WO2017146226A1 - ベンゾオキサゾール化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法 - Google Patents
ベンゾオキサゾール化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法 Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
- A61K31/4427—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems
- A61K31/4439—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems containing a five-membered ring with nitrogen as a ring hetero atom, e.g. omeprazole
Definitions
- the present invention relates to an agricultural and horticultural insecticide containing a condensed heterocyclic compound, particularly a benzoxazole compound or a salt thereof as an active ingredient, and a method for using the same.
- Patent Documents 1 to 7 Such a document does not disclose any compound in which a cycloalkylpyridyl group is bonded to a benzoxazole compound.
- R 1 represents a halo (C 1 -C 3 ) alkoxy group; a halo (C 1 -C 3 ) alkylsulfinyl group; or a halo (C 1 -C 3 ) alkylsulfonyl group.
- R 2 represents a hydrogen atom; or a cyano group.
- m represents 0; 1; or 2.
- R 2 represents (b) a hydrogen atom; or (b2) a cyano group.
- m represents 0, 1, or 2.
- the benzoxazole compounds or salts thereof of the present invention not only have excellent effects as agricultural and horticultural insecticides, but also against pests parasitic on domestic animals such as non-human dogs and cats, cattle and sheep, etc. Has an effect.
- halo means “halogen atom” and represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
- halo (C 1 -C 3 ) alkoxy group means that one or two or more halogen atoms may be substituted at the substitutable position of the (C 1 -C 3 ) alkoxy group. When is 2 or more, the halogen atoms may be the same or different.
- monofluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, perfluoroethoxy group, heptafluoronormal propoxy group Represents a heptafluoroisopropoxy group and the like.
- halo (C 1 -C 3 ) alkylsulfinyl group means that one or two or more halogen atoms may be substituted at the substitutable position of the (C 1 -C 3 ) alkylsulfinyl group. When there are two or more halogen atoms, the halogen atoms may be the same or different.
- monofluoromethylsulfinyl group for example, monofluoromethylsulfinyl group, difluoromethylsulfinyl group, trifluoromethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, 1,1,2,2-tetrafluoroethylsulfinyl group, perfluoroethylsulfinyl group , A heptafluoronormal propylsulfinyl group, a heptafluoroisopropylsulfinyl group, and the like.
- halo (C 1 -C 3 ) alkylsulfonyl group means that 1 or 2 or more halogen atoms may be substituted at the substitutable position of the (C 1 -C 3 ) alkylsulfonyl group. When there are two or more halogen atoms, the halogen atoms may be the same or different.
- monofluoromethylsulfonyl group difluoromethylsulfonyl group, trifluoromethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, 1,1,2,2-tetrafluoroethylsulfonyl group, perfluoroethylsulfonyl group , A heptafluoronormal propylsulfonyl group, a heptafluoroisopropylsulfonyl group, and the like.
- Examples of the salt of the benzoxazole compound represented by the general formula (1) of the present invention include inorganic acid salts such as hydrochloride, sulfate, nitrate and phosphate, acetate, fumarate, maleate and shu Examples include organic acid salts such as acid salts, methanesulfonic acid salts, benzenesulfonic acid salts, paratoluenesulfonic acid salts, and salts with inorganic or organic bases such as sodium ions, potassium ions, calcium ions, and trimethylammonium salts. it can.
- inorganic acid salts such as hydrochloride, sulfate, nitrate and phosphate, acetate, fumarate, maleate and shu
- organic acid salts such as acid salts, methanesulfonic acid salts, benzenesulfonic acid salts, paratoluenesulfonic acid salts, and salts with inorganic or organic bases such as sodium
- the benzoxazole compound represented by the general formula (1) and salts thereof of the present invention may have one or more asymmetric centers in the structural formula, and two or more optical isomers and diastereoisomers may be present.
- the present invention includes all the optical isomers and a mixture in which they are contained in an arbitrary ratio.
- R 1 is a halo (C 1 -C 3 ) alkoxy group or a halo (C 1 -C 3 ) alkylsulfinyl group.
- R 2 is a hydrogen atom, and m is 2. More preferably, R 1 is a halo (C 1 -C 3 ) alkylsulfinyl group, R 2 is a hydrogen atom, and m is 2.
