WO2009088070A1 - (heterocyclic methyl)azolylmethylcyclopentanol derivative and intermediate thereof, process for production of the derivative, and agricultural or horticultural preparation and protective agent for industrial material each comprising the derivative - Google Patents

Abstract

Disclosed are: a novel (heterocyclic methyl)azolylmethylcyclopentanol derivative and an intermediate thereof; a process for producing the derivative; and an agricultural or horticultural preparation and a protective agent for an industrial material, each of which comprises the (heterocyclic methyl)azolylmethylcyclopentanol derivative as an active ingredient. Specifically disclosed is a (heterocyclic methyl)azolylmethylcyclopentanol derivative represented by the chemical formula (I). (I) wherein R1 and R2 independently represent a hydrogen atom or a C1-C5 alkyl group; R3 represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group; and A represents a nitrogen atom or a methine group.

Description

(Heterocyclic methyl) azolylmethylcyclopentanol derivatives and intermediates thereof, methods for producing the same, agricultural and horticultural agents containing the same, and industrial material protecting agents

The present invention relates to a (heterocyclic methyl) azolylmethylcyclopentanol derivative and an intermediate thereof, a production method thereof, and an agricultural and horticultural drug and an industrial material protective agent containing this derivative as an active ingredient.

As a bactericidal active ingredient of agricultural and horticultural chemicals, derivatives of azoles that are hetero 5-membered rings containing one or more nitrogen atoms in the ring have been proposed.

Among them, as an example of an azole derivative having a structure bonded to a cyclopentane having a substituent, Patent Document 1 discloses a structure in which an azolylmethyl group and a substituted benzyl group are bonded to adjacent carbon atoms on the cyclopentane ring. Azole derivatives having the following are disclosed: Patent Document 2 discloses an azole derivative having a structure in which an azolylmethyl group and a cycloalkyl group or a cycloalkylmethyl group are bonded to adjacent carbon atoms on a cyclopentane ring.
Japanese Patent Publication No. 6-25140 Japanese Patent Laid-Open No. 2-145576

However, a compound having a structure in which an azolylmethyl group and a heterocyclic methyl group are bonded to adjacent carbon atoms on the cyclopentane ring has not been reported, and the usefulness of such a compound has not yet been studied.

Therefore, the present invention provides a novel (heterocyclic methyl) azolylmethylcyclopentanol derivative useful as an antibacterial active ingredient for agricultural and horticultural agents, and the (heterocyclic methyl) azolylmethylcyclopentanol derivative as an active ingredient. The main purpose is to provide a contained agricultural and horticultural chemical.

The present invention first provides a (heterocyclic methyl) azolylmethylcyclopentanol derivative represented by the chemical formula (I). *

Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group. Represents a nitrogen atom or a methine group.)
Next, the present invention provides an agricultural and horticultural agent characterized by containing a (heterocyclic methyl) azolylmethylcyclopentanol derivative represented by the chemical formula (I) as an active ingredient. In addition, the present invention provides an industrial material protective agent characterized by containing this derivative as an active ingredient.

Moreover, this invention is represented by Chemical formula (I) including the process of adding the azole ring of Chemical formula (VII) to the epoxy group of the oxaspiro heptane derivative represented by Chemical formula (V) in presence of a base. A method for producing a (heterocyclicmethyl) azolylmethylcyclopentanol derivative is provided.

(Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group.)

(In the formula, A represents a nitrogen atom or a methine group.)
This production method may further include a step of obtaining the oxaspiroheptane derivative from the cyclopentanone derivative represented by the chemical formula (IV).

(Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group.)

Furthermore, the present invention also provides an oxaspiroheptane derivative represented by the chemical formula (V) and a cyclopentanone derivative represented by the chemical formula (IV).

Hereinafter, preferred embodiments for carrying out the present invention will be described with reference to the drawings. In addition, embodiment described below shows an example of typical embodiment of this invention, and, thereby, the range of this invention is not interpreted narrowly.

A) (Heterocyclic methyl) azolylmethylcyclopentanol derivative The (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention is represented by the chemical formula (I). Hereinafter, the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention will be described in detail.

In the chemical formula (I), R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. The alkyl group of C1 to C5 may be any of primary, secondary, and tertiary, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s- Examples thereof include a butyl group, a cyclopropylmethyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group.

In the chemical formula (I), R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group. Examples of the heterocyclic group include 3- to 8-membered saturated or unsaturated heterocyclic groups containing 1 to 4 atoms selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom. A 5- or 6-membered heterocyclic group is preferable. Examples of the fused heterocyclic group include 8- to 10-membered fused heterocyclic groups containing 1 to 4 of at least one atom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom. Or the condensed heterocyclic group which the 6-membered heterocyclic ring condensed is preferable.

Specific examples of the 5-membered or 6-membered heterocyclic group include a furyl group, a tetrahydrofuryl group, a thienyl group, a pyrrolyl group, a pyrrolinyl group, a pyrrolidinyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, and an imidazolyl group. Imidazolinyl group, imidazolidinyl group, pyrazolyl group, pyrazolinyl group, pyrazolidinyl group, triazolyl group, oxadiazolyl group, thiadiazolyl group, tetrazolyl group and other 5-membered heterocyclic groups, pyranyl group, pyridyl group, piperidinyl group, dioxanyl group, oxazinyl group, Examples thereof include 6-membered heterocyclic groups such as morpholinyl group, thiazinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, and triazinyl group. Preferable examples of the 5-membered or 6-membered heterocyclic group include a furyl group, a thienyl group, a thiazolyl group, a pyridyl group, and a pyridazinyl group.

Specific examples of the condensed heterocyclic group in which a 5- or 6-membered heterocyclic ring is condensed include a benzofuranyl group, an isobenzofuranyl group, a dihydrobenzofuranyl group, a dihydroisobenzofuranyl group, a benzothienyl group, and an isobenzothienyl group. Group, dihydrobenzothienyl group, dihydroisobenzothienyl group, tetrahydrobenzothienyl group, indolyl group, isoindolyl group, benzoxazolyl group, benzothiazolyl group, indazolyl group, benzimidazolyl group, benzodioxolanyl group, benzodioxanyl group Group, chromenyl group, chromanyl group, isochromanyl chromonyl group, chromonyl group, quinolyl group, isoquinolyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, indolizinyl group, quinolidinyl group, imidazopyridyl group, Fuchirijiniru group, pteridinyl group, dihydro benzoxazinyl group, dihydro benzoxazolyl nonyl, dihydrobenzo oxadiazole nonyl, benzothiadiazole oxa group and the like. Preferable examples of the condensed heterocyclic group in which a 5- or 6-membered heterocyclic ring is condensed include a benzofuranyl group, a benzothienyl group, and a benzothiazolyl group.

