WO2016158821A1 - テトラゾリノン化合物及びその用途 - Google Patents
テトラゾリノン化合物及びその用途 Download PDFInfo
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- WO2016158821A1 WO2016158821A1 PCT/JP2016/059819 JP2016059819W WO2016158821A1 WO 2016158821 A1 WO2016158821 A1 WO 2016158821A1 JP 2016059819 W JP2016059819 W JP 2016059819W WO 2016158821 A1 WO2016158821 A1 WO 2016158821A1
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- Prior art keywords
- compound
- present
- group optionally
- halogen atoms
- halogen
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- 0 Cc1cc(OCc(c(*)ccc2)c2N2N=NNC2=O)c(C)cc1-c1n[n](C2CC2)c(*)c1 Chemical compound Cc1cc(OCc(c(*)ccc2)c2N2N=NNC2=O)c(C)cc1-c1n[n](C2CC2)c(*)c1 0.000 description 2
- GVVRXLDPUIOWIJ-UHFFFAOYSA-N Cc1cc(OC)c(C)cc1-c1n[nH]cc1 Chemical compound Cc1cc(OC)c(C)cc1-c1n[nH]cc1 GVVRXLDPUIOWIJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
Definitions
- the present invention relates to a plant disease control agent and its use.
- Patent Document 1 Conventionally, various compounds have been developed to control plant diseases (see Patent Document 1).
- An object of the present invention is to provide a compound having an excellent control effect against plant diseases.
- the present inventor has found that the compound represented by the following formula (I) has an excellent control effect against plant diseases. That is, the present invention is as follows. [1] Formula (I) [Wherein R 1 represents a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a C1-C3 alkoxy group optionally having one or more halogen atoms, a halogen atom, A cyano group, or a C1-C3 alkylthio group optionally having one or more halogen atoms; R 2 is a C1-C3 alkyl group optionally having one or more halogen atoms, a C1-C3 alkoxy group optionally having one or more halogen atoms, a hydrogen atom, a halogen atom, or one or more Represents a C3-C4 cycloalkyl group optionally having a
- a tetrazolinone compound represented by the following (hereinafter referred to as the present compound).
- a plant disease control agent containing the tetrazolinone compound according to [1] (hereinafter also referred to as the present invention control agent).
- plant diseases can be controlled.
- halogen atoms means that when two or more halogen atoms are present, these halogen atoms may be the same or different from each other.
- C1-C3 means having 1 to 3 carbon atoms.
- a halogen atom represents a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- Examples of the compound of the present invention include the following compounds.
- a tetrazolinone compound in which R 1 is a hydrogen atom in the compound of the present invention A tetrazolinone compound in which R 1 is a hydrogen atom or a methyl group in the compound of the present invention.
- a tetrazolinone compound in which R 1 is a hydrogen atom or a methyl group and R 2 is a methyl group in the compound of the present invention.
- a tetrazolinone compound in which R 1 is a hydrogen atom or a methyl group and R 2 is a methoxy group in the compound of the present invention.
- tetrazolinone wherein R 1 is a hydrogen atom or a C1-C3 alkyl group, and R 2 is a C1-C3 alkyl group, a C1-C3 alkoxy group, a hydrogen atom, a halogen atom, or a C3-C4 cycloalkyl group
- R 1 is a hydrogen atom or a methyl group
- R 2 is a methyl group, a methoxy group, a hydrogen atom, a chlorine atom, or a cyclopropyl group in the compound of the present invention.
- the compound of the present invention can be produced, for example, by the following production method.
- the compound of the present invention comprises a compound represented by formula (A1) (hereinafter referred to as compound (A1)) and a compound represented by formula (A2) (hereinafter referred to as compound (A2)) as a copper compound and a base. It can manufacture by making it react in presence of.
- X 11 represents a dihydroxyboranyl group, a dialkoxyboranyl group or a 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl group, and other symbols are as defined above. Represents the same meaning.
- the reaction is usually performed in a solvent.
- Examples of the solvent used in the reaction include hydrocarbons such as n-hexane, cyclohexane, toluene and xylene (hereinafter referred to as hydrocarbons), diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glyco- Ethers such as rudimethyl ether, methyl tert-butyl ether and diisopropyl ether (hereinafter referred to as ethers), halogenated hydrocarbons such as chloroform, dichloromethane and chlorobenzene (hereinafter referred to as halogenated hydrocarbons), Acid amides such as dimethylformamide, 1,3-dimethyl-2-imidazolidinone and N-methylpyrrolidone (hereinafter referred to as acid amides), esters such as ethyl acetate and methyl acetate (hereinafter referred to as esters) ), Sulfoxides such as dimethyl s
- Examples of the copper compound used in the reaction include copper (II) acetate.
- Examples of the base used in the reaction include organic bases such as triethylamine, pyridine, 2,2′-bipyridine, diazabicycloundecene (hereinafter referred to as organic bases), sodium carbonate, sodium hydrogen carbonate, carbonic acid Examples include carbonates such as potassium.
- the compound (A2) is usually used in a proportion of 1 to 10 mol, the copper compound in a proportion of 1 to 10 mol, and the base in a proportion of 1 to 10 mol with respect to 1 mol of the compound (A1).
- a dehydrating agent such as molecular sieves can be used as necessary, and it is used in a proportion of 100 to 500 mass percent with respect to 1 mol of the compound (A1).
- the reaction temperature is usually in the range of ⁇ 20 to 150 ° C.
- the reaction time is usually in the range of 0.1 to 120 hours.
- the compound of the present invention can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
- Compound (A1) and compound (A2) are known or can be produced according to known methods.
- the compound of the present invention comprises a compound represented by formula (A3) (hereinafter referred to as compound (A3)) and a compound represented by formula (A4) (hereinafter referred to as compound (A4)) in the presence of a base. It can manufacture by making it react.
- X 12 represents a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group or a p-toluenesulfonyloxy group, and other symbols have the same meanings as described above.
- the reaction can be produced according to a known method.
- a compound represented by formula (B2) (hereinafter referred to as compound (B2)) is obtained by combining a compound represented by formula (B1) (hereinafter referred to as compound (B1)) and compound (A2) with a copper compound and a base. It can manufacture by making it react in presence of. [Wherein X 13 represents a C1-C5 alkyl group, and other symbols have the same meaning as described above. ] The reaction can be carried out according to the method described in Production Method A. Compound (B1) is known or can be produced according to a known method.
- Reference manufacturing method B Compound (A3) can be produced by reacting compound (B2) with an acid. [Wherein the symbols have the same meaning as described above. ] The said reaction can be implemented according to the method of WO2014 / 051165 using an acid etc.
- Each compound produced by the above production method and reference production method can also be isolated by other known means such as concentration, concentration under reduced pressure, extraction, phase transfer, crystallization, recrystallization, chromatography, etc. -It may be possible to purify.
- the form of the compound of the present invention may be the compound of the present invention alone.
- the compound of the present invention is mixed with a solid carrier, a liquid carrier, a surfactant, etc., and if necessary, a fixing agent or a dispersing agent.
- Additives for preparations such as stabilizers, wettable powder, granular wettable powder, flowable powder, granules, dry flowable powder, emulsion, aqueous liquid, oil, smoke, aerosol, micro It is used in the form of capsules.
- These preparations contain the compound of the present invention in a weight ratio of usually 0.1 to 99%, preferably 0.2 to 90%.
- solid carrier examples include clays (for example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fubasamic clay, bentonite, acidic clay), talc, and other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated carbon). , Calcium carbonate, hydrated silica) and the like.
- liquid carrier examples include water, alcohols, ketones (eg, acetone, methyl ethyl ketone, cyclohexanone), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (Eg, n-hexane, kerosene), esters, nitriles, ethers, acid amides, and halogenated hydrocarbons.
- ketones eg, acetone, methyl ethyl ketone, cyclohexanone
- aromatic hydrocarbons eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene
- aliphatic hydrocarbons Eg, n-hexane, kerosene
- esters nitriles, ethers, acid amides, and halogenated hydrocarbon
- surfactant examples include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyoxyethylene glycol ethers, polyvalent Examples include alcohol esters and sugar alcohol derivatives.
- formulation adjuvants include, for example, fixing agents, dispersants, and stabilizers.
- casein gelatin, polysaccharides (eg, starch, arabic gum, cellulose derivatives, alginic acid), lignin derivatives, Bentonite, sugars, synthetic water-soluble polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol) ), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, fatty acid or ester thereof, and the like.
- polysaccharides eg, starch, arabic gum, cellulose derivatives, alginic acid
- lignin derivatives Bentonite
- sugars synthetic water-soluble polymers (eg, polyvinyl alcohol, polyvinyl pyr
- the compound of the present invention may be used by mixing with various oils such as mineral oil and vegetable oil, or surfactants.
- Oils that can be specifically mixed and used as surfactants are Nimbus (registered trademark), Assist (registered trademark), Aureo (registered trademark), Iharol (registered trademark), Silwet L-77 (registered trademark), BreakThru (registered trademark), Sundance II (registered trademark), Induce (registered trademark), Penetrator (registered trademark), AgriDex (registered trademark), Lutensol A8 (registered trademark), NP-7 (registered trademark), Triton (registered trademark) , Nufilm (registered trademark), Emulator NP7 (registered trademark), Emulad (registered trademark), TRITON X 45 (registered trademark), AGRAL 90 (registered trademark), AGROTIN (registered trademark), ARPON (registered trademark), EnSpray N ( Recorded trademark), BANOLE (register
- the compound of the present invention is applied as the control agent of the present invention.
- the method of the present invention is not particularly limited as long as the control agent of the present invention can be practically applied, but for example, treatment to plants such as foliage spraying, soil treatment, etc.
- Examples of the treatment include seed treatment such as treatment and seed disinfection.
- the treatment amount of the compound of the present invention depends on the type of plant to be treated, the type and occurrence frequency of plant diseases to be controlled, formulation form, treatment time, treatment method, treatment place, weather conditions, etc.
- the compound of the present invention is usually 1 to 500 g per 1000 m 2 when it is treated on the foliage of the plant or on the soil where the plant is grown.
- Emulsions, wettable powders, flowables and the like are usually treated by diluting with water and spraying.
- the concentration of the compound of the present invention is usually 0.0005 to 2% by weight.
- Powders, granules, etc. are usually processed without dilution.
- the compound of the present invention can be used as a plant disease control agent in agricultural land such as fields, paddy fields, lawns, orchards.
- the compound of the present invention can control diseases of the cultivated land in the cultivated lands where the “plants” and the like listed below are cultivated.
- Agricultural crops corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc., vegetables; solanaceous vegetables (eggplant, tomato, pepper , Peppers, potatoes, etc.), cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), cruciferous vegetables (radish, turnip, horseradish, cold rabi, Chinese cabbage, cabbage, mustard, broccoli, cauliflower -, Etc.), Asteraceae vegetables (burdock, garlic, artichoke, lettuce, etc.), Liliaceae vegetables (green onion, onion, garlic, asparagus), Aceraceae vegetables (carrot, parsley, celery, American redfish, etc.) , Red vegetables (spinach, chard, etc.), perilla vegetables (perilla, mint, basil) ), Strawberry, sweet potato, yam, taro, etc.,
- Trees other than fruit trees Cha, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black bean, peach tree, tsuga, rat, Pine, spruce, yew).
- plants include genetically modified crops.
- Rice blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), idiot seedling (Gibberella fujikuroi), yellow dwarf (Sclerophthora macrospora); wheat powdery mildew (Erysiphe) graminis), red mold (Fusarium graminearum, F. avenaceum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P.
- plague (Phytophthora parasitica, Phytophthora citrophthora); apple monilia (Monilinia) mali), rot (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), spotted leaf disease (Alternaria alternata apple pathotype), black star disease (Venturia inaequalis), anthracnose (Glomerella cingulata), brown spot disease (Diplocarpon mali) Botryosphaeria berengeriana, plague (Phytophtora cactorum); pear black spot (Venturia nashicola, V.
- pirina black spot (Alternaria alternata Japanese pear pathotype), red star disease (Gymnosporangium haraeanum); Disease (Monilinia fructicola), black scab (Cladosporium carpophilum), phomopsis sp.
- Seed disease or early growth of various crops caused by Aspergillus, Penicillium, Fusarium, Gibberella, Tricoderma, Thielaviopsis, Rhizopus, Mucor, Corticium, Phoma, Rhizoctonia, and Diplodia Disease.
- Viral diseases of various crops mediated by Polymixa genus or Olpidium genus.
- Rice seed blight (Burkholderia plantarii); Cucumber spotted bacterial disease (Pseudomonas syringae pv. Lachrymans); Eggplant blight (Ralstonia solanacearum); Citrus scab (Xanthomonas citiri); carotovora) etc.
- room temperature usually indicates 10 to 30 ° C.
- 1 H NMR represents a proton nuclear magnetic resonance spectrum
- tetramethylsilane was used as an internal standard substance
- chemical shift ( ⁇ ) was expressed in ppm.
- Reference production example 2 15.0 g of 1- (2,5-dimethyl-4-hydroxyphenyl) ethanone, 1- ⁇ 2- (bromomethyl) -3-methylphenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one A mixture of 1 g, potassium carbonate 18.1 g, and acetonitrile 125 mL was stirred with heating under reflux for 5 hours. The reaction solution was filtered through Celite (registered trademark), and then the filtrate was concentrated under reduced pressure. Ethyl acetate was added to the residue and washed with saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain 29.0 g of intermediate (6A) shown below.
- Reference production example 4 At room temperature, 2.5 g of 55% sodium hydride and 4.81 g of ethyl acetate were added to 100 mL of tetrahydrofuran, and the mixture was stirred for 0.5 hours. Next, 10.0 g of intermediate (6A), 0.019 g of dibenzo-18-crown-6, and 1.38 g of ethanol were added to the resulting mixture, and the mixture was stirred for 6 hours under heating to reflux. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the intermediate (9A) shown below.
- HA101-1 to HA101-96 can be obtained.
- HA101-1 to HA101-96 (hereinafter referred to as the present compound A) are tetrazolinone compounds shown below [wherein R 1 and R 2 are any one of the following substituent numbers 1 to 96]. ] Is represented. In the following [Substituent No.], c-Pr represents a cyclopropyl group, and CN represents a cyano group. For example, [7; H, CHF 2 ] represents that the substituent number is 7, R 1 is a hydrogen atom, and R 2 is a difluoromethyl group.
- HA101-7 represents a compound having the substituent number 7 in the compound represented by the formula (HA101), and represents a compound represented by the following structure.
- Formulation Example 1 A formulation is obtained by thoroughly pulverizing and mixing 50 parts of any one of the compounds A of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of magnesium lauryl sulfate, and 45 parts of synthetic silicon hydroxide.
- Formulation Example 2 20 parts of any one of the compounds A of the present invention and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol and finely pulverized by a wet pulverization method. Thereafter, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added thereto, and further 10 parts of propylene glycol is added and mixed by stirring to obtain a preparation.
- Formulation Example 3 A formulation is obtained by thoroughly pulverizing and mixing 2 parts of any one of the compounds A of the present invention, 88 parts of kaolin clay and 10 parts of talc.
- Formulation Example 4 A formulation is obtained by thoroughly mixing 5 parts of any one of the compounds A of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.
- Formulation Example 5 2 parts of any one of the compounds A of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are thoroughly pulverized and mixed, and then kneaded with water. The preparation is obtained by combining and granulating and drying.
- Formulation Example 6 20 parts of any one compound of the present compound A; 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (weight ratio 1: 1) and water are mixed to make a total amount of 100 parts, and pulverized The preparation is obtained by processing using a machine.
- test examples are shown.
- the control effect is obtained by visually observing the area of the lesion on the test plant at the time of the survey, and comparing the area of the lesion on the plant treated with the compound of the present invention with the area of the lesion on the untreated plant. evaluated.
- the inhibition rate was determined by measuring the absorbance of the bacteria in the titer plate (96 wells) at a wavelength of 550 nm, treating the value obtained from this absorbance as the growth degree, the growth degree of each well treated with the compound of the present invention, and no treatment. It evaluated by comparing with the growth degree of.
- Test example 1 A plastic pot was filled with soil, and barley (variety: Mikamo Golden) was sown there and allowed to grow in a greenhouse for 7 days.
- the compound 1, 2, or 3 of the present invention formulated according to the method described in Formulation Example 6 was adjusted with water so that the concentration was 500 ppm, and the foliage was sprayed so as to adhere well to the leaf surface of the barley. .
- Test example 2 A plastic pot was filled with soil, rice (cultivar; Nipponbare) was sown therein, and grown in a greenhouse for 20 days. Thereafter, the compound 1, 2, or 3 of the present invention formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration is 500 ppm, and the foliage is sufficiently adhered to the leaf surface of rice. Scattered. After spraying, the plants were air-dried, and the sprayed rice was contacted with rice seedlings (variety: Nihonbare) affected by rice blast fungus (Magnaporthe grisea) under high humidity at 24 ° C in the daytime and 20 ° C at night. After leaving for days, the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test example 3 A plastic pot was stuffed with soil, seeded with green beans (variety; Nagahama peas) and grown in a greenhouse for 8 days.
- the compound 1, 2, or 3 of the present invention formulated according to the method described in Formulation Example 6 was adjusted with water to a concentration of 500 ppm and sprayed on the foliage so as to adhere well to the kidney leaf surface. After spraying, the plants were air-dried, and a mycelia-containing PDA medium of sclerotia sclerotium was placed on the kidney leaf surface. After the inoculation, all kidney beans were placed under high humidity only at night, and the lesion area was examined 4 days after the inoculation. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test example 4 A plastic pot was filled with soil, and wheat (variety: Apogee) was sown therein and grown in a greenhouse for 10 days.
- the compound 1, 2, or 3 of the present invention formulated according to the method described in Formulation Example 6 was adjusted with water to a concentration of 500 ppm, and sprayed on the foliage so as to adhere well to the leaves of the wheat. .
- the plants were air-dried, and after 4 days, sprayed with a water suspension of Septoria tritici spores.
- the plants were placed under high humidity at 18 ° C. for 3 days, then placed under illumination for 14 to 18 days, and then the lesion area was examined.
- the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 5 A plastic pot was filled with soil, and cucumber (variety: Sagamihanjiro) was sown there and allowed to grow in a greenhouse for 12 days.
- the compound 1, 2, or 3 of the present invention formulated according to the method described in Formulation Example 6 was adjusted with water so that the concentration became 500 ppm, and sprayed on the foliage so that it adhered sufficiently to the cucumber leaf surface. After spraying, the plants were air-dried and sprinkled with spore powdery mildew (QoI resistant strain in which the 143rd amino acid residue of cytochrome b was mutated from glycine to alanine among the genes encoding cytochrome b). The plants were cultivated in a greenhouse at 24 ° C. during the day and 20 ° C. during the night for 8 days, and then the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 6 A plastic pot was filled with soil, and wheat (variety: Shirogane) was sown therein and allowed to grow in a greenhouse for 9 days.
- the compound 1, 2, 3, 4, 5, or 6 of the present invention formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, and sufficiently adheres to the leaf surface of the wheat
- the foliage was sprayed like so.
- the plants were air-dried and cultivated at 20 ° C. under illumination for 5 days, and then sprinkled with spores of wheat rust fungus (Puccinia recondita). After inoculation, the plants were placed at 23 ° C. under dark and humid conditions for 1 day, then cultivated at 20 ° C. under illumination for 8 days, and the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 7 A plastic pot was filled with soil, and soybeans (variety: Kurosengoku) were sown therein and grown in a greenhouse for 13 days.
- the compound 1, 2, 3, 4 or 5 of the present invention formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, and is sufficiently adhered to the leaves of the soybean.
- the foliage was sprayed on the ground. After spraying, the plants were air-dried, and after 4 days, spray-inoculated with an aqueous suspension of soybean rust fungus (Phakopsora pachyrhizi). After inoculation, the plants were placed in a humid room at 23 ° C. in the daytime and 20 ° C. at night for one day, and then cultivated in the greenhouse for 14 days. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 8 A plastic pot was filled with soil, and barley (variety: Mikamo Golden) was sown there and allowed to grow in a greenhouse for 7 days.
- the compound 1, 2, 3, 4, 5, or 6 of the present invention formulated according to the method described in Formulation Example 6 is suspended in water to a concentration of 200 ppm, and the resulting solution is used as the barley.
- the foliage was sprayed so as to adhere well to the leaf surface. After spraying, the plants were air-dried, and after 2 days, sprayed with a water suspension of barley cloud spore (Rhynchosporium secalis) spores. After inoculation, the plants were placed under high humidity in a greenhouse at 23 ° C. during the day and 20 ° C. during the night, and then cultivated in the greenhouse for 7 days. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 9 A plastic pot was filled with soil, and cucumber (variety: Sagamihanjiro) was sown there and allowed to grow in a greenhouse for 19 days.
- the present compound 1, 2, 3, 4 or 5 formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, and is sufficiently adhered to the cucumber leaf surface.
- the foliage was sprayed. After spraying, the plants were air-dried, and one day later, sprayed and inoculated with a water suspension of cucumber brown spot fungus (Corynespora cassicola) spores. After inoculation, the plants were cultivated for 7 days under high humidity at 24 ° C in the daytime and 20 ° C at night, and then the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 10 A plastic pot was filled with soil, and cucumber (variety: Sagamihanjiro) was sown there and allowed to grow in a greenhouse for 19 days.
- the compound 1, 2, 3, 4, 5, or 6 of the present invention formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, and adheres sufficiently to the cucumber leaf surface. So that the foliage was sprayed. After spraying, the plants were air-dried, and one day later, sprayed and inoculated with an aqueous suspension of cucumber anthracnose fungus (Colletotrichum lagenarium) spores. After inoculation, it was first placed at 23 ° C.
- the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 11 A plastic pot was filled with soil, and cucumber (variety: Sagamihanjiro) was sown there and allowed to grow in a greenhouse for 19 days.
- the compound 1, 2, or 3 of the present invention formulated according to the method described in Formulation Example 6 was adjusted with water so that the concentration was 200 ppm, and sprayed on the foliage so as to adhere well to the cucumber leaf surface. After spraying, the plants were air-dried, and one day later, a water suspension of Pseudoperonospora cubis zoospores was spray-inoculated. After inoculation, it was first placed at 23 ° C. under high humidity for 1 day, and then cultivated in a greenhouse at 24 ° C. during the day and 20 ° C. during the night, and then the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 12 Soil was packed in a plastic pot, soybean (variety: Tachinagaha) was sown there, and allowed to grow in a greenhouse for 13 days. Thereafter, an aqueous suspension of Cercospora sojina spores was spray-inoculated, and after inoculation, the plants were placed in a 23 ° C. greenhouse under high humidity for 4 days. 5 days after inoculation, the present compound 1, 2, 3, 4, 5, or 6 formulated according to the method described in Formulation Example 6 was adjusted with water so that the concentration became 200 ppm, and the soybean leaves The foliage was sprayed so as to adhere well to the surface. After spraying, the plants were air-dried and cultivated in a greenhouse for 14 days, and then the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 13 A plastic pot was filled with soil, and cucumber (variety: Sagamihanjiro) was sown there and allowed to grow in a greenhouse for 14 days.
- the compound 1 or 2 of the present invention formulated according to the method described in Formulation Example 6 was adjusted with water so as to contain 0.25 mg / mL, and the root of the cucumber seedling was attached to the obtained liquid.
- a mycelia-containing PDA medium of sclerotia sclerotia was placed on the cucumber leaf surface. After inoculation, all cucumbers were placed under high humidity only at night, and the lesion area was examined 4 days after inoculation. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 14 The compound 1, 2, 3, 4, 5 or 6 of the present invention is diluted with dimethyl sulfoxide so as to contain 150 ppm, and 1 ⁇ L is dispensed into a titer plate (96-well), and then a tomato leaf mold fungus (Cladosporium fulvum, cytochrome) is prepared in advance.
- a tomato leaf mold fungus (Cladosporium fulvum, cytochrome) is prepared in advance.
- 150 ⁇ L of a potato broth liquid medium (PDB medium) inoculated with spores of a QoI resistant strain in which the 129th amino acid residue of cytochrome b was mutated from phenylalanine to leucine was dispensed. After culturing the plate at 18 ° C.
- Test Example 15 A plastic pot was filled with soil, and barley (variety: Mikamo Golden) was sown there and allowed to grow in a greenhouse for 7 days.
- the compound 1, 2, 3, 4, 5 or 6 of the present invention formulated according to the method described in Formulation Example 6 is adjusted with water to a concentration of 200 ppm, and adheres sufficiently to the leaf surface of the barley. So that the foliage was sprayed. After spraying, the plants were air-dried, and two days later, an aqueous suspension of barley net spore fungus (Pyrenophora teres) spores was spray-inoculated. After inoculation, the plants were placed under high humidity in a greenhouse at 23 ° C. during the day and 20 ° C. during the night, and then cultivated in the greenhouse for 7 days. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 16 A plastic pot was filled with soil, rice (cultivar; Nipponbare) was sown therein, and grown in a greenhouse for 20 days. Thereafter, the present compound 1, 2, 3, 4, 5, or 6 formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, The foliage was sprayed to ensure sufficient adhesion. After spraying, the plants were air-dried, and the sprayed rice was contacted with rice seedlings (variety: Nihonbare) affected by rice blast fungus (Magnaporthe grisea) under high humidity at 24 ° C in the daytime and 20 ° C at night. After leaving for days, the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 17 A plastic pot was stuffed with soil, seeded with green beans (variety; Nagahama peas) and grown in a greenhouse for 8 days.
- the present compound 1, 2, 3, 4 or 5 formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, and is sufficiently adhered to the kidney leaf surface.
- the foliage was sprayed. After spraying, the plants were air-dried, and a mycelia-containing PDA medium of sclerotia sclerotium was placed on the kidney leaf surface. After the inoculation, all kidney beans were placed under high humidity only at night, and the lesion area was examined 4 days after the inoculation. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 18 A plastic pot was filled with soil, and wheat (variety: Apogee) was sown therein and grown in a greenhouse for 10 days.
- the compound 1, 2, 3, 4, 5, or 6 of the present invention formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, and sufficiently adheres to the leaf surface of the wheat
- the foliage was sprayed like so.
- the plants were air-dried, and after 4 days, sprayed with a water suspension of Septoria tritici spores.
- the plants were placed under high humidity at 18 ° C. for 3 days, then placed under illumination for 14 to 18 days, and then the lesion area was examined.
- the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- Test Example 19 A plastic pot was filled with soil, and cucumber (variety: Sagamihanjiro) was sown there and allowed to grow in a greenhouse for 12 days.
- the compound 1, 2, 3, 4, 5, or 6 of the present invention formulated according to the method described in Formulation Example 6 is adjusted with water so that the concentration becomes 200 ppm, and adheres sufficiently to the cucumber leaf surface. So that the foliage was sprayed. After spraying, the plants were air-dried and sprinkled with spore powdery mildew (QoI resistant strain in which the 143rd amino acid residue of cytochrome b was mutated from glycine to alanine among the genes encoding cytochrome b). The plants were cultivated in a greenhouse at 24 ° C. during the day and 20 ° C. during the night for 8 days, and then the lesion area was examined. As a result, the lesion area in the plant treated with the compound of the present invention was 30% or less of the lesion area in the untreated plant.
- the compound of the present invention has a controlling effect against plant diseases and is useful as an active ingredient of a plant disease controlling agent.
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Abstract
Description
すなわち、本発明は以下のとおりである。
〔1〕 式(I)
〔式中、R1は、水素原子、1以上のハロゲン原子を有していてもよいC1-C3アルキル基、1以上のハロゲン原子を有していてもよいC1-C3アルコキシ基、ハロゲン原子、シアノ基、又は1以上のハロゲン原子を有していてもよいC1-C3アルキルチオ基を表し;
R2は、1以上のハロゲン原子を有していてもよいC1-C3アルキル基、1以上のハロゲン原子を有していてもよいC1-C3アルコキシ基、水素原子、ハロゲン原子、又は1以上のハロゲン原子を有していてもよいC3-C4シクロアルキル基を表す。〕
で示されるテトラゾリノン化合物(以下、本発明化合物と記す)。
〔2〕 R1が、水素原子、又は1以上のハロゲン原子を有していてもよいC1-C3アルキル基である、〔1〕に記載のテトラゾリノン化合物。
〔3〕 〔1〕に記載のテトラゾリノン化合物を含有する植物病害防除剤(以下、本発明防除剤とも記す)。
〔4〕 〔1〕に記載のテトラゾリノン化合物の有効量を植物又は土壌に処理することによる、植物病害の防除方法。
〔5〕 植物病害を防除するための〔1〕に記載のテトラゾリノン化合物の使用。
本明細書において、
「1以上のハロゲン原子を有していてもよい」とは、2以上のハロゲン原子を有する場合、それらのハロゲン原子は互いに同一でも異なっていてもよいことを意味する。
本明細書において、例えば「C1-C3」とは、炭素原子数が1乃至3であることを意味する。
本発明化合物において、R1が水素原子又はメチル基であるテトラゾリノン化合物。
本発明化合物において、R1が水素原子又はC1-C3アルキル基であるテトラゾリノン化合物。
本発明化合物において、R1が水素原子又は1以上のハロゲン原子を有していてもよいC1-C3アルキル基であるテトラゾリノン化合物。
本発明化合物において、R2がメチル基であるテトラゾリノン化合物。
本発明化合物において、R2がメトキシ基であるテトラゾリノン化合物。
本発明化合物において、R2がメチル基又はメトキシ基であるテトラゾリノン化合物。
本発明化合物において、R2がC1-C3アルキル基又はC1-C3アルコキシ基であるテトラゾリノン化合物。
本発明化合物において、R2が1以上のハロゲン原子を有していてもよいC1-C3アルキル基又は1以上のハロゲン原子を有していてもよいC1-C3アルコキシ基であるテトラゾリノン化合物。
本発明化合物において、R1が水素原子又はC1-C3アルキル基であり、R2がC1-C3アルキル基又はC1-C3アルコキシ基であるテトラゾリノン化合物。
本発明化合物において、R1がメチル基であり、R2がメチル基又はメトキシ基であるテトラゾリノン化合物。
本発明化合物において、R1が水素原子又はメチル基であり、R2がメチル基であるテトラゾリノン化合物。
本発明化合物において、R1が水素原子又はメチル基であり、R2がメトキシ基であるテトラゾリノン化合物。
本発明化合物において、R1が水素原子又はメチル基であり、R2がメチル基、メトキシ基、水素原子、塩素原子、又はシクロプロピル基であるテトラゾリノン化合物。
本発明化合物は、式(A1)で示される化合物(以下、化合物(A1)と記す。)と式(A2)で示される化合物(以下、化合物(A2)と記す。)とを銅化合物及び塩基の存在下で反応させることにより製造することができる。
〔式中、X11はジヒドロキシボラニル基、ジアルコキシボラニル基又は4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン-2-イル基を表し、その他の記号は前記と同じ意味を表す。〕
該反応は、通常溶媒中で行われる。
該反応に用いられる溶媒としては、例えば、n-ヘキサン、シクロヘキサン、トルエン、キシレン等の炭化水素類(以下、炭化水素類と記す。)、ジエチルエーテル、テトラヒドロフラン、1,4-ジオキサン、エチレングリコ-ルジメチルエ-テル、メチルtert-ブチルエーテル、ジイソプロピルエーテル等のエーテル類(以下、エーテル類と記す。)、クロロホルム、ジクロロメタン、クロロベンゼン等のハロゲン化炭化水素類(以下、ハロゲン化炭化水素類と記す。)、ジメチルホルムアミド、1,3-ジメチル-2-イミダゾリジノン、N-メチルピロリドン等の酸アミド類(以下、酸アミド類と記す。)、酢酸エチル、酢酸メチル等のエステル類(以下、エステル類と記す。)、ジメチルスルホキシド等のスルホキシド類(以下、スルホキシド類と記す。)、アセトニトリル、プロピオニトリル等のニトリル類(以下、ニトリル類と記す。)、メタノール、エタノール、プロパノール、ブタノール等のアルコール類(以下、アルコール類と記す。)、水及びこれらの混合物等が挙げられる。
該反応に用いられる銅化合物としては例えば、酢酸銅(II)等が挙げられる。
該反応に用いられる塩基としては例えば、トリエチルアミン、ピリジン、2,2’-ビピリジン、ジアザビシクロウンデセン等の有機塩基類(以下、有機塩基類と記す。)、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等の炭酸塩が挙げられる。
該反応は通常化合物(A1)1モルに対して、化合物(A2)が1~10モルの割合で、銅化合物が1~10モルの割合で、塩基が1~10モルの割合で用いられる。
該反応は、必要に応じてモレキュラーシーブス等の脱水剤を用いることができ、化合物(A1)1モルに対して、100~500質量パーセントの割合で用いられる。
該反応の反応温度は通常-20~150℃の範囲である。該反応の反応時間は通常0.1~120時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより本発明化合物を単離することができる。
化合物(A1)および化合物(A2)は、公知であるか、公知の方法に準じて製造することができる。
本発明化合物は、式(A3)で示される化合物(以下、化合物(A3)と記す。)と式(A4)で示される化合物(以下、化合物(A4)と記す。)とを塩基の存在下で反応させることにより製造することができる。
〔式中、X12は塩素原子、臭素原子、ヨウ素原子、メタンスルホニルオキシ基またはp-トルエンスルホニルオキシ基を表し、その他の記号は前記と同じ意味を表す。〕
該反応は公知の方法に準じて製造することができる。
式(B2)で示される化合物(以下、化合物(B2)と記す。)は式(B1)で示される化合物(以下、化合物(B1)と記す。)と化合物(A2)とを銅化合物及び塩基の存在下で反応させることにより製造することができる。
〔式中、X13はC1-C5アルキル基を表し、その他の記号は前記と同じ意味を表す。〕
該反応は製造法Aに記載の方法に準じて実施することができる。
化合物(B1)は公知であるか、公知の方法に準じて製造することができる。
化合物(A3)は化合物(B2)と酸とを反応させることにより製造することができる。
〔式中、記号は前記と同じ意味を表す。〕
前記反応は、酸などを使用して、WO2014/051165に記載の方法に準じて実施することができる。
液体担体としては、例えば、水、アルコ-ル類、ケトン類(例えば、アセトン、メチルエチルケトン、シクロヘキサノン)、芳香族炭化水素類(例えば、ベンゼン、トルエン、キシレン、エチルベンゼン、メチルナフタレン)、脂肪族炭化水素類(例えば、n-ヘキサン、灯油)、エステル類、ニトリル類、エ-テル類、酸アミド類、ハロゲン化炭化水素類が挙げられる。
本発明の防除方法における、本発明化合物の処理量は、処理する植物の種類、防除対象である植物病害の種類や発生頻度、製剤形態、処理時期、処理方法、処理場所、気象条件等によっても異なるが、植物の茎葉に処理する場合又は植物を栽培する土壌に処理する場合は、本発明化合物は、1000m2あたり、通常1~500gである。
乳剤、水和剤、フロアブル剤等は通常水で希釈して散布することにより処理する。この場合、本発明化合物の濃度は、通常0.0005~2重量%である。粉剤、粒剤等は通常希釈することなくそのまま処理する。
果樹;仁果類(リンゴ、セイヨウナシ、ニホンナシ、カリン、マルメロ等)、核果類(モモ、スモモ、ネクタリン、ウメ、オウトウ、アンズ、プル-ン等)、カンキツ類(ウンシュウミカン、オレンジ、レモン、ライム、グレ-プフル-ツ等)、堅果類(クリ、クルミ、ハシバミ、ア-モンド、ピスタチオ、カシュ-ナッツ、マカダミアナッツ等)、液果類(ブル-ベリ-、クランベリ-、ブラックベリ-、ラズベリ-等)、ブドウ、カキ、オリ-ブ、ビワ、バナナ、コ-ヒ-、ナツメヤシ、ココヤシ等、
果樹以外の樹;チャ、クワ、花木、街路樹(トネリコ、カバノキ、ハナミズキ、ユ-カリ、イチョウ、ライラック、カエデ、カシ、ポプラ、ハナズオウ、フウ、プラタナス、ケヤキ、クロベ、モミノキ、ツガ、ネズ、マツ、トウヒ、イチイ)等。
Aspergillus属、Penicillium属、Fusarium属、Gibberella属、Tricoderma属、Thielaviopsis属、Rhizopus属、Mucor属、Corticium属、Phoma属、Rhizoctonia属、及びDiplodia属菌等によって引き起こされる、各種作物の種子病害又は生育初期の病害。Polymixa属又はOlpidium属等によって媒介される各種作物のウイルス病。
イネの苗立枯細菌病(Burkholderia plantarii);キュウリの斑点細菌病(Pseudomonas syringae pv. Lachrymans);ナスの青枯病(Ralstonia solanacearum)、カンキツのかいよう病(Xanthomonas citiri);ハクサイの軟腐病(Erwinia carotovora)等。
本明細書において、室温とは通常10~30℃を示す。1H NMRとはプロトン核磁気共鳴スペクトルを示し、内部標準物質としてテトラメチルシランを用い、ケミカルシフト(δ)をppmで表記した。
参考製造例1に記載の中間体(1A)0.49g、シクロプロピルボロン酸0.31g、酢酸銅(II)0.26g、ピリジン0.38g、モレキュラーシーブ4A0.63g及びアセトニトリル20mlの混合物を9時間加熱還流した。反応液をセライト(登録商標)でろ過した後、ろ液を減圧濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付し、下記で示される本発明化合物1を0.33g得た。
式(a)
で示される化合物において、R1及びR2が[表1]で示される化合物。
なお、本発明化合物1とは、式(a)で示される化合物において、R1及びR2が[表1]の本発明化合物1に記載の組み合わせの化合物を表す。
本発明化合物1:
1H-NMR (CDCl3) δ: 7.52-7.41 (3H, m), 7.09-7.06 (2H, m), 6.74 (1H, s), 6.27 (1H, d, J = 2.3 Hz), 5.26 (2H, s), 3.93 (3H, s), 3.64-3.60 (1H, m), 3.59 (3H, s), 2.39 (3H, s), 1.97 (3H, s), 1.17-1.13 (2H, m), 1.04-0.99 (2H, m).
本発明化合物2:
1H-NMR (CDCl3) δ: 7.44 (1H, d, J = 2.3 Hz), 7.42-7.38 (2H, m), 7.31 (1H, s), 7.28 (1H, d, J = 2.5 Hz), 6.69 (1H, s), 6.28 (1H, d, J = 2.3 Hz), 5.04 (2H, s), 3.64 (3H, s), 3.64-3.59 (1H, m), 2.51 (3H, s), 2.41 (3H, s), 2.06 (3H, s), 1.17-1.14 (2H, m), 1.04-1.01 (2H, m).
本発明化合物3:
1H-NMR (CDCl3) δ: 7.43-7.38 (2H, m), 7.29-7.26 (2H, m), 6.67 (1H, s), 6.08 (1H, s), 5.03 (2H, s), 3.64 (3H, s), 3.38-3.32 (1H, m), 2.50 (3H, s), 2.40 (3H, s), 2.39 (3H, s), 2.05 (3H, s), 1.23-1.19 (2H, m), 1.06-1.01 (2H, m).
参考製造例6に記載の中間体(11A)0.06g、1-{2-(ブロモメチル)フェニル}-4-メチル-1,4-ジヒドロテトラゾール-5-オン0.08g、炭酸カリウム0.04g、及びアセトニトリル125mLの混合物を加熱還流下5時間攪拌した。得られた残渣をシリカゲルカラムクロマトグラフィーに付し、下記で示される本発明化合物4を0.08g得た。
式(a)で示される化合物において、R1及びR2が[表2]で示される化合物。
本発明化合物4:
1H-NMR (CDCl3) δ: 7.72 (1H, d, J = 7.7 Hz), 7.55-7.47 (3H, m), 7.44 (1H, s), 7.34 (1H, s), 6.66 (1H, s), 6.29-6.28 (1H, m), 5.16 (2H, s), 3.68 (3H, s), 3.65-3.59 (1H, m), 2.39 (3H, s), 2.16 (3H, s), 1.18-1.14 (2H, m), 1.04-0.99 (2H, m).
本発明化合物5
1H-NMR (CDCl3) δ: 7.61 (1H, dd, J = 8.2, 1.4 Hz), 7.48-7.39 (3H, m), 7.30 (1H, s), 6.71 (1H, s), 6.28 (1H, d, J = 2.3 Hz), 5.32 (2H, s), 3.64-3.59 (1H, m), 3.61 (3H, s), 2.41 (3H, s), 2.00 (3H, s), 1.18-1.14 (2H, m), 1.04-0.99 (2H, m).
本発明化合物6
1H-NMR (CDCl3) δ: 7.45-7.41 (2H, m), 7.31 (1H, s), 7.27-7.25 (2H, m), 6.73 (1H, s), 6.29 (1H, d, J = 2.3 Hz), 5.26 (2H, s), 3.67-3.59 (1H, m), 3.63 (3H, s), 2.42 (3H, s), 2.15-2.11 (1H, m), 2.05 (3H, s), 1.18-1.14 (2H, m), 1.05-0.97 (4H, m), 0.78-0.74 (2H, m).
参考製造例3に記載の中間体(8A)、エタノール40mL、ヒドラジン一水和物8.5mLを加えて終夜撹拌し再び反応液を減圧下濃縮し、ヘキサン及びtert-ブチルメチルエーテルで洗浄し、下記で示される中間体(2A)16.2gを得た。
中間体(1A):
1H-NMR (CDCl3)δ: 7.60 (1H, d, J = 2.0 Hz), 7.47 (1H, t, J = 8.2 Hz), 7.13-7.06 (3H, m), 6.78 (1H, s), 6.35 (1H, d, J = 2.0 Hz), 5.29 (2H, s), 3.95 (3H, s), 3.61 (3H, s), 2.36 (3H, s), 1.98 (3H, s).
中間体(2A):
1H NMR (CDCl3)δ: 7.62 (1H, d, J = 2.0 Hz), 7.43 (2H, m), 7.29 (1H, m), 7.19 (1H, s), 6.73 (1H, s), 6.37 (1H, d, J = 1.8 Hz), 5.06 (2H, s), 3.65 (3H, s), 2.52 (3H, s), 2.39 (3H, s), 2.08 (3H, s).
中間体(3A):
1H NMR (CDCl3)δ: 7.45-7.40 (3H, m), 7.30-7.27 (1H, m), 7.17 (1H, bs), 6.71 (1H, s), 6.13 (1H, s), 5.05 (2H, s), 3.65 (3H, s), 2.52 (3H, s), 2.38 (3H, s), 2.35 (3H, s), 2.07 (3H, s).
1H-NMR (CDCl3) δ: 7.60 (1H, s), 7.21 (1H, s), 6.72 (1H, s), 6.36 (1H, d, J = 1.2 Hz), 3.86 (3H, s), 2.40 (3H, s), 2.20 (3H, s).
1-(2,5-ジメチル-4-ヒドロキシフェニル)エタノン15.0g、1-{2-(ブロモメチル)-3-メチルフェニル}-4-メチル-1,4-ジヒドロテトラゾール-5-オン25.1g、炭酸カリウム18.1g、及びアセトニトリル125mLの混合物を加熱還流下5時間攪拌した。反応液をセライト(登録商標)でろ過した後、ろ液を減圧濃縮した。残さに酢酸エチルを加え、飽和炭酸水素ナトリウム水溶液で洗浄した。有機層を無水硫酸マグネシウムで乾燥した後、減圧下濃縮し、下記で示される中間体(6A)29.0gを得た。
中間体(5A):
1H-NMR (CDCl3) δ: 7.50-7.46 (2H, m), 7.11-7.06 (2H, m), 6.73 (1H, s), 5.32 (2H, s), 3.95 (3H, s), 3.62 (3H, s), 2.52 (3H, s), 2.51 (3H, s), 1.98 (3H, s).
中間体(6A):
1H-NMR (CDCl3) δ: 7.53 (1H, s), 7.46-7.40 (2H, m), 7.28 (1H, dd, J = 7.2, 2.3 Hz), 6.66 (1H, s), 5.08 (2H, s), 3.64 (3H, s), 2.55 (3H, s), 2.53 (3H, s), 2.50 (3H, s), 2.09 (3H, s).
中間体(5A)10g、及びN,N-ジメチルホルムアミドジエチルアセタール14mLの混合物を24時間加熱還流し、反応液を減圧下濃縮し、下記で示される中間体(7A)を得た。
中間体(7A):
1H-NMR (CDCl3)δ: 7.47 (1H, t, J = 8.3 Hz), 7.41 (1H, s), 7.11-7.05 (3H, m), 6.69 (1H, s), 5.34 (1H, d, J = 12.7 Hz), 5.27 (2H, s), 3.94 (3H, s), 3.61 (3H, s), 3.06 (3H, bs), 2.89 (3H, bs), 2.37 (3H, s), 2.21 (3H, s).
中間体(8A):
1H-NMR (CDCl3)δ: 7.46-7.40 (3H, m), 7.27 (1H, dd, J = 6.7, 2.6 Hz), 7.14 (1H, s), 6.64 (1H, s), 5.35 (1H, d, J = 12.7 Hz), 5.04 (2H, s), 3.65 (3H, s), 3.08 (3H, bs),2.88 (3H, bs), 2.51 (3H, s), 2.39 (3H, s), 1.88 (3H, s).
室温下、テトラヒドロフラン100mLに、55%水素化ナトリウム2.5g、及び酢酸エチル4.81gを加え、0.5時間攪拌した。次に、得られた混合物に、中間体(6A)10.0g、ジベンゾ-18-クラウン-6を0.019g、及びエタノール1.38gを加え、加熱還流下6時間攪拌した。反応混合物に水を加え、酢酸エチルで抽出し、有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した後、減圧下濃縮し、下記で示される中間体(9A)を得た。
中間体(9A)
1H-NMR (CDCl3) δ: 7.47-7.40 (3H, m), 7.29 (1H, s), 6.66 (1H, s), 5.84 (1H, s), 5.07 (2H, s), 3.64 (3H, s), 2.50 (3H, s), 2.50 (3H, s), 2.15 (3H, s), 2.06 (3H, s).
中間体(1A)の代わりに中間体(4A)を用い、製造例1に記載の方法に準じて、下記で示される中間体(10A)を得た。
中間体(10A)
1H-NMR (CDCl3) δ: 7.44 (1H, d, J = 2.3 Hz), 7.34 (1H, s), 6.68 (1H, s), 6.29 (1H, d, J = 2.3 Hz), 3.84 (3H, s), 3.65-3.60 (1H, m), 2.43 (3H, s), 2.20 (3H, s), 1.19-1.15 (2H, m), 1.05-1.00 (2H, m).
中間体(10A)2.00g、臭化水素酸14mL及び酢酸14mlの混合物を9時間加熱還流した。反応液を減圧下濃縮した。反応混合物に水を加え、酢酸エチルで抽出した。得られた残渣をヘキサンで洗浄し、下記で示される中間体(11A)を0.54g得た。
中間体(11A)
1H-NMR (DMSO-D6) δ: 9.22 (1H, s), 7.74 (1H, d, J = 2.3 Hz), 7.21 (1H, s), 6.62 (1H, s), 6.33 (1H, d, J = 2.3 Hz), 3.73-3.68 (1H, m), 2.29 (3H, s), 2.09 (3H, s), 1.07-1.03 (2H, m), 0.97-0.92 (2H, m).
HA101-1~HA101-96(以下、本発明化合物Aと記す)は、下記で示されるテトラゾリノン化合物〔式中、R1及びR2は、下記の置換基番号1~96のいずれか表す。〕を表す。下記の[置換基番号]において、c-Prとはシクロプロピル基を表し、CNとはシアノ基を表す。例えば[7;H,CHF2]とは置換基番号が7であり、R1が水素原子であり、R2がジフルオロメチル基であることを表す。
[1;H,H]、[2;F,H]、[3;Cl,H]、[4;CN,H]、[5;CH3,H]、[6;CH2CH3,H]、[7;CHF2,H]、[8;CF3,H]、[9;OCH3,H]、[10;OCH2CH3,H]、[11;SCH3,H]、[12;SCHF2,H]、[13;H,Cl]、[14;F,Cl]、[15;Cl,Cl]、[16;CN,Cl]、[17;CH3,Cl]、[18;CH2CH3,Cl]、[19;CHF2,Cl]、[20;CF3,Cl]、[21;OCH3,Cl]、[22;OCH2CH3,Cl]、[23;SCH3,Cl]、[24;SCHF2,Cl]、[25;H,CH3]、[26;F,CH3]、[27;Cl,CH3]、[28;CN,CH3]、[29;CH3,CH3]、[30;CH2CH3,CH3]、[31;CHF2,CH3]、[32;CF3,CH3]、[33;OCH3,CH3]、[34;OCH2CH3,CH3]、[35;SCH3,CH3]、[36;SCHF2,CH3]、[37;H,CH2CH3]、[38;F,CH2CH3]、[39;Cl,CH2CH3]、[40;CN,CH2CH3]、[41;CH3,CH2CH3]、[42;CH2CH3,CH2CH3]、[43;CHF2,CH2CH3]、[44;CF3,CH2CH3]、[45;OCH3,CH2CH3]、[46;OCH2CH3,CH2CH3]、[47;SCH3,CH2CH3]、[48;SCHF2,CH2CH3]、[49;H,CHF2]、[50;F,CHF2]、[51;Cl,CHF2]、[52;CN,CHF2]、[53;CH3,CHF2]、[54;CH2CH3,CHF2]、[55;CHF2,CHF2]、[56;CF3,CHF2]、[57;OCH3,CHF2]、[58;OCH2CH3,CHF2]、[59;SCH3,CHF2]、[60;SCHF2,CHF2]、[61;H,c-Pr]、[62;F,c-Pr]、[63;Cl,c-Pr]、[64;CN,c-Pr]、[65;CH3,c-Pr]、[66;CH2CH3,c-Pr]、[67;CHF2,c-Pr]、[68;CF3,c-Pr]、[69;OCH3,c-Pr]、[70;OCH2CH3,c-Pr]、[71;SCH3,c-Pr]、[72;SCHF2,c-Pr]、[73;H,OCH3]、[74;F,OCH3]、[75;Cl,OCH3]、[76;CN,OCH3]、[77;CH3,OCH3]、[78;CH2CH3,OCH3]、[79;CHF2,OCH3]、[80;CF3,OCH3]、[81;OCH3,OCH3]、[82;OCH2CH3,OCH3]、[83;SCH3,OCH3]、[84;SCHF2,OCH3]、[85;H,OCH2CH3]、[86;F,OCH2CH3]、[87;Cl,OCH2CH3]、[88;CN,OCH2CH3]、[89;CH3,OCH2CH3]、[90;CH2CH3,OCH2CH3]、[91;CHF2,OCH2CH3]、[92;CF3,OCH2CH3]、[93;OCH3,OCH2CH3]、[94;OCH2CH3,OCH2CH3]、[95;SCH3,OCH2CH3]、[96;SCHF2,OCH2CH3]
防除効果は、調査時の供試植物上の病斑の面積を目視観察し、本発明化合物を処理した植物の病斑の面積と、無処理の植物の病斑の面積とを比較することにより評価した。
また阻害率は、550nm波長でタイタープレート(96ウェル)内菌の吸光度を測定し、この吸光度から得られた値を生育度として扱い、本発明化合物を処理した各ウェルの生育度と、無処理の生育度とを比較することにより評価した。
プラスチックポットに土壌を詰め、そこにオオムギ(品種;ミカモゴールデン)を播種し、温室で7日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2又は3を、濃度が500ppmとなるように水で調整し、上記オオムギの葉面に充分付着するように茎葉散布した。散布後植物を風乾し、2日後にオオムギ網斑病菌(Pyrenophora teres)胞子の水懸濁液を噴霧接種した。接種後植物を昼間23℃、夜間20℃の温室内で多湿下に3日間置き、次に温室内で7日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにイネ(品種;日本晴)を播種し、温室内で20日間生育させた。その後、製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、又は3を濃度が500ppmとなるように水で調整し、上記イネの葉面に充分付着するように茎葉散布した。散布後、植物を風乾し、昼間24℃、夜間20℃多湿下で、前記散布処理をしたイネと、イネいもち病菌(Magnaporthe grisea)に罹病したイネ苗(品種;日本晴)とを接触させながら6日間置いた後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、インゲン(品種;長鶉菜豆)を播種し、温室内で8日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、又は3を濃度が500ppmとなるように水で調整し、上記インゲン葉面に充分付着するように茎葉散布した。散布後植物を風乾し、インゲン菌核病菌(Sclerotinia sclerotiorum)の菌糸含有PDA培地をインゲン葉面上に置いた。接種後全てのインゲンは夜間のみ多湿下におき、接種4日後に病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにコムギ(品種;アポジ-)を播種し、温室内で10日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、又は3を濃度が500ppmとなるように水で調整し、上記コムギの葉面に充分付着するように茎葉散布した。散布後植物を風乾し、4日後にコムギ葉枯病菌(Septoria tritici)胞子の水懸濁液を噴霧接種した。接種後植物を18℃多湿下に3日間置き、次に照明下に14日から18日間置いた後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにキュウリ(品種;相模半白)を播種し、温室内で12日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、又は3を濃度が500ppmとなるように水で調整し、上記キュウリ葉面に充分付着するように茎葉散布した。散布後植物を風乾し、キュウリうどんこ病菌(Sphaerotheca fuliginea、チトクロームbをコードする遺伝子のうち、チトクロームbの143番目のアミノ酸残基がグリシンからアラニンに変異したQoI耐性株)胞子をふりかけ接種した。植物を昼間24℃、夜間20℃の温室で8日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにコムギ(品種;シロガネ)を播種し、温室内で9日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5、又は6を濃度が200ppmとなるように水で調整し、上記コムギの葉面に充分付着するように茎葉散布した。散布後植物を風乾し、20℃、照明下で5日間栽培した後、コムギのさび病菌(Puccinia recondita)の胞子をふりかけ接種した。接種後植物を23℃、暗黒多湿下に1日間置いた後、20℃、照明下で8日間栽培し、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにダイズ(品種;黒千石)を播種し、温室内で13日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、又は5を濃度が200ppmとなるように水で調整し、上記ダイズの葉面に充分付着するように茎葉散布した。散布後植物を風乾し、4日後にダイズさび病菌(Phakopsora pachyrhizi)胞子の水懸濁液を噴霧接種した。接種後植物を昼間23℃、夜間20℃の温室内で多湿下に1日間置き、次に温室内で14日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにオオムギ(品種;ミカモゴールデン)を播種し、温室で7日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5、又は6を濃度が200ppmとなるように水で懸濁し、得られた液を、上記オオムギの葉面に充分付着するように茎葉散布した。散布後植物を風乾し、2日後にオオムギ雲形病菌(Rhynchosporium secalis)胞子の水懸濁液を噴霧接種した。接種後植物を昼間23℃、夜間20℃の温室内で多湿下に3日間置き、次に温室内で7日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにキュウリ(品種;相模半白)を播種し、温室内で19日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、又は5を濃度が200ppmとなるように水で調整し、上記キュウリ葉面に充分付着するように茎葉散布した。散布後植物を風乾し、1日後にキュウリ褐斑病菌(Corynespora cassiicola)胞子の水懸濁液を噴霧接種した。接種後は昼間24℃、夜間20℃の多湿下で7日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにキュウリ(品種;相模半白)を播種し、温室内で19日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5、又は6を濃度が200ppmとなるように水で調整し、上記キュウリ葉面に充分付着するように茎葉散布した。散布後植物を風乾し、1日後にキュウリ炭そ病菌(Colletotrichum lagenarium)胞子の水懸濁液を噴霧接種した。接種後はじめは23℃、多湿下に1日間置き、続いて昼間24℃、夜間20℃の温室で6日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにキュウリ(品種;相模半白)を播種し、温室内で19日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、又は3を濃度が200ppmとなるように水で調整し、上記キュウリ葉面に充分付着するように茎葉散布した。散布後植物を風乾し、1日後にキュウリべと病菌(Pseudoperonospora cubensis)遊走子の水懸濁液を噴霧接種した。接種後はじめは23℃、多湿下に1日間置き、続いて昼間24℃、夜間20℃の温室で6日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにダイズ(品種;タチナガハ)を播種し、温室内で13日間生育させた。その後ダイズ斑点病菌(Cercospora sojina)胞子の水懸濁液を噴霧接種し、接種後植物を23℃の温室内で多湿下に4日間置いた。接種5日後に製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5、又は6を濃度が200ppmとなるように水で調整し、上記ダイズの葉面に充分付着するように茎葉散布した。散布後植物を風乾し温室内で14日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにキュウリ(品種;相模半白)を播種し、温室内で14日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1又は2を0.25mg/mL含有するように水で調整し、得られた液中にキュウリ苗の根部をつけた。8日後にキュウリ菌核病菌(Sclerotinia sclerotiorum)の菌糸含有PDA培地をキュウリ葉面上に置いた。接種後全てのキュウリは夜間のみ多湿下におき、接種4日後に病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
本発明化合物1、2、3、4、5、又は6を150ppm含有するようにジメチルスルホキシドで希釈し、タイタープレート(96ウェル)に1μL分注したのち、あらかじめトマト葉かび病菌(Cladosporium fulvum、チトクロームbをコードする遺伝子のうち、チトクロームbの129番目のアミノ酸残基がフェニルアラニンからロイシンに変異したQoI耐性株)の胞子を接種したジャガイモ煎汁液体培地(PDB培地)を150μL分注した。このプレートを6日間、18℃で培養しトマト葉かび病菌を増殖させたのち、タイタープレートの各ウェルの550nmの吸光度を測定し、この吸光度から得られた値をトマト葉かび病菌の生育度として計算した。その生育度をもとに次式により阻害率を求めた。
阻害率=100×(A-B)/A
A:無処理区の菌の生育度
B:処理区の菌の生育度
その結果、本発明化合物を処理した各ウェルの阻害率はいずれも80%以上であった。
プラスチックポットに土壌を詰め、そこにオオムギ(品種;ミカモゴールデン)を播種し、温室で7日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5又は6を濃度が200ppmとなるように水で調整し、上記オオムギの葉面に充分付着するように茎葉散布した。散布後植物を風乾し、2日後にオオムギ網斑病菌(Pyrenophora teres)胞子の水懸濁液を噴霧接種した。接種後植物を昼間23℃、夜間20℃の温室内で多湿下に3日間置き、次に温室内で7日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにイネ(品種;日本晴)を播種し、温室内で20日間生育させた。その後、製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5、又は6を濃度が200ppmとなるように水で調整し、上記イネの葉面に充分付着するように茎葉散布した。散布後、植物を風乾し、昼間24℃、夜間20℃多湿下で、前記散布処理をしたイネと、イネいもち病菌(Magnaporthe grisea)に罹病したイネ苗(品種;日本晴)とを接触させながら6日間置いた後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、インゲン(品種;長鶉菜豆)を播種し、温室内で8日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、又は5を濃度が200ppmとなるように水で調整し、上記インゲン葉面に充分付着するように茎葉散布した。散布後植物を風乾し、インゲン菌核病菌(Sclerotinia sclerotiorum)の菌糸含有PDA培地をインゲン葉面上に置いた。接種後全てのインゲンは夜間のみ多湿下におき、接種4日後に病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにコムギ(品種;アポジ-)を播種し、温室内で10日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5、又は6を濃度が200ppmとなるように水で調整し、上記コムギの葉面に充分付着するように茎葉散布した。散布後植物を風乾し、4日後にコムギ葉枯病菌(Septoria tritici)胞子の水懸濁液を噴霧接種した。接種後植物を18℃多湿下に3日間置き、次に照明下に14日から18日間置いた後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
プラスチックポットに土壌を詰め、そこにキュウリ(品種;相模半白)を播種し、温室内で12日間生育させた。製剤例6に記載の方法に準じて製剤化された本発明化合物1、2、3、4、5、又は6を濃度が200ppmとなるように水で調整し、上記キュウリ葉面に充分付着するように茎葉散布した。散布後植物を風乾し、キュウリうどんこ病菌(Sphaerotheca fuliginea、チトクロームbをコードする遺伝子のうち、チトクロームbの143番目のアミノ酸残基がグリシンからアラニンに変異したQoI耐性株)胞子をふりかけ接種した。植物を昼間24℃、夜間20℃の温室で8日間栽培した後、病斑面積を調査した。その結果、本発明化合物を処理した植物における病斑面積はいずれも、無処理の植物における病斑面積の30%以下であった。
Claims (5)
- R1が、水素原子、又は1以上のハロゲン原子を有していてもよいC1-C3アルキル基である請求項1に記載のテトラゾリノン化合物。
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US15/556,453 US10053448B2 (en) | 2015-03-31 | 2016-03-28 | Substituted tetrazolinones for controlling plant diseases |
CN201680018991.3A CN107428737A (zh) | 2015-03-31 | 2016-03-28 | 四唑啉酮化合物及其用途 |
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JP2014097979A (ja) * | 2013-10-17 | 2014-05-29 | Sumitomo Chemical Co Ltd | 有害生物防除組成物及びその用途 |
JP2015027978A (ja) * | 2012-09-28 | 2015-02-12 | 住友化学株式会社 | テトラゾリノン化合物及びその用途 |
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