- the benzoxazole compound or salts thereof of the present invention can be produced, for example, by the following production method, but the present invention is not limited to these.
- R 1 is the same as described above, and m represents 1 or 2.
- the benzoxazole compound represented by the general formula (1a) of the present invention can be produced by the following steps [a] to [c].
- Step [a] A step of producing a compound represented by the general formula (2-1) by reacting a compound represented by the general formula (2) with an aminophenol compound.
- Step [b] A step of producing a compound represented by the general formula (1-1) by intramolecular cyclization of the compound represented by the general formula (2-1).
- Step [c] A step of producing a benzoxazole compound represented by the general formula (1a) by oxidizing the compound represented by the general formula (1-1).
- step [a] The compound represented by the general formula (2-1) is commercially available from carboxylic acid chloride derived from the compound represented by the general formula (2) by a usual method in organic synthesis. It can be produced by reacting an easily available aminophenol compound with a base and an inert solvent.
- Examples of the base that can be used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride and the like.
- Alkali metal hydrides, acetates such as potassium acetate, alkali metal alkoxides such as potassium t-butoxide, sodium methoxide, sodium ethoxide, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undeck- Examples include tertiary amines such as 7-ene, nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine, and the amount used is a carboxylic acid derived from the compound represented by the general formula (2) Usually used in the range of 1 to 10 moles compared to chloride It is.
- the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
- Aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated compounds such as methylene chloride, chloroform and carbon tetrachloride.
- Hydrocarbons such as chlorobenzene and dichlorobenzene
- chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran
- esters such as ethyl acetate, dimethylformamide, dimethylacetamide
- Inert solvents such as amides such as acetone, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, and the like. Or a mixture of two or more Kill.
- the amount used may be appropriately selected from the range of usually 0.1 to 100 L with respect to 1 mol of carboxylic acid chloride derived from the compound represented by formula (2).
- each reactant may be used in an equimolar amount, but any of the reactants can be used in excess.
- the reaction temperature can usually be carried out from room temperature to the boiling point of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it can be usually in the range of several minutes to 48 hours.
- the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
- Step [b] The compound represented by the general formula (1-1) is described in Synthesis 1981, 1-28 in the presence of an inert solvent in the compound represented by the general formula (2-1). (Preferably using azodicarboxylic acid diesters and triphenylphosphine (PPh 3 )).
- step [c] The benzoxazole compound represented by the general formula (1a) is produced by reacting the compound represented by the general formula (1-1) with an oxidizing agent in an inert solvent. Can do.
- oxidizing agent used in this reaction examples include peroxides such as hydrogen peroxide, perbenzoic acid, and m-chloroperbenzoic acid.
- peroxides such as hydrogen peroxide, perbenzoic acid, and m-chloroperbenzoic acid.
- the amount of these oxidizing agents to be used can be appropriately selected in the range of usually 1 to 5 moles relative to the compound represented by the general formula (1-1).
- the inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit this reaction, and examples thereof include chain or cyclic ethers such as diethyl ether, tetrahydrofuran, and dioxane, and aromatic carbonization such as benzene, toluene, and xylene.
- chain or cyclic ethers such as diethyl ether, tetrahydrofuran, and dioxane
- aromatic carbonization such as benzene, toluene, and xylene.
- Hydrogens, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, nitriles such as acetonitrile, esters such as ethyl acetate, formic acid, acetic acid, etc.
- the reaction temperature in this reaction may be appropriately selected from the range of usually ⁇ 10 ° C. to the reflux temperature of the inert solvent used.
- the reaction time varies depending on the reaction scale, reaction temperature and the like, and is not constant, but may be appropriately selected in the range of usually several minutes to 48 hours.
- the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
- R 1 is the same as described above, Boc is a tertiary butoxycarbonyl group, R is a (C 1 -C 3 ) alkyl group, and X is a halogen atom.
- the “(C 1 -C 3 ) alkyl group” refers to a methyl group, an ethyl group, a normal propyl group, or an isopropyl group.
- the intermediate of the present compound represented by the general formula (2 ′) can be produced by the following steps [d] to [l].
- Step [d] A step of producing a compound represented by the general formula (2′-h) by converting a halogen atom at the 2-position of dichloropyridinecarboxylic acid (2′-i) into an ester group.
