WO2010074021A1 - Substituted 1-(1-chlorocylcopropyl)-2-(1h-1,2,4-triazol-1-yl)-2-propen-1-ol derivative, method for producing same and agricultural/horticultural chemical and industrial material-protecting agent comprising same - Google Patents

Abstract

Provided is a novel compound which exhibits excellent effects of controlling agricultural/horticultural diseases, regulating plant growth and protecting industrial materials and can give preferable properties to an agricultural/horticultural chemical and an industrial material-protecting agent. A substituted 1-(1-chlorocyclopropyl)-2-(1H-1,2,4-triazol-1-yl)-2-propen-1-ol derivative represented by general formula (I). In general formula (I), X represents a halogen atom; and n represents an integer of 0 to 5.

Description

Substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivatives, process for producing the same, and agricultural and horticultural agents containing the same And industrial material protective agents

The present invention relates to a novel substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative, its production method and The present invention relates to agricultural and horticultural chemicals and industrial material protective agents.

A variety of properties are conventionally required for agricultural and horticultural agents and industrial material protective agents used to protect plants and industrial materials from harmful microorganisms. For example, agricultural and horticultural chemicals are required to be low in toxicity to human livestock and excellent in handling safety, to exhibit a high control effect against a wide range of plant diseases and to be excellent in sustainability. Furthermore, the agricultural and horticultural agents are also desired to have a plant growth regulating effect that increases the yield by controlling the growth of various agricultural crops and horticultural plants to enhance the quality. Similarly, a wider spectrum is required for industrial material protective agents.

“Substituted 2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivatives” have heretofore been known compounds exhibiting bactericidal activity and plant growth regulating effects. For example, Patent Document 1 contains a substituted 2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative as an azole compound represented by a predetermined general formula A disinfectant is disclosed (see claim 3, etc.). Patent Document 2 discloses substituted 2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol as a triazolylpropenol derivative represented by a predetermined general formula. A fungicide or plant growth regulator composition containing a derivative is disclosed (see claim 14 of the document).

Patent Document 2 discloses “substituted 1- (cycloalkyl) -2- (1H--) as a substituted 2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative. 1,2,4-triazol-1-yl) -2-propen-1-ol derivatives ”. The literature mentions a wide range of substituents as substituents on the cycloalkyl ring of this derivative. However, in any of “Table 1” to “Table 4” listed in the literature, substituted 1- (cycloalkyl) -2 having a chlorine atom at the 1-position of the cycloalkyl ring (cyclopropyl group) -(1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivatives are not exemplified. Further, the substituted 1- (cycloalkyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivatives studied in the examples of the literature are cycloalkyl Only compounds having an alkyl substituent (methyl group or ethyl group) at the 1-position of the ring (cyclopropyl group).

JP 54-41875 A JP 57-53471 A

The present invention is a novel compound capable of imparting desirable properties to agricultural and horticultural chemicals and industrial material protective agents, exhibiting excellent agricultural and horticultural disease controlling effects, plant growth regulating effects and industrial material protective effects The main purpose is to provide

In order to solve the above problems, the present inventors have conducted a detailed study on the chemical structure and physiological activity of 2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivatives. The inventors have found that the compounds of the present invention represented by the following general formula (I) have excellent physiological activity, and have completed the present invention.
That is, the present invention relates to substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propene-1 represented by the following general formula (I): -Provide all derivatives.

(In the formula, “X” represents a halogen atom, and “n” represents an integer of 0 to 5.)
This substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative has a cyclopropyl group (cycloalkyl ring) position 1 Has a chlorine atom.
This derivative is in particular E-3- (4-chlorophenyl) -1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propene-1- Can be all.
The present invention also contains this substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative as an active ingredient. An agricultural and horticultural agent or an industrial material protective agent is provided.
Furthermore, the present invention includes a step of reducing a carbonyl compound represented by the following general formula (II), wherein the substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2, Also provided is a process for the preparation of 4-triazol-1-yl) -2-propen-1-ol derivatives.

(In the formula, “X” represents a halogen atom, and “n” represents an integer of 0 to 5.)

According to the present invention, the present invention exhibits an excellent agricultural and horticultural disease control effect, plant growth control effect, industrial material protective effect, and imparts desired properties to agricultural and horticultural chemicals and industrial material protective agents. Novel compounds capable of

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.

1. Substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivatives Substituted 1- (1-chlorocyclopropyl) according to the present invention ) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivatives are represented by the following general formula (I): Hereinafter, this is abbreviated as “compound (I)”.

In the general formula (I), examples of the halogen atom represented by “X” include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom, more preferably a fluorine atom, a chlorine atom and a bromine atom, still more preferably. It is a chlorine atom. “N” represents an integer of 0 to 5, preferably 1 to 2, and more preferably 1. When “n” is 1, it is particularly preferred that the halogen atom is in the 4-position. When “n” is an integer of 2 or more, “X” may be the same or different.