The substituent that the heterocyclic group or the condensed heterocyclic group has is not particularly limited, and examples thereof include halogeno groups such as a fluoro group, a chloro group, a bromo group, and an iodo group, a C1-C4 alkyl group, and a C1-C4 group. A halogenated alkyl group, a C1-C4 alkoxy group, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted phenyl group, and the like. Examples of the substituent of the phenoxy group or the phenyl group include a halogeno group such as a fluoro group, a chloro group, a bromo group, and an iodo group, a C1 to C4 alkyl group, a C1 to C4 halogenated alkyl group, and a C1 to C4 group. Examples include C4 alkoxy groups.

The number of substituents of the heterocyclic group or the condensed heterocyclic group and the phenoxy group or the phenyl group is not particularly limited, and one or a plurality of places may be substituted. Substitution is preferred. When the number of substitutions is 2 or more, they may be substituted with the same substituent or may be substituted with different substituents.

In addition, the position of the substituent in the case where the heterocyclic group or the condensed heterocyclic group, and the phenoxy group or the phenyl group have a substituent is not particularly limited.

In the chemical formula (I), A represents a nitrogen atom or a methine group.

The (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention may have geometric isomers and optical isomers due to the presence of asymmetric carbon in the cyclopentane skeleton. Compound (I) includes isomers and mixtures of each isomer in any ratio.

The (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention has low toxicity to humans and the like and is highly safe in handling. In addition, it exhibits excellent agricultural and horticultural disease control effects on a wide range of plant diseases, plant growth control effects and industrial material protection effects.

B) Method for producing (heterocyclic methyl) azolylmethylcyclopentanol derivative FIG. 1 is a conceptual diagram for explaining an example of a method for producing a (heterocyclic methyl) azolylmethylcyclopentanol derivative of the formula (I) It is. An example of a preferred method for producing the (heterocyclicmethyl) azolylmethylcyclopentanol derivative according to the present invention will be described below with reference to the drawings.

The (heterocyclic methyl) azolylmethylcyclopentanol derivative of the chemical formula (I) obtained by the following production method should be appropriately selected depending on the compounds of the formulas (II) to (VII) used and reaction conditions. Shall be able to. In the formulas (II) to (VII), R ¹ , R ² , R ³ and A are the same as described above.

First, a heterocyclic methyl group (VI) is introduced into a ketoester derivative represented by the formula (II) to obtain a heterocyclic ketoester derivative (III) (first step). Next, the heterocyclic ketoester derivative is derived into a cyclopentanone derivative represented by the formula (IV) (second step). An oxaspiroheptane derivative represented by the formula (V) is synthesized from the cyclopentanone derivative (third step), and then an azole ring represented by the formula (VII) is added to the oxaspiroheptane derivative. To obtain a (heterocyclicmethyl) azolylmethylcyclopentanol derivative of the formula (I) (fourth step).

In the first step, the heterocyclic ketoester derivative represented by the formula (III) is obtained by alkylating the 1-position of the ketoester derivative represented by the formula (II) with a base and a heterocyclic methyl halide (VI). . At this time, the solvent to be used is not particularly limited, but a polar organic solvent is preferably used. The reaction temperature in the first step is not particularly limited and can be set in a temperature range from room temperature to the boiling point of the solvent used, but is preferably 20 to 100 ° C.

Here, the ketoester derivative represented by the formula (II) which is the starting material in the first step can be synthesized by a conventionally known method. As a specific method, for example, J. Org. Med. Chem. 29, 411 (1986) and J. Org. Org. Chem. 29, 2781 (1964).

In the second step, the cyclopentanone derivative represented by the formula (IV) can be obtained by hydrolyzing and decarboxylating the heterocyclic ketoester derivative represented by the formula (III). This hydrolysis and decarboxylation reaction can be performed under both basic and acidic conditions.

When this step is carried out under basic conditions, the solvent used is not particularly limited, but it is desirable to use a mixed solvent of water, lower alcohol and aromatic hydrocarbon. Further, the base used is not particularly limited, but sodium hydroxide or potassium hydroxide is preferably used. The reaction temperature at this time is not particularly limited, but is preferably 40 ° C. to the reflux point, more preferably 70 ° C. to the reflux point.

In addition, when this step is performed under acidic conditions, the solvent used is not particularly limited, but it is preferable to use acetic acid as a solvent in addition to water. As the catalyst, an inorganic acid such as hydrochloric acid or hydrobromic acid is used. The reaction temperature at this time is not particularly limited, but is preferably 50 ° C. to the reflux point, more preferably 80 ° C. to the reflux point.

In the third step, the oxaspiroheptane derivative represented by the formula (V) is cyclized by adding a methylene group to the carbonyl group of the cyclopentanone derivative represented by the formula (IV) by sulfonium methylide or oxosulfonium methylide. Or after converting the carbonyl group to a methylene group, the methylene group is oxidized, or iodohydrin obtained by combining metal samarium and diiodomethane is cyclized by alkali treatment. As these specific methods, conventionally known methods can be used. For example, the methods described in JP-B-6-25140 and JP-A-5-271197 can be used.

In the fourth step, the (heterocyclic methyl) azolylmethylcyclopentanol derivative of the formula (I) is bonded to the azole group of the formula (VII) in the presence of a base on the epoxy group of the oxaspiroheptane derivative of the formula (V). Can be obtained. At this time, the base used is not particularly limited, but sodium hydride and potassium carbonate are preferably used. The solvent used in this step is not particularly limited, but an organic solvent, particularly an aprotic polar solvent such as dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone, etc. is preferably used. Further, the reaction temperature in this step is not particularly limited, but is preferably in the range of 0 ° C to 100 ° C.

C) Agricultural and horticultural agents The (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention is suitably used as an active ingredient of agricultural and horticultural agents. The agricultural and horticultural chemicals containing the (heterocyclic methyl) azolylmethylcyclopentanol derivative as an active ingredient will be described below.

The following diseases can be mentioned as plant diseases in which the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention has a controlling action. Soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia oryzae), rice sesame leaf blight (Cochliobolus miyabeanus), rice white leaf blight (Xanthomonas oryzae), rice crustaceae (Rhizoctonia) Nuclear disease (Helminthosporiumsigmoideun), rice idiom (Gibberellafujikuroi), rice seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaera leucotricha), apple black rot (Venturia inaequaliss), apple morinia Deciduous leaf disease (Alternaria alternata), Apple rot disease (Valsa mali), Pear black spot disease (Alternaria kikuchiana), Pear powdery mildew (Phyllactinia pyri), Pear red rot (Gymnosporangium asiaticum), Pear black rot (cola) Powdery mildew (Uncinula necator), grape beet disease (Plasmopara viticola), grape late rot (Glomerella cingulata), barley powdery mildew (Erysiphe graminis) sp. ), Wheat red rust (Puccinia recondita), wheat yellow rust (Puccinia striiformis), wheat eye rot (Pseudocercosporella herpotrichoides), wheat red rust (Fusarium graminearum, Microdochium nivale), wheat Leaf blight (Septoria tritici), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber anthracnose (Colletotrichum lagenarium), cucumber downy mildew (Pseudoperonospora cubensis), cucumber gray plague (Phytophthora capsi) Erysiphe cichoracearum), tomato ring rot (Alternaria solani), eggplant powdery mildew (Erysiphe cichoracearum), strawberry powdery mildew (Sphae rotheca humuli), tobacco powdery mildew (Erysiphe cichoracearum), sugar beet brown spot disease (Cercospora beticola), corn smut (Ustillaga maydis), berries of Monasteria fruit tree (Monilinia fructicola), gray mold disease causing various crops (Botrytis cinerea), Sclerotiniasclerotiorum, etc.

Moreover, the (heterocyclic methyl) azolylmethyl cyclopentanol derivative based on this invention shows the plant growth control effect which adjusts growth with respect to a wide range of crops and horticultural plants, and increases a yield and quality. Examples of such crops include: Wheat, barley, buckwheat and other barley, rice, rapeseed, sugar cane, corn, maize, soybeans, peas, peanuts, sugar beet, cabbage, garlic, radish, carrot, apple, pear, mandarin orange, orange, lemon and other citrus fruits, Peach, cherry peach, avocado, mango, papaya, capsicum, cucumber, melon, strawberry, tobacco, tomato, eggplant, turf, chrysanthemum, azalea and other ornamental plants.

The form in which the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention is used as an active ingredient of an agricultural and horticultural disease control agent is not particularly limited. For example, it may be used alone without any other components. If necessary, it may be mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation adjuvants to be used in various forms such as powders, wettable powders, granules and emulsions. At that time, the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention is used as an active ingredient in these preparations in an amount of 0.1 to 95% by weight, more preferably 0.5 to 90% by weight, It is preferable to formulate it so as to contain 2 to 80% by weight.

In addition, the substance used as the formulation adjuvant is not particularly limited, and can be appropriately selected in consideration of the purpose of use and desired effect. Suitable carriers, diluents, surfactants and the like are exemplified below. .

As the solid carrier, talc, kaolin, bentonite, diatomaceous earth, white carbon, clay and the like can be used.

As the liquid diluent, water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide (DMSO), dimethylformamide, alcohol or the like can be used.

The surfactant is preferably used depending on its effect, and polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate, or the like can be used as an emulsifier. As the dispersant, lignin sulfonate, dibutyl naphthalene sulfonate, or the like can be used. As the wetting agent, an alkyl sulfonate, an alkyl phenyl sulfonate, or the like can be used. Since this compound contains a 1,2,4-triazole group or an imidazole group, it can be used in the form of an inorganic acid salt, an organic acid salt or a metal complex.

The method for using the agricultural and horticultural chemical according to the present invention is not particularly limited. For example, it may be used as it is, diluted to a predetermined concentration with a diluent such as water, or a plurality of types. The (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention may be mixed.

There are two types of the above-mentioned preparations that are used as they are, and ones that are diluted to a predetermined concentration with a diluent such as water. The concentration of the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention when diluted is preferably in the range of 0.001 to 1.0%. The amount of the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention is 20 to 5000 g, more preferably 50 to 1000 g, per 1 ha of agricultural or horticultural land such as fields, fields, orchards and greenhouses. . Since these use concentrations and amounts vary depending on the dosage form, use time, use method, use place, target crop, etc., it is of course possible to increase or decrease without limiting to the above range.

Further, the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention is combined with other active ingredients such as other fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, etc. Can also be used.

<Fungicide>
Acibenzolar S methyl, 2-phenylphenol (OPP), azaconazole, azoxystrobin, amisulbrom, bixaphene, benalaxyl, benomyl, bench avaricarb-isopropyl, bicarbonate, biphenyl, viteltanol, blasticidin-S, borax, bordeaux, boscalid, Bromuconazole, bronopol, bupirimate, secbutyramine, calcium polysulfide, captafor, captan, carbendazim, carboxin, carpropamide, quinomethionate, chloronebu, chloropicrin, chlorothalonil, clozolinate, cyazofamide, cyflufenamide, simoxanil, cyproconil, cyprodiazole Dazomet, debacarb, diclofuranide, diclocimet, dichrome , Dichlorane, diethofencarb, difenoconazole, diflumethrin, dimethomorph, dimethoxystrobin, diniconazole, dinocup, diphenylamine, dithianone, dodemorph, dozine, edifenfoss, epoxiconazole, etapoxam, ethoxyquin, etridiazole, enestroborone, famidone Fenarimol, fenbuconazole, fenflam, fenhexamide, phenoxanyl, fenpicuronyl, fenpropidin, fenpropimorph, fentin, felvam, ferrimzone, fluazinam, fludioxonil, flumorph, fluoromide, floxastrobin, fluquinconazole, flusilazole, flusulfamide , Flutolanil, furtriafol, pho Rupet, Focetyl-aluminum, Fuberidazole, Furaxil, Furatopir, Fluopicolide, Fluopyram, Guazatine, Hexachlorobenzene, Hexaconazole, Himexazole, Imazalil, Imibenconazole, Iminotazine, Ipconazole, Iprobenfos, Iprodione, Iprovalithiol , Kasugamycin, copper preparations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper, crezooxime methyl, mancocapper, mancozeb, maneb, mandipropamide, mepanipyrim, mepronil, metalaxyl, metconazole , Methylam, metminosoutrobin, myrdiomycin, microbutanyl, nitrotal-isopropyl, nuarimo , Off-race, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxyl, oxytetracycline, orisatrobin, pefazoate, penconazole, pencyclon, penthiopyrad, pyribencarb, fusalide, picoxystrobin, piperaline, polyoxin, probenazole, prochloraz, procymidone, Propamocarb, propiconazole, propinebole, proquinazide, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroxylone, quinoxyphene, quintozen, silthiofam, cimeconazole, spiroxamine, sulfur and sulfur preparation, tebuconazole, teclophthalam, technazene, technazene Tetraconazole, thiabendazole, tifluzamide, thiof Nate-methyl, thiram, thiazinyl, tolcrophos-methyl, tolylfluanid, triadimethone, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, trifolin, triticonazole, validamycin, vinclozoline, Zineb, ziram, zoxamide, etc.

<Insecticide / Acaricide>
Abamectin, Acephate, Acrinathrin, Alanicarb, Aldicarb, Alletrin, Amitraz, Avermectin, Azadirachtin, Azamethifos, Azinphos-ethyl, Azinphos-methyl, Azocycline, Bacillus filmus, Bacillus subtilis, Bacillus thuringibulbbenthulbenbencarb , Benzoxymate, Bifenazite, Bifenthrin, Bioallethrin, Bioresmethrin, Bistriflurone, Buprofezin, Butocaboxin, ButoxyCarboxin, Kazusafos, Carbaryl, Carbofuran, Carbosulfan, Cartap, CGA 50439, Chlordein, Chloretifos, Chlorphenapal Chlorfenvin foss, chlorfluazuron , Chlormefos, Chlorpyrifos, Chlorpyrifosmethyl, Chromaphenozide, Chlofenthedin, Clothianidin, Chlorantraliniprole, Counpafos, Cryolite, Cyanophos, Cycloproton, Cyfluthrin, Cyhalothrin, Cihexatin, Cipermethrin, Ciphenothrin , Cyromazine, ciazapyr, sienopyrfen, DCIP, DDT, deltamethrin, demeton-S-methyl, diafenthiuron, diazinon, dichlorophen, dichloropropene, dichlorovos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimethoate, dimethylvinphos, dinobutone, Dinotefuran, emamectin, endosulfan, EPN, esfenvalerate, etiophencarb, ethion, ethiprole, Etofenprox, etoprofos, etoxazole, famflu, fenamifos, phenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, phenothiocarb, phenoxycarb, fenpropatoline, fenpyroximate, fenthionate, fenvalerate, fipronil, flonicamid, fluaclopyrim, flucyclolone Flucitrinate, flufenoxuron, flumethrin, fulvalinate, fulvendiamide, formethanate, fostiazete, halfenprox, furthiocarb, halohenozide, gamma-HCH, heptenofos, hexaflumuron, hexithiax, hydramethylnon, imidacloprid , Imiprothrin, indoxacarb, isoprocarb, isoxa On, lufenuron, malathion, mecarbam, methammetamidfos, methidathion, metiocarb, methomyl, metoprene, methosrin, methoxyphenozide, metorcarb, milbemectin, monocrotophos, nared, nicotine, nitenpyram, novaluron, nobiflumetron, oxidemetholone Tonmethyl, parathion, permethrin, phentoate, folate, fosaron, fosmet, fosfamidon, foxime, pirimicarb, pirimiphos methyl, profenofos, propoxur, prothiophos, pymetrozine, pyracrofos, pyrethrin, pyridaben, pyridalyl, pyrimidifene, pyriproxy Fen, Pyrifluquinazone, Pyriprole, Quinarfos, Silafluophene, Su Nosad, Spirodiclofen, Spiromethifene, Spirotetramat, Sulfamide, Sulfotep, SZI-121, Tebufenozide, Tebufenpyrad, Tebupyrimfos, Teflubenzuron, Tefurthrin, Temefos, Terbufos, Tetrachlorbinfos, Thiacloprid, Thiamethoxam Thiomethone, tolfenpyrad, tralomethrin, tralopyril, triazamate, triazophos, trichlorfone, triflumuron, bamidithione, varifenal, XMC, xylylcarb and the like.

<Plant growth regulator>
Ansimidol, 6-benzylaminopurine, paclobutrazole, diclobutrazole, uniconazole and the like.

D) Industrial Material Protecting Agent Further, the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention exhibits an excellent effect of protecting the material from a wide range of harmful microorganisms that attack the industrial material. Examples of such microorganisms include the following. Aspergillus sp., Trichoderma sp., Penicillium sp., Geotrichum sp., Chaetomium sp., Cadhola (Cadophora sp.), Ceratostomella sp., Cladosporium sp., Corticium sp., Lentinus sp., Lenzites sp., Forma sp. , Polysticus sp., Pullularia sp., Stereum sp., Trichosporium sp., Aerobacter sp., Bacillus sp., Desulfobibrio (Desulfovibrio sp.), Pseudomonas sp., Flavobacterium sp., Micrococcus sp.).

Aspergillus sp., Penicillium Chsp., Ketotomium sp., Myrothecium sp., Curvularia sp., Gliomastixsp., Mennoniella Memnoniella sp.), Sarcopodium sp., Stschybotryssp., Stemphylium S., Zygorhynchus sp., Bacillus sp., Staphylococcus. Such.

Wood-modifying fungi, Tyromyces palustris, Kawariotake (Coriolus versicolor), Aspergillus sp., Penicillium sp., Rhizopussp., Aureobasidium sp., Aureobasidium sp. (Gliocladum sp.), Cladosporium sp., Ketomium (Spae), Trichodermasp.

Aspergillus sp., Penicillium sp., Ketomium (Chaetomiumsp.), Cladosporium sp., Mucor sp., Paecilomycessp., Pilobus (Pilobus) sp.), pullularia (Pullulariasp.), trichosporon (Trichosporon sp.), trichothecium (Tricothecium sp.), rubber and plastic-degrading microorganisms such as Aspergillus (sp.), Penicillium (Penicilliumsp.), Rhizopus sp. ), Trichodermasp., Ketomium (Chaetomium sp.), Myrotheciumsp., Streptomyces sp., Pseudomonas sp., Bacillus sp., Micrococcus sp. , Sererratiasp., Margarinomyces s sp.), Monascus sp.

Aspergillus sp., Penicillium sp., Cladosporium sp., Aureobasidium sp., Gliocladium sp., Botrio dipro Deer (Botryodiplodiasp.), Macrosporum (Macrosporium sp.), Monilia (Monilia sp.), Forma (Phoma sp.), Pullularia ((Pullularia sp.), Sporotrichumsp.), Trichoderma sp., Bacillus (Proteus sp.), Pseudomonas sp., Serratia sp.

Although the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention can be used alone as an industrial material protective agent, it is usually dissolved or dispersed in a liquid carrier, or mixed with a solid carrier, and if necessary, an emulsifier , Dispersing agents, spreading agents, penetrating agents, wetting agents, stabilizers, etc. are added and formulated into various forms such as wettable powders, powders, granules, tablets, pastes, suspensions, sprays, etc. . In these preparations, the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention is used as an active ingredient in an amount of 0.1 to 95% by weight, more preferably 0.5 to 90% by weight, and even more preferably 2%. Contains up to 80% by weight.

Carriers used as formulation adjuvants include, as liquid carriers, water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, cellosolve, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, Dimethyl ether, diethyl ether, dioxane, tetrahydrofuran, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, methylnaphthalene, etc.), aliphatic hydrocarbons (eg, gasoline, kerosene, kerosene, machine oil, fuel oil, etc.) Acid amides (eg, dimethylformamide, N-methylpyrrolidone, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate, glycerin esters of fatty acids, etc.), nitriles (For example, aceto Tolyl, etc.), and dimethyl sulfoxide and the like can be used. As the solid carrier, fine powders or granular materials such as kaolin clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, urea, ammonium sulfate can be used.

Examples of emulsifiers and dispersants used as formulation adjuvants include soaps, alkylsulfonic acids, alkylarylsulfonic acids, dialkylsulfosuccinic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxides, anhydrosorbitol Surfactants such as systems can be used.

There are two types of the above preparations, one that is used as it is and one that is diluted to a predetermined concentration with a diluent such as water. The concentration of the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention when used after dilution varies depending on the dosage form and purpose of use, but is 0.005 to 5% by weight, preferably 0.01 to 1% by weight. It is preferable to adjust by adding a solvent, a diluent, an extender or the like as appropriate.

The (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention should be formulated in combination with a fungicide, insecticide, acaricide, anti-degradation agent, etc., similar to the agricultural and horticultural agents described above. You can also. Thereby, the performance as an industrial material protective agent can be improved.

In the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention, since an asymmetric carbon exists in the cyclopentane skeleton, geometric isomers and optical isomers may exist. As well as mixtures of each isomer in any ratio. Therefore, the agricultural and horticultural agents according to the present invention include those containing these isomers alone or as a mixture as active ingredients.

The agricultural and horticultural agent containing the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention as an active ingredient can be used for foliage spraying, soil treatment, seed treatment, etc. to plant disease occurrence sites. .

Hereinafter, the present invention will be specifically described with reference to production examples, formulation examples, and test examples. First, a manufacturing example is shown. Moreover, this invention is not limited to the manufacture example shown below, unless the summary is exceeded. As the compound used in the present invention, commercially available products can be used as appropriate. In addition, the measurement of the physical-property value of the target compound obtained in each Example was performed on the conditions shown below. *

<Measurement equipment>
For the nuclear magnetic resonance spectrum (NMR) measurement, a Fourier transform nuclear magnetic resonance apparatus (400 MHz) was used, and tetramethylsilane (TMS) was used as an internal standard. The chemical shift delta δ was expressed in ppm. The coupling constant J is expressed in hertz (Hz). The notations d, t, q, and m represent d (doublet), t (triplet), q (quadlet), and m (multiplet), respectively. For the infrared absorption spectrum (IR) measurement, an infrared spectrophotometer was used, and the solid substance was measured as a KBr disk. The wavelength unit is wave number (cm ⁻¹ ).

<Production Example 1>
c-5- (6-Chloro-3-pyridylmethyl) -2,2-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (Compound No. 2)
2. Under nitrogen flow, 1.04 g (26 mmol) of 60% sodium hydride was washed with hexane, suspended in 8 ml of anhydrous DMF, and 3,3-dimethyl-2-oxocyclopentanecarboxylic acid methyl ester under ice cooling. A solution obtained by dissolving 54 g (21 mmol) in 20 ml of anhydrous DMF was added dropwise. After stirring at room temperature for 10 minutes, a solution of 2.8 g (17 mmol) of 6-chloro-3-pyridylmethyl chloride dissolved in 8 ml of anhydrous DMF was added dropwise, and the mixture was heated to 80 ° C. and stirred for 2 hours. After allowing to cool, the reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 4.8 g of a brown oil.

8 ml of acetic acid and 10 ml of 48% hydrobromic acid were added to 4.8 g of the oily substance obtained above, and the mixture was heated to reflux for 1 hour. After allowing to cool, the reaction mixture was poured into ice water, neutralized with 2N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (silica gel 60, 230-400 mesh, Merck, hexane / ethyl acetate = 4: 1) to give a pale yellow oil 5- ( 6.12 g (8.9 mmol) of 6-chloro-3-pyridylmethyl) -2,2-dimethylcyclopentanone (IV-2) was obtained. Yield 52%.
¹ H NMR (CDCl ₃ ) δ: 0.87 (s, 3H), 1.09 (s, 3H), 1.47 to 1.81 (m, 3H), 1.96 to 2.03 (m, 1H), 2.41 to 2.49 (m, 1H), 2.66 (dd, 1H, J = 8.5, 14.2 Hz), 3.06 (dd, 1H, J = 4.6, 14 .2 Hz), 7.24 (d, 1 H, J = 8.1 Hz), 7.47 (dd, 1 H, J = 2.5, 8.1 Hz), 8.20 (d, 1 H, J = 2. 4Hz)

Under nitrogen flow, 0.95 g (12.1 mmol) of 60% sodium hydride washed with hexane was suspended in 5 ml of anhydrous DMSO, and 5.25 g (23.8 mmol) of trimethylsulfoxonium iodide was added thereto. After stirring at room temperature for 1 hour, a solution prepared by dissolving 1.56 g (6.5 mmol) of the cyclopentanone derivative (IV-2) obtained above in 3 ml of anhydrous DMSO was added dropwise thereto. Stir at room temperature for 30 hours. The reaction solution was poured into ice water and extracted with benzene. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting oil was purified by silica gel column chromatography (silica gel 60, 230-400 mesh, Merck, hexane / ethyl acetate = 5/1) to obtain the desired c-7- (6- 0.40 g of chloro-3-pyridylmethyl) -4,4-dimethyl-1-oxaspiro [2.4] heptane (V-2) was obtained as a colorless oil. Yield: 23%.
¹ H NMR (CDCl ₃ ) δ: 0.85 (s, 3H), 0.97 (s, 3H), 1.42 to 1.53 (m, 2H), 1.63 to 1.81 (m, 2H), 2.56 (d, 1H, J = 4.4 Hz), 2.36 to 2.62 (m, 1H), 2.71 (d, 1H, J = 4.3 Hz), 7.22 ( d, 1H, J = 8.1 Hz), 7.47 (dd, 1H, J = 2.5, 8.1 Hz), 8.20 (d, 1H, J = 2.4 Hz)

Under a nitrogen stream, 95 mg (2.4 mmol) of 60% sodium borohydride washed with hexane was suspended in 4 ml of anhydrous DMF, and 0.20 g (2.9 mol) of 1,2,4-triazole was added thereto. After stirring at room temperature for 15 minutes, a solution prepared by dissolving 0.27 g (1.1 mmol) of the above oxaspiroheptane derivative (V-2) in 3 ml of anhydrous DMF was added dropwise thereto. The mixture was stirred at 70 ° C. for 6 hours, and further stirred at 120 ° C. for 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained crystals were purified by silica gel column chromatography (silica gel 60, 230-400 mesh, Merck, エ チ ル ethyl acetate only) to give 0.26 g of the desired compound (Compound No. 2) as white crystals. Obtained. Yield: 83%.

<Production Example 2>
c-2- (6-Chloro-3-pyridylmethyl) -c-5-isopropyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (Compound No. 5)
Under a nitrogen stream, 67 mg (1.7 mmol) of 60% sodium hydride washed with hexane was suspended in 3 ml of anhydrous DMF, and 0.12, g (1.7 mmol) of 1,2,4-triazole was added thereto. After stirring at room temperature for 15 minutes, c-4- (6-chloro-3-pyridylmethyl) -c-7-isopropyl-1-oxaspiro synthesized in the same manner as (V-2) in Production Example 1 above 2.4] A solution of 0.22 g (0.8 mmol) of heptane (V-5) dissolved in 3 ml of anhydrous DMF was added dropwise. After stirring this at 85 ° C. for 6 hours, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained crystals were purified by silica gel column chromatography (silica gel 60, 230-400 mesh, Merck, ethyl acetate only) to give 0.19 g of the desired compound (Compound No. 5) as white crystals. Obtained. Yield: 69%.

<Production Example 3>
c-5- (5-Bromo-2-enyl) -2,2-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (Compound No. 14)
Under a nitrogen stream, 0.60 g (4.0 mmol) of samarium was suspended in 3 ml of anhydrous THF, and a solution obtained by dissolving 0.60 g (2.1 mmol) of 1,2-diiodoethane in 2 ml of anhydrous THF was added dropwise thereto, and the solution was added at room temperature. Stir for hours. Under cooling with ice water, 5- (5-bromo-2-enyl) -2,2-dimethylcyclopentanone (IV-14) 0 produced in the same manner as in (IV-2) of Production Example 1 was added thereto. A solution prepared by dissolving 30 g (1.1 mmol) and 0.57 g (2.1 mmol) of diiodomethane in 5 ml of anhydrous THF was added dropwise. After stirring at room temperature for 2 hours, 2N aqueous sodium hydroxide solution was added, and the mixture was further stirred for 1 hour. After neutralizing with 2N hydrochloric acid, hexane was extracted. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained oil was purified by silica gel column chromatography (Wako gel C-300, Wako, hexane / ethyl acetate = 30/1) to obtain the desired c-4- (5-bromo -2-Tenyl) -2,2-dimethyl-1-oxaspiro [2.4] heptane (V-14) was obtained as a pale yellow oil (0.09 g). Yield: 29%.
¹ H NMR (CDCl ₃ ) δ: 0.84 (S, 3H), 0.97 (S, 3H), 1.47 to 1.56 (m, 2H), 1.62 to 1.69 (m, 1H), 1.88 to 1.95 (m, 1H), 2.48 to 2.68 (m, 3H), 2.61 (d, 1H, J = 4.4 Hz), 2.70 (d, 1H, J = 4.4 Hz), 6.54 (d, 1H, J = 3.6 Hz), 6.83 (d, 1H, J = 3.6 Hz)

In a nitrogen stream, 18% (0.45 mmol) of 60% sodium borohydride was washed with hexane, suspended in 1 ml of DMF, and 32 mg (0.46 mmol) of 1,2,4-triazole was added thereto. After stirring at room temperature for 15 minutes, a solution prepared by dissolving 0.09 g (0.3 mmol) of the oxaspiroheptane derivative (V-14) in 1 ml of DMF was added thereto, followed by stirring at 90 ° C. for 3 hours. After allowing to cool, the mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting oil was purified by (Wako gel C-300, Wako, hexane / ethyl acetate = 1/1) to obtain 52 mg of the desired compound (Compound No. 14) as white crystals. It was. Yield: 47%.

By operations according to the above Production Examples 1 to 3, Compound Nos. 1, 3, 4, 6 to 13 and 15 to 33 represented by the following general formula (I) were produced. Tables 1 and 2 show the structure and melting point of each compound. Tables 3 to 9 show IR data and ¹ H NMR data obtained for each compound.

Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group. Represents a nitrogen atom or a methine group.)

(In the table, R ¹ , R ² and R ³ respectively correspond to R ¹ , R ² and R ³ in the formula (I).)

(In the table, R ¹ , R ² and R ³ respectively correspond to R ¹ , R ² and R ³ in the formula (I).)

Subsequently, formulation examples and test examples were shown, and the effectiveness of the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to the present invention was verified. In addition, this invention is not limited to the manufacture example shown below, a test example, etc., unless the summary is exceeded. *

<Formulation example 1; powder>
A formulation was prepared by pulverizing and mixing 3 parts by weight of Compound 1, 40 parts by weight of clay, and 57 parts by weight of talc, and used as a dust.

<Formulation example 2; wettable powder>
A wettable powder was prepared by pulverizing and mixing 50 parts by weight of Compound 3, 50 parts by weight of lignin sulfonate, 3 parts by weight of alkyl sulfonate, and 42 parts by weight of diatomaceous earth, and diluted with water for use.

<Formulation example 3; granule>
Compound 5 (5 parts by weight), bentonite (43 parts by weight), clay (45 parts by weight), lignin sulfonate (7 parts by weight) are uniformly mixed, mixed with water, processed and granulated with an extrusion granulator, and granulated. Used as an agent.

<Formulation Example 4; Emulsion>
20 parts by weight of Compound 7, 10 parts by weight of polyoxyethylene alkyl allyl ether, 3 parts by weight of polyoxyethylene sorbitan monolaurate and 67 parts by weight of xylene were uniformly mixed and used as an emulsion.

For the purpose of verifying the bactericidal effect of the compound according to the present invention, a test using a preparation containing the compound produced in the above production example as an active ingredient under conditions suitable for practical use was conducted.

<Test Example 1>
A test was conducted on the control effect of wheat powdery mildew. Compounds of the present invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 27, 28, 29, 30, 31, 32, 33 were used, and the wettable powder formulated according to the method of Formulation Example 2 was diluted and suspended in water to a predetermined concentration (100 mg / l). A ratio of 100 liters / 10a (Earl) to 1 to 2 leaf stage wheat (variety: Norin 64) grown using a square plastic pot (size: 6.4 cm × 6.4 cm) Scattered with. The sprayed leaves were air-dried and then sprinkled with wheat powdery mildew spores on the diseased leaves and managed in a greenhouse (temperature: 20-24 ° C., relative humidity: 20-70 RH). On the 10th day after the inoculation, the morbidity was investigated based on the survey criteria shown in Table 10, and the control value of each compound was calculated according to the formula (1).

As a result, at an active ingredient concentration of 100 mg / L, the compounds 1, 2, 5, 10, 14, 15, 19, 21, 22, 23, 24, 26, 28, 29, 30, 31, 32, and 33 have a control value. A high control effect of 80% or more was exhibited. *

<Test Example 2>
A test was conducted on the control effect of wheat red rust. Compounds of the present invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 27, 28, 29, 30, 31, 32, 33 were used, and the wettable powder formulated according to the method of Formulation Example 2 was diluted and suspended in water to a predetermined concentration (100 mg / l). This suspension was sprayed at a rate of 100 liters / 10a (Earl) to 1 to 2 leaf wheat (variety: Abukumawase) grown using a square plastic pot (size: 6.4 cm × 6.4 cm). did. The sprayed leaves were air-dried and then spray-inoculated with a suspension of wheat red rust fungus summer spores collected from the diseased leaves and kept at 23-25 ° C. under high humidity conditions for 24 hours. After that, it was left in a glass greenhouse (temperature: 20 to 24 ° C., relative humidity: 20 to 70 RH), and on the 10th day after inoculation, the morbidity was investigated for 10 tubes according to the survey criteria shown in Table 11, The control value was calculated from the average morbidity by the above formula (1).

As a result, compounds 2, 5, 6, 8, 10, 13, 14, 15, 17, 19, 21, 24, and 28 showed a high control effect with a control value of 80% or more at an effective concentration of 100 mg / L. . *

<Test Example 3>
It tested about the control effect of green beans mold. Compounds of the present invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 27, 28, 29, 30, 31, 32, 33 were used, and the wettable powder formulated according to the method of Formulation Example 2 was diluted and suspended in water to a predetermined concentration (100 mg / l). This suspension was cultivated in an unglazed pot (three-size bowl) with a diameter of 9 cm to the green beans (variety: real gold) at the time of the first true leaf at a rate of 100 liters / 10a (Earl) with a spray gun. Scattered. After air-drying of the sprayed leaves, two round slices (diameter 4 mm) of gray mold fungus-containing agar previously cultivated for 3 days at 20 ° C. using sugar-added potato broth agar medium directly per leaf at the center of the leaf It was allowed to adhere and kept under high humidity conditions at 20-23 ° C. On the third day after the inoculation, the morbidity was investigated by 4 points per test area according to the survey criteria shown in Table 12, and the control value was calculated by the above formula (1) from the average morbidity per one.

As a result, at an active ingredient concentration of 100 mg / l, compounds 2, 5, 9, 10, 13, 14, 15, 16, 17, 19, 21, 24, 29, 31, 33 have a high control value of 80% or more. Showed the effect. *

<Test Example 4>
The effect of seed treatment on the control of wheat powdery mildew was examined. Compounds of the present invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 2 mg each of 27, 28, 29, 30, 31, 32, and 33 was weighed and dissolved in 18 μl of DMSO. This was smeared in a vial on each 1 g wheat seed. One day later, 1/10 000a pots were seeded with wheat seeds subjected to the above treatment at a rate of 10 grains / pot and cultivated in the greenhouse with lower water supply. In the greenhouse, diseased wheat seedlings were placed as an inoculum and kept in an infectious state at all times. After 7 days, 14 days, 28 days and 56 days after sowing, the morbidity was investigated according to the survey criteria shown in Table 13, and the control value was calculated by the above formula (1). Based on the control value of the treated group at the time when the untreated group became morbidity level 3 or more, it was set as the “powder control index” according to the criteria shown in Table 14.

(The control value is rounded off to the nearest decimal place.)

As a result, the compounds 2, 5, 9, 14, 15, 21, 22, 23, 24, 26, 27, 28, 29, 31, and 32 have a control index of 3 or more against foliar powdery mildew in seed treatment. Indicated. *

<Test Example 5>
Tests were conducted on the antibacterial activity of various plant pathogens and industrial material pests of gray mold, rice seedling fungus, wheat red mold, and wheat wilt. Compounds of the present invention 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 1 mg each of 27, 28, 29, 30, 31, 32, and 33 was weighed and dissolved in 2 ml of DMSO. 0.6 ml of this solution was added to 60 ml of PDA medium (potato-dextrose agar medium) at around 60 ° C.
In addition to l, well mixed in a 100 ml Erlenmeyer flask, poured into a petri dish and solidified to prepare a plate medium containing the compound of the present invention having a final concentration of 5 mg / l. On the other hand, a test bacterium previously cultured on a plate medium was punched out with a cork borer having a diameter of 4 mm and inoculated on the drug-containing plate medium. After inoculation, the cells are cultured for 2 to 3 days at a suitable temperature for growth of each bacterium (for example, reference can be made to the literature LIST OF CULTURES 1996 microorganisms 10th edition Foundation Fermentation Research Institute). Was measured by the diameter of the fungus. From the obtained result and the fungus diameter on the untreated flat plate, the hyphal elongation suppression rate was calculated by the formula (2). The calculated mycelial elongation inhibition rate was evaluated in five stages according to the criteria shown in Table 15.

(In the formula, R represents the rate of inhibition of hyphal elongation (%), dc represents the diameter of the fungus on the untreated plate, and dt represents the diameter of the fungus on the treated plate.)

For gray mold fungus (Botrytis cinerea), the active ingredient concentration is 5 mg / l and the compounds 2, 5, 8, 9, 10, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 , 29, 30, 31, and 33 showed a mycelium elongation inhibitory effect having a high evaluation of 5.

For the rice seedling fungus (Gibberella fujikuroi), the active ingredient concentration is 5 mg / l, and the compounds 2, 5, 8, 9, 10, 13, 14, 15, 16, 17, 19, 20, 21, 29, 30, 31, and 33 showed a high mycelial elongation inhibitory effect of evaluation 5.

For Fusarium graminearum, the active ingredient concentration is 5 mg / l, and the compounds 2, 5, 8, 9, 10, 13, 14, 15, 16, 17, 19, 20, 21, 33 are A high hyphal elongation suppression effect of evaluation 5 was shown. *

For wheat blight fungus (Phaeosphaeria nodorum), the active ingredient concentration is 5 mg / l, and the compounds 8, 10, 13, 14, 15, 16, 17, 19, 20, 21, 29, 30, 31, 33 are A high hyphal elongation suppression effect of evaluation 5 was shown.

In addition, at a concentration of 50 mg / l, by the same method, Aspergillus sp., Trichoderma sp., Penicillium Psp., Krai, which are deteriorated microorganisms such as paper, pulp, fiber, leather and paint For Dosborium (Cladosporium sp.), Mucor (Mucor sp.), Aureobasidium sp., Curvularia (Curvularia sp.), Wood-modifying fungi Tyromyces palustris, Kawaratake (Coriolus versicolor) The result of evaluating the hyphal elongation suppression rate. As a result, a high mycelial elongation inhibitory effect with a rating of 5 was recognized for compounds 2, 5, 9, 10, 13, 14, 15, 17, 19, 21, 24, and 28.

<Test Example 6>
6). Wheat chief prevention test A test was conducted to determine the effect of wheat chief. Compounds of the present invention 1,2,3,4,5,6,7,8,9,10,13,14,15,16,17,18,19,20,21,22,23,24,26, 2 mg each of 27, 28, 29, 30, 31, 32, and 33 was weighed and dissolved in 18 μl of DMSO. This was smeared in a vial on each 1 g wheat seed. One day later, 1 / 10000a pot was seeded with the above-treated wheat seeds at a rate of 10 grains / pot and cultivated in the greenhouse with lower water supply. Ten days after the sowing, the plant height of the seedlings in each treatment area was investigated at 10 locations, and the plant height suppression rate was determined by the following formula.

R = 100 (hc−ht) / hc
(In the formula, “R” represents the plant height inhibition rate (%), “hc” represents the average plant height of the untreated group, and “ht” represents the average plant height of the group treated with each compound.)

According to the following criteria, the obtained plant height inhibition rate was evaluated in five stages. As a result, a high growth control effect with an evaluation of 4 or more was observed for compounds 10, 13, 19, 26 and 33.
5: Plant height suppression rate of 50% or more 4: Plant height suppression rate of less than 50 to 30% or more 3: Plant height suppression rate of less than 30 to 20% or more 2: Plant height suppression rate of less than 20 to 10% Above 1: Plant height suppression rate is less than 10%

It is a conceptual diagram for demonstrating an example of the manufacturing method of the (heterocyclic methyl) azolylmethyl cyclopentanol derivative based on this invention.

Claims (6)

1. A (heterocyclic methyl) azolylmethylcyclopentanol derivative represented by the chemical formula (I).
   

   

   Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group. Represents a nitrogen atom or a methine group.)
2. An agricultural or horticultural agent or an industrial material protective agent containing the (heterocyclic methyl) azolylmethylcyclopentanol derivative according to claim 1 as an active ingredient.
3. Represented by the above formula (I) (heterocyclic methyl), which comprises a step of adding an azole ring of the formula (VII) to the epoxy group of the oxaspiroheptane derivative represented by the formula (V) in the presence of a base. A method for producing an azolylmethylcyclopentanol derivative.
   

   

   (Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group.)
   

   

   (In the formula, A represents a nitrogen atom or a methine group.)
4. Furthermore, the manufacturing method of Claim 3 including the process of obtaining the said oxa spiro heptane derivative from the cyclopentanone derivative represented by Chemical formula (IV).
   

   

   
   (Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group.)
5. An oxaspiroheptane derivative represented by the chemical formula (V).
   

   

   (Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group.)
6. A cyclopentanone derivative represented by the chemical formula (IV).
   

   

   (Wherein R ¹ and R ² represent a hydrogen atom or a C1-C5 alkyl group. R ³ represents a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed heterocyclic group.)
   

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