- Step [e] A step of producing a compound represented by the general formula (2′-g) by protecting the carboxyl group of the compound represented by the general formula (2′-h) as a tertiary butyl ester.
- Step [f] The compound represented by the general formula (2′-f) is produced by reacting the compound represented by the general formula (2′-g) with the compound represented by the general formula (5). Process.
- Step [g] A compound represented by the general formula (2′-e) is produced by deprotecting the protected carboxyl group as a tertiary butyl ester of the compound represented by the general formula (2′-f).
- Step [h] A step of producing a compound represented by the general formula (2′-d) by subjecting the compound represented by the general formula (2′-e) to a Crutius rearrangement reaction.
- Step [i] A step of producing a compound represented by the general formula (2′-c) by deprotecting the Boc-protected amino group of the compound represented by the general formula (2′-d). .
- Step [j] A step of producing the compound represented by the general formula (2′-b) by converting the amino group of the compound represented by the general formula (2′-c) to a halogen atom by Sandmeyer reaction.
- Step [k] A compound represented by the general formula (2′-a) by converting a halogen atom of the compound represented by the general formula (2′-b) into a cyclopropyl group by a cross-coupling reaction. Manufacturing process.
- Step [l] A step of producing an intermediate represented by the general formula (2 ′) by hydrolyzing the ester group of the compound represented by the general formula (2′-a).
- Step [d] The compound represented by the general formula (2′-h) is produced by reacting a commercially available dichloropyridinecarboxylic acid (2′-i) according to the method described in JP-A-2005-272338. be able to.
- the corresponding carboxylic acid chloride can be produced by reacting the compound represented by the general formula (2′-h) with a chlorinating agent in the presence of an inert solvent.
- solvent used in this reaction examples include ethers such as tetrahydrofuran (THF), ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dichloromethane, chloroform and the like.
- ethers such as tetrahydrofuran (THF), ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane
- aromatic hydrocarbons such as toluene and xylene, dichloromethane, chloroform and the like.
- Halogenated hydrocarbons and mixtures thereof may be mentioned, and the amount used may be appropriately selected from the range of usually 0.1 to 100 L with respect to 1 mol of the compound represented by the general formula (2′-h). good.
- Examples of the chlorinating agent used in this reaction include thionyl chloride and oxalyl dichloride.
- the amount used thereof can be usually 1 to 10 times the molar amount of the compound represented by the general formula (2'-h).
- the reaction temperature in this reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
- the target carboxylic acid chloride can be produced by distilling off the solvent, excess chlorinating agent and the like.
- the compound represented by the general formula (2′-g) is prepared by subjecting a carboxylic acid chloride prepared from the compound represented by the general formula (2′-h) to tertiary butyl alcohol in the presence of a base and an inert solvent. It can manufacture by making it react.
- solvent used in this reaction examples include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and halogenation such as dichloromethane and chloroform.
- ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane
- aromatic hydrocarbons such as toluene and xylene
- halogenation such as dichloromethane and chloroform.
- examples thereof include hydrocarbons and mixtures thereof, and the amount used may be appropriately selected from the range of usually 0.1 to 100 L with respect to 1 mol of carboxylic acid chloride.
- Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, acetates such as sodium acetate and potassium acetate, potassium t Alkali metal alkoxides such as butoxide, sodium methoxide, sodium ethoxide, tertiary amines such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, pyridine, dimethyl
- Examples thereof include nitrogen-containing aromatic compounds such as aminopyridine, and the amount thereof can be used in the range of usually 1 to 10 mol per mol of carboxylic acid chloride.
- Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, acetates such as sodium acetate and potassium acetate, potassium t Alkali metal alkoxides such as butoxide, sodium methoxide, sodium ethoxide, tertiary amines such as triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, pyridine, dimethyl Nitrogen-containing aromatic compounds such as aminopyridine can be mentioned, and the amount used is usually in the range of 1 to 10 moles compared to the compound represented by the general formula (2′-g). The Moreover, when using the alkali metal salt of the compound represented by General formula (5), it is not necessary to use a base.
- inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bi
- the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
- aromatic hydrocarbons such as benzene, toluene and xylene
- halogens such as methylene chloride, chloroform and carbon tetrachloride.
- Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
- the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, Use alone or in combination of two or more Door can be.
- the amount used may be appropriately selected from the range of usually 0.1 to 100 L with respect to 1 mol of the compound represented by the general formula (2'-g).
- reaction temperature can usually be carried out from ⁇ 10 ° C. in the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it can be usually in the range of several minutes to 48 hours.
- the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
- the compound represented by the general formula (2′-e) can be produced by reacting the compound represented by the general formula (2′-f) in the presence of an acid and / or an inert solvent.
- Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid, sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid.
- inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid
- organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid
- sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid.
- An acid etc. can be illustrated, The usage-amount should just be suitably selected from the range of 1 time mole-10 times mole normally with respect to the compound represented by general formula (2'-f).
- the acids can be used as a solvent.
- the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
- aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, etc.
- Halogenated hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide
- the inert solvent include amides such as dimethylacetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, and these inert solvents Is used alone or in combination of two or more It is possible.
- the amount used may be appropriately selected from the range of usually 0.1 to 100 L with respect to 1 mol of the compound represented by the general formula (2'-f). Moreover, when using the said acids as a solvent, it is not necessary to use a solvent.
- the reaction temperature in this reaction can be carried out usually from room temperature to the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it can be usually in the range of several minutes to 48 hours.
- the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
- the compound represented by the general formula (2′-d) is a compound represented by the formula (2′-e), A. Chem. Soc. According to the method described in 1972, 94, 6203-6205, it can be produced by reacting DPPA (diphenyl phosphate azide) in the presence of tertiary butyl alcohol.
- DPPA diphenyl phosphate azide
- the compound represented by the general formula (2′-c) can be produced by reacting the compound represented by the general formula (2′-d) in the presence of an acid and an inert solvent.
- Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid, sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid.
- inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid
- organic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid and benzoic acid
- sulfones such as methanesulfonic acid and trifluoromethanesulfonic acid.
- An acid etc. can be illustrated,
- the usage-amount should just be suitably selected from the range of 1 time mole-10 times mole normally with respect to the compound represented by general formula (2'-d). In some cases, it can also be used as a solvent.
- the inert solvent used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.
- aromatic hydrocarbons such as benzene, toluene and xylene
- halogens such as methylene chloride, chloroform and carbon tetrachloride.
- Hydrocarbons halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, chain or cyclic ethers such as diethyl ether, methyl tertiary butyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethyl
- the inert solvent include amides such as acetamide, ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethyl sulfoxide and 1,3-dimethyl-2-imidazolidinone, Use alone or in combination of two or more Door can be.
- the amount used may be appropriately selected from the range of usually 0.1 to 100 L with respect to 1 mol of the compound represented by the general formula (2'-d).
- the reaction temperature in this reaction can be carried out usually from ⁇ 10 ° C. in the boiling range of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it is usually within the range of several minutes to 48 hours. good.
- the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
- the compound represented by the general formula (2′-a) is obtained by cross-coupling the compound represented by the general formula (2′-b) with cyclopropylboronic acid in the presence of a transition metal catalyst, a base and an inert solvent. It can manufacture by performing reaction.
- transition metal catalyst used in this reaction examples include PdCl 2 (dppf) acetone complex, and the amount used is usually 0.01 mol% with respect to the compound represented by the general formula (2′-b). It may be appropriately selected from the range of ⁇ 100 mol%.
- Examples of the base used in this reaction include potassium phosphate (tribasic) and the like, and the amount used is usually 1 to 10 times the mol represented by the compound represented by the general formula (2′-b). What is necessary is just to select suitably from the range of a mole.
- inert solvent used in this reaction examples include ether solvents such as diethyl ether and THF, and the amount used is usually 0 with respect to 1 mol of the compound represented by the general formula (2′-b). It may be appropriately selected from the range of 1 to 100L.
- the compound represented by the general formula (2′-b) and cyclopropylboronic acid may be used in an equimolar amount, but any of the reactants may be used in excess.
- the reaction temperature can be carried out usually from room temperature to the boiling point of the inert solvent used, and the reaction time is not constant depending on the reaction scale and reaction temperature, but it may be usually in the range of several minutes to 48 hours.
- the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.