Compound (I) has the following geometric isomers (E type and Z type). (I-E) represents an E-type compound in which a triazolyl group and a phenyl group are bonded to the trans position, and (I-Z) represents a Z-type compound bonded to the cis position. Compound (I) can be used in a state where only one of these geometric isomers is separated or in a state where both are mixed, but it is preferable to use a separated E-type compound.

 

The combinations of “X”, “n” and isomeric forms in Compound (I) are exemplified in “Table 1”.

(In the table, “-” indicates unsubstituted (n = 0). The number before the halogen atom indicates the carbon atom bonded to the double bond when the phenyl ring has a substituent. (The bond position is the first position.)

Since Compound (I) has a 1,2,4-triazolyl group, it forms an acid addition salt of an inorganic acid or an organic acid or a metal complex. When compound (I) is blended in the agricultural and horticultural chemicals and industrial material protecting agents described later, it can also be blended as part of an acid addition salt or metal complex.

2. Next, a method for producing compound (I) according to the present invention will be described. This production method is characterized in that a carbonyl compound represented by the following general formula (II) (hereinafter abbreviated as “compound (II)”) is reduced with a reducing agent to produce compound (I). Reaction formula (1) showing the reduction from compound (II) to compound (I) is shown below.

Reaction formula (1)

The reaction is usually performed by mixing compound (II) and a reducing agent in a solvent. The solvent is not particularly limited as long as it does not participate in the reaction shown in the reaction formula (1), but ethers such as diethyl ether, tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and isopropanol, benzene, toluene, Aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as petroleum ether, hexane, methylcyclohexane, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, etc. Can be used. As the solvent, water, acetonitrile, ethyl acetate, acetic anhydride, acetic acid, pyridine, dimethyl sulfoxide, or the like can be used. Two or more of these solvents may be used in combination. Furthermore, the solvent composition which consists of a some solvent which does not form a uniform layer mutually can also be used. In this case, it may be better to add a phase transfer catalyst such as a conventional quaternary ammonium salt or crown ether to the reaction system.

The reducing agent is not particularly limited, and preferred examples include metal hydride compounds such as sodium borohydride and lithium aluminum hydride, and aluminum alkoxides such as aluminum isopropoxide.

When sodium borohydride is used as the reducing agent, suitable solvents include ethers such as diethyl ether, tetrahydrofuran and dioxane, and alcohols such as methanol, ethanol and isopropanol. The amount of sodium borohydride to be used with respect to compound (II) is usually 0.1 to 5 times mol, preferably 0.2 to 2 times mol. The reaction temperature is usually -80 to 100 ° C, preferably -20 to 50 ° C. The reaction time is usually 0.1 hour to several days, preferably 0.1 hour to 1 day.

Also, when lithium aluminum hydride is used as the reducing agent, examples of suitable solvents include ethers such as diethyl ether, tetrahydrofuran, and dioxane. The amount of lithium aluminum hydride used relative to compound (II) is usually 0.05 to 5 times mol, preferably 0.1 to 3 times mol. The reaction temperature is usually -100 to 100 ° C, preferably -80 to 50 ° C. The reaction time is usually 0.05 hours to several days, preferably 0.1 hour to 1 day.

Furthermore, when aluminum isopropoxide is used as the reducing agent, suitable solvents include alcohols such as isopropanol and aromatic hydrocarbons such as benzene, toluene and xylene. The amount of aluminum isopropoxide used relative to compound (II) is usually 0.2 to 10 times mol, preferably 0.5 to 5 times mol. The reaction temperature is usually 0 to reflux point, preferably room temperature to reflux point. The reaction time is usually 0.1 hour to several days, preferably 0.5 hour to 2 days. In this case, the obtained aluminum compound is decomposed with dilute sulfuric acid or an aqueous sodium hydroxide solution, and then extracted with an organic solvent hardly soluble in water.

3. Method for Producing Compound (II) Compound (II) used in the method for producing Compound (I) according to the present invention described above is represented by “1- (1-chlorocyclopropyl) -2 represented by the following chemical formula (III): — (1H-1,2,4-triazol-1-yl) ethanone ”(hereinafter abbreviated as“ compound (III) ”) and a benzaldehyde compound represented by the general formula (IV) (hereinafter“ compound ( IV) ") can be obtained by reacting in a suitable solvent in the presence of a base catalyst. Reaction formula (2) showing the formation of compound (II) from compound (III) and compound (IV) is shown below.

Reaction formula (2)

The solvent used in the reaction can be alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene, toluene and xylene, and ethers such as diethyl ether, tetrahydrofuran and dioxane. Moreover, acetic acid, acetic anhydride, etc. can also be used for a solvent. In addition, the solvent used is not limited to these.

Bases that can be used as catalysts include alkali metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, or alkaline earth metal hydroxides, sodium methoxide, sodium ethoxide, potassium t-butoxide, and other alkali metal. Alkali metal carbonates such as alkoxide, sodium carbonate and potassium carbonate, alkaline earth metal carbonates such as calcium carbonate and barium carbonate, acetates such as sodium acetate and potassium acetate, triethylamine, dipropylamine, pyrrolidine, piperidine, And organic amines such as morpholine.

The amount of compound (IV) used relative to compound (III) is usually 0.5 to 10 times mol, and more preferably 0.5 to 2 times mol. The amount of the base used relative to compound (III) is usually 0.01 to 10 times mol, more preferably 0.1 to 5 times mol. The reaction temperature is usually from 0 to the reflux point, preferably from room temperature to the reflux point. The reaction time is usually 0.1 hour to several days, preferably 0.5 hour to 2 days.

Compound (III) can be produced by a known method, and compound (IV) can be a commercially available product or a product produced by a known method.

4). Agricultural and horticultural chemicals and industrial material protective agents The agricultural and horticultural chemicals or industrial material protective agents according to the present invention contain compound (I) as an active ingredient.

(1) Agricultural and horticultural chemicals Compound (I) exhibits a controlling effect against a wide range of plant diseases. Examples of applicable diseases include the following.

Soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia grisea), rice sesame leaf blight (Cochliobolus miyabeanus), rice white leaf blight (Xanthomonas oryzae), rice rot (Rhizoctonia sol) Nuclear disease (Helminthosporium sigmoideun), rice seedling disease (Gibberella fujikuroi), rice seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaera leucotricha), apple black rot (Venturia inaequalis), apple peach linear Apple spotted leaf blight (Alternaria alternata), apple rot blight (Valsa mali), pear black blight (Alternaria kikuchiana), pear powdery mildew (Phyllactinia pyri), pear red blight (Gymnosporangium asiaticum), pear , Grape powdery mildew (Uncinula necator), grape mildew (Plasmopara viticola), grape late rot (Glomerella cingulata), barley powdery mildew (Erysiphe gra) minis f. sp hordei), barley black rust (Puccinia graminis), barley yellow rust (Puccinia striiformis), barley spotted potato (Pyrenophora graminea), barley cloud (Rhynchosporium secalis), wheat . Sp tritici), wheat red rust (Puccinia recondita), wheat yellow rust (Puccinia striiformis), wheat eyespot () ), Wheat leaf blight (Septoria tritici), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber anthracnose (Colletotrichum lagenarium), cucumber beetle (Pseudoperonospora cubensis), cucumber gray plague (Phytophthora Erysiphe cichoracearum, tomato ring-shaped disease (Alternaria solani), eggplant powdery mildew (Erysiphe cichoracearum), strawberry powdery mildew ( Sphaerotheca humuli), tobacco powdery mildew (Erysiphe cichoracearum), sugar beet brown rot (Cercospora beticola), corn smut (Ustillaga maydis), fruit tree fruit tree Monilinia fructicola, gray mold (Botrytis cinerea), Sclerotinia sclerotiorum, etc.

Examples of applied plants include wild plants, plant cultivars, plants obtained by conventional biological breeding such as crossbreeding or protoplast fusion, plant cultivars, genetically modified plants and plant cultivars obtained by genetic manipulation. Can be mentioned. Examples of genetically modified plants and plant cultivars include herbicide-tolerant crops, pest-tolerant crops incorporating insecticidal protein production genes, disease-resistant crops incorporating resistance-inducing substance production genes for diseases, improved crops, improved yields Examples include crops, crops with improved shelf life, and crops with improved yield. Specific examples of genetically modified plant cultivars include those containing registered trademarks such as ROUNDUP READY, LIBERTY LINK, CLEARFIELD, YIELDGARD, HERCULEX, BOLLGARD and the like.

(2) Plant Growth Action Compound (I) also has the effect of regulating the growth and increasing the yield of a wide variety of crops and horticultural plants and the quality of the product. 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.

(3) Industrial material protection effect Furthermore, compound (I) shows the outstanding effect which protects material from the extensive harmful microorganisms which invade industrial material. Examples of such microorganisms include the following.

Aspergillus sp., Trichoderma sp., Penicillium GGeotrichum 、 sp., Ketomium Chsp., Cadhola (Cadophora sp.), Ceratostomella sp., Cladosporium sp., Corticium sp., Lentinus sp., Lenzites sp., Forma (Phoma sp.) , Polysticus sp., Pullularia sp., Stereum sp., Trichosporium sp., Aerobacter sp., Bacillus ビ sp., Desulfobibrio (Desulfovibrio sp.), Pseudomonas sp., Flavobacterium sp., Microco Aspergillus sp., Penicillium Chsp., Ketomium Msp., Myrothecium sp., Curvularia sp., Glioma stick, such as Micrococcus sp. (Gliomastix sp.), Mennoniella (Memnoniella sp.), Sarcopodium (Sarcopodium ス タ sp.), Stachybotrys (Stschybotrys sp.), Stemphylium (Stemphylium ジ sp.), Digolynx (Zygorhynchus sp.), Bacillus (bacillus) .), Staphylococcus sp., And other wood-modified bacteria such as Tyromyces palustris, Kawariotake (Coriolus versicolor), Aspergillus Asp., Penicillium sp., Rhizopus (Rhizopus sp.) , Aureobasidium sp., Glioclad um sp.), Cladosporium sp., Ketomium (Chaetomium sp.), Trichoderma sp., and other skin-degrading microorganisms such as Aspergillus sp., Penicillium sp., Ketomium ( Chaetomium sp.), Cladosporium sp., Mucor sp., Paecilomyces sp., Pilobus sp., Pullularia sp., Trichosporon sp., Trichosporon sp. (Tricothecium sp.), Rubber and plastic degrading microorganisms such as Aspergillus sp., Penicillium (Penicillium sp.), Rhizopus sp., Trichoderma sp., Ketotomium sp., Milotesium (Myrothecium sp.), Streptomyces sp., Pseudomonas sp. , Bacillus (sp.), Micrococcus (sp.), Serratia (sp.), Margarinomyces (sp.), Monascus sp., Monascus sp., Aspergillus sp. ), Penicillium Psp., Cladosporium sp., Aureobasidium sp., Gliocladium sp., Botryodiplodia sp., Macrospo Limon (Macrosporium sp.), Monilia (Monilia sp.), Forma (Phoma sp.), Pullularia ((Pullularia sp.), Sporotrichum sp., Trichoderma sp., Bacillus (sp.) , Proteus sp., Pseudomonas sp., Serratia sp.

(4) Formulation In order to apply Compound (I) as an active ingredient of agricultural and horticultural medicine, it may be left as it is without adding any other components, but usually a solid carrier, liquid carrier, surfactant, other formulation aids It is mixed with an agent and formulated into various forms such as powders, wettable powders, granules, and emulsions.

These preparations are formulated so as to contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 80% by weight of the compound (I) as an active ingredient.

Examples of carriers, diluents, and surfactants used as formulation adjuvants include talc, kaolin, bennite, diatomaceous earth, white carbon, and clay as solid carriers. Liquid diluents include water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, alcohol and the like. Surfactants should be used properly depending on their effects, such as polyoxyethylene alkylaryl ether and polyoxyethylene sorbitan monolaurate as emulsifiers, wetting agents such as lignin sulfonate and dibutylnaphthalene sulfonate as dispersants. Examples thereof include alkyl sulfonates and alkylphenyl sulfonates.

Some preparations are used as they are, while others are diluted to a predetermined concentration with a diluent such as water. The concentration of compound (I) when used after dilution is preferably in the range of 0.001 to 1.0%.

In addition, the amount of compound (I) used is 20 to 5000 g, more preferably 50 to 2000 g, per 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., they can be increased or decreased without sticking to the above range.

Furthermore, the compound (I) can be used in combination with other active ingredients such as fungicides, insecticides, acaricides and herbicides as exemplified below to enhance performance as agricultural and horticultural agents.

<Antimicrobial substances>
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, pefrazoate, orisatrobin, 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, amisulbrom, sedaxane, flutianil, varifenal, amethoctrazine, dimoxystrobin, metolaphenone, hydroxyisoxazole, metasulfocarb, etc.

<Insecticide / acaricide / nematicide>
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, metam, methamidophos, methidathion, methiocarb, methomyl, methoprene, methosrin, methoxyphenozide, metorcarb, milbemectin, monocrotophos, nared, nicotine, nitenpyram, novaluron, nobiflumetron, ometomethytoyl, ometomethyton , Parathion, permethrin, phentoate, folate, fosaron, fosmet, fosfamidon, foxime, pirimicarb, pirimiphos methyl, profenofos, propoxur, prothiophos, pymetrozine, pyracrofos, pyrethrin, pyridaben, pyridalyl, pyrimidifene, pyriproxyfen, Pyrifluquinazone, piliprolol, quinalphos, silafluophene, Pinosad, Spirodiclofen, Spiromethifene, Spirotetramat, Sulfamide, Sulfotep, SZI-121, Tebufenozide, Tebufenpyrad, Tebupyrimfos, Teflubenzuron, Tefurthrin, Temefos, Terbufos, Tetrachlorbinfos, Thiacloprid, Thiamethioxam, Thiodixam Thiomethone, tolfenpyrad, tralomethrin, tralopyril, triazamate, triazophos, trichlorfon, triflumuron, bamidithione, varifenal, XMC, xylylcarb, imisiaphos, lepimectin and the like.

<Plant growth regulator>
Ansimidol, 6-benzylaminopurine, paclobutrazole, diclobutrazole, uniconazole, methylcyclopropene, mepiquat chloride, ethephone, chlormequat chloride, inabenfide, prohexadione and its salts, trinexapac Ethyl etc. Jasmonic acid as a plant hormone, brassinosteroid, gibberellin and the like.

In order to apply the compound (I) as an active ingredient of an industrial material protective agent, it may be used alone without adding other components, but it is generally dissolved or dispersed in a suitable liquid carrier, or a solid carrier And if necessary, further add emulsifier, dispersant, spreader, penetrant, wetting agent, stabilizer, etc., wettable powder, powder, granule, tablet, paste, suspension, It can be used as a dosage form such as a spray material. Moreover, you may mix | blend another fungicide, an insecticide, a degradation inhibitor, etc.

As the liquid carrier, any liquid may be used as long as it does not react with the active ingredient. For example, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol, cellosolve, etc.), ketones (for example, 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, machinery Oil, fuel oil, etc.), acid amides (eg, dimethylformamide, N-methylpyrrolidone, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate, fatty acid glycerin ester) etc), Tolyl compounds (e.g., acetonitrile), and dimethyl sulfoxide and the like can be used.

As the solid support, fine powders or granular materials such as kaolin clay, bentonite, acid clay, pyrophyllite, talc, diatomite, calcite, urea, ammonium sulfate can be used.

As emulsifiers and dispersants, surfactants such as soaps, alkylsulfonic acids, alkylarylsulfonic acids, dialkylsulfosuccinic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxides, anhydrosorbitols, etc. Can be used.

When compound (I) is contained in the preparation as an active ingredient, the content varies depending on the dosage form and intended purpose, but it is generally appropriate to add it at a concentration of 0.1 to 99.9% by weight. is there. In actual use, it is preferable to adjust the treatment concentration by adding a solvent, a diluent, an extender or the like as appropriate so that the treatment concentration is usually 0.005 to 5% by weight, preferably 0.01 to 1% by weight. . Compound (I) can also be formulated in combination with antibacterial substances, insecticides, deterioration inhibitors and the like, similar to the above-mentioned agricultural and horticultural agents. Thereby, the performance as an industrial material protective agent can be improved.

Hereinafter, production examples, formulation examples, and test examples of Compound (I) will be shown to specifically describe the present invention. The present invention is not limited to the production examples shown below unless the gist thereof is exceeded.

<Production Example 1>
1. E-3- (4-Chlorophenyl) -1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol (compound (I- 1)) Synthesis E-3- (4-Chlorophenyl) -1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-one (Compound (II-E)), 0.754 g (2.45 mmol) was dissolved in 10 ml methanol and cooled on ice. Sodium borohydride 0.092 mg (2.43 mmol) was added, and it stirred under ice-cooling for 0.5 hour. 10 ml of water and 0.15 ml of acetic acid were added to the reaction mixture, and the mixture was 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 residue was purified with a silica gel column (eluent: chloroform) to obtain the desired product (compound (I-1)).

The yield of compound (I-1) was 0.429 g, and the yield was 57%. Compound (I-1) was a white solid and had a melting point of 137 ° C. Moreover, the measured value of the NMR spectrum was as follows.
¹ H-NMR (CDCl ₃ , 400 MHz) δ:
0.53-0.59 (1H, m), 0.72-0.78 (1H, m), 0.84-0.90 (1H, m), 1.04-1.10 (1H, m), 4.42 (1H, J = 10.4 Hz, d), 5.19 ( 1H, J = 10.4 Hz, d), 6.96 (1H, s), 7.41-7.47 (4H, m), 8.08 (1H, s), 8.43 (1H, s).

<Production Example 2>
2. Z-3- (4-Chlorophenyl) -1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol (compound (I- 2)) Synthesis Z-3- (4-Chlorophenyl) -1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-one (Compound (II-Z)), 0.252 g (0.82 mmol) was dissolved in 3 ml methanol and ice-cooled. Sodium borohydride 0.031 mg (0.82 mmol) was added, and it stirred at room temperature for 3 hours. 10 ml of water and 0.1 ml of acetic acid were added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain the desired product (Compound (I-2)).

The yield of compound (I-2) was 0.21 g, and the yield was 83%. Compound (I-2) was a white solid and had a melting point of 123 ° C. Moreover, the measured value of the NMR spectrum was as follows.
¹ H-NMR (CDCl ₃ , 400 MHz) δ:
0.68-0.93 (4H, m), 3.19 (1H, J = 7.2 Hz, d), 4.40 (1H, J = 7.2 Hz, d), 6.78-6.80 (2H, m), 7.00 (1H, s), 7.19 -7.22 (2H, m), 7.94 (1H, s), 8.15 (1H, s).

<Production Examples 3 to 8>
3. Compounds (I-3) to (I-6), (I-18) and (I-19) shown in “Table 2” were synthesized by a method according to Production Examples 1 and 2. The physical properties of each compound are shown in the table.

<Reference production example>
4). Synthesis of Intermediate Compound (II-E) and Intermediate Compound (II-Z) 1- (1-Chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) ethanone (Compound ( III)), 4.00 g (21.55 mmol) and 4-chlorobenzaldehyde (compound of Xn = 4-Cl in compound (IV)), 3.03 g (21.55 mmol) were dissolved in 30 ml acetic anhydride. 2.97 g (21.55 mmol) of potassium carbonate was added and stirred at 100 ° C. for 6 hours. The reaction solution was filtered, the filtrate was concentrated under reduced pressure, the residue was dissolved in chloroform, the organic layer was washed with water, saturated aqueous sodium hydrogen carbonate, and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (eluent: hexane / ethyl acetate = 2/1 to 1/1) to obtain compound (II-E) and compound (II-Z). .

Compound (II-E) is a compound of Xn = 4-Cl and isomer type E in Compound (II). The yield was 0.79 g, and the yield was 12%. Compound (II-E) was an oil. Moreover, the measured value of the NMR spectrum was as follows.
¹ H-NMR (CDCl ₃ , 400 MHz) δ:
1.47-1.51 (2H, m), 1.84-1.88 (2H, m), 7.15 (1H, s), 7.29-7.31 (2H, m), 7.37-7.39 (2H, m), 8.08 (1H, s), 8.38 (1H, s).

Compound (II-Z) is a compound of Xn = 4-Cl, isomer type Z in compound (II). The yield was 2.00 g, and the yield was 30%. Compound (II-Z) was a yellow solid and had a melting point of 77 ° C. Moreover, the measured value of the NMR spectrum was as follows.
¹ H-NMR (CDCl ₃ , 400 MHz) δ:
1.34-1.37 (2H, m), 1.69-1.73 (2H, m), 6.86-6.88 (2H, m), 7.27-7.30 (2H, m), 7.82 (1H, s), 8.09 (1H, s), 8.19 (1H, s).

<Formulation example 1>
1. Hydrate The formulation shown in “Table 3” below is pulverized and mixed to obtain a wettable powder, which is diluted with water and used. In addition, the formulation example demonstrated below can change the mixing ratio of an active ingredient, a carrier (diluent), and an adjuvant in a wide range. Here, “parts” in each formulation example represents “parts by weight”.

<Formulation example 2>
2. Powder The composition shown in Table 4 below is pulverized and mixed to be used as a powder.

<Formulation example 3>
3. Granules The ingredients shown in Table 5 below are uniformly mixed, water is added and kneaded, and processed and dried into granules with an extrusion granulator to obtain granules.

<Formulation example 4>
4). emulsion
The following formulation shown in Table 6 is uniformly mixed and used as an emulsion.

<Test Example 1>
1. Cucumber gray mold control effect test To the cucumber in the cotyledon stage (variety: SHARP1) cultivated using a square plastic pot (6 cm × 6 cm), the wettable powder prepared in Formulation Example 1 was added to water at a predetermined concentration ( The suspension was diluted to 50 mg / l) and sprayed at a rate of 1,000 L / ha. After the sprayed leaves were air-dried, a paper disc (diameter 8 mm) impregnated with a spore solution of gray mold was placed and kept at 20 ° C. under high humidity. On the 4th day after inoculation, the morbidity of cucumber gray mold was investigated, and the control value was calculated by the following formula. In the formula, “morbidity” was in accordance with “Table 7”.

For comparison, “E-3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1H-1,2,4-triazol-1-yl) — represented by the following chemical formula: A similar test was conducted using a wettable powder prepared according to Formulation Example 1 for “2-propen-1-ol” (Comparative Compound (1)). This comparative compound (1) is disclosed in “Substituted 1- (cycloalkyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol disclosed in Patent Document 2 above. One of the “derivatives”.

 

Control value (%) = (1-average morbidity in sprayed area ÷ 平均 average morbidity in non-sprayed area) x 100

 

Table 8 shows the results of the control effect test. In the wettable powder containing the compound (I-1) according to the present invention, a remarkably high control effect was recognized as compared with the comparative compound (1).

 

<Test Example 2>
2. Cucumber gray mold control effect test Wet powder (compound (I-2)) prepared according to Formulation Example 1 to a cotyledon cucumber (variety: SHARP1) cultivated using a square plastic pot (6 cm x 6 cm) ) Was diluted with water to a predetermined concentration (250 mg / l) and sprayed at a rate of 1,000 L / ha. After the sprayed leaves were air-dried, a paper disc (diameter 8 mm) impregnated with a spore solution of gray mold was placed and kept at 20 ° C. under high humidity. On the 4th day after inoculation, the morbidity of cucumber gray mold was investigated, and the control value was calculated in the same manner as in Test Example 1.

For comparison, “Z-3- (4-chlorophenyl) -1- (1-methylcyclopropyl) -2- (1H-1,2,4-triazol-1-yl) — represented by the following chemical formula: A similar test was conducted using a wettable powder prepared according to Formulation Example 1 for “2-propen-1-ol” (Comparative Compound (2)). This comparative compound (2) is disclosed in “Substituted 1- (cycloalkyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol disclosed in Patent Document 2 above. One of "derivatives".

 

Table 9 shows the results of the control effect test. In the wettable powder containing the compound (I-2) according to the present invention, a remarkably high control effect was recognized as compared with the comparative compound (2).

 

<Test Example 3>
3. Wheat red rust control effect test (2nd leaf stage)
To the wheat at the second leaf stage cultivated using a square plastic pot (6 cm × 6 cm) (variety: Norin 61), the wettable powder prepared in Preparation Example 1 was added to water at a predetermined concentration (12.5 mg / L) was diluted and suspended and sprayed at a rate of 1,000 L / ha. The sprayed leaves were air-dried and then spray-inoculated with spores of wheat red rust fungus (adjusted to 200 cells / field of view, added with Grameen S to 60 ppm) and kept at 25 ° C. under high humidity for 48 hours. After that, it was managed in the greenhouse. On the 9th to 14th day after inoculation, the morbidity of wheat rust was investigated, and the control value was calculated by the following formula. In the formula, “morbidity” was in accordance with “Table 10”.

Control value (%) = (1-average morbidity in sprayed area ÷ 平均 average morbidity in non-sprayed area) x 100

 

Table 11 shows the results of the control effect test. In the wettable powder containing the compound (I-1) according to the present invention, a remarkably high control effect was recognized as compared with the comparative compound (1).

 

<Test Example 4>
4). Wheat red rust control effect test (2nd leaf stage)
To the wheat in the second leaf stage (variety: Norin 61) grown using a square plastic pot (6 cm x 6 cm), a wettable powder (compound (I-2)) prepared according to Formulation Example 1 The suspension was diluted with water to a predetermined concentration (50 mg / L) and sprayed at a rate of 1,000 L / ha. The sprayed leaves were air-dried and then spray-inoculated with spores of wheat red rust fungus (adjusted to 200 cells / field of view, added with Grameen S to 60 ppm) and kept at 25 ° C. under high humidity for 48 hours. After that, it was managed in the greenhouse. On the 9th to 14th day after the inoculation, the morbidity of wheat rust was investigated, and the control value was calculated in the same manner as in Test Example 3.

Table 12 shows the results of the control effect test. In the wettable powder containing the compound (I-2) according to the present invention, a remarkably high control effect was recognized as compared with the comparative compound (2).

 

<Test Example 5>
5). Wheat red mold control effect test (flowering period)
The wet head prepared in Formulation Example 1 was diluted and suspended in water at a predetermined concentration (100 mg / L) and sprayed at a rate of 1,000 L / ha on the wheat ears of the flowering stage (variety: Norin 61). . After air-drying the head, spray inoculate with wheat spore mold spores (adjusted to 2 × 10 ⁵ cells / ml, containing Gramine S at a final concentration of 60 ppm and sucrose at a final concentration of 0.5%), and 20 ° C high humidity Kept under conditions. On the 4th to 7th day after inoculation, the morbidity of wheat head blight was investigated, and the control value was calculated by the following formula. In the formula, “morbidity” was in accordance with “Table 13”.

Control value (%) = (1-average morbidity in sprayed area ÷ 平均 average morbidity in non-sprayed area) x 100

 

The results of the control effect test are shown in “Table 14”. In the wettable powder containing the compound (I-1) according to the present invention, a remarkably high control effect was recognized as compared with the comparative compound (1).

<Test Example 6>
6). Wheat red mold control effect test (flowering period)
In the wheat head of the flowering period (variety: Norin 61), the wettable powder (compound (I-2)) prepared according to Formulation Example 1 is diluted with water to a prescribed concentration (250 mg / L) and suspended. Sprayed at a rate of L / ha. After air-drying the head, spray inoculate wheat spore fungus spores (adjusted to 2 × 10 ⁵ cells / ml, containing Gramine S with a final concentration of 60 ppm and sucrose with a final concentration of 0.5%), and high humidity at 20 ° C. Kept under conditions. On the 4th to 7th days after the inoculation, the morbidity of wheat red mold was investigated, and the control value was calculated in the same manner as in Test Example 5.

The results of the control effect test are shown in “Table 15”. In the wettable powder containing the compound (I-2) according to the present invention, a remarkably high control effect was recognized as compared with the comparative compound (2).

 

<Test Example 7>
7). Antibacterial test against various pathogenic bacteria and harmful microorganisms In this test example, the antibacterial activity of the compound according to the present invention against various phytopathogenic fungi and industrial material harmful microorganisms was examined.

Compounds (I-1) to (I-3), (I-5) and (I-18) were dissolved in 2 ml of dimethyl sulfoxide. Add 0.6 ml of this solution to 60 ml of PDA medium (potato-dextrose-aggar medium) at around 60 ° C., mix well in a 100 ml ml Erlenmeyer flask, solidify by pouring into a petri dish (see “Table 16” below). The plate medium containing each compound was prepared.

The test bacteria cultured on a normal plate medium were punched out with a cork borer having a diameter of 4 mm and inoculated on the plate medium containing the above-mentioned compounds. After inoculation, the cells were cultured for 1 to 3 days at the optimum temperature for growth of each fungus (see “Fellow Institute of Fermentation“ LIST OF CULTURES 1996 microorganisms 10th edition ”), and the growth of the fungi was measured by the fungus diameter. The growth degree of the bacteria obtained on the plate medium containing each compound was compared with the growth degree of the bacteria on the normal plate medium, and the hyphal elongation inhibition rate was determined by the following formula.

R = 100 (dc−dt) / dc
(In the formula, “R” represents the mycelial elongation inhibition rate (%), “dc” represents the diameter of the fungus on a normal plate medium, and “dt” represents the diameter of the fungus on a plate medium containing each compound. )

Table 16 shows the results of five-stage evaluation of the obtained hyphal elongation inhibition rate according to the following criteria.
5: Mycelium elongation inhibition rate of 90% or more 4: Mycelium elongation inhibition rate of less than 90 to 70% or more 3: Mycelium elongation inhibition rate of less than 70 to 40% or more 2: Mycelium elongation inhibition rate of 40 Less than 20% or more 1: Hypha elongation suppression rate is less than 20%

 

In the table, abbreviations such as “Pn” indicate the following microorganisms.
“Pn”: wheat blight fungus (Phaeosphaeria nodorum)
"Ph": Wheat eye spot disease fungus (Pseudocercoporella herpotrichoides)
“Fg”: Fusarium graminearum
"Un": Barley Bare Smut Fungus (Ustilago nuda)
"Po": Rice blast fungus (Pyricularia oryzae)
"Gf": Rice idiotic fungus (Giberella fujikuroi)
"Am": Alternaria alternata
“Ss”: Sclerotinia sclerotiorum
"Bc": Botrysis cinerea
"Fc": Fusarium oxysporum
"R.sec": Rhynchosporium secalis

In addition, at a concentration of 50 mg / l, by the same method, aspergillus (spider), Trichoderma sp., Penicillium (penicillium sp), which are deteriorated microorganisms such as paper, pulp, fiber, leather and paint, Cladosporium sp., Mucor .sp., Aureobasidium sp., Curvularia sp., Wood-changing fungus Tyromyces palustris, Coralus versicolor As a result of evaluating the hyphal elongation inhibition rate, high antibacterial properties of evaluation 4 or higher were observed for compound (I-1) and compound (I-18).

<Test Example 8>
8). Rice length prevention test Compounds (I-1) to (I-3), (I-5), (I-18) 36 mg were dissolved in 3.6 ml of dimethyl sulfoxide and smeared in 180 g of rice seeds in a vial. did. After soaking and germination treatment, seedling boxes were sown at a rate of 180 g / box, germinated in a seedling container and then cultivated in a 35 ° C. greenhouse. Ten days after 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 plant height suppression rate obtained was evaluated in five stages. As a result, the compounds (I-1), (I-3), (I-5), and (I-18) were evaluated with a rating of 4 or more. High growth control effect was observed.
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%

The substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative according to the present invention is a fungicide for agriculture and horticulture. Not only useful as an active ingredient, but also from plant growth regulators that increase the yield and improve the quality of various crops and horticultural plants, and from a wide range of harmful microorganisms that invade industrial materials It is also useful as an industrial material protective agent showing the effect of protecting the material.

Claims (4)

1. A substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative represented by the following general formula (I):
   

   

   (In the formula, “X” represents a halogen atom, and “n” represents an integer of 0 to 5.)
2. Agricultural and horticultural use containing the substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol derivative according to claim 1 as an active ingredient Chemicals or industrial material protective agents.
3. The substituted 1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazole-1- of claim 1 comprising a step of reducing a carbonyl compound represented by the following general formula (II): Yl) -2-propen-1-ol derivatives.
   

   

   (In the formula, “X” represents a halogen atom, and “n” represents an integer of 0 to 5.)
4. E-3- (4-Chlorophenyl) -1- (1-chlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) -2-propen-1-ol.