WO2009116558A1 - 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative and herbicide containing the same as active ingredient - Google Patents

1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative and herbicide containing the same as active ingredient Download PDF

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WO2009116558A1
WO2009116558A1 PCT/JP2009/055251 JP2009055251W WO2009116558A1 WO 2009116558 A1 WO2009116558 A1 WO 2009116558A1 JP 2009055251 W JP2009055251 W JP 2009055251W WO 2009116558 A1 WO2009116558 A1 WO 2009116558A1
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group
formula
compound
present
active ingredient
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PCT/JP2009/055251
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French (fr)
Japanese (ja)
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至 岡田
麻紀子 牛江
貴史 中山
英世 藤井
誠司 柿沼
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アグロカネショウ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to novel pyrazole carboxamide derivatives and herbicides containing them as active ingredients.
  • weed control by herbicides is essential for labor saving, improvement of crop productivity, and landscape protection in cultivation of agricultural and horticultural crops and in management of green areas such as parks, recreation facilities and roads. For this reason, research and development of herbicides has been actively carried out for many years, and various herbicides have been put to practical use at present. However, the emergence of weeds that have acquired resistance to conventionally used herbicides has also become a problem.
  • weeds such as mizuaoi, azenas, izohakobe, chikasigusa, anifish, and konagi are all over the place Control of these weeds is becoming more difficult every year.
  • environmental pollution such as pollution damage to the surrounding cultivation land due to rainfall infiltration migration or runoff, gasification, etc., groundwater contamination, pollution damage to subsequent crops due to soil residue is also a problem.
  • Patent Document 1 As compounds most similar to the present invention, the following herbicidally active compounds are known (eg, Patent Document 1 and Non-patent Documents 1 and 2).
  • this compound remains undegraded in the soil for a long period of time and there is a risk of soil contamination and adverse effects on subsequent crops, and the effect of reducing the amount of sprayed water is inferior. It has not been put into practical use because it has problems such as the difficulty in securing areas and the effect of large-scale spraying situations or uneven spraying.
  • pyrazole carboxamide derivatives are known to have insecticidal, acaricidal, bactericidal, herbicidal or medicinal activity, depending on the type of three substituents on the pyrazole ring and the amino group of carboxamide moiety.
  • the following microbicides have been developed as 1-alkylpyrazole-4-carboxamide derivatives (for example, Patent Documents 2 to 8).
  • Patent Documents 12 to 13 The following compounds have been developed as acaricides (eg, Patent Documents 12 to 13).
  • herbicidally active compounds are known as 1-phenylpyrazole-4-carboxamide (for example, Patent Documents 14 to 15).
  • acaricides are disclosed as pyrazole-5-carboxamide derivatives (for example, Patent Document 16).
  • insecticides for example, insecticides and acaricides (for example, Patent Document 17).
  • Patent Document 20 reports N-aralkyl-1-phenylpyrazole-3-carboxamide derivatives having insecticidal and acaricidal activity.
  • Patent Document 21 describes N-hydroxy-4-halo-5-unsubstituted-1-phenylpyrazole-3-carboxamide derivatives, for example, Patent Document 22.
  • N-alkyl-4-unsubstituted-5-alkyl-1-phenylpyrazole-3-carboxamide derivatives are also disclosed in, for example, Patent Document 23, N-alkyl-4-unsubstituted-1,5- Diphenylpyrazole-3-carboxamide derivatives have been described.
  • Patent Document 24 describes the herbicidal activity of N-alkyl-4-halo-1,5-diphenylpyrazole-3-carboxamide.
  • N-alkyl-4-unsubstituted-5-alkoxy-1-phenylpyrazole-3-carboxamide derivatives having pharmaceutical activity are described in Non-Patent Document 3 and Non-Patent Document 4, but the description related to pesticidal activity There is no.
  • N-methyl-4-bromo-5-methoxy-1-phenylpyrazole-3-carboxamide is described, for example, in Non-Patent Document 5, but it has no pharmaceutically activity but also completely describes pesticide activity.
  • 1-phenylpyrazole-3-carboxamide derivatives for example, compounds having the following bactericidal activity are disclosed (for example, Patent Documents 25 to 31).
  • the present invention provides a highly safe and useful chemical substance as an active ingredient of a herbicide, which exhibits high control effect on various weeds and has reduced problems such as soil contamination and effects on subsequent crops. It is.
  • the present invention relates to a 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative represented by and a herbicide containing the derivative as an active ingredient.
  • R 1 and R 2 each represent a hydrogen atom, a halogen atom, a C 1 to C 4 alkyl group, a trifluoromethyl group, a nitro group, a cyano group, C 1 to an alkoxy group having C 4, difluoromethoxy group, trifluoromethoxy group, a difluoromethylthio group, a trifluoromethylthio group, difluoromethyl sulfinyl group, a difluoromethyl sulfonyl group, trifluoromethyl sulfinyl group, or a trifluoromethylsulfonyl group.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned suitably, for example.
  • C 1 to C 4 alkyl group for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, etc.
  • the alkoxy group of C 1 ⁇ C 4, for example, a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, isobutoxy group, sec- butoxy group, C 1 such as t- butoxy such as linear or branched alkoxy group having ⁇ C 4 are preferably exemplified.
  • R 1 is a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a difluoromethoxy group, a trifluoromethoxy group or the like
  • R 2 is preferably a hydrogen atom.
  • R 3 represents a hydroxyl group, a C 1 to C 4 alkoxy group, an amino group, a C 1 to C 4 alkylamino group, a C 2 to C 4 N, N-dialkylamino group or a C 2 to C 4 N -Represents an alkyl N-alkoxyamino group.
  • the range of the C 1 to C 4 alkoxy group is as described above, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxyl group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group.
  • a C 1 to C 4 linear or branched alkoxy group such as t-butoxy group.
  • the C 1 to C 4 alkylamino group is a C 1 to C 4 alkyl group wherein the alkyl group of the amino group is a C 1 to C 4 alkyl group.
  • Examples of such a C 1 to C 4 alkylamino group include a methylamino group and the like , C 1 -C 4 straight such as ethylamino group, n-propylamino group, isopropylamino group, cyclopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino group, t-butylamino group, etc.
  • the C 2 -C 4 N, N-dialkylamino group is one in which the nitrogen atom of the amino group is substituted with two alkyl groups, and the range of the alkyl group is the total number of carbon atoms in the alkyl group Is 2 to 4, and specifically, for example, C 2 to C 4 N, N-dialkylamino groups such as dimethylamino, diethylamino, methylethylamino, methylpropylamino and the like are preferably mentioned.
  • N-alkyl N-alkoxyamino group for example, methylmethoxyamino group, methylethoxyamino group, methyl-n-propoxyamino group, ethylmethoxy group, n-propylmethoxy group and the like are preferable. It can be mentioned.
  • R 3 for example, a methylamino group or a cyclopropylamino group is preferable.
  • the compounds of the present invention represented by the above formula (I) are novel compounds.
  • the compound of the present invention can be produced, for example, according to the following reaction formula 1, in accordance with, for example, JP-A-60-172,967 (Patent Document 1). Reaction formula 1
  • R 1 , R 2 and R 3 are as defined in the above formula (I), and X represents a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group, an ethoxy group or a propoxy group.
  • X represents a chlorine atom or a bromine atom
  • a solvent for example, benzene, or an aromatic hydrocarbon such as toluene or xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone or the like Ketones; halogenated hydrocarbons such as chloroform and methylene chloride; water; esters such as methyl acetate and ethyl acetate; or tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide, etc.
  • the reaction can be performed in the presence of a base at, for example, 0 ° C. to 30 ° C., preferably 0 ° C. to 5 ° C., using a polar solvent of As a base, for example, sodium hydroxide, potassium hydroxide, pyridine or triethylamine can be used.
  • a base for example, sodium hydroxide, potassium hydroxide, pyridine or triethylamine can be used.
  • X is a hydroxyl group, a methoxy group, an ethoxy group or a propoxy group
  • the reaction can be carried out at 5 to 100.degree. C., preferably 20 to 80.degree.
  • the solvent was distilled off under reduced pressure and water was added. After that, extract with water-insoluble benzene, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; esters such as ethyl acetate, and wash with saturated saline, and then anhydrous sodium sulfate After drying with a desiccant such as, the solvent may be distilled off under reduced pressure.
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as chloroform and methylene chloride
  • esters such as ethyl acetate, and wash with saturated saline, and then anhydrous sodium sulfate
  • the solvent may be distilled off under reduced pressure.
  • R 1 , R 2 and R 4 are as defined in the above formula (III).
  • the above reaction can be carried out in the presence or absence of a solvent and a base.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; water; methyl acetate And esters such as ethyl acetate; polar solvents such as acetonitrile, N, N-dimethylformamide, N-methyl pyrrolidone and dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; methanol, ethanol, propanol, ethylene glycol and the like Or mixed solvents of the above solvents.
  • Examples of the base include alkali metal hydrates such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate Sodium hydrogen carbonate; alkali metal hydrogen carbonates such as potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; metal alkoxides such as sodium methoxide and sodium ethoxide.
  • the reaction temperature is, for example, 5 to 100 ° C., preferably 0 to 50 ° C.
  • mineral acids such as hydrochloric acid and sulfuric acid
  • acidification with organic acids such as acetic acid and propionic acid
  • the solvent is distilled off under reduced pressure, water is added, and then benzene insoluble in water, aromatic hydrocarbons such as toluene and xylene; halogen based hydrocarbons such as chloroform and dichloromethane
  • Extraction with an ester such as ethyl acetate and the like, washing with saturated brine, drying with a desiccant such as anhydrous sodium sulfate, and evaporation of the solvent under reduced pressure may be carried out.
  • the above reaction can be carried out in the presence or absence of a solvent and in the presence of a base.
  • a solvent include water; alcohols such as methanol, ethanol, propanol and ethylene glycol, and mixed solvents of the above solvents.
  • the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate Examples thereof include alkali metal carbonates such as sodium and potassium hydrogen carbonate; and alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate.
  • the reaction temperature is, for example, 5 to 150 ° C., preferably 10 to 110 ° C.
  • the precipitate is acidified after being acidified with a mineral acid such as hydrochloric acid or sulfuric acid; acetic acid or an organic acid such as propionic acid It may be filtered and washed with water and then dried.
  • R 1 and R 2 are as defined in the formula (I), and Z represents a chlorine atom or a bromine atom.
  • the compound of formula (VI) is reacted with a halogenating agent to give a compound of formula (VII).
  • the above reaction can be carried out in the presence or absence of a solvent.
  • the solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane.
  • halogenating agent examples include thionyl chloride, thionyl bromide, oxalyl chloride, oxalyl bromide, phosphorus pentachloride, phosphorus pentabromide, phosphorus trichloride and the like.
  • the reaction temperature is, for example, 5 to 100 ° C., preferably 20 to 90 ° C.
  • the reaction solution is concentrated under reduced pressure, and the obtained residue is dissolved with a hydrocarbon such as hexane or heptane which does not dissolve the desired product very much. It may be dried after washing.
  • the herbicide of the present invention containing the compound of the present invention represented by the formula (I) as an active ingredient has an excellent herbicidal effect on various weeds of agricultural land and non-agricultural land. Above all, it is useful as an active ingredient of a foliage treating herbicide for upland field annual weeds.
  • weeds for example, crabgrass, enokologsa, pokeweed, bluefish, shiroza, ichibi, chickweed, morning glory and the like can be mentioned.
  • weeds to be controlled by the compounds of the present invention are not limited to those exemplified above.
  • the herbicide of the present invention containing the compound of the present invention represented by the formula (I) as an active ingredient has high safety to crops such as wheat, barley, sorghum, corn, cotton and beets.
  • the compound of the present invention represented by the formula (I) may be used alone, but it is preferably used as a composition to which a pesticide adjuvant widely used in the art is added.
  • the dosage form of the herbicide is not particularly limited, for example, the form of an emulsion, a wettable powder, a powder, a flowable, a fine granule, a granule, a tablet, an oil and the like is preferable.
  • One or two or more of the compounds of the present invention can be blended as an active ingredient.
  • Pesticide adjuvants used to produce herbicides are, for example, substances having effects such as enhancement of the effect of herbicide, stabilization, improvement of dispersibility, and enhancement of crop safety, for example, carriers (Diluents), spreaders, emulsifiers, wetting agents, dispersants, disintegrants, wetting agents and the like can be used.
  • Liquid carriers include, for example, water; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, butanol and glycol; ketones such as acetone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; Naphthalene; cyclohexane; animal and vegetable oils; or fatty acids and the like can be mentioned.
  • examples of the solid carrier include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, saw dust, nitrocellulose, starch, gum arabic and the like.
  • emulsifying agent and the dispersing agent usual surfactants can be used.
  • anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethyl ammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine and the like;
  • An ionic surfactant; a nonionic surfactant; or a zwitterionic surfactant etc. can be used.
  • spreading agents such as polyoxyethylene fatty acid ester and polyoxyethylene alkyl ester
  • wetting agents such as dialkyl sulfosuccinate
  • fixing agents such as carboxyl methyl cellulose and polyvinyl alcohol
  • collapse such as sodium lignin sulfonate and sodium lauryl sulfate Agents can be used.
  • the content of the active ingredient in the herbicide of the present invention is, for example, selected from the range of 0.01 to 99.5%, and may be suitably determined according to various conditions such as the formulation form, application method and the like.
  • the emulsion for example, about 1 to 90% by mass, preferably 10 to 40% by mass
  • in the wettable powder for example, about 1 to 90% by mass, preferably 10 to 80% by mass
  • about 0.5 to 20% by mass preferably 1 to 10% by mass
  • a flowable for example, about 1 to 90% by mass, preferably 10 to 50% by mass. It is preferred to manufacture.
  • an emulsion of a stock solution can be prepared by mixing a solvent, a surfactant and the like with the compound of the present invention which is an active ingredient, and this stock solution is Can be diluted and applied.
  • the compound of the present invention, which is the active ingredient can be mixed with water, surfactant, etc. to produce a stock solution, and this stock solution is further diluted with water to a predetermined concentration when used. Can be applied.
  • the compound of the present invention as an active ingredient, a solid carrier, a surfactant and the like can be mixed and manufactured, and when used, it can be applied diluted with water to a predetermined concentration.
  • the compound of the present invention as an active ingredient, a solid carrier and the like can be mixed and applied as they are.
  • the manufacturing method of each above-mentioned formulation form is not limited to the above-mentioned thing, those skilled in the art can select suitably according to the kind of an active ingredient, the purpose of application, etc.
  • herbicide of the present invention other herbicides, insecticides, acaricides, fungicides, growth regulators, fertilizers, as long as the activity of the compound of the present invention of the formula (I) which is the active ingredient is not impaired.
  • the compounds of the present invention can be used in the same manner as conventional herbicides, and for example, soil treatment or foliage treatment is carried out using the compounds of the present invention before germination, early germination and growth stage of upland weeds. be able to.
  • the application amount of the herbicide of the present invention can be appropriately selected depending on the application method, purpose, time, weeding condition and the like, but the amount of active ingredient is usually 0.001 kg to 10 kg per hectare, for example. Is preferably 0.003 kg to 3 kg.
  • Example 2 Synthesis of 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-carboxylic acid
  • Ethyl 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-carboxylate obtained in Example 1 A mixture of 9.02 g, 2.40 g of sodium hydroxide, 40 ml of ethyl alcohol and 40 ml of water was heated to reflux for 1 hour. After cooling to room temperature, hydrochloric acid is added to acidify and crystals are collected by filtration, washed with water and dried to obtain 8.10 g of the compound of the present invention (No. 4) described in Table 1. The melting point was 140-142 ° C.
  • Example 3 Synthesis of N-methyl-1- (4-chlorophenyl) -5-difluoromethylpyrazole-3-carboxamide 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-obtained in Example 2
  • the solution was heated under reflux for 1 hour in 5 ml of thionyl chloride and concentrated under reduced pressure.
  • the resulting residue was added to 1.16 g of 40% aqueous methylamine solution and stirred at room temperature for 1 hour.
  • the mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was washed with hexane to obtain 0.35 g of the compound of the present invention (No. 31) described in Table 2.
  • the melting point was 167-169 ° C.
  • Example 4 Synthesis of Nn-propyl-1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-carboxamide 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-obtained in Example 1 3.01 g of ethyl carboxylate and 0.18 g of n-propylamine were stirred in 10 ml of methanol at room temperature for 18 hours. The mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 2.50 g of a compound (No. 33) described in Table 2 below. The melting point was 128-130 ° C. Other than that, the compound of the present invention was prepared similarly. Tables 1 and 2 below describe the compounds of the invention prepared according to the examples.
  • formulation examples of a herbicide containing the compound of the present invention as an active ingredient are shown.
  • the scope of the present invention is not limited at all by the following formulation examples.
  • all being "part" in an Example represents a mass part.
  • Formulation Example 2 Hydrating agent Compound of the present invention (20 parts), Carplex # 80 (20 parts), ST kaolin clay (50 parts), sodium lignin sulfonate (5 parts) and Lunox P-as a wetting agent 65 L (5 parts) was uniformly mixed and ground in a jet air mill to obtain a wettable powder.
  • Formulation Example 3 Granule
  • the compound of the present invention (5 parts), bentonite (30 parts), clay (60 parts) and sodium lignin sulfonate (5 parts) were uniformly ground and mixed, water was added and thoroughly mixed. Thereafter, the mixture was extruded and granulated, and dried and sized to obtain granules.
  • the compounds of the present invention show excellent herbicidal effects even when the amount of water sprayed is small, and are stable even in areas where water is difficult to secure, in large-scale spraying situations, and also in uneven spraying. Exhibit excellent weeding effects.
  • the 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative compound of the present invention has an excellent control effect on various weeds and is effective as a herbicide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

Disclosed is a 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative having excellent herbicidal activity. The carboxamide derivative is represented by formula (I). (In the formula, R1 and R2 independently represent a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a trifluoromethyl group, a nitro group, a cyano group, a C1-C4 alkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a difluoromethylthio group, trifluoromethylthio group, a difluoromethylsulfinyl group, a difluoromethylsulfonyl group, a trifluoromethylsulfinyl group or a trifluoromethylsulfonyl group; and R3 represents a hydroxyl group, a C1-C4 alkoxy group, an amino group, a C1-C4 alkylamino group, a C2-C4 N,N-dialkylamino group or a C2-C4 N-alkyl-N-alkoxyamino group.)

Description

１-フェニル-５-ジフルオロメチルピラゾール-４-カルボキサミド誘導体及びこれを有効成分とする除草剤1-Phenyl-5-difluoromethylpyrazole-4-carboxamide derivative and herbicide containing the same as an active ingredient
　本発明は、新規なピラゾールカルボキサミド誘導体及びこれらを有効成分として含有する除草剤に関する。 The present invention relates to novel pyrazole carboxamide derivatives and herbicides containing them as active ingredients.
　従来、農園芸作物の栽培や、公園、レクリエーション施設、道路などの緑地管理にあたり、除草剤による雑草防除は省力化や作物生産性向上、景観保護のためには必要不可欠である。そのため長年にわたって除草剤の研究開発が積極的に行われ、現在多種多様な除草剤が実用化されている。
　しかしながら、従来汎用の除草剤に対して抵抗性を獲得した雑草の出現も問題となっている。例えば桑園ではビピリジリウム系除草剤に抵抗性を示すハルジオンが確認されており、近年では水田栽培におけるスルホニルウレア系除草剤抵抗性雑草として、ミズアオイ、アゼナ類、ミゾハコベ、キカシグサ、イヌホタルイ、コナギなどが各地で出現し、これらの雑草に対する防除が年々困難になっている。また、降雨による土壌浸透移行や流亡、ガス化などによる周辺栽培地への薬害や地下水汚染、土壌残留による後作物への薬害といった環境汚染も問題となっている。 Conventionally, weed control by herbicides is essential for labor saving, improvement of crop productivity, and landscape protection in cultivation of agricultural and horticultural crops and in management of green areas such as parks, recreation facilities and roads. For this reason, research and development of herbicides has been actively carried out for many years, and various herbicides have been put to practical use at present.
However, the emergence of weeds that have acquired resistance to conventionally used herbicides has also become a problem. For example, in the vineyard, hardione resistant to bipyridinium herbicides has been confirmed, and in recent years, as a sulfonylurea herbicide-resistant weed in paddy field cultivation, weeds such as mizuaoi, azenas, izohakobe, chikasigusa, anifish, and konagi are all over the place Control of these weeds is becoming more difficult every year. In addition, environmental pollution such as pollution damage to the surrounding cultivation land due to rainfall infiltration migration or runoff, gasification, etc., groundwater contamination, pollution damage to subsequent crops due to soil residue is also a problem.
　一方、気候変動や輸入飼料の使用などに伴い、従来の栽培地に無かった外来種の雑草の出現も問題となっている。例えばトウモロコシ栽培におけるイチビ、ワルナスビ、アレチウリ、ショクヨウガヤツリなどが出現しており、汎用除草剤では充分に満足な防除ができない雑草が増加している。
　このように、今日においても更に作物に対して薬害を及ぼすことがなく対象雑草のみを選択的に枯殺する除草剤、又は作物栽培地以外の場所に発生する多種多様な雑草を速やかに枯殺する除草剤、かつ環境汚染軽減のため、より低薬量で高い除草効果があり、かつ目的達成後は速やかに分解される化合物が必要となっている。 On the other hand, with the change of climate and the use of imported feed, the emergence of alien species of weeds, which were not found in conventional cultivation areas, has also become a problem. For example, in corn cultivation, Ibi, Harunasbi, Arechiuri, and Stag beetle have appeared, and weeds that can not be sufficiently satisfactorily controlled by general-purpose herbicides are increasing.
Thus, even today, herbicides that selectively kill only target weeds without causing phytotoxicity to crops even more rapidly, or various types of weeds that occur anywhere else than the crop cultivation site are rapidly killed. There is a need for herbicides and compounds that have high herbicidal effects at lower doses and that can be quickly degraded after the purpose is achieved to reduce environmental pollution.
　本発明と最も類似した化合物として、以下の除草活性化合物があることが知られている（例えば、特許文献１及び非特許文献１～２）。 As compounds most similar to the present invention, the following herbicidally active compounds are known (eg, Patent Document 1 and Non-patent Documents 1 and 2).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　しかしながら、この化合物は、長期間にわたり土壌中において分解されずに残留し、土壌汚染や後作物に悪影響を及ぼす危険性があること、また散布水量を少なくした場合の効果が劣ることから、水の確保が困難な地域や、大規模散布場面あるいは不均一な散布において効果が劣るといった問題があること等から実用化には至っていない。 However, this compound remains undegraded in the soil for a long period of time and there is a risk of soil contamination and adverse effects on subsequent crops, and the effect of reducing the amount of sprayed water is inferior. It has not been put into practical use because it has problems such as the difficulty in securing areas and the effect of large-scale spraying situations or uneven spraying.
　一方、ピラゾールカルボキサミド誘導体は、ピラゾール環上の３個の置換基とカルボキサミド部分のアミノ基の種類により、それぞれ、殺虫、殺ダニ、殺菌、除草活性あるいは医薬活性を有することが知られている。例えば、１-アルキルピラゾール-４-カルボキサミド誘導体として下記のような殺菌剤が開発されている（例えば、特許文献２～８）。 On the other hand, pyrazole carboxamide derivatives are known to have insecticidal, acaricidal, bactericidal, herbicidal or medicinal activity, depending on the type of three substituents on the pyrazole ring and the amino group of carboxamide moiety. For example, the following microbicides have been developed as 1-alkylpyrazole-4-carboxamide derivatives (for example, Patent Documents 2 to 8).
Figure JPOXMLDOC01-appb-C000003
 一般名：フラメトピル
Figure JPOXMLDOC01-appb-C000003
 Common Name: Flametopill
Figure JPOXMLDOC01-appb-C000004
 一般名：ペンチオピラド
Figure JPOXMLDOC01-appb-C000004
 Common Name: Penthiopyrade
Figure JPOXMLDOC01-appb-C000005
 一般名：bixafen
Figure JPOXMLDOC01-appb-C000005
 Common Name: bixafen
Figure JPOXMLDOC01-appb-C000006
 一般名：sedaxane
Figure JPOXMLDOC01-appb-C000006
 Common Name: sedaxane
Figure JPOXMLDOC01-appb-C000007
 一般名：isopyrazam
Figure JPOXMLDOC01-appb-C000007
 Common name: isopyrazam
　また、下記除草剤が開発されている（例えば、特許文献９～１１）。 In addition, the following herbicides have been developed (for example, Patent Documents 9 to 11).
Figure JPOXMLDOC01-appb-C000008
 開発コードNo.：EL-177
Figure JPOXMLDOC01-appb-C000008
 Development code No .: EL-177
Figure JPOXMLDOC01-appb-C000009
 開発コードNo.：KPP-297
Figure JPOXMLDOC01-appb-C000009
 Development code No .: KPP-297
Figure JPOXMLDOC01-appb-C000010
 開発コードNo.：KPP-856
Figure JPOXMLDOC01-appb-C000010
 Development code No .: KPP-856
　殺ダニ剤として下記の化合物が開発されている（例えば、特許文献１２～１３）。 The following compounds have been developed as acaricides (eg, Patent Documents 12 to 13).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 　１-フェニルピラゾール-４-カルボキサミドとして、下記除草活性化合物が知られている（例えば、特許文献１４～１５）。
Figure JPOXMLDOC01-appb-C000012
 The following herbicidally active compounds are known as 1-phenylpyrazole-4-carboxamide (for example, Patent Documents 14 to 15).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　ピラゾール-５-カルボキサミド誘導体としては、下記殺ダニ剤が開示されている（例えば、特許文献１６）。 The following acaricides are disclosed as pyrazole-5-carboxamide derivatives (for example, Patent Document 16).
Figure JPOXMLDOC01-appb-C000014
 一般名：テブフェンピラド
Figure JPOXMLDOC01-appb-C000014
 Common name: tebufen pilade
　殺虫、殺ダニ剤として、例えば、以下の化合物が知られている（例えば、特許文献１７）。 For example, the following compounds are known as insecticides and acaricides (for example, Patent Document 17).
Figure JPOXMLDOC01-appb-C000015
 一般名：トルフェンピラド
Figure JPOXMLDOC01-appb-C000015
 Common Name: Tolfenpilado
　また、殺虫剤として、以下の化合物が知られている（例えば、特許文献１８～１９）。 In addition, the following compounds are known as insecticides (eg, Patent Documents 18 to 19).
Figure JPOXMLDOC01-appb-C000016
 一般名：クロラントニルピロール
Figure JPOXMLDOC01-appb-C000016
 Common Name: Chlorantylpyrrole
　１-フェニルピラゾール-３-カルボキサミド誘導体については、例えば、特許文献２０に殺虫及び殺ダニ活性を有するN-アラルキル-１-フェニルピラゾール-３-カルボキサミド誘導体が報告されている。また、除草剤の薬害軽減作用を有する物質として、例えば、特許文献２１には、N-ヒドロキシ-4-ハロ-5-非置換-１-フェニルピラゾール-３-カルボキサミド誘導体が、例えば、特許文献２２には、N-アルキル-４-非置換-５-アルキル-1-フェニルピラゾール-３-カルボキサミド誘導体が、また、例えば、特許文献２３には、N-アルキル-４-非置換-1,5-ジフェニルピラゾール-３-カルボキサミド誘導体が記載されている。また、例えば、特許文献２４には、N-アルキル-４-ハロ-1,5-ジフェニルピラゾール-３-カルボキサミドの除草活性に関する記載がある。 For 1-phenylpyrazole-3-carboxamide derivatives, for example, Patent Document 20 reports N-aralkyl-1-phenylpyrazole-3-carboxamide derivatives having insecticidal and acaricidal activity. Moreover, as a substance having a safening effect of a herbicide, for example, Patent Document 21 describes N-hydroxy-4-halo-5-unsubstituted-1-phenylpyrazole-3-carboxamide derivatives, for example, Patent Document 22. In addition, N-alkyl-4-unsubstituted-5-alkyl-1-phenylpyrazole-3-carboxamide derivatives are also disclosed in, for example, Patent Document 23, N-alkyl-4-unsubstituted-1,5- Diphenylpyrazole-3-carboxamide derivatives have been described. Also, for example, Patent Document 24 describes the herbicidal activity of N-alkyl-4-halo-1,5-diphenylpyrazole-3-carboxamide.
　更に、医薬活性を有するN-アルキル-４-非置換-５-アルコキシ-1-フェニルピラゾール-３-カルボキサミド誘導体が、非特許文献３及び非特許文献４に記載されているが、農薬活性に関する記載はない。また、N-メチル-4-ブロモ-5-メトキシ-1-フェニルピラゾール-3-カルボキサミドが、例えば、非特許文献５に記載されているが、医薬活性がないばかりか農薬活性については全く記載されていない。
　更に、１-フェニルピラゾール-３-カルボキサミド誘導体として、例えば、下記殺菌活性を有する化合物が開示されている（例えば、特許文献２５～３１）。 Furthermore, N-alkyl-4-unsubstituted-5-alkoxy-1-phenylpyrazole-3-carboxamide derivatives having pharmaceutical activity are described in Non-Patent Document 3 and Non-Patent Document 4, but the description related to pesticidal activity There is no. In addition, N-methyl-4-bromo-5-methoxy-1-phenylpyrazole-3-carboxamide is described, for example, in Non-Patent Document 5, but it has no pharmaceutically activity but also completely describes pesticide activity. Not.
Furthermore, as 1-phenylpyrazole-3-carboxamide derivatives, for example, compounds having the following bactericidal activity are disclosed (for example, Patent Documents 25 to 31).
特開昭60-172967号公報Japanese Patent Application Laid-Open No. 60-172967 特許第2638966号公報Patent No. 2638966 gazette 特開2001-151770号公報JP 2001-151770 A 特表2005-530694号公報Japanese Patent Application Publication No. 2005-530694 特表2005-532271号公報Japanese Patent Application Publication No. 2005-532271 特表2006-511485号公報Japanese Patent Application Publication No. 2006-511485 特表2008-515834号公報Japanese Patent Application Publication No. 2008-515834 ＷＯ2008-113447号公報WO 2008-113447 特開昭60-172968号公報Japanese Patent Application Laid-Open No. 60-172968 ＷＯ2001-23358号公報WO 2001-23358 特開2002-348280号公報JP 2002-348280 A 特開2006-56788号公報JP 2006-56788 A 特開2006-199637号公報Unexamined-Japanese-Patent No. 2006-199637 特開昭60-172968号公報Japanese Patent Application Laid-Open No. 60-172968 特開昭61-72757号公報Japanese Patent Application Laid-Open No. 61-72757 特許第1838897号公報Patent No. 1838897 gazette 特許第2861104号公報Patent No. 2861104 特表2004-538328号公報Japanese Patent Publication No. 2004-538328 特表2005-502716号公報Japanese Patent Application Publication No. 2005-502716 特開昭64-25763号公報Japanese Patent Application Laid-Open No. 64-25763 特開昭63-91373号公報Japanese Patent Application Laid-Open No. 63-91373 特開平1-283274号公報Unexamined-Japanese-Patent No. 1-283274 特開昭63-115867号公報Japanese Patent Application Laid-Open No. 63-115867 特開平8-12654号公報Japanese Patent Application Laid-Open No. 8-21654 特開平11-171867号公報Unexamined-Japanese-Patent No. 11-171867 gazette 特開平11-199566号公報Japanese Patent Application Laid-Open No. 11-199566 特開2000-103784号公報JP 2000-103784 A 特開2000-169453号公報JP 2000-169453 A 特開2001-240592号公報JP, 2001-240592, A 特開2002-205985号公報Japanese Patent Laid-Open No. 2002-205985 特開2002-265452号公報JP 2002-265452 A
　本発明は、各種雑草に対して高い防除効果を示し、かつ土壌汚染や後作物への影響等の問題が軽減された、安全性の高く、除草剤の有効成分として有用な化学物質を提供することにある。 The present invention provides a highly safe and useful chemical substance as an active ingredient of a herbicide, which exhibits high control effect on various weeds and has reduced problems such as soil contamination and effects on subsequent crops. It is.
　本発明者等は、上記の課題を解決すべく鋭意努力した結果、下記の式で示される１-フェニル-５-ジフルオロメチルピラゾール-４-カルボキサミド誘導体（以下、総称として、「本発明の化合物」と言う）が、上記の特徴を有する有用な化合物であることを見出し、本発明を完成するに至ったものである。即ち、本発明は、下記式(I)、 As a result of earnest efforts by the present inventors to solve the above problems, 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative represented by the following formula (hereinafter referred to as "the compound of the present invention as a generic term") Is found to be a useful compound having the above characteristics, and the present invention has been completed. That is, the present invention relates to the following formula (I):
Figure JPOXMLDOC01-appb-C000017
 　　　　　　　(I)
Figure JPOXMLDOC01-appb-C000017
 (I)
で表される１-フェニル-５-ジフルオロメチルピラゾール-４-カルボキサミド誘導体及びこの誘導体を有効成分として含む除草剤に関するものである。 The present invention relates to a 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative represented by and a herbicide containing the derivative as an active ingredient.
　式(I)で表される本発明の化合物において、Ｒ1及びＲ2は、水素原子、ハロゲン原子、Ｃ1～Ｃ4のアルキル基、トリフルオロメチル基、ニトロ基、シアノ基、Ｃ1～Ｃ4のアルコキシ基、ジフルオロメトキシ基、トリフルオロメトキシ基、ジフルオロメチルチオ基、トリフルオロメチルチオ基、ジフルオロメチルスルフィニル基、ジフルオロメチルスルホニル基、トリフルオロメチルスルフィニル基、又はトリフルオロメチルスルホニル基を示す。
　ハロゲン原子としては、例えば、フッ素原子や、塩素原子、臭素原子、ヨウ素原子等が好適に挙げられる。
　Ｃ1～Ｃ4のアルキル基としては、例えば、メチル基や、エチル基、n-プロピル基、イソプロピル基、シクロプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基等のＣ1～Ｃ4の直鎖、分岐鎖もしくは環状アルキル基などが好適に挙げられる。
　Ｃ1～Ｃ4のアルコキシ基としては、例えば、メトキシ基や、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、t-ブトキシ基等のＣ1～Ｃ4の直鎖もしくは分岐鎖アルコキシ基などが好適に挙げられる。
　特にＲ1としては、水素原子や塩素原子、臭素原子、フッ素原子、ジフルオロメトキシ基、トリフルオロメトキシ基などであり、Ｒ2としては水素原子が好ましい。 In the compound of the present invention represented by the formula (I), R 1 and R 2 each represent a hydrogen atom, a halogen atom, a C 1 to C 4 alkyl group, a trifluoromethyl group, a nitro group, a cyano group, C 1 to an alkoxy group having C 4, difluoromethoxy group, trifluoromethoxy group, a difluoromethylthio group, a trifluoromethylthio group, difluoromethyl sulfinyl group, a difluoromethyl sulfonyl group, trifluoromethyl sulfinyl group, or a trifluoromethylsulfonyl group.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned suitably, for example.
As the C 1 to C 4 alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, etc. And C 1 -C 4 straight-chain, branched or cyclic alkyl groups, and the like.
The alkoxy group of C 1 ~ C 4, for example, a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, isobutoxy group, sec- butoxy group, C 1 such as t- butoxy such as linear or branched alkoxy group having ~ C 4 are preferably exemplified.
In particular, R 1 is a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a difluoromethoxy group, a trifluoromethoxy group or the like, and R 2 is preferably a hydrogen atom.
　Ｒ3は、ヒドロキシル基、Ｃ1～Ｃ4のアルコキシ基、アミノ基、Ｃ1～Ｃ4のアルキルアミノ基、Ｃ2～Ｃ4のＮ，Ｎ－ジアルキルアミノ基又はＣ2～Ｃ4のＮ－アルキルＮ－アルコキシアミノ基を示す。
　Ｃ1～Ｃ4のアルコキシ基の範囲は、上記の通りであり、例えば、メトキシ基や、エトキシ基、n-プロポキシル基、イソプロポキシル基、n-ブトキシ基、イソブトキシ基、sec-ブトキシ基、t-ブトキシ基等のＣ1～Ｃ4の直鎖もしくは分岐鎖アルコキシ基などが好適に挙げられる。
　Ｃ1～Ｃ4のアルキルアミノ基は、アミノ基のアルキル基が、Ｃ1～Ｃ4のアルキル基であり、このようなＣ1～Ｃ4のアルキルアミノ基としては、例えば、メチルアミノ基や、エチルアミノ基、n-プロピルアミノ基、イソプロピルアミノ基、シクロプロピルアミノ基、n-ブチルアミノ基、イソブチルアミノ基、sec-ブチルアミノ基、t-ブチルアミノ基等のＣ1～Ｃ4の直鎖、分岐鎖もしくは環状アルキル基のアミノ基が好適に挙げられる。
　Ｃ2～Ｃ4のＮ，Ｎ－ジアルキルアミノ基は、アミノ基の窒素原子が二つのアルキル基で置換されているものであり、そのアルキル基の範囲は、アルキル基の炭素数のトータルの数が２～４であり、具体的には、例えば、ジメチルアミノ基や、ジエチルアミノ基、メチルエチルアミノ基、メチルプロピルアミノ基等のＣ2～Ｃ4のＮ，Ｎ－ジアルキルアミノ基が好適に挙げられる。
　Ｃ2～Ｃ4のＮ－アルキルＮ－アルコキシアミノ基としては、例えば、メチルメトキシアミノ基、メチルエトキシアミノ基、メチル-n-プロポキシアミノ基、エチルメトキシ基、n-プロピルメトキシ基等が好適に挙げられる。
　Ｒ3としては、例えば、メチルアミノ基や、シクロプロピルアミノ基が好ましい。 R 3 represents a hydroxyl group, a C 1 to C 4 alkoxy group, an amino group, a C 1 to C 4 alkylamino group, a C 2 to C 4 N, N-dialkylamino group or a C 2 to C 4 N -Represents an alkyl N-alkoxyamino group.
The range of the C 1 to C 4 alkoxy group is as described above, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxyl group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group. And a C 1 to C 4 linear or branched alkoxy group such as t-butoxy group.
The C 1 to C 4 alkylamino group is a C 1 to C 4 alkyl group wherein the alkyl group of the amino group is a C 1 to C 4 alkyl group. Examples of such a C 1 to C 4 alkylamino group include a methylamino group and the like , C 1 -C 4 straight such as ethylamino group, n-propylamino group, isopropylamino group, cyclopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino group, t-butylamino group, etc. Preferred are amino groups of chain, branched or cyclic alkyl groups.
The C 2 -C 4 N, N-dialkylamino group is one in which the nitrogen atom of the amino group is substituted with two alkyl groups, and the range of the alkyl group is the total number of carbon atoms in the alkyl group Is 2 to 4, and specifically, for example, C 2 to C 4 N, N-dialkylamino groups such as dimethylamino, diethylamino, methylethylamino, methylpropylamino and the like are preferably mentioned. Be
As the C 2 to C 4 N-alkyl N-alkoxyamino group, for example, methylmethoxyamino group, methylethoxyamino group, methyl-n-propoxyamino group, ethylmethoxy group, n-propylmethoxy group and the like are preferable. It can be mentioned.
As R 3 , for example, a methylamino group or a cyclopropylamino group is preferable.
　前記式(I)で表される本発明の化合物は、新規化合物である。
　本発明の化合物は、例えば、特開昭60-172967号公報（特許文献１）に準じて、例えば、下記反応式１に従って製造することができる。
反応式１ The compounds of the present invention represented by the above formula (I) are novel compounds.
The compound of the present invention can be produced, for example, according to the following reaction formula 1, in accordance with, for example, JP-A-60-172,967 (Patent Document 1).
Reaction formula 1
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記式中、Ｒ1、Ｒ2及びＲ3は、前記式(I)で定義したとおりであり、Ｘは、塩素原子、臭素原子、水酸基、メトキシ基、エトキシ基又はプロポキシ基を示す。
　上記式(II)において、Ｘが、塩素原子や、臭素原子を示す場合には、溶媒として、例えば、ベンゼンや、トルエン、キシレン等の芳香族炭化水素；アセトンや、メチルエチルケトン、メチルイソブチルケトン等のケトン類；クロロホルムや、塩化メチレン等のハロゲン化炭化水素；水；酢酸メチルや、酢酸エチル等のエステル類；又はテトラヒドロフラン、アセトニトリル、ジオキサン、N,N-ジメチルホルムアミド、N-メチルピロリドン又はジメチルスルホキシド等の極性溶媒等を用い、例えば、0℃～30℃、好ましくは、0℃～5℃で塩基の存在下反応を行うことが出来る。塩基としては、例えば、水酸化ナトリウムや、水酸化カリウム、ピリジン又はトリエチルアミン等を用いることが出来る。
　また、式(II)において、Ｘが、水酸基、メトキシ基、エトキシ基、又はプロポキシ基である場合には、溶媒の非存在下、又は、メチルアルコールや、エチルアルコール、プロピルアルコール等のアルコール中で、例えば、5～100℃、好ましくは、20～80℃で反応を行うことが出来る。 In the above formulae, R 1 , R 2 and R 3 are as defined in the above formula (I), and X represents a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group, an ethoxy group or a propoxy group.
In the above formula (II), when X represents a chlorine atom or a bromine atom, as a solvent, for example, benzene, or an aromatic hydrocarbon such as toluene or xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone or the like Ketones; halogenated hydrocarbons such as chloroform and methylene chloride; water; esters such as methyl acetate and ethyl acetate; or tetrahydrofuran, acetonitrile, dioxane, N, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide, etc. The reaction can be performed in the presence of a base at, for example, 0 ° C. to 30 ° C., preferably 0 ° C. to 5 ° C., using a polar solvent of As a base, for example, sodium hydroxide, potassium hydroxide, pyridine or triethylamine can be used.
Further, in the formula (II), when X is a hydroxyl group, a methoxy group, an ethoxy group or a propoxy group, in the absence of a solvent or in an alcohol such as methyl alcohol, ethyl alcohol or propyl alcohol. For example, the reaction can be carried out at 5 to 100.degree. C., preferably 20 to 80.degree.
　反応後、目的物である式(I)で表される本発明の化合物を単離するには、水に溶解する溶媒を用いた場合は、減圧下、溶媒を留去し、水を加えた後、水に不溶のベンゼンや、トルエン、キシレン等の芳香族炭化水素；クロロホルム、塩化メチレン等のハロゲン化炭化水素；酢酸エチル等のエステル類で抽出し、飽和食塩水で洗浄後、無水硫酸ナトリウム等の乾燥剤で乾燥後、溶媒を減圧下で留去すれば良い。水に不溶の溶媒を用いた場合は、水を加えた後分液し、有機相を飽和食塩水で洗浄後、無水硫酸ナトリウム等の乾燥剤で乾燥後、溶媒を減圧下で留去すれば良い。溶媒留去後、得られた残渣はそのままでも十分純品であることもあるが、不純な場合には目的物を余り溶解しないヘキサン、ヘプタン等の炭化水素で洗浄するか、再結晶又はカラムクロマトグラフィーで精製すれば純品が得られる。
　出発原料の式(II)の化合物の一部である下式(III)、 After the reaction, in order to isolate the desired compound of the present invention represented by the formula (I), when a solvent dissolved in water was used, the solvent was distilled off under reduced pressure and water was added. After that, extract with water-insoluble benzene, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and methylene chloride; esters such as ethyl acetate, and wash with saturated saline, and then anhydrous sodium sulfate After drying with a desiccant such as, the solvent may be distilled off under reduced pressure. When a solvent insoluble in water is used, water is added and then separated, and the organic phase is washed with saturated saline and then dried with a desiccant such as anhydrous sodium sulfate and the solvent is distilled off under reduced pressure. good. After evaporation of the solvent, the obtained residue may be sufficiently pure as it is, but if it is impure, it may be washed with a hydrocarbon such as hexane, heptane or the like which does not dissolve the object significantly, or recrystallization or column chromatography Purification by chromatography yields a pure product.
The following formula (III) which is a part of the compound of the formula (II) as the starting material,
Figure JPOXMLDOC01-appb-C000019
 　　　　(III)

(式中、Ｒ1及びＲ2は、前記式(II)で定義したとおりであり、Ｒ4が、Ｒ3で説明したのと同様に、Ｃ1～Ｃ4のアルコキシ基を示す。) で表される１-フェニル-５-ジフルオロメチル-４-カルボン酸エステル誘導体は、文献未記載の新規化合物であり、下記反応式に従って合成することができる。
反応式２
Figure JPOXMLDOC01-appb-C000019
 (III)

(Wherein, R 1 and R 2 are as defined in the formula (II), and R 4 represents a C 1 to C 4 alkoxy group as described for R 3 ). The 1-phenyl-5-difluoromethyl-4-carboxylic acid ester derivative to be represented is a novel compound not described in the literature, and can be synthesized according to the following reaction formula.
Reaction formula 2
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
(上記式中、Ｒ1、Ｒ2及びＲ4は、前記式(III)で定義した通りである。)
　上記反応は、溶媒及び塩基の存在下、又は非存在下に行うことができる。溶媒としては、本反応に直接関与しないものならば、特に限定されず、例えば、ベンゼンや、トルエン、キシレン等の芳香族炭化水素；クロロホルムや、ジクロロメタン等のハロゲン化炭化水素；水；酢酸メチルや、酢酸エチル等のエステル類；アセトニトリル、N,N-ジメチルホルムアミド、N-メチルピロリドン又はジメチルスルホキシド等の極性溶媒；テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル等のエーテル類；メタノールや、エタノール、プロパノール、エチレングリコール等のアルコール類又は上記溶媒の混合溶媒が挙げられる。塩基としては、例えば、水酸化ナトリウムや、水酸化カリウム等のアルカリ金属水和物；水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；炭酸水素ナトリウムや、炭酸水素カリウム等のアルカリ金属炭酸水素塩；炭酸カルシウムや、炭酸マグネシウム等のアルカリ土類金属炭酸塩；ナトリウムメトキシドや、ナトリウムエトキシド等の金属アルコキシドが挙げられる。反応温度は、例えば、5～100℃、好ましくは、0～50℃である。 (In the above formula, R 1 , R 2 and R 4 are as defined in the above formula (III).)
The above reaction can be carried out in the presence or absence of a solvent and a base. The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane; water; methyl acetate And esters such as ethyl acetate; polar solvents such as acetonitrile, N, N-dimethylformamide, N-methyl pyrrolidone and dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; methanol, ethanol, propanol, ethylene glycol and the like Or mixed solvents of the above solvents. Examples of the base include alkali metal hydrates such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate Sodium hydrogen carbonate; alkali metal hydrogen carbonates such as potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; metal alkoxides such as sodium methoxide and sodium ethoxide. The reaction temperature is, for example, 5 to 100 ° C., preferably 0 to 50 ° C.
　反応後、目的物である式(III)で表される本発明の化合物を単離するには、塩酸、硫酸等の鉱酸；酢酸、プロピオン酸等の有機酸で酸性にした後、水に溶解する溶媒を用いた場合は、減圧下溶媒を留去し、水を加えた後、水に不溶のベンゼンや、トルエン、キシレン等の芳香族炭化水素；クロロホルムや、ジクロロメタン等のハロゲン系炭化水素；酢酸エチル等のエステル類で抽出し、飽和食塩水で洗浄後、無水硫酸ナトリウム等の乾燥剤で乾燥し、減圧下で溶媒を留去すれば良い。水に不溶の溶媒を用いた場合は、反応混合物に水を加えた後分液し、有機層を飽和食塩水で洗浄後、無水硫酸ナトリウム等の乾燥剤で乾燥後減圧下で溶媒を留去すればよい。留去後得られた残渣はそのままでも十分純品であることもあるが、不純な場合には目的物を余り溶解しないヘキサン、ヘプタン等の炭化水素で洗浄するか、再結晶又はカラムクロマトグラフィーで精製すれば純品が得られる。
　出発原料の式(II)の化合物の中でXが水酸基で示される下記式(VI)は下記式(III)を加水分解することによって合成することができる。
反応式３ After the reaction, in order to isolate the compound of the present invention represented by the target compound (III), mineral acids such as hydrochloric acid and sulfuric acid; acidification with organic acids such as acetic acid and propionic acid; When a solvent that dissolves is used, the solvent is distilled off under reduced pressure, water is added, and then benzene insoluble in water, aromatic hydrocarbons such as toluene and xylene; halogen based hydrocarbons such as chloroform and dichloromethane Extraction with an ester such as ethyl acetate and the like, washing with saturated brine, drying with a desiccant such as anhydrous sodium sulfate, and evaporation of the solvent under reduced pressure may be carried out. When a solvent insoluble in water is used, water is added to the reaction mixture and then separated, and the organic layer is washed with saturated brine, dried with a desiccant such as anhydrous sodium sulfate and the solvent is distilled off under reduced pressure. do it. The residue obtained after evaporation may be sufficiently pure as it is, but if it is impure, it may be washed with a hydrocarbon such as hexane or heptane which does not dissolve the object very much, or by recrystallization or column chromatography. If refined, a pure product is obtained.
Among the compounds of the formula (II) as starting materials, the following formula (VI) in which X is represented by a hydroxyl group can be synthesized by hydrolysis of the following formula (III).
Reaction formula 3
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
(式中、Ｒ1、Ｒ2及びＲ4は、前記式(III)で定義したとおりである。)
　上記反応は、溶媒の存在下又は非存在下、塩基の存在下行うことができる。溶媒としては、例えば、水；メタノール、エタノール、プロパノール、エチレングリコール等のアルコール類又は上記溶媒の混合溶媒が挙げられる。塩基としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属炭酸塩；炭酸カルシウム、炭酸マグネシウム等のアルカリ土類金属炭酸塩が挙げられる。反応温度は、例えば、5～150℃、好ましくは、10～110℃である。反応後、目的物である式(VI)で表される化合物を単離するには、塩酸や、硫酸等の鉱酸；酢酸や、プロピオン酸等の有機酸で酸性にした後、析出物を濾取し水洗後乾燥すれば良い。 (Wherein, R 1 , R 2 and R 4 are as defined in the above formula (III))
The above reaction can be carried out in the presence or absence of a solvent and in the presence of a base. Examples of the solvent include water; alcohols such as methanol, ethanol, propanol and ethylene glycol, and mixed solvents of the above solvents. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonate Examples thereof include alkali metal carbonates such as sodium and potassium hydrogen carbonate; and alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate. The reaction temperature is, for example, 5 to 150 ° C., preferably 10 to 110 ° C. After the reaction, in order to isolate the compound represented by the formula (VI) which is the target product, the precipitate is acidified after being acidified with a mineral acid such as hydrochloric acid or sulfuric acid; acetic acid or an organic acid such as propionic acid It may be filtered and washed with water and then dried.
反応式４ Reaction formula 4
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
(上記式中、Ｒ1及びＲ2は、前記式(I)で定義した通りであり、Ｚは、塩素原子や、臭素原子を示す。)
　式(VI)の化合物をハロゲン化剤と反応させると、式(VII)の化合物が得られる。上記反応は、溶媒の存在下又は非存在下に行うことができる。溶媒としては、本反応に直接関与しないものならば特に限定されず、例えば、ベンゼンや、トルエン、キシレン等の芳香族炭化水素；クロロホルムや、ジクロロメタン等のハロゲン化炭化水素が挙げられる。ハロゲン化剤としては、例えば、塩化チオニルや、臭化チオニル、塩化オキサリル、臭化オキサリル、五塩化リン、五臭化リン、三塩化リン等が挙げられる。反応温度は、例えば、5～100℃、好ましくは、20～90℃である。反応後、目的物である式(VII)で表される化合物を単離するには、反応液を減圧下濃縮し、得られた残渣を目的物をあまり溶解しないヘキサン、ヘプタン等の炭化水素で洗浄後乾燥すればよい。 (In the above formulae, R 1 and R 2 are as defined in the formula (I), and Z represents a chlorine atom or a bromine atom.)
The compound of formula (VI) is reacted with a halogenating agent to give a compound of formula (VII). The above reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform and dichloromethane. Examples of the halogenating agent include thionyl chloride, thionyl bromide, oxalyl chloride, oxalyl bromide, phosphorus pentachloride, phosphorus pentabromide, phosphorus trichloride and the like. The reaction temperature is, for example, 5 to 100 ° C., preferably 20 to 90 ° C. After the reaction, in order to isolate the desired compound represented by the formula (VII), the reaction solution is concentrated under reduced pressure, and the obtained residue is dissolved with a hydrocarbon such as hexane or heptane which does not dissolve the desired product very much. It may be dried after washing.
　式(I)で示される本発明化合物を有効成分として含有する本発明の除草剤は、農耕地及び非農耕地の種々の雑草に対して優れた除草効果を有する。中でも特に畑地一年生雑草に対する茎葉処理除草剤の有効成分として有用である。
　そのような雑草としては、例えば、メヒシバや、エノコログサ、ノビエ、アオビユ、シロザ、イチビ、ハコベ、アサガオなどが挙げられる。もっとも、本発明の化合物の防除対象となる雑草は、上記に例示したものに限定されることではない。また、式(I)で示される本発明の化合物を有効成分として含有する本発明の除草剤は、コムギや、オオムギ、ソルガム、トウモロコシ、ワタ、ビート等の作物に対して高い安全性を有する。式(I)で示される本発明の化合物を除草剤として使用する場合には単独で用いてもよいが、当業界で汎用される農薬補助剤を加えた組成物として用いるのが好ましい。
　除草剤の剤型は特に限定されないが、例えば、乳剤や、水和剤、粉剤、フロアブル剤、細粒剤、粒剤、錠剤、油剤等の形態とすることが好適である。本発明の化合物の１種又は２種以上を有効成分として配合することができる。 The herbicide of the present invention containing the compound of the present invention represented by the formula (I) as an active ingredient has an excellent herbicidal effect on various weeds of agricultural land and non-agricultural land. Above all, it is useful as an active ingredient of a foliage treating herbicide for upland field annual weeds.
As such weeds, for example, crabgrass, enokologsa, pokeweed, bluefish, shiroza, ichibi, chickweed, morning glory and the like can be mentioned. However, weeds to be controlled by the compounds of the present invention are not limited to those exemplified above. In addition, the herbicide of the present invention containing the compound of the present invention represented by the formula (I) as an active ingredient has high safety to crops such as wheat, barley, sorghum, corn, cotton and beets. When the compound of the present invention represented by the formula (I) is used as a herbicide, it may be used alone, but it is preferably used as a composition to which a pesticide adjuvant widely used in the art is added.
Although the dosage form of the herbicide is not particularly limited, for example, the form of an emulsion, a wettable powder, a powder, a flowable, a fine granule, a granule, a tablet, an oil and the like is preferable. One or two or more of the compounds of the present invention can be blended as an active ingredient.
　除草剤を製造するために用いられる農薬補助剤としては、例えば、除草剤の効果の向上、安定化、分散性の向上、作物に対する安全性の向上等の作用を有する物質であり、例えば、担体(希釈剤)や、展着剤、乳化剤、湿展剤、分散剤、崩壊剤、湿潤剤等を用いることができる。液体担体としては、例えば、水；トルエン、キシレン等の芳香族炭化水素；メタノール、ブタノール、グリコール等のアルコール類；アセトン等のケトン類；ジメチルホルムアミド等のアミド類；ジメチルスルホキシド等のスルホキシド類；メチルナフタレン；シクロヘキサン；動植物油；又は脂肪酸等を挙げることができる。 Pesticide adjuvants used to produce herbicides are, for example, substances having effects such as enhancement of the effect of herbicide, stabilization, improvement of dispersibility, and enhancement of crop safety, for example, carriers (Diluents), spreaders, emulsifiers, wetting agents, dispersants, disintegrants, wetting agents and the like can be used. Liquid carriers include, for example, water; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, butanol and glycol; ketones such as acetone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; Naphthalene; cyclohexane; animal and vegetable oils; or fatty acids and the like can be mentioned.
　また、固体担体としては、例えば、クレーや、カオリン、タルク、珪藻土、シリカ、炭酸カルシウム、モンモリオナイト、ベントナイト、長石、石英、アルミナ、鋸屑、ニトロセルロース、デンプン、アラビアゴム等が挙げられる。乳化剤、分散剤としては通常の界面活性剤を使用することが出来、例えば、高級アルコール硫酸ナトリウムや、ステアリルトリメチルアンモニウムクロライド、ポリオキシエチレンアルキルフェニルエーテル、ラウリルベタイン等の陰イオン系界面活性剤；陽イオン界面活性剤；非イオン系界面活性剤；又は両性イオン系界面活性剤等を用いることができる。また、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルエステル等の展着剤、ジアルキルスルホサクシネート等の湿展剤；カルボキシルメチルセルロース、ポリビニルアルコール等の固着剤；リグニンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等の崩壊剤を用いることができる。 Further, examples of the solid carrier include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, saw dust, nitrocellulose, starch, gum arabic and the like. As the emulsifying agent and the dispersing agent, usual surfactants can be used. For example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethyl ammonium chloride, polyoxyethylene alkylphenyl ether, lauryl betaine and the like; An ionic surfactant; a nonionic surfactant; or a zwitterionic surfactant etc. can be used. In addition, spreading agents such as polyoxyethylene fatty acid ester and polyoxyethylene alkyl ester, wetting agents such as dialkyl sulfosuccinate; fixing agents such as carboxyl methyl cellulose and polyvinyl alcohol; collapse such as sodium lignin sulfonate and sodium lauryl sulfate Agents can be used.
　本発明の除草剤における有効成分の含有量は、例えば、0.01～99.5％の範囲から選ばれ、製剤形態、施用方法等の種々の条件により適宜決定すればよい。例えば、乳剤では、例えば、約1～90質量％程度、好ましくは、10～40質量％、水和剤では、例えば、約1～90質量％程度、好ましくは、10～80質量％、粉剤では、例えば、約0.5～20質量％程度、好ましくは、1～10質量％、フロアブル剤では、例えば、約1～90質量％程度、好ましくは、10～50質量％の有効成分を含有するように製造することが好適である。 The content of the active ingredient in the herbicide of the present invention is, for example, selected from the range of 0.01 to 99.5%, and may be suitably determined according to various conditions such as the formulation form, application method and the like. For example, in the emulsion, for example, about 1 to 90% by mass, preferably 10 to 40% by mass, in the wettable powder, for example, about 1 to 90% by mass, preferably 10 to 80% by mass, For example, about 0.5 to 20% by mass, preferably 1 to 10% by mass, and in the case of a flowable, for example, about 1 to 90% by mass, preferably 10 to 50% by mass. It is preferred to manufacture.
　例えば、乳剤の場合、有効成分である本発明の化合物に対して、溶剤及び界面活性剤等を混合して原液の乳剤を製造することが出来、更にこの原液を、使用に際して、所定濃度に水で希釈して施用することができる。
　フロアブル剤の場合、有効成分である本発明の化合物に対して、水及び界面活性剤等を混合して原液を製造することが出来、更にこの原液を、使用に際して、所定濃度に水で希釈して施用することができる。
　水和剤の場合、有効成分の本発明の化合物、固形担体及び界面活性剤等を混合して製造し、更に使用に際して、所定濃度に水で希釈して施用することができる。
　粉剤の場合、有効成分としての本発明の化合物、固形担体等を混合してそのまま施用することが出来る。もっとも、上記の各製剤形態の製造方法は上記のものに限定されることはなく、有効成分の種類や施用目的等に応じて当業者が適宜選択することができるものである。 For example, in the case of an emulsion, an emulsion of a stock solution can be prepared by mixing a solvent, a surfactant and the like with the compound of the present invention which is an active ingredient, and this stock solution is Can be diluted and applied.
In the case of the flowable agent, the compound of the present invention, which is the active ingredient, can be mixed with water, surfactant, etc. to produce a stock solution, and this stock solution is further diluted with water to a predetermined concentration when used. Can be applied.
In the case of a wettable powder, the compound of the present invention as an active ingredient, a solid carrier, a surfactant and the like can be mixed and manufactured, and when used, it can be applied diluted with water to a predetermined concentration.
In the case of powders, the compound of the present invention as an active ingredient, a solid carrier and the like can be mixed and applied as they are. However, the manufacturing method of each above-mentioned formulation form is not limited to the above-mentioned thing, those skilled in the art can select suitably according to the kind of an active ingredient, the purpose of application, etc.
　本発明の除草剤には、有効成分である式(I)の本発明の化合物の活性を損なわない限り、他の除草剤や、殺虫剤、殺ダニ剤、殺菌剤、生育調節剤、肥料、土壌改良剤等の任意の有効成分を配合してもよい。
　本発明の化合物は、通常の除草剤と同様にして使用することができ、例えば、畑地雑草の発芽前や、発芽初期、生育期に、本発明の化合物を用いて土壌処理あるいは茎葉処理を行うことができる。本発明の除草剤の施用量は、施用方法や、目的、時期、雑草の発生状況等により適宜選択することができるが、通常１ヘクタール当り、有効成分量で、例えば、0.001kg～10kg、好ましくは、0.003kg～3kgであることが好適である。 In the herbicide of the present invention, other herbicides, insecticides, acaricides, fungicides, growth regulators, fertilizers, as long as the activity of the compound of the present invention of the formula (I) which is the active ingredient is not impaired. You may mix | blend arbitrary active ingredients, such as a soil conditioner.
The compounds of the present invention can be used in the same manner as conventional herbicides, and for example, soil treatment or foliage treatment is carried out using the compounds of the present invention before germination, early germination and growth stage of upland weeds. be able to. The application amount of the herbicide of the present invention can be appropriately selected depending on the application method, purpose, time, weeding condition and the like, but the amount of active ingredient is usually 0.001 kg to 10 kg per hectare, for example. Is preferably 0.003 kg to 3 kg.
　次に、本発明について、合成例、製剤例及び試験例によって、更に具体的に説明するが、本発明の範囲は、これらの合成例、製剤例及び試験例によって何ら限定されるものではない。 Next, the present invention will be more specifically described by Synthesis Examples, Formulation Examples and Test Examples, but the scope of the present invention is not limited at all by these Synthesis Examples, Formulation Examples and Test Examples.
＜実施例１＞　1-(4-クロロフェニル)-5-ジフルオロメチルピラゾール-4-カルボン酸エチルの合成
　上記反応式２に従って、2-(エトキシメチレン)-4,4-ジフルオロアセト酢酸エチルエステル11.1gと、4-クロロフェニルヒドラジン塩酸塩8.95gとを水50ml及びトルエン50ml中で1時間加熱還流した。反応液を分液し、水相を飽和食塩水で洗浄し、減圧下濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーで精製して、表１に記載の本発明の化合物(No.3)10.2gを得た。融点は、42-44℃であった。
1H-NMR(CDCl3)δppm：1.40(3H,t)、4.38(2H,q)、7.48(4H,m)、7.48(1H,t)、8.10(1H,s) <Example 1> Synthesis of ethyl 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-carboxylate According to the above reaction formula 2, 11.1 g of 2- (ethoxymethylene) -4,4-difluoroacetoacetic acid ethyl ester And 4.95 g of 4-chlorophenylhydrazine hydrochloride were heated to reflux for 1 hour in 50 ml of water and 50 ml of toluene. The reaction mixture was separated, and the aqueous phase was washed with saturated brine and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 10.2 g of the compound of the present invention (No. 3) described in Table 1. The melting point was 42-44 ° C.
1 H-NMR (CDCl 3 ) δ ppm: 1.40 (3H, t), 4.38 (2H, q), 7.48 (4H, m), 7.48 (1H, t), 8.10 (1H, s)
＜実施例２＞　1-(4-クロロフェニル)-5-ジフルオロメチルピラゾール-4-カルボン酸の合成
　実施例１で得た1-(4-クロロフェニル)-5-ジフルオロメチルピラゾール-4-カルボン酸エチル9.02g、水酸化ナトリウム2.40g、エチルアルコール40mlと水40mlの混合物を1時間加熱還流した。室温に冷却後、塩酸を加えて酸性にし、結晶を濾取後、水洗、乾燥して表１に記載の本発明の化合物(No.4)8.10gを得た。融点は140-142℃であった。 <Example 2> Synthesis of 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-carboxylic acid Ethyl 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-carboxylate obtained in Example 1 A mixture of 9.02 g, 2.40 g of sodium hydroxide, 40 ml of ethyl alcohol and 40 ml of water was heated to reflux for 1 hour. After cooling to room temperature, hydrochloric acid is added to acidify and crystals are collected by filtration, washed with water and dried to obtain 8.10 g of the compound of the present invention (No. 4) described in Table 1. The melting point was 140-142 ° C.
＜実施例３＞　N-メチル-1-(4-クロロフェニル)-5-ジフルオロメチルピラゾール-3-カルボキサミドの合成
　実施例２で得た1-(4-クロロフェニル)-5-ジフルオロメチルピラゾール-4-カルボン酸0.41gを塩化チオニル5ml中で1時間加熱還流後、減圧下濃縮した。得られた残渣を、40％メチルアミン水溶液1.16g中に加え、室温で1時間撹拌した。酢酸エチルで抽出し、有機層を飽和食塩水で洗浄後、無水硫酸ナトリウムで乾燥した。減圧下濃縮し、得られた残渣をヘキサンで洗浄して表２に記載の本発明の化合物(No.３１)0.35gを得た。融点は、167-169℃であった。 <Example 3> Synthesis of N-methyl-1- (4-chlorophenyl) -5-difluoromethylpyrazole-3-carboxamide 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-obtained in Example 2 The solution was heated under reflux for 1 hour in 5 ml of thionyl chloride and concentrated under reduced pressure. The resulting residue was added to 1.16 g of 40% aqueous methylamine solution and stirred at room temperature for 1 hour. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting residue was washed with hexane to obtain 0.35 g of the compound of the present invention (No. 31) described in Table 2. The melting point was 167-169 ° C.
＜実施例４＞　N-n-プロピル-1-(4-クロロフェニル)-5-ジフルオロメチルピラゾール-4-カルボキサミドの合成
　実施例１で得た1-(4-クロロフェニル)-5-ジフルオロメチルピラゾール-4-カルボン酸エチル3.01gと、n-プロピルアミン0.18gとを、メタノール10ml中、室温で18時間撹拌した。減圧下濃縮し、得られた残渣をシリカゲルカラムクロマトグラフィーで精製して、以下の表２に記載の化合物(No.３３)2.50gを得た。融点は、128-130℃であった。
　その他、同様にして、本発明の化合物を調製した。以下の表１及び２には、実施例により製造された本発明の化合物を記載する。 <Example 4> Synthesis of Nn-propyl-1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-carboxamide 1- (4-chlorophenyl) -5-difluoromethylpyrazole-4-obtained in Example 1 3.01 g of ethyl carboxylate and 0.18 g of n-propylamine were stirred in 10 ml of methanol at room temperature for 18 hours. The mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 2.50 g of a compound (No. 33) described in Table 2 below. The melting point was 128-130 ° C.
Other than that, the compound of the present invention was prepared similarly. Tables 1 and 2 below describe the compounds of the invention prepared according to the examples.
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000024
Figure JPOXMLDOC01-appb-I000025
1) 1H-NMR(CDCl3)δppm：1.40(3H,t)、4.40(2H,q)、7.4-7.7(6H,m)、8.10(1H,s)。
2) 1H-NMR(CDCl3)δppm：1.40(3H,t)、4.40(2H,q)、7.2-7.6(5H,m)、8.13(1H,s)。
3) 1H-NMR(CDCl3)δppm：1.40(3H,t)、2.43(3H,s)、4.40(2H,q)、7.3-7.5(5H,m)、8.10(1H,s)。
4) 1H-NMR(CDCl3)δppm：1.40(3H,t)、4.38(2H,q)、4.88(3H,s)、7.0-7.5(5H,m)、8.04(1H,s)。
Figure JPOXMLDOC01-appb-I000025
1) 1 H-NMR (CDCl 3 ) δ ppm: 1.40 (3 H, t), 4.40 (2 H, q), 7.4-7.7 (6 H, m), 8. 10 (1 H, s).
2) 1 H-NMR (CDCl 3 ) δ ppm: 1.40 (3 H, t), 4.40 (2 H, q), 7.2-7.6 (5 H, m), 8.13 (1 H, s).
3) 1 H-NMR (CDCl 3 ) δ ppm: 1.40 (3H, t), 2.43 (3H, s), 4.40 (2H, q), 7.3-7.5 (5H, m), 8.10 (1H, s).
4) 1 H-NMR (CDCl 3 ) δ ppm: 1.40 (3H, t), 4.38 (2H, q), 4.88 (3H, s), 7.0-7.5 (5H, m), 8.04 (1H, s).
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-I000027
Figure JPOXMLDOC01-appb-I000027
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000031
5) 1H-NMR(CDCl3)δppm：1.40(3H,t)、4.40(2H,q)、7.35-7.69(5H,m)、8.09(1H,s)。
6) 1H-NMR(CDCl3)δppm：1.40(3H,t)、4.38(2H,q)、6.51(1H,t)、7.21-7.67(5H,m)、8.08(1H,s)。
Figure JPOXMLDOC01-appb-I000031
5) 1 H-NMR (CDCl 3 ) δ ppm: 1.40 (3H, t), 4.40 (2H, q), 7.35-7.69 (5H, m), 8.09 (1H, s).
6) 1 H-NMR (CDCl 3 ) δ ppm: 1.40 (3H, t), 4.38 (2H, q), 6.51 (1H, t), 7.21-7.67 (5H, m), 8.08 (1H, s).
　以下、本発明の化合物を有効成分として含む除草剤の製剤例を示す。なお、本発明の範囲は、下記の製剤例によって何ら限定されることはない。また、実施例において部とあるのは全て質量部を表す。 Hereinafter, formulation examples of a herbicide containing the compound of the present invention as an active ingredient are shown. The scope of the present invention is not limited at all by the following formulation examples. Moreover, all being "part" in an Example represents a mass part.
＜製剤例1＞　乳剤
　本発明の化合物(10部)、キシレン(60部)、Ｎ－メチル－2－ピロリドン(20部)及び乳化剤としてのソルポール3005X(10部)を均一に混合溶解して、乳剤を得た。 Formulation Example 1 Emulsion A compound of the present invention (10 parts), xylene (60 parts), N-methyl-2-pyrrolidone (20 parts) and Sorpol 3005X (10 parts) as an emulsifier are uniformly mixed and dissolved. An emulsion was obtained.
＜製剤例２＞　水和剤
　本発明の化合物(20部)、カープレックス＃80(20部)、STカオリンクレー(50部)、リグニンスルホン酸ナトリウム(5部)及び湿潤剤としてのルノックスP-65L(5部)をジェットエアーミルにて均一に混合粉砕して、水和剤を得た。 Formulation Example 2 Hydrating agent Compound of the present invention (20 parts), Carplex # 80 (20 parts), ST kaolin clay (50 parts), sodium lignin sulfonate (5 parts) and Lunox P-as a wetting agent 65 L (5 parts) was uniformly mixed and ground in a jet air mill to obtain a wettable powder.
＜製剤例３＞　粒剤
　本発明の化合物(5部)、ベントナイト(30部)、クレー(60部)及びリグニンスルホン酸ナトリウム(5部)を均一に粉砕混合し、水を加えてよく練り合わせた後、押し出し造粒し、乾燥整粒して粒剤を得た。 Formulation Example 3 Granule The compound of the present invention (5 parts), bentonite (30 parts), clay (60 parts) and sodium lignin sulfonate (5 parts) were uniformly ground and mixed, water was added and thoroughly mixed. Thereafter, the mixture was extruded and granulated, and dried and sized to obtain granules.
＜試験例１＞　除草効果試験
　表面積160cm2のアルミポットに畑土壌を充填し、メヒシバ、アオビユ、シロザの種子を播種し、約0.5cm覆土した後、温室で育成し、メヒシバが3葉期になった時期に、有効成分量が所定の割合となるように製剤例１に準じて調製した本発明の化合物3kg/haを茎葉部及び土壌部へ均一に散布した。薬液散布14日後に各雑草に対する除草効果を下記の基準に従って調査し、表３に示す結果を得た。なお、化合物No.は、表１及び表２の化合物No.に対応する。表３から明らかなように、本発明の化合物は、雑草に対して優れた除草効果を示す。 <Test Example 1> Herbicidal Efficacy Test Field soil is filled in an aluminum pot having a surface area of 160 cm 2 and sown seeds of crabgrass, bluegrass and shiroza are covered with about 0.5 cm of soil, and then grown in a greenhouse, crabgrass at three leaf stages At that time, 3 kg / ha of the compound of the present invention prepared according to Preparation Example 1 such that the amount of the active ingredient was a predetermined ratio was uniformly dispersed to the stem and leaf and the soil. The herbicidal effect on each weed was investigated according to the following criteria 14 days after chemical solution spraying, and the results shown in Table 3 were obtained. The compound No. corresponds to the compound No. in Table 1 and Table 2. As apparent from Table 3, the compounds of the present invention show excellent herbicidal effects on weeds.
調査基準
10　 100％抑制の除草効果
9　　90～99％抑制の除草効果
8　  80～89％抑制の除草効果
7　  70～79％抑制の除草効果
6　  60～69％抑制の除草効果
5　  50～59％抑制の除草効果
4　  40～49％抑制の除草効果
3　  30～39％抑制の除草効果
2　  20～29％抑制の除草効果
1　  1～19％抑制の除草効果 Survey criteria
10 100% suppression weeding effect
9 90-99% suppression of weeding effect
8 Weeding effect of 80 to 89% suppression
7 Weeding effect of 70 to 79% suppression
Weeding effect of 6 60-69% suppression
5 50-59% suppression of weeding effect
Weeding effect of 4 40-49% suppression
Weeding effect of 3 30-39% suppression
Weeding effect of 2 20-29% suppression
Weeding effect of 1 1-19% suppression
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
（表３の続き）
　  化合物No.        処理量kg/ha　  メヒシバ　　　　アオビユ　　　シロザ　　　
　　　76               3              10              10            10
　　　77               3              10              10            10
　　　78               3              10              10            10
　　　79               3              10              10            10
　　　80               3              10              10            10
　　　81               3              10              10            10
　　　82               3              10              10            10
　　　83               3              10              10            10
　　　84               3              10              10            10
　　　85               3              10              10            10         (Continuation of Table 3)
Compound No. Throughput kg / ha crabgrass Aobilu Shiroza
76 3 10 10 10
77 3 10 10 10
78 3 10 10 10
79 3 10 10 10
80 3 10 10 10
81 3 10 10 10
82 3 10 10 10
83 3 10 10 10
84 3 10 10 10
85 3 10 10 10
＜試験例２＞　処理後日数による除草効果試験
　表面積160cm2のアルミポットに畑土壌を充填し、有効成分量が所定の割合となるように製剤例１に準じて調製した本発明の化合物と、本発明の化合物に近似する公知化合物Ａとを、それぞれ1.5kg/haの量で土壌表面へ均一に散布した。薬液散布１、３０及び６０日後にメヒシバ、アサガオの種子を播種し、試験例１と同様の基準で調査し、以下の表４に示す結果を得た。なお、化合物No.は、表２の化合物No.に対応し、化合物Ａの構造式は、以下に示すとおりである。
　表４から明らかなように、本発明の化合物は、処理後速やかに分解され、環境や後作物に対する負荷の少ない優れたものである。 <Test Example 2> Herbicidal effect test according to the number of days after treatment A field soil is filled in an aluminum pot having a surface area of 160 cm 2 , and the compound of the present invention prepared according to Formulation Example 1 such that the amount of the active ingredient becomes a predetermined ratio. A known compound A similar to the compound of the present invention was uniformly sprayed on the soil surface in an amount of 1.5 kg / ha each. Seeds of crabgrass and morning glory were sowed 1, 30, and 60 days after chemical solution spraying, and investigations were conducted based on the same criteria as in Test Example 1, and the results shown in Table 4 below were obtained. The compound No. corresponds to the compound No. in Table 2, and the structural formula of the compound A is as shown below.
As apparent from Table 4, the compounds of the present invention are rapidly degraded after the treatment, and are excellent ones with less load on the environment and subsequent crops.
Figure JPOXMLDOC01-appb-T000033
 　　　　　　　　　　　　　　　　　　　　　　　　　　　　*散布から播種までの日数
Figure JPOXMLDOC01-appb-T000033
 * Number of days from spraying to sowing
Figure JPOXMLDOC01-appb-C000034
 化合物Ａ
Figure JPOXMLDOC01-appb-C000034
 Compound A
＜試験例３＞　散布水量別除草効果試験
　表面積160cm2のアルミポットに畑土壌を充填し、アオビユの種子を播種し、約0.5cm覆土した後、温室で育成し、アオビユが4葉期になった時期に、有効成分量が所定の割合となるように製剤例１に準じて調製した本発明の化合物と、化合物Ａとを、0.025、0.0125kg/haの量で散布水量がha当り500リットル（Ｌ）及び250Ｌになるように希釈し、茎葉部及び土壌部へ均一に散布した。薬液散布14日後に各雑草に対する除草効果を試験例1と同様の基準で調査し、以下の表５に示す結果を得た。なお、化合物No.は表２の化合物No.に対応し、化合物Ａは、試験例２で定義したとおりである。
　表５から明らかなように、本発明の化合物は、散布水量が少ない場合においても優れた除草効果を示し、水の確保が困難な地域や大規模散布場面、また不均一な散布においても安定して優れた除草効果を示す。 <Test Example 3> Herbicidal effect test according to the amount of sprayed water Field soil is filled in an aluminum pot having a surface area of 160 cm 2 and sown with Aobiru seeds and covered with soil for about 0.5 cm, and then grown in a greenhouse. The compound of the present invention prepared according to Formulation Example 1 such that the amount of the active ingredient becomes a predetermined ratio at the same time, and the compound A in an amount of 0.025, 0.0125 kg / ha The solution was diluted to (L) and 250 L and uniformly sprayed to stems and leaves and soil. The herbicidal effect on each weed was examined 14 days after chemical solution spraying based on the same criteria as in Test Example 1, and the results shown in Table 5 below were obtained. The compound No. corresponds to the compound No. in Table 2, and the compound A is as defined in Test Example 2.
As apparent from Table 5, the compounds of the present invention show excellent herbicidal effects even when the amount of water sprayed is small, and are stable even in areas where water is difficult to secure, in large-scale spraying situations, and also in uneven spraying. Exhibit excellent weeding effects.
Figure JPOXMLDOC01-appb-T000035
 　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　*ha当りの散布水量
Figure JPOXMLDOC01-appb-T000035
 * Sprayed water volume per ha
　本発明の１-フェニル-５-ジフルオロメチルピラゾール-４-カルボキサミド誘導体化合物は、各種雑草に対して優れた防除効果を有し、除草剤として有効である。 The 1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative compound of the present invention has an excellent control effect on various weeds and is effective as a herbicide.

Claims (4)

  1. 　下記式(I)、
    Figure JPOXMLDOC01-appb-C000001
     　　　　　　(I)

    （式中、Ｒ1及びＲ2は、それぞれ独立に、水素原子、ハロゲン原子、Ｃ1～Ｃ4のアルキル基、トリフルオロメチル基、ニトロ基、シアノ基、Ｃ1～Ｃ4のアルコキシ基、ジフルオロメトキシ基、トリフルオロメトキシ基、ジフルオロメチルチオ基、トリフルオロメチルチオ基、ジフルオロメチルスルフィニル基、ジフルオロメチルスルホニル基、トリフルオロスルメチルフィニル基、又はトリフルオロメチルスルホニル基を示す。
    　Ｒ3は、ヒドロキシル基、Ｃ1～Ｃ4のアルコキシ基、アミノ基、Ｃ1～Ｃ4のアルキルアミノ基、Ｃ2～Ｃ4のN,N-ジアルキルアミノ基又はＣ2～Ｃ4のN-アルキルN-アルコキシアミノ基を示す。）
    で表される１-フェニル-５-ジフルオロメチルピラゾール‐４-カルボキサミド誘導体。     The following formula (I),
    Figure JPOXMLDOC01-appb-C000001
     (I)

    (Wherein, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a C 1 to C 4 alkyl group, a trifluoromethyl group, a nitro group, a cyano group, a C 1 to C 4 alkoxy group, And a difluoromethoxy group, a trifluoromethoxy group, a difluoromethylthio group, a trifluoromethylthio group, a difluoromethylsulfinyl group, a difluoromethylsulfonyl group, a trifluorothromethyl methylfinyl group, or a trifluoromethylsulfonyl group.
    R 3 represents a hydroxyl group, a C 1 to C 4 alkoxy group, an amino group, a C 1 to C 4 alkylamino group, a C 2 to C 4 N, N-dialkylamino group or a C 2 to C 4 N -Represents an alkyl N-alkoxyamino group. )
    1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivative represented by
  2. 　式(I)において、Ｒ3が、メチルアミノ基又はシクロプロピルアミノ基である請求項１記載のカルボキサミド誘導体。 The carboxamide derivative according to claim 1, wherein R 3 in the formula (I) is a methylamino group or a cyclopropylamino group.
  3. 　式(I)において、Ｒ1とＲ2とが、水素原子であるか、又はＲ1が、フェニル基の４位において塩素原子、臭素原子、フッ素原子、ジフルオロメトキシ基又はトリフルオロメトキシ基であり、かつＲ2が、水素原子である請求項１記載のカルボキサミド誘導体。 In formula (I), R 1 and R 2 are a hydrogen atom, or R 1 is a chlorine atom, a bromine atom, a fluorine atom, a difluoromethoxy group or a trifluoromethoxy group at the 4-position of the phenyl group And R 2 is a hydrogen atom.
  4. 　請求項１～３のいずれかに記載のカルボキサミド誘導体を有効成分として含有する除草剤。 A herbicide comprising the carboxamide derivative according to any one of claims 1 to 3 as an active ingredient.
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