- the agricultural and horticultural insecticide containing the benzoxazole compound represented by the general formula (1) of the present invention or a salt thereof as an active ingredient is a variety of agricultural and forestry, horticulture, which harms paddy rice, fruit trees, vegetables, other crops and florets, Suitable for pest control such as stored grain or sanitary pests or nematodes.
- Examples of the pests or nematodes include the following. Lepidoptera (Lepidoptera) pests such as Parasa consocia, Redwood (Anomis mesogona), Papilio xuthus, Matsumuraeses azukivora, Ostrinia scapulalis, African exotic empti (Spod) (Hyphantria cunea), Awanoiga (Ostrinia furnacalis), Ayayoto (Pseudaletia separata), Iga (Tinea translucens), Bactra furfuryla, Parnara guttata, Ira inferens), Brachmia triannulella, Monema flavescens, Iraqusinu Waiba (Trichoplusia ni), Pleuroptya ruralis, Cystidia couaggaria, Lampides boeticus, Males flamingo (Helicoverpa armigera) Phararodonta man
- Hemiptera pests, for example, Nezara antennata, red beetle (Stenotus rubrovittatus), red beetle (Graphosoma rubrolineatum), red beetle (Trigonotylus coelestialium), Aeschynteles maculatus), red beetle (Creontiades pallidifer), red beetle bug (Dysdercus cingulatus), red beetle (Chrysomphalus ficus), red beetle (Aonidiella aurantii), red crab beetle (Graptops) Scale insects (Icerya purchasi), Japanese beetle (Piezodorus hybneri), Japanese beetle (Lagynotomus elongatus), Japanese white beetle (Thaia subrufa), Japanese black beetle (Scotinophara luridaito) , St
- Coleoptera (Coleoptera) pests include, for example, Xystrocera globosa, Aobaarie-hane-kakushi (Paederus fuscipes), Ahanamuri (Eucetonia roelofsi), Azuki beetle (Callosobruchus chinensis), Arimodosium (Hypera postica), rice weevil (Echinocnemus squameus), rice beetle (Oulema oryzae), rice beetle (Oulema oryzae), rice beetle (Donacia provosti), rice weevil (Lissorhoptruss (Epilachna varivestis), common bean weevil (Acanthoscelides obtectus), western corn rootworm (Diabrotica virgifera virgifera), beetle weevil (Involvulus cupreus), potato beetle (Aulacophora f
- Culex pipiens pallens red flies fly (Pegomya hyoscyami), red spider fly (Liriomyza huidobrensis), house fly (Musca domestica), rice flies Flies Fruit flies (Rhacochlaena japonica), fruit flies (Muscina stabulans), fruit flies such as fruit flies (Megaselia spiracularis), giant butterflies (Clogmia albipunctata), mushroom moth (Tipula aino), hormone moth (Pipula) rhynchus), Anopheles sinensis, Japanese flies (Hylemya brassicae), Soybean fly (Asphondylia sp.), Panax fly (Delia platura), Onion fly (Delia antiqua) RRen ), Ceratitis capitata, Bradysia agrestis, sugar beetle fly (P
- Hymenoptera Pristomyrmex ⁇ ponnes
- Arbatidae Moneorumium pharaohnis
- Pheidole noda Athalia rosae
- Cristoforma Kuriphilus
- Hornets black bee (Athalia infumata infumata), horned bee (Arge g pagana), Japanese bee (Athalia ⁇ japonica), cricket (Acromyrmex spp.), Fire ant (Solenopsis spp.), Apple honey bee (Arlen ali) (Ochetellus glaber) and the like.
- insects of the order Diptera Hortocoryphus lineosus
- Kera Gryllotalpa sp.
- Coago Oxya hyla intricata
- Cobainago Oxya yezoensis
- Tosama locust Locusta migrago
- Oneya Homorocoryphus jezoensis
- emma cricket Teogryllus emma
- Thrips examples of thrips of the order Thrips (Selenothrips rubrocinctus), thrips (Stenchaetothrips biformis), Thrips thrips (Haplothrips , Lithrips floridensis, Thrips simplex, Thrips nigropilosus, Helothripes Leeuwenia pasanii), Shiritakuthamis (Litotetothrips pasaniae), Citrus srips (Scirtothrips citri), Hempothrips chinensis, Soybean thrips (Mycterothrips glycines), Da Thrips setