sodium alkylbenzenesulfonate 5 parts And pulverized finely, and then kneaded with an appropriate amount of water and kneaded to form a clay. Then, the clay-like material is granulated and dried to obtain a wettable powder with an active ingredient of 40%.

[0110]

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents. (Test Example 1) Apple Scab Control Test (Prevention Test) Apple seedlings (cultivar “Kunimitsu”, 3
At the 4th leaf stage), the emulsion of Example was sprayed at a concentration of 200 ppm of the active ingredient. After air-drying at room temperature, conidia of the apple scab ( Venturia inaequalis ) were inoculated and kept in a room at 20 ° C. and high humidity for 2 weeks, in which light and dark were repeated every 12 hours. 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 value of 75% or more. The compound numbers correspond to the compound numbers in Table 2. Compound number: 3,4,6,7,8,10,12

(Test Example 2) Test for controlling common bean gray mold Green beans cultivated in seedling bats (variety "Naga quail")
Was cut off and the emulsion of the compound of the present invention of Example 4 was immersed in a chemical solution adjusted to a concentration of 200 ppm of the active ingredient. After immersion, air-dry at room temperature, and bean gray mold ( Bot)
rytis cinerea ). The inoculated flower was placed on an untreated kidney leaf, and kept in a high humidity constant temperature room (20 ° C.) where light and dark were repeated every 12 hours for 7 days.
The lesion diameter on the leaves was compared with that of untreated leaves, and the control value was determined. As a result, the following compounds exhibited excellent control values of 75% or more. The compound numbers correspond to the compound numbers in Table 2. Compound number: 3,4,6,7,8,10,12

Continuation of the front page (72) Inventor Yukio Hirai 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd. Odawara Research Laboratories (72) Inventor Hajime Yokota 2-2-1 Otemachi, Chiyoda-ku, Tokyo F-term in Nippon Soda Co., Ltd. (Reference) 4C050 AA01 BB05 BB06 CC08 EE03 EE04 FF02 FF05 GG02 GG03 GG04 HH04 4H011 AA01 AC01 AC04 AD01 BA01 BB09 BC03 BC05 BC07 BC18 BC19 BC20 DA02 DA15 DA16 DH03 DH14

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein R ₁ represents a hydrogen atom, a hydroxy group, a halogen atom, a C _1-8 alkyl group, a C _2-8 alkenyl group,
_2-8 alkynyl group, C _3-8 cycloalkyl group, C
_{A 3-8} cycloalkenyl group, a C _1-8 haloalkyl group,
A heterocyclic group which may have a substituent, an aryl group which may have a substituent, an amino group, a C _1-8 alkylamino group, a C _1-8 haloalkylamino group, a C _1-8 alkyl ( Haloalkyl) amino group or C _1-8 dialkylamino group. Here, the heterocyclic group represents a pyridyl group, a pyrrolidinyl group, a piperazinyl group, a morpholinyl group or a piperidyl group. R ₂ represents a C _1-8 haloalkyl group; R ₃ represents a hydrogen atom, a C _1-4 alkyl group or an optionally substituted aryl group; L is a halogen atom, C _{1- 4} alkyl _{group, C 1-3} haloalkyl _group, a _{C 1-4} alkoxy or _{C 1-3} haloalkoxy group. n represents 0 or an integer of 1 to 5, and A represents N or CH. ) Or a salt thereof. 2. A compound of the general formula (2) (Wherein R ₂ , L and n represent the same meaning as described above, and R ₄
Represents a C _1-4 alkyl group or a phenyl group which may have a substituent. And a compound represented by the general formula (3): (Wherein A and R ₃ have the same meanings as described above), characterized by reacting with a compound represented by the following general formula (4): (Wherein, A, R ₂ , R ₃ , L and n have the same meanings as described above). 3. A compound of the general formula (1) (Wherein A, R ₁ , R ₂ , R ₃ , L and n have the same meanings as described above), which contains one or more of the azolopyrimidine compounds or salts thereof as an active ingredient. A pesticidal agent, characterized in that: