WO1996038425A1 - Triazolone derivatives, use thereof, and intermediates for the preparation thereof - Google Patents
Triazolone derivatives, use thereof, and intermediates for the preparation thereof Download PDFInfo
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- WO1996038425A1 WO1996038425A1 PCT/JP1996/001434 JP9601434W WO9638425A1 WO 1996038425 A1 WO1996038425 A1 WO 1996038425A1 JP 9601434 W JP9601434 W JP 9601434W WO 9638425 A1 WO9638425 A1 WO 9638425A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Definitions
- the present invention relates to a triazolone derivative, its use, and its production intermediate.
- the present invention provides a compound represented by the general formula (I):
- X represents a methyl group or a halogen atom
- Y and Z are the same or different and represent a hydrogen atom, a methyl group or a halogen atom.
- a plant disease controlling agent characterized by containing the triazolone derivative (hereinafter, referred to as the compound of the present invention) as an active ingredient.
- the present invention further provides a compound of the general formula ( ⁇ ) (I)
- the halogen atom represented by X, Y or Z includes a chlorine atom, a bromine atom And a fluorine atom.
- the triazolone compound of the general formula ( ⁇ ) and / or the triazolone compound of the general formula ( ⁇ ) preferred embodiments thereof include:
- the compound of the present invention is, for example, a triazolone compound represented by the general formula ( ⁇ ) and usually 0.5 to 10 equivalents of methanol or an alkali metal salt thereof (sodium salt, potassium salt or lithium salt). ) And, if necessary, in the presence of a base, usually in a solvent, usually at a temperature of 20 ° C to 200 ° C. Can be.
- Solvents that can be used vary depending on the type of alkali metal salt used and the type of base used.
- examples include aliphatic hydrocarbons such as hexane, heptane, lignin, petroleum ether, benzene, toluene, and xylene.
- ethers such as dimethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, etc.
- Examples of usable bases include inorganic bases such as sodium hydroxide, hydroxide hydroxide, sodium carbonate, carbonate carbonate, sodium hydride and the like, and alkali metal methoxide such as sodium methoxide.
- reaction solution After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent, concentration, and the like, and if necessary, further purification by chromatography, recrystallization, or the like, to isolate the compound of the present invention.
- the compound of the present invention comprises a triazolone compound represented by the above general formula ( ⁇ ), and usually 0.5 to 5 equivalents thereof.
- Solvents that can be used vary depending on the type of raw materials and bases used, but for example, aliphatic hydrocarbons such as hexane, heptane, lignin, petroleum ether, and aromatic hydrocarbons such as benzene, toluene, and xylene.
- Halogenated hydrocarbons such as hydrogen, carbon form, carbon tetrachloride, dichloroethane, carbon benzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, isophorone, cyclohexanone, methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl sorb, methylene glycol, glycer Alcohols such as ethylene, esters such as ethyl formate, ethyl acetate, butyl acetate, and getyl carbonate; nitrated compounds such as nitroethane and nitrobenzene; nitriles such as
- Examples of usable bases include, for example, inorganic bases such as sodium hydroxide, potassium oxide, sodium carbonate, potassium carbonate and sodium hydride, and alkali metal methoxides such as sodium methoxide.
- reaction solution After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent, concentration, and the like, and if necessary, further purification by chromatography, recrystallization, or the like, to isolate the compound of the present invention.
- the triazolone compound of the general formula (m) can be produced, for example, according to the method described in Production Example 2 of the intermediate described below.
- the compound of the present invention When used as an active ingredient of a plant disease controlling agent, it may be used as it is without adding any other components.However, it is usually mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliary agents for formulation. Into emulsions, wettable powders, suspensions, granules, powders, liquids, etc.
- These preparations usually contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 95%, preferably 1 to 90%.
- the solid carrier examples include fine powders and granular materials such as kaolin clay, atta plargite clay, bentonite, acid clay, pyrophyllite, tanolek, diatomaceous earth, calcite, knollemi powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide.
- Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosol, ketones such as acetone, cyclohexanone and isophorone, soybean oil, cottonseed oil and the like.
- Vegetable oils dimethyl sulfoxide, acetonitrile, water and the like can be mentioned.
- Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfates, alkyl (aryl) sulfates.
- Anionic surfactants such as sulfonic acid salts, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphate ester salts, polyoxyethylene alkyl ether, polyoxy ethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block copolymer
- non-ionic surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.
- Pharmaceutical adjuvants include ligninsulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), PAP (acidic isopropyl phosphate) and the like.
- formulations may be used as they are or diluted with water and sprayed on foliage, or may be used in various forms such as dusting, granulating and mixing with soil, or applying to soil.
- it by using it in combination with other plant disease controlling agents, it is expected that the controlling effect is enhanced.
- it can be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, and soil conditioners.
- the compound of the present invention can be used as an active ingredient of a plant disease controlling agent for paddy fields, fields, orchards, tea fields, pastures, lawns, and the like.
- the application rate is usually from 0.1 g to 50 g, preferably from 0.05 g to 20 g, per arel, emulsion and water.
- the application concentration is usually 0.0001% to 0.5%, preferably 0.0005% to 0.2%. Preparations, dusts, etc. are applied without dilution.
- Me represents a methyl group
- mp represents a melting point
- 1,1-Dimethyl-1- (2,6-dimethylphenyl) semicarbazide A solution of 2.07 g (10.0 fractions ol) of dioxane in bis (trichloromethyl) carbonate [triphosgene] 3.00 g (10.0 mols) is added to 100 ml of dioxane. The solution was dropped at 5 ° C or less. After completion, the mixture was stirred at the same temperature for 30 minutes and then heated and stirred at a bath temperature of 65 for 6 hours. To the resulting reaction solution was added aqueous sodium hydrogen carbonate, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and concentrated to obtain 2.07 g (87% yield) of 1-methyl-3-chloro-4- (2,6-dimethylphenyl) -1,1,2,4-triazolone.
- each of the compounds (1) to (8) of the present invention 25 parts of each of the compounds (1) to (8) of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed, and the particle size of the active ingredient is 5 ⁇ m or less. To obtain each suspension.
- Formulation Example 5 10 parts of the compounds (1) to (8) of the present invention, 1 part of polyoxyethylenestyrylphenyl ether and 89 parts of water are mixed to obtain each liquid preparation.
- Test Examples show that the compound of the present invention is useful as an active ingredient of a plant disease controlling agent.
- the compounds of the present invention are indicated by the compound numbers in Table 1.
- the control efficacy was determined by visually observing the disease state of the test plant at the time of the survey, that is, the degree of the bacterial flora such as leaves and stems, and the extent of the lesions. If no bacterial flora or lesions were observed, 5 or 10% The test was conducted with a compound of "4" if it was recognized to a degree, "3" if it was about 30%, “2” if it was about 50%, "1” if it was about 70%, and more. If there is no difference from the onset state of the disease, there is no difference, and it is evaluated as “0” and evaluated on a 6-point scale.
- Test example 1 Rice blast control test (preventive effect)
- a plastic pot was filled with sandy loam, rice (Nipponbare) was sown, and grown in a greenhouse for 20 days. Thereafter, the test reagent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the resulting solution was sprayed on foliage so as to sufficiently adhere to the rice leaf surface. After spraying, the plants were air-dried, sprayed with a spore suspension of the blast fungus, and inoculated. After inoculation, they were left at 28 ° C and high humidity for 6 days, and their control efficacy was examined. The results are shown in Table 3.
- Test example 2 Rice sheath blight control test (preventive effect)
- the test agent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the resulting solution was sprayed on the foliage of the rice so as to sufficiently adhere to the leaf surface. After spraying, the plants were air-dried and inoculated with a bran culture mycelium of the sheath blight fungus at the root. After inoculation, the plants were placed at 28 ° C and in a humid environment for 4 days, and the control efficacy was examined. The results are shown in Table 3.
- Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days.
- the test agent prepared as an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration, and the resulting solution was sprayed with foliage so as to sufficiently adhere to the leaves of the wheat seedlings. After spraying, a spore suspension of wheat eye spot bacterium was inoculated to the root of the wheat and kept at 15 ° C and high humidity for 14 days, and the control effect was examined. The results are shown in Table 3.
- Test Example 4 Wheat powdery mildew control test (Therapeutic effect)
- Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days.
- the wheat seedlings that had developed the second leaf were sprinkled with wheat powdery mildew and inoculated. After inoculation, grow in a greenhouse at 23 ° C for 3 days, dilute with water water to a prescribed concentration the suspension prepared as described in Formulation Example 4, and attach it sufficiently to the leaves of the wheat.
- Foliage was sprayed as if to do. After spraying, they were grown for additional 7 days under lighting, and their control efficacy was investigated. The results are shown in Table 3.
- Plastic pots were filled with sandy loam, sown with Kiuri (Sagami Hanjiro), and grown for 12 days in a greenhouse.
- the test agent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the resulting solution was sprayed on the foliage of the cucumber seedlings so as to sufficiently adhere to the leaves. After spraying, a spore suspension of Cucumber powdery mildew was inoculated. After inoculation, they were grown at 25 ° C under light for 7 days, and their control efficacy was examined. The results are shown in Table 3. Table 3
- the compound of the present invention exhibits an excellent control effect on plant diseases, and can be used as a plant disease controlling agent.
- the chlorotriazolone compound of the formula ( ⁇ ) or the triazolone compound of the formula ( ⁇ ) is an intermediate of the compound of the present invention. Available as
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Abstract
Triazolone derivatives of general formula (I); a plant disease control agent comprising the derivative as the active principle; and intermediates for the preparation of the derivatives, wherein X is methyl or halogeno; and Y and Z are each independently H, methyl or halogeno. The triazolone derivatives of the general formula (I) exhibit an excellent control effect against plant diseases.
Description
明 細 書 トリアゾロン誘導体、 その用途およびその製造中間体 技術分野 - 本発明はトリアゾロン誘導体、 その用途およびその製造中間体に関する。 背景技術 TECHNICAL FIELD The present invention relates to a triazolone derivative, its use, and its production intermediate. Background art
従来、 国際特許出願公開明細書 WO 9 5 / 1 4 0 0 9号にある種のトリア、/、口 ン誘導体が殺菌剤の有効成分として使用しうることが記載されているが、 該化合 物は殺菌効力等の点で必ずしも常に充分とは言いがたい。 Heretofore, International Patent Application Publication No. WO95 / 14009 describes that certain tori, /, and mouth derivatives can be used as an active ingredient of a fungicide. Is not always sufficient in terms of bactericidal efficacy and the like.
発明の開示 Disclosure of the invention
本発明者らは優れた植物病害防除剤を見 、出すべく鋭意検討した結果、 下記一 般式 （ I ) で示されるトリアゾロン誘導体が植物病害に対し優れた防除効果を示 すことを見い出し本発明を完成した。 Means for Solving the Problems The inventors of the present invention have studied and studied an excellent plant disease controlling agent, and as a result, have found that a triazolone derivative represented by the following general formula (I) exhibits an excellent controlling effect on plant diseases. Was completed.
即ち、 本発明は、 一般式 （I ) That is, the present invention provides a compound represented by the general formula (I):
( I )
(I)
〔式中、 Xはメチル基またはハロゲン原子を表わし、 Yおよび Zは、 同一または 相異なり、 水素原子、 メチル基またはハロゲン原子を表わす。 〕 [In the formula, X represents a methyl group or a halogen atom, and Y and Z are the same or different and represent a hydrogen atom, a methyl group or a halogen atom. ]
で示されるトリァゾロン誘導体 （以下、 本発明化合物と記す。 ） およびそれを有 効成分として含有することを特徴とする植物病害防除剤を提供する。 And a plant disease controlling agent characterized by containing the triazolone derivative (hereinafter, referred to as the compound of the present invention) as an active ingredient.
本発明は、 さらに、 本発明化合物の製造中間体として有用な、 一般式 （Π )
( I )The present invention further provides a compound of the general formula (式) (I)
〔式中、 X， Yおよび zは前記と同じ意味を表す。 〕 [Wherein, X, Y and z represent the same meaning as described above. ]
で示されるクロロトリアゾロン化合物、 ならびに、 一般式 （noA chlorotriazolone compound represented by the general formula (no
〔式中、 Qは臭素原子または塩素原子を表わし、 Zは 記と同じ意味を表わす。 〕 で示されるトリァゾロン化合物をも提供する。 [In the formula, Q represents a bromine atom or a chlorine atom, and Z represents the same meaning as described above. ] It also provides the triazolone compound shown by these.
一般式 （Π ) で表わされる本発明のクロロトリアゾロン化合物または/および —般式 （ΠΙ) で表わされるトリァゾロン化合物において X、 Y又は Zで表わされ るハロゲン原子としては、 塩素原子、 臭素原子、 フッ素原子等があげられる。 本発明化合物、 一般式 （Π ) のクロ口トリァゾロン化合物または/および一般 式 （ΠΙ) のトリァゾロン化合物において、 その好ましい態様として、 In the chlorotriazolone compound of the present invention represented by the general formula (Π) and / or the triazolone compound represented by the general formula (ΠΙ), the halogen atom represented by X, Y or Z includes a chlorine atom, a bromine atom And a fluorine atom. In the compound of the present invention, the triazolone compound of the general formula (Π) and / or the triazolone compound of the general formula (ΠΙ), preferred embodiments thereof include:
Xがメチル基である化合物； A compound wherein X is a methyl group;
Zが水素原子または 4一塩素原子である化合物； Compounds wherein Z is a hydrogen atom or a quaternary chlorine atom;
Yが水素原子、 メチル基または塩素原子である化合物さらには、 Compounds wherein Y is a hydrogen atom, a methyl group or a chlorine atom,
Yが 5—メチル基である化合物があげられる。 Compounds in which Y is a 5-methyl group are mentioned.
次に、 本発明化合物の製造法について説明する。 Next, a method for producing the compound of the present invention will be described.
本発明化合物は、 例えば、 前記一般式 （Π ) で示されるクロ口トリァゾロン化 合物と、 それに対し通常 0. 5〜1 0当量のメタノールまたはそのアルカリ金属塩 (ナトリウム塩、 カリウム塩またはリチウム塩） とを、 必要に応じ塩基の存在下、 通常溶媒中、 通常一 2 0 °C〜2 0 0 °Cで、 反応させることによって製造すること
ができる。 The compound of the present invention is, for example, a triazolone compound represented by the general formula (Π) and usually 0.5 to 10 equivalents of methanol or an alkali metal salt thereof (sodium salt, potassium salt or lithium salt). ) And, if necessary, in the presence of a base, usually in a solvent, usually at a temperature of 20 ° C to 200 ° C. Can be.
使用し得る溶媒としては、 用いるアル力リ金属塩や塩基の種類等によっても異 なるが、 例えばへキサン、 ヘプタン、 リグ口イン、 石油エーテル等の脂肪族炭化 水素、 ベンゼン、 トルエン、 キシレン等の芳香族炭化水素、 クロ口ホルム、 四塩 化炭素、 ジクロロェタン、 クロ口ベンゼン、 ジクロロベンゼン等のハロゲン化炭 ィ匕水素、 ジェチルエーテル、 ジイソプロピルエーテル、 ジォキサン、 テトラヒド 口フラン、 エチレングリコールジメチルエーテル等のエーテル類、 アセトン、 メ チルェチルケトン、 メチルイソブチルケトン、 イソホロン、 シクロへキサノン等 のケトン類、 ニトロェタン、 ニトロベンゼン等のニトロ化物、 ァセトニトリル、 イソブチロニトリル等の二トリル類、 ピリジン、 トリェチルァミン、 N， N—ジ ェチルァニリン、 トリブチルァミン、 N—メチルモルホリン等の第三級ァミン、 ホルムアミ ド、 N， N—ジメチルホルムアミ ド、 N， N—ジメチルァセトアミ ド、 ァセトアミ ド等の酸アミ ド類、 ジメチルスルホキシド、 スルホラン等の硫黄化合 物、 メタノール、 水等あるいはそれらの混合物が挙げられる。 Solvents that can be used vary depending on the type of alkali metal salt used and the type of base used.Examples include aliphatic hydrocarbons such as hexane, heptane, lignin, petroleum ether, benzene, toluene, and xylene. Aromatic hydrocarbons, chloroform, tetrachlorocarbon, halogenated hydrocarbons such as dichloroethane, cyclobenzene, dichlorobenzene, etc., ethers such as dimethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, etc. , Acetone, methylethyl ketone, methyl isobutyl ketone, ketones such as isophorone and cyclohexanone, nitrated compounds such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N -Tertiary amines such as diethylaniline, tributylamine and N-methylmorpholine, formamides, acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and acetoamide, Examples thereof include sulfur compounds such as dimethyl sulfoxide and sulfolane, methanol, water and the like, and mixtures thereof.
使用し得る塩基としては、 例えば水酸化ナトリウム、 水酸化力リゥム、 炭酸ナ トリウム、 炭酸力リゥム、 水素化ナトリゥム等の無機塩基、 ナトリウムメ トキシ ド等のアル力リ金属メ トキシド等が挙げられる。 Examples of usable bases include inorganic bases such as sodium hydroxide, hydroxide hydroxide, sodium carbonate, carbonate carbonate, sodium hydride and the like, and alkali metal methoxide such as sodium methoxide.
反応終了後の反応液は、 有機溶媒抽出、 濃縮等の通常の後処理を行い、 必要な らばクロマトグラフィー、 再結晶等によってさらに精製することにより、 本発明 化合物を単離することができる。 After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent, concentration, and the like, and if necessary, further purification by chromatography, recrystallization, or the like, to isolate the compound of the present invention.
一般式 （Π ) のクロ口トリァゾロン化合物は、 J. H. Cooleyらの J. Org. Cloth triazolone compounds of the general formula (Π) are described in J. Org.
Chem. 54， 1048- 1051 (1989)に記載の方法または該方法におけるホスゲンにかえ てクロ口蟻酸トリクロロメチル 〔ジホスゲン〕 やビス （トリクロロメチル） カー ボネート 〔トリホスゲン〕 を用いる方法等により、 製造することができる。 Chem. 54, 1048-1051 (1989), or by using trichloromethyl chloroformate [diphosgene] or bis (trichloromethyl) carbonate [triphosgene] instead of phosgene in the above method. Can be.
本発明化合物は、 前記一般式 （ΠΙ) のトリアゾロン化合物と、 それに対し通常 0. 5〜 5当量の、 The compound of the present invention comprises a triazolone compound represented by the above general formula (ΠΙ), and usually 0.5 to 5 equivalents thereof.
一般式 （W)
General formula (W)
〔式中、 Xおよび Yは前記と同じ意味を表わす。 〕 [Wherein, X and Y represent the same meaning as described above. ]
で示される化合物とを、 塩基存在下、 通常溶媒中、 通常— 2 0 °C〜 2 0 0 °Cで、 反応させることによって製造することもできる。 Can also be produced by reacting the compound represented by with a base in the presence of a base, usually in a solvent, usually at −20 ° C. to 200 ° C.
使用し得る溶媒としては、 用いる原料や塩基の種類等によっても異なるが、 例 えばへキサン、 ヘプタン、 リグ口イン、 石油エーテル等の脂肪族炭化水素、 ベン ゼン、 トルエン、 キシレン等の芳香族炭化水素、 クロ口ホルム、 四塩化炭素、 ジ クロロェタン、 クロ口ベンゼン、 ジクロロベンゼン等のハロゲン化炭化水素、 ジ ェチルエーテル、 ジイソプロピルエーテル、 ジォキサン、 テトラヒドロフラン、 エチレングリコールジメチルエーテル等のエーテル類、 アセトン、 メチルェチル ケトン、 メチルイソブチルケトン、 イソホロン、 シクロへキサノン等のケトン類、 メタノール、 エタノール、 イソプロパノール、 tーブタノール、 ォクタノール、 シクロへキサノール、 メチルセ口ソルブ、 ジェチレングリコ一ル、 グリセリン等 のアルコール類、 蟻酸ェチル、 酢酸ェチル、 酢酸ブチル、 炭酸ジェチル等のエス テル類、 ニトロェタン、 ニトロベンゼン等のニトロ化物、 ァセトニトリル、 イソ ブチロニトリル等の二トリル類、 ピリジン、 トリェチルァミン、 N， N—ジェチ ルァニリン、 トリブチルァミン、 N—メチルモルホリン等の第三級ァミン、 ホル ムアミ ド、 N, N—ジメチルホルムアミ ド、 N， N—ジメチルァセトアミ ド、 ァ セトアミ ド等の酸ァミ ド類、 ジメチルスルホキシド、 スルホラン等の硫黄化合物、 水等あるいはそれらの混合物が挙げられる。 Solvents that can be used vary depending on the type of raw materials and bases used, but for example, aliphatic hydrocarbons such as hexane, heptane, lignin, petroleum ether, and aromatic hydrocarbons such as benzene, toluene, and xylene. Halogenated hydrocarbons such as hydrogen, carbon form, carbon tetrachloride, dichloroethane, carbon benzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, isophorone, cyclohexanone, methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl sorb, methylene glycol, glycer Alcohols such as ethylene, esters such as ethyl formate, ethyl acetate, butyl acetate, and getyl carbonate; nitrated compounds such as nitroethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; pyridine; triethylamine; Tertiary amines such as luaniline, tributylamine and N-methylmorpholine, acid amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide and acetateamide And sulfur compounds such as dimethylsulfoxide and sulfolane; water; and mixtures thereof.
使用し得る塩基としては、 例えば水酸化ナトリウム、 K酸化カリウム、 炭酸ナ トリウム、 炭酸力リウム、 水素化ナトリウム等の無機塩基、 ナトリウムメ トキシ ド等のアルカリ金属メ トキシド等が挙げられる。 Examples of usable bases include, for example, inorganic bases such as sodium hydroxide, potassium oxide, sodium carbonate, potassium carbonate and sodium hydride, and alkali metal methoxides such as sodium methoxide.
本製造法において、 必要に応じ、 ベンジルトリェチルアンモニゥムクロリ ド等
の相関移動触媒を用いることもできる。 In this production method, if necessary, benzyltriethylammonium chloride, etc. May be used.
反応終了後の反応液は、 有機溶媒抽出、 濃縮等の通常の後処理を行い、 必要な らばクロマトグラフィー、 再結晶等によってさらに精製することにより、 本発明 化合物を単離することができる。 After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent, concentration, and the like, and if necessary, further purification by chromatography, recrystallization, or the like, to isolate the compound of the present invention.
一般式 （m) のトリアゾロン化合物は、 例えば、 後記中間体の製造例 2に記載 の方法に準じて製造することができる。 The triazolone compound of the general formula (m) can be produced, for example, according to the method described in Production Example 2 of the intermediate described below.
本発明化合物が効力を有する植物病害としては、 イネのいもち病 The plant diseases for which the compound of the present invention is effective include rice blast
(Pyricularia oryzae) 、 こま葉枯 (Cochl iobolus miyabeanus)^ 紋枯病 (Rhizoctonia solani) 、 ムギ類のうどんこ病 (Erysiphe graminis f . sp. (Pyricularia oryzae), Koma leaf blight (Cochl iobolus miyabeanus) ^ Sheath blight (Rhizoctonia solani), Powdery mildew on wheat (Erysiphe graminis f. Sp.
hordei, f. sp. tri tici)、 赤かび病 (Gibberel la zeae)、 さび病 (Puccinia stri i formis, P. gramini s, P. recondi ta, P. hordei) 、 雪腐病 (Typhula sp.， Micronectriel la nival is)^ 裸黒穂病 (Usti lago tri tici, U. nuda)、 眼紋病 (Pseudocercosporel la herpotrichoides) 、 雲开病 (Rhynchosporium secal is) 、 葉枯病 (Septoria tri tici) 、 ふ枯病 (Leptosphaeria nodorun 、 カンキッの黒 点病 (Diaporthe ci tri)、 そうか病 (Elsinoe fawcetti) 、 果実腐敗病 hordei, f. sp. tri tici), Fusarium head blight (Gibberel la zeae), Rust (Puccinia stri i formis, P. gramini s, P. recondi ta, P. hordei), Snow rot (Typhula sp., Micronectriel la nival is) ^ Smut (Usti lago tri tici, U. nuda), Eye spot disease (Pseudocercosporel la herpotrichoides), Cloud disease (Rhynchosporium secal is), Leaf blight (Septoria tri tici), Blight (Leptosphaeria nodorun, citrus black spot (Diaporthe ci tri), scab (Elsinoe fawcetti), fruit rot
(Penici I l ium degi tatum, P. i tal i cum) 、 リンゴのモ二リア病 (Sclerotinia mal i) 、 腐りん病 (Valsa mal i) 、 うどんこ病 (Podosphaera leucotricha)、 斑 点落葉病 (Al ternaria mal i)ヽ 黒星病 (Venturia inaequal i s)、 ナシの黒星病 (Venturia nashicola)、 黒斑病 (Al ternaria kikuchiana) 亦星病 (Penici I lium degi tatum, P. ital i cum), apple morilia (Sclerotinia mal i), rot (Valsa mal i), powdery mildew (Podosphaera leucotricha), spot leaf spot ( Al ternaria mal i) ヽ Scab (Venturia inaequal is), Pear scab (Venturia nashicola), Black spot (Al ternaria kikuchiana)
(Gymnosporangium haraeanum)^ モモの灰星病 (Sclerotinia cinerea)^ 黒星病 (Cladosporium car ophi lum) 、 フォモプシス腐敗病 (Phomopsis sp. ) 、 ブド ゥの黒とう病 (Elsinoe ampel ina) 、 晚腐病 (Glomerel la cingulate) 、 うどん こ病 (Unc inula necator) 、 さび病 (Phakopsora ampelopsidis)^ ベと病 (Gymnosporangium haraeanum) ^ Peach ash (Sclerotinia cinerea) ^ Scab (Cladosporium car ophi lum), Phomopsis rot (Phomopsis sp.), Budo ド (Elsinoe ampel ina), 晚 rot (Glomerel) la cingulate), powdery mildew (Unc inula necator), rust (Phakopsora ampelopsidis) ^ Downy mildew
(Plasmopara vi ticola)、 力キの炭そ病 (Gloeosporium kakiリ、 落桌柄 (Plasmopara vi ticola), anthracnose of iki (Gloeosporium kaki li
(Cercospora kaki, Mycosphaerel la nawae) ゥリ類の炭そ病 （Col letotrichum lagenarium)s うどんこ病 (Sphaerotheca ful iginea) 、 つる枯病 (Cercospora kaki, Mycosphaerel la nawae) Anthracnose of cole (Col letotrichum lagenarium) s Powdery mildew (Sphaerotheca ful iginea), vine blight
(Mycosphaerel la melonis ヽ ベと病 (Pseudoperonospora cubensis) 卜マ卜 の輪紋病 (Al ternaria solani)、 葉かび病 (Cladosporium fulvum)、 疫病 (Mycosphaerel la melonis ヽ downy mildew (Pseudoperonospora cubensis) Tomato ring rot (Alternaria solani), leaf mold (Cladosporium fulvum), plague
(Phytophthora infestans) 、 ナスの褐紋病 (Phomopsi s vexans) 、 うどんこ病
(Erysiphe cichoracearum) 、 アブラナ科野菜の黒斑病 (Al ternaria japonica)、 白斑病 (Cercosporel la brassicae)、 ネギのさび病 (Puccinia al l i i) 、 ダイズ の紫斑病 (Cercospora kikuchi i)、 黒とう病 (Elsinoe glycines) 、 黒点病(Phytophthora infestans), Eggplant brown spot (Phomopsi s vexans), Powdery mildew (Erysiphe cichoracearum), Brassica vegetables black spot (Alternaria japonica), white spot (Cercosporel la brassicae), green onion rust (Puccinia al lii), soybean purpura (Cercospora kikuchi i), black spot Elsinoe glycines), Black spot disease
(Diaporthe phaseolorum var. sajae 、 インゲンの炭そ病 (Col letotrichum l indemuthianum) 、 ラッカセィの黒法病 (Cercosporidium personatumA 掲斑病(Diaporthe phaseolorum var. Sajae, bean anthracnose (Col letotrichum l indemuthianum), black rot of Lachasey (Cercosporidium personatumA leprosy)
(Cercospora arachidicola) ェン卜ゥのうどんこ病 (Erysiphe pisi ) 、 ジャ ガイモの夏疫病 (Al ternaria solani)、 疫病 (Phytophthora infenstans)、 イチ ゴのうどんこ病 (Sphaerotheca humul i)、 チヤの網もち病 （Exobasidium reticulatum)、 白星病 (Elsinoe leucospi la) 、 タノ、'コの赤星病 (Al ternaria longipes 、 うどんこ病 (Erysi he ci choracearum) 、 炭そ病 (Col letotrichum tabacum) 、 テンサイの褐斑病 (Cercospora beticola)、 バラの黒星病 (Cercospora arachidicola) Powdery mildew (Erysiphe pisi) of potatoes, summer blight of potatoes (Al ternaria solani), plague (Phytophthora infenstans), strawberry powdery mildew (Sphaerotheca humul i) Disease (Exobasidium reticulatum), White scab (Elsinoe leucospi la), Tano, 'Ko scab (Al ternaria longipes), Powdery mildew (Erysi he ci choracearum), Anthracnose (Col letotrichum tabacum), Brown spot of sugar beet (Cercospora beticola), rose scab
(Di locarpon rosae) つどんこ (Sphaerotheca pannosa 、 キクの褐斑病 (Septoria chrysanthemト indieリ、 白さび (Puccinia-horiana) ^ 種々の作物 の灰 Sかび病 (Botrytis cinerea) 、 菌核病 (Sclerotinia sclerotiorum) 、 等 が挙げられる。 (Di locarpon rosae) Tong (Sphaerotheca pannosa, chrysanthemum brown spot (Septoria chrysanthem indili), white rust (Puccinia-horiana) ^ ash of various crops S Mold (Botrytis cinerea), sclerotia ), And the like.
本発明化合物を植物病害防除剤の有効成分として用いる場合は、 他の何らの成 分も加えずそのままでもよいが、 通常は固体担体、 液体担体、 界面活性剤その他 の製剤用補助剤と混合して、 乳剤、 水和剤、 懸濁剤、 粒剤、 粉剤、 液剤等に製剤 す When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, it may be used as it is without adding any other components.However, it is usually mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliary agents for formulation. Into emulsions, wettable powders, suspensions, granules, powders, liquids, etc.
これらの製剤には有効成分として本発明化合物を、 重量比で、 通常 0. 1〜9 5 %、 好ましくは 1〜 9 0 %含有する。 These preparations usually contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 95%, preferably 1 to 90%.
固体担体としては、 カオリンクレー、 アツタパルジャイトクレー、 ベントナイ ト、 酸性白土、 パイロフィライト、 タノレク、 珪藻土、 方解石、 クノレミ粉、 尿素、 硫酸アンモニゥム、 合成含水酸化珪素等の微粉末あるいは粒状物が挙げられ、 液 体担体としては、 キシレン、 メチルナフタレン等の芳香族炭化水素、 イソプロパ ノール、 エチレングリコ一ル、 セロソルフ"等のアルコール、 アセトン、 シクロへ キサノン、 イソホロン等のケトン、 大豆油、 綿実油等の植物油、 ジメヂルスルホ キシド、 ァセトニトリル、 水等が挙げられ、 乳化、 分散、 湿展等のために用いら れる界面活性剤としては、 アルキル硫酸エステル塩、 アルキル （ァリール） スル
ホン酸塩、 ジアルキルスルホコハク酸塩、 ポリオキシエチレンアルキルァリール エーテルリン酸エステノレ塩等の陰イオン界面活性剤、 ポリオキシエチレンアルキ ルエーテル、 ポリオキシエチレンアルキルァリールエーテル、 ポリオキシェチレ ンポリオキシプロピレンブロックコポリマ一、 ソルビタン脂肪酸エステル、 ポリ ォキシエチレンソルビタン脂肪酸エステル等の非イオン界面活性剤等が挙げられ る。 製剤用補助剤としては、 リグニンスルホン酸塩、 アルギン酸塩、 ポリビニル アルコール、 アラビアガム、 C M C (カルボキシメチルセルロース） 、 P A P (酸性リン酸イソプロピル） 等が挙げられる。 Examples of the solid carrier include fine powders and granular materials such as kaolin clay, atta plargite clay, bentonite, acid clay, pyrophyllite, tanolek, diatomaceous earth, calcite, knollemi powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosol, ketones such as acetone, cyclohexanone and isophorone, soybean oil, cottonseed oil and the like. Vegetable oils, dimethyl sulfoxide, acetonitrile, water and the like can be mentioned. Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfates, alkyl (aryl) sulfates. Anionic surfactants such as sulfonic acid salts, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphate ester salts, polyoxyethylene alkyl ether, polyoxy ethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block copolymer And non-ionic surfactants such as sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters. Pharmaceutical adjuvants include ligninsulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), PAP (acidic isopropyl phosphate) and the like.
これらの製剤は、 このままであるいは水で希釈して茎葉散布するか、 または、 土壌に散粉、 散粒して混和するかあるいは土壌施用する等の種々の形態で使用す る。 また、 他の植物病害防除剤と混合して用いることにより、 防除効力の増強を 期待できる。 さらに、 殺虫剤、 殺ダニ剤、 殺線虫剤、 除草剤、 植物生長調節剤、 肥料、 土壌改良剤と混合して用いることもできる。 These formulations may be used as they are or diluted with water and sprayed on foliage, or may be used in various forms such as dusting, granulating and mixing with soil, or applying to soil. In addition, by using it in combination with other plant disease controlling agents, it is expected that the controlling effect is enhanced. In addition, it can be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, and soil conditioners.
なお、 本発明化合物は、 水田、 畑地、 果樹園、 茶園、 牧草地、 芝生地等の植物 病害防除剤の有効成分として用いることができる。 The compound of the present invention can be used as an active ingredient of a plant disease controlling agent for paddy fields, fields, orchards, tea fields, pastures, lawns, and the like.
本発明化合物を植物病害防除剤の有効成分として用いる場合、 その施用量は、 1アールあたり、 通常 0 1 g〜5 0 g、 好ましくは 0. 0 5 g〜2 0 gであり、 乳剤、 水和剤、 懸濁剤、 液剤等を水で希釈して施用する場合、 その施用濃度は通 常 0. 0001%〜0. 5 %、 好ましくは 0. 0005%〜0. 2 %であり、 粒剤、 粉剤等はなん ら希釈することなくそのまま施用する。 When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, the application rate is usually from 0.1 g to 50 g, preferably from 0.05 g to 20 g, per arel, emulsion and water. When applying a water-based preparation, suspension, liquid preparation, etc., diluted with water, the application concentration is usually 0.0001% to 0.5%, preferably 0.0005% to 0.2%. Preparations, dusts, etc. are applied without dilution.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
次に製造例、 製剤例、 試験例等にて本発明を更に詳細に説明するが、 本発明は これらの例に限定されるものではない。 Next, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, Test Examples, and the like, but the present invention is not limited to these Examples.
先ず、 本発明化合物の製造例を示す。 尚、 本発明化合物番号は後記表 1に記載 のものである。 First, Production Examples of the compound of the present invention will be shown. The compound number of the present invention is as shown in Table 1 below.
製造例 1 (本発明化合物 ( 2 ) の製造） Production Example 1 (Production of Compound (2) of the Present Invention)
1—メチル一 3—クロロー 4一 〔2— （2—メチルフエノキシ） メチル一 6— メチルフヱニル〕 — 1， 2， 4一トリァゾロン 〔後記中間体の製造例 1にて製造〕 0. 60 g ( 1 . 7 5 mmol) および 2 8 %ナトリウムメ トキシドのメタノール溶液 1.
7 g (8.8mmol) をメタノール 5 mlに溶解させ、 4時間加熱還流した。 反応液を 氷水にあけ、 酢酸ェチルで抽出した。 抽出液を水洗後、 濃縮し、 残渣をシリカゲ ルクロマトグラフィー （溶出液；酢酸ェチル： n—へキサン = 1 ： 1) に付し、 1—メチル一3—メ トキシ一 4— 〔2— （2—メチルフエノキシ） メチル一6— メチルフヱニル〕 一 1, 2， 4—トリァゾロン 0.25 g (収率 42%) を得た。 製造例 2 (本発明化合物 （ 1 ) の製造） 1-Methyl-3-chloro-4- [2- (2-methylphenoxy) methyl-6-methylphenyl] -1,2,4-triazolone [Prepared in Intermediate Production Example 1 described below] 0.60 g (1. (75 mmol) and 28% sodium methoxide in methanol 1. 7 g (8.8 mmol) was dissolved in 5 ml of methanol, and the mixture was heated under reflux for 4 hours. The reaction solution was poured into ice water and extracted with ethyl acetate. The extract was washed with water, concentrated, and the residue was subjected to silica gel chromatography (eluent; ethyl acetate: n-hexane = 1: 1) to give 1-methyl-3-methoxy-1- (2- ( 2-methylphenoxy) methyl-6-methylphenyl] 1,1,2,4-triazolone 0.25 g (42% yield) was obtained. Production Example 2 (Production of Compound (1) of the Present Invention)
1—メチル一 3—メ トキシー 4— 〔2— (ブロ乇メチル） 一 6—メチルフエ二 ノレ〕 一 1， 2, 4一トリァゾロン 〔後記中間体の製造例 2にて製造〕 0.80 g (2. 56mmol) および 2， 5—キシレノール 0.38 g (3.07讓 ol) を N， N—ジメ チルホルムアミ ド 5 mlに溶解させ、 ここに炭酸カリウム 0.42 g (3.07mmol) を加えて 60〜 70 °Cで 6時間攪拌した。 反応液に氷水を加えて酢酸ェチルで抽 出した。 抽出液を水洗後、 濃縮し、 残渣をシリカゲルクロマトグラフィー （溶出 液；酢酸ェチル： n—へキサン = 1 ： 1) に付し、 1—メチル一 3—メ トキシー 4— 〔2— (2, 5—ジメチルフエノキシ） メチル一 6—メチルフエニル〕 一 1， 2, 4—トリアゾロン 0.79 g (収率 87 %) を得た。 1-Methyl-3-methoxy 4- [2- (Bromethyl) -16-methylphenone] 1,1,4-Triazolone [Prepared in Intermediate Production Example 2 below] 0.80 g (2. 56 mmol) and 0.38 g (3.07 benzyl) of 2,5-xylenol are dissolved in 5 ml of N, N-dimethylformamide, and 0.42 g (3.07 mmol) of potassium carbonate is added thereto, and the mixture is heated at 60 to 70 ° C for 6 hours. Stirred. Ice water was added to the reaction solution, and extracted with ethyl acetate. The extract was washed with water, concentrated, and the residue was subjected to silica gel chromatography (eluent: ethyl acetate: n- hexane = 1: 1) to give 1-methyl-13-methoxy-4 -— [2- (2, (2, There was obtained 0.79 g (yield 87%) of 5-dimethylphenoxy) methyl-6-methylphenyl] -1,2,4-triazolone.
次に本発明化合物の具体例のいくつかを化合物番号および物性値と共に表 1に 示す。 （一般式 （I) で示される化合物の置換基の定義で示す。 ） Next, some specific examples of the compounds of the present invention are shown in Table 1 together with the compound numbers and physical properties. (It is shown by the definition of the substituent of the compound represented by the general formula (I).)
尚、 表 1において M eはメチル基を表わし、 以下の記述において mpは融点を 表わす。
In Table 1, Me represents a methyl group, and in the following description, mp represents a melting point.
表 1 化合物番号 X Y Z 物性値 Table 1 Compound No.X Y Z Physical properties
(1) Me 5一 Me H mp 1 43. 3°C(1) Me 5-1 Me H mp 1 43.3 ° C
(2) Me H H m p 1 2 1. 3 C(2) Me H H m p 1 2 1.3 C
(3) Me 4一 C 1 H mp 1 42. 6°C (3) Me 4-1 C 1 H mp 1 42.6 ° C
4ゾ し 1 rl rl mp 1 20. 3°C 4 zone 1 rl rl mp 1 20.3 ° C
(5) Me H 4 -C 1 mp 1 39. 7°C(5) Me H 4 -C 1 mp 1 39.7 ° C
(6) Me 4 -Me H (6) Me 4 -Me H
(7) C 1 5 -C 1 H (7) C 15 -C 1 H
( 8 ) Me H 4 -Me 次に、 本発明化合物を製造する際の中間体化合物である前記一般式 （Π) で示 されるクロロトリアゾロン化合物の製造例を示す。 (8) Me H 4 -Me Next, a production example of the chlorotriazolone compound represented by the above general formula (Π), which is an intermediate compound for producing the compound of the present invention, will be described.
中間体の製造例 1 Production example 1 of intermediate
1， 1—ジメチル一 4一 〔2— （2—メチルフエノキシ） メチル一6—メチル フエニル〕 セミカルバジド 2.00 g (6.39議 ol) の塩化メチレン溶液を、 クロ 口蟻酸トリクロロメチル 〔ジホスゲン〕 1.90 g (9.59mmol) の塩化メチレン溶 液に氷冷下滴下した。 完了後、 1時間氷冷下で攪拌した後、 5時間加熱還流させ、 生じた反応液を炭酸水素ナトリウム水に注加し分液した。 有機層を水で洗浄した 後、 濃縮し、 残渣をシリカゲルカラムクロマトグラフィー （溶出液；酢酸ェチル n—へキサン- 1 ： 1) に付し、 1一メチル一 3—クロ口一 4— 12 - (2—メ チルフエノキシ） メチルー 6—メチルフエ二ル〕 一 1， 2， 4_トリァゾロン 1. 6 5 g (収率 75%) を得た。 1,1-Dimethyl-1- [2- (2-methylphenoxy) methyl-6-methylphenyl] semicarbazide 2.00 g (6.39 mol) of a methylene chloride solution was added to 1.90 g (9.59 mmol) of trichloromethyl chloroformate [diphosgene]. ) Was added dropwise to the methylene chloride solution under ice-cooling. After completion, the mixture was stirred for 1 hour under ice-cooling, heated under reflux for 5 hours, and the resulting reaction solution was poured into aqueous sodium hydrogen carbonate and separated. The organic layer is washed with water, concentrated, and the residue is subjected to silica gel column chromatography (eluent; ethyl acetate n-hexane-1: 1) to give 1-methyl-13-chloro-1-4-1-2. (2-Methylphenoxy) methyl-6-methylphenyl] 1,1,2,4-triazolone 1.65 g (yield 75%) was obtained.
mp 128.6 °C mp 128.6 ° C
同様にして製造される一般式 （Π) で示されるクロロトリアゾロン化合物の例 を以下に示す。 Examples of the chlorotriazolone compound represented by the general formula (Π) similarly produced are shown below.
1—メチルー 3—クロ口一 4— 〔2— (2—クロロフエノキシ） メチルー 6—
メチルフェニル〕 一 1， 2， 4— トリァゾロン m p 88.8°C 1-Methyl-3 -Chloro-1- 4-2- [2-Chlorophenoxy) methyl-6 Methylphenyl] 1, 2, 4-triazolone mp 88.8 ° C
1—メチルー 3—クロロー 4— 〔2— (2—メチル一 4—クロロフエノキシ） メチル一 6 _メチルフエニル〕 一 1， 2， 4一トリァゾロン mp 188.9 °C 次に、 前記一般式 （IE) で示されるトリァゾロン化合物の製造例を示す。 1-Methyl-3-chloro-4- [2- (2-Methyl-14-chlorophenoxy) methyl-16-methylphenyl] 1-1,2,4-Triazolone mp 188.9 ° C Next, in the general formula (IE), A production example of the indicated triazolone compound is shown.
中間体の製造例 2 Production example 2 of intermediate
1， 1—ジメチル一4— (2， 6—ジメチルフエニル） セミカルバジド 2.07 g (10.0画 ol) のジォキサン溶液をビス （トリクロロメチル） カーボネート 〔トリホスゲン〕 3.00 g (10.0譲 ol) をジォキサン 1 00mlに溶かした溶 液に 5 °C以下で滴下した。 完了後、 30分間同一温度で攪拌した後、 バス温 65 でで 6時間加熱攪拌した。 生じた反応液に炭酸水素ナトリゥム水を注加し酢酸ェ チルで抽出した。 有機層を水で洗浄した後、 濃縮し、 1—メチルー 3—クロ口— 4—— （2， 6—ジメチルフヱニル） 一 1, 2， 4一トリァゾロン 2.07 g (収率 87 %) を得た。 1,1-Dimethyl-1- (2,6-dimethylphenyl) semicarbazide A solution of 2.07 g (10.0 fractions ol) of dioxane in bis (trichloromethyl) carbonate [triphosgene] 3.00 g (10.0 mols) is added to 100 ml of dioxane. The solution was dropped at 5 ° C or less. After completion, the mixture was stirred at the same temperature for 30 minutes and then heated and stirred at a bath temperature of 65 for 6 hours. To the resulting reaction solution was added aqueous sodium hydrogen carbonate, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and concentrated to obtain 2.07 g (87% yield) of 1-methyl-3-chloro-4- (2,6-dimethylphenyl) -1,1,2,4-triazolone.
m p 84. 5 °C m p 84.5 ° C
1—メチル一 3—クロ口一 4一 （2， 6—ジメチルフヱニル） 一 1， 2， 4— トリァゾロン 10.0 g (42麵 ol) の N， N—ジメチルホルムアミ ド溶液を 5 °C以 下で攪拌しながらナトリウムメ トキシド 2.70g (50誦 ol) の N， N—ジメチル ホルムアミ ド （1 00ml) 溶液に滴下した。 完了後、 同一温度で 1時間攪拌し た後、 室温でさらに 3時間攪拌した。 生じた反応液を氷水にあけ、 酢酸ェチルで 抽出した。 有機層を水洗後、 濃縮し、 n—へキサンを加えて晶析、 ろ過すること により、 1—メチル一 3—メ トキシ一 4一 （2， 6—ジメチルフエニル） 一 1， 2, 4一トリァゾロン 6. 1 6 g (収率 63 %) を得た。 1-Methyl-3-chloro-1,4- (2,6-dimethylphenyl) 1-1,2,4-triazolone 10.0 g (42 (ol) of N, N-dimethylformamide solution at 5 ° C or less With stirring, a solution of 2.70 g (50 ol) of sodium methoxide was added dropwise to a solution of N, N-dimethylformamide (100 ml). After completion, the mixture was stirred at the same temperature for 1 hour, and further stirred at room temperature for 3 hours. The resulting reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer is washed with water, concentrated, n-hexane is added, and the mixture is crystallized and filtered to give 1-methyl-13-methoxy-14- (2,6-dimethylphenyl) 1-1,2,4. 6.16 g (63% yield) of triazolone was obtained.
mp. 1 5 1. 9 C mp. 1 5 1.9 C
1一メチル一 3—メ トキシー 4 _ (2， 6—ジメチルフエニル） 1， 2， 4 一トリァゾロン 16.2g (69.2議 ol) および N—ブロモコハク酸イミ ド 14.0g (78. 9誦 ol ) を四塩化炭素（700ml) に加え、 これに触媒量のァゾビスイソプチロニト リルを加えて、 加熱還流下 5時間反応させた。 反応液をろ過し、 ろ液を濃縮した 後、 残渣をシリ力ゲル力ラムクロマトグラフィー （溶出液；酢酸ェチル： トルェ ン = 1 ： 1) に付した後、 得られた粗結晶をエタノールから再結晶して、 1ーメ
チルー 3—メ トキシー 4一 〔2— （ブロモメチル） 一 6—メチルフエニル〕 一 1， 2, 4一トリァゾロン 13.0 g (収率 6 0%) を得た。 1-Methyl-3-methoxy-4_ (2,6-dimethylphenyl) 1,2,4-triazolone 16.2 g (69.2 ol) and N-bromosuccinic acid imide 14.0 g (78.9 ol) In addition to carbon tetrachloride (700 ml), a catalytic amount of azobisisobutyronitrile was added thereto, and the mixture was reacted with heating under reflux for 5 hours. After filtering the reaction solution and concentrating the filtrate, the residue was subjected to silica gel gel chromatography (eluent; ethyl acetate: toluene = 1: 1), and the obtained crude crystals were re-used from ethanol. Crystallize 13.0 g (yield: 60%) of tyl-3-methoxy-4- [2- (bromomethyl) -16-methylphenyl] 1-1,2,4-triazolone was obtained.
m 1 1 4. 3°C m 1 1 4.3 ° C
上記と同様にして、 As above,
1一メチル _ 3—クロ口一 4— (2， 6—ジメチル一 4一クロ口フエ二ル） 一 1， 2, 4一トリァゾロン （mp. 1 3 6. 5 °C) および 1ーメチルー 3—メ トキシ - 4 - (2, 6—ジメチル一 4一クロ口フエ二ル） 一 1， 2， 4—トリァゾロン (mp. 1 3 3. 2°C) を経て、 1—メチルー 3—メ トキシー 4一 〔 2— (ブ 口モメチル） 一 4—クロ口一 6—メチルフエニル〕 一 1， 2， 4一トリァゾロン (mp. 1 2 4. 5 °C) を製造することができる。 1-Methyl _ 3—Chloro-4- (2,6-dimethyl-14-Chlorophenyl) 1-1,2,4-Triazolone (mp. 136.5 ° C) and 1-methyl-3- Methoxy-4-(2,6-dimethyl-14-chlorophenol) 1,2,4-triazolone (mp.133.2 ° C), then 1-methyl-3-methoxy-4 It is possible to produce 1- [2- (bromomethyl) -14-chloro-1-6-methylphenyl] 1-1,2,4-triazolone (mp. 124.5 ° C).
次に製剤例を示す。 なお、 本発明化合物は表 1の化合物番号で示し、 部は重量 部を表わす。 Next, formulation examples are shown. The compounds of the present invention are indicated by the compound numbers in Table 1, and parts represent parts by weight.
製剤例 1 Formulation Example 1
本発明化合物 （1) 〜 （8) の各々 5 0部、 リグニンスルホン酸カルシウム 3 部、 ラウりル硫酸ナトリウム 2部および合成含水酸化珪素 45部をよく粉砕混合 して各々の水和剤を得る。 製剤例 2 50 parts of each of the compounds (1) to (8) of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder. . Formulation Example 2
本発明化合物 （1) 〜（8) の各々 1 0部、 ポリオキシエチレンスチリルフヱ ニルエーテル 1 4部、 ドデシルベンゼンスルホン酸カルシウム 6部およびキシレ ン 7 0部をよく混合して各々の乳剤を得る。 10 parts of each of the compounds (1) to (8) of the present invention, 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene are mixed well to obtain each emulsion. .
製剤例 3 Formulation Example 3
本発明化合物 （1)〜 （8) の各々 2部、 合成含水酸化珪素 1部、 リグニンス ルホン酸カルシウム 2部、 ベントナイ ト 3 0部および力オリンクレー 6 5部をよ く粉砕混合し、 水を加えてよく練り合わせた後、 造粒乾燥して各々の粒剤を得る。 製剤例 4 2 parts of each of the compounds of the present invention (1) to (8), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of force olin clay are mixed and pulverized, and water is added. After well kneading, granulate and dry to obtain each granule. Formulation Example 4
本発明化合物 （1) 〜 （8) の各々 2 5部、 ポリオキシエチレンソルビタンモ ノォレエ一ト 3部、 CMC 3部および水 6 9部を混合し、 有効成分の粒度が 5 ミ ク口ン以下になるまで湿式粉砕して各々の懸濁剤を得る。 25 parts of each of the compounds (1) to (8) of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed, and the particle size of the active ingredient is 5 μm or less. To obtain each suspension.
製剤例 5
本発明化合物 （1 ) 〜（8 ) 1 0部、 ポリオキシエチレンスチリルフヱニルェ 一テル 1部および水 8 9部を混合して、 各々の液剤を得る。 Formulation Example 5 10 parts of the compounds (1) to (8) of the present invention, 1 part of polyoxyethylenestyrylphenyl ether and 89 parts of water are mixed to obtain each liquid preparation.
次に、 本発明化合物が植物病害防除剤の有効成分として有用であることを試験 例で示す。 なお、 本発明化合物は表 1の化合物番号で示す。 Next, Test Examples show that the compound of the present invention is useful as an active ingredient of a plant disease controlling agent. The compounds of the present invention are indicated by the compound numbers in Table 1.
また、 比較対照に用いた化合物は表 2の化合物記号で示す。 The compounds used for comparison are indicated by the compound symbols in Table 2.
表 2 Table 2
試験例 1 イネいもち病防除試験 （予防効果） Test example 1 Rice blast control test (preventive effect)
プラスチックポッ卜に砂壌土を詰め、 イネ （日本晴） を播種し、 温室内で 2 0 日間育成した。 その後、 製剤例 1に準じて水和剤にした供試薬剤を水で希釈して 所定濃度にし、 それをそのイネ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、 いもち病菌の胞子懸濁液を噴霧、 接種した。 接種後、 2 8 °C、 多 湿下で 6日間置いた後、 防除効力を調査した。 その結果を表 3に示す。 A plastic pot was filled with sandy loam, rice (Nipponbare) was sown, and grown in a greenhouse for 20 days. Thereafter, the test reagent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the resulting solution was sprayed on foliage so as to sufficiently adhere to the rice leaf surface. After spraying, the plants were air-dried, sprayed with a spore suspension of the blast fungus, and inoculated. After inoculation, they were left at 28 ° C and high humidity for 6 days, and their control efficacy was examined. The results are shown in Table 3.
試験例 2 イネ紋枯病防除試験 （予防効果） Test example 2 Rice sheath blight control test (preventive effect)
プラスチックポッ卜に砂壌土を詰め、 イネ （日本晴） を播種し、 温室内で 2 0
日間育成した。 製剤例 1に準じて水和剤にした供試薬剤を水で希釈して所定濃度 にし、 それをその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、 紋枯病菌のフスマ培養菌糸を根元において接種した。 接種後、 2 8 °C、 多湿下で 4日間置いた後、 防除効力を調査した。 その結果を表 3に示す。 Fill plastic pots with sandy loam and sow rice (Nipponbare). Nurtured for days. The test agent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the resulting solution was sprayed on the foliage of the rice so as to sufficiently adhere to the leaf surface. After spraying, the plants were air-dried and inoculated with a bran culture mycelium of the sheath blight fungus at the root. After inoculation, the plants were placed at 28 ° C and in a humid environment for 4 days, and the control efficacy was examined. The results are shown in Table 3.
試験例 3 コムギ眼紋病防除試験 （予防効果） Test Example 3 Wheat eye spot control test (preventive effect)
プラスチックポッ卜に砂壌土を詰め、 コムギ （農林 7 3号） を播種し、 温室内 で 1 0日間育成した。 製剤例 2に準じて乳剤にした供試薬剤を水で希釈して所定 濃度にし、 それをそのコムギの幼苗の葉面に充分付着するように茎葉散布した。 散布後、 コムギ眼紋病菌の胞子懸濁液をコムギの株元に接種し、 1 5 °C多湿下で 1 4日間保った後、 防除効力を調査した。 その結果を表 3に示す。 Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. The test agent prepared as an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration, and the resulting solution was sprayed with foliage so as to sufficiently adhere to the leaves of the wheat seedlings. After spraying, a spore suspension of wheat eye spot bacterium was inoculated to the root of the wheat and kept at 15 ° C and high humidity for 14 days, and the control effect was examined. The results are shown in Table 3.
試験例 4 コムギぅどんこ病防除試験 （治療効果） Test Example 4 Wheat powdery mildew control test (Therapeutic effect)
プラスチックポッ卜に砂壌土を詰め、 コムギ （農林 7 3号） を播種し、 温室内 で 1 0日間育成した。 第 2葉が展開したそのコムギの幼苗にコムギうどんこ病菌 をふりかけ、 接種した。 接種後、 2 3 °Cの温室で 3日間育成し、.製剤例 4に準じ て懸濁剤にした供試薬剤を水で希釈して所定濃度にし、 それをそのコムギの葉面 に充分付着するように茎葉散布した。 散布後、 さらに照明下で 7日間育成し、 防 除効力を調査した。 その結果を表 3に示す。 Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. The wheat seedlings that had developed the second leaf were sprinkled with wheat powdery mildew and inoculated. After inoculation, grow in a greenhouse at 23 ° C for 3 days, dilute with water water to a prescribed concentration the suspension prepared as described in Formulation Example 4, and attach it sufficiently to the leaves of the wheat. Foliage was sprayed as if to do. After spraying, they were grown for additional 7 days under lighting, and their control efficacy was investigated. The results are shown in Table 3.
試験例 5 キユウリうどんこ病防除試験 （予防効果） Test Example 5 Test for Control of Powdery Mildew (Preventive Effect)
プラスチックポットに砂壌土を詰め、 キユウリ （相模半白） を播種し、 温室内 で 1 2日間育成した。 製剤例 1に準じて水和剤にした供試薬剤を水で希釈して所 定濃度にし、 それをそのキュゥリの幼苗の葉面に充分付着するように茎葉散布し た。 散布後、 キユウリうどんこ病菌の胞子懸濁液を接種した。 接種後、 2 5 °C、 照明下で 7日間生育し、 防除効力を調査した。 その結果を表 3に示す。
表 3 Plastic pots were filled with sandy loam, sown with Kiuri (Sagami Hanjiro), and grown for 12 days in a greenhouse. The test agent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the resulting solution was sprayed on the foliage of the cucumber seedlings so as to sufficiently adhere to the leaves. After spraying, a spore suspension of Cucumber powdery mildew was inoculated. After inoculation, they were grown at 25 ° C under light for 7 days, and their control efficacy was examined. The results are shown in Table 3. Table 3
産業上の利用可能性 Industrial applicability
本発明化合物は植物病害に対し優れた防除効果を示し、 植物病害防除剤として 利用でき、 式 （Π ) のクロロトリアゾロン化合物又は式 （ΙΠ) のトリァゾロン化 合物は、 本発明化合物の中間体として利用できる。
The compound of the present invention exhibits an excellent control effect on plant diseases, and can be used as a plant disease controlling agent. The chlorotriazolone compound of the formula (Π) or the triazolone compound of the formula (ΙΠ) is an intermediate of the compound of the present invention. Available as
Claims
1. 一般式 （ I ) 1. General formula (I)
で示されるトリアゾロン誘導体。 A triazolone derivative represented by the formula:
2. Xがメチル基である請求項 1記載のトリァゾロン誘導体。 2. The triazolone derivative according to claim 1, wherein X is a methyl group.
3. Zが水素原子または 4 _塩素原子である請求項.1または 2記載のトリアゾ 口ン誘導体。 3. The triazopine derivative according to claim 1 or 2, wherein Z is a hydrogen atom or a 4-chlorine atom.
4. Zが水素原子である請求項 1または 2記載のトリァゾ口ン誘導体。 4. The triazopine derivative according to claim 1, wherein Z is a hydrogen atom.
5. Yが水素原子、 メチル基または塩素原子である請求項 1、 2、 3または 4 記載の卜リアゾロン誘導体。 5. The triazolone derivative according to claim 1, 2, 3, or 4, wherein Y is a hydrogen atom, a methyl group, or a chlorine atom.
6. Yが水素原子または 5—メチル基である請求項 1、 2、 3または 4記載の トリァゾロン誘導体。 6. The triazolone derivative according to claim 1, 2, 3, or 4, wherein Y is a hydrogen atom or a 5-methyl group.
7. 一般式 （ I ) の化合物が下記式： 7. The compound of the general formula (I) has the following formula:
8. 一般式 （ I ) の化合物が下記式：
8. The compound of the general formula (I) has the following formula:
9. 請求項 1〜 8のいづれかに記載のトリアゾロン誘導体を有効成分として含 有することを特徴とする植物病害防除剤。 9. A plant disease controlling agent comprising the triazolone derivative according to any one of claims 1 to 8 as an active ingredient.
10. —般式 （Π ) 10. —General formula (Π)
( H )(H)
〔式中、 xはメチル基またはハロゲン原子を表わし、 γおよび zは、 同一または 相異なり、 水素原子、 メチル基またはハロゲン原子を表わす。 〕 [In the formula, x represents a methyl group or a halogen atom, and γ and z are the same or different and represent a hydrogen atom, a methyl group or a halogen atom. ]
で示されるクロロトリアゾロン化合物。 A chlorotriazolone compound represented by the formula:
11. 一般式 （III) 11. General formula (III)
〔式中、 Qは臭素原子または塩素原子を表わし、 Zは水素原子、 メチル基または ハロゲン原子を表わす。 〕 [In the formula, Q represents a bromine atom or a chlorine atom, and Z represents a hydrogen atom, a methyl group or a halogen atom. ]
で示されるトリアゾロン化合物。
A triazolone compound represented by the formula:
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU57812/96A AU5781296A (en) | 1995-05-29 | 1996-05-28 | Triazolone derivatives, use thereof, and intermediates for t he preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| JP13052695 | 1995-05-29 | ||
| JP7/130526 | 1995-05-29 | ||
| JP8/98058 | 1996-04-19 | ||
| JP8098058A JPH0948766A (en) | 1995-05-29 | 1996-04-19 | Triazolone derivative, its use and intermediate thereof |
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| Country | Link |
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| AU (1) | AU5781296A (en) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005652A2 (en) * | 1996-08-01 | 1998-02-12 | E.I. Du Pont De Nemours And Company | Arthropodicidal and fungicidal cyclic amides |
| WO1998023156A1 (en) * | 1996-11-26 | 1998-06-04 | E.I. Du Pont De Nemours And Company | Methyl substituted fungicides and arthropodicides |
| WO1999005139A1 (en) * | 1997-07-21 | 1999-02-04 | Basf Aktiengesellschaft | 2-[pyrazolyl and triazolyl-3'-oxymethylene]-phenyl-isoxazolones, triazolones and tetrazolones as pesticides and fungicides |
| US6200997B1 (en) | 1998-02-05 | 2001-03-13 | Basf Aktiengesellschaft | Heterocyclyl-substituted phenyl compounds, processes and intermediates for their preparation and their use for controlling harmful fungi and animal pests |
| US6489487B1 (en) | 1998-08-03 | 2002-12-03 | Sumitomo Chemical Company, Limited | Triazolone derivatives, use thereof, and intermediates therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994004514A1 (en) * | 1992-08-26 | 1994-03-03 | Fmc Corporation | Herbicidal 2-[(4-heterocyclic-phenoxymethyl)phenoxy]-alkanoates |
| WO1995014009A1 (en) * | 1993-11-19 | 1995-05-26 | E.I. Du Pont De Nemours And Company | Fungicidal cyclic amides |
-
1996
- 1996-04-19 JP JP8098058A patent/JPH0948766A/en active Pending
- 1996-05-28 WO PCT/JP1996/001434 patent/WO1996038425A1/en active Application Filing
- 1996-05-28 AU AU57812/96A patent/AU5781296A/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994004514A1 (en) * | 1992-08-26 | 1994-03-03 | Fmc Corporation | Herbicidal 2-[(4-heterocyclic-phenoxymethyl)phenoxy]-alkanoates |
| WO1995014009A1 (en) * | 1993-11-19 | 1995-05-26 | E.I. Du Pont De Nemours And Company | Fungicidal cyclic amides |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005652A2 (en) * | 1996-08-01 | 1998-02-12 | E.I. Du Pont De Nemours And Company | Arthropodicidal and fungicidal cyclic amides |
| WO1998005652A3 (en) * | 1996-08-01 | 1998-06-11 | E I De Pount De Nemours And Co | Arthropodicidal and fungicidal cyclic amides |
| WO1998023156A1 (en) * | 1996-11-26 | 1998-06-04 | E.I. Du Pont De Nemours And Company | Methyl substituted fungicides and arthropodicides |
| WO1999005139A1 (en) * | 1997-07-21 | 1999-02-04 | Basf Aktiengesellschaft | 2-[pyrazolyl and triazolyl-3'-oxymethylene]-phenyl-isoxazolones, triazolones and tetrazolones as pesticides and fungicides |
| US6200997B1 (en) | 1998-02-05 | 2001-03-13 | Basf Aktiengesellschaft | Heterocyclyl-substituted phenyl compounds, processes and intermediates for their preparation and their use for controlling harmful fungi and animal pests |
| US6489487B1 (en) | 1998-08-03 | 2002-12-03 | Sumitomo Chemical Company, Limited | Triazolone derivatives, use thereof, and intermediates therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0948766A (en) | 1997-02-18 |
| AU5781296A (en) | 1996-12-18 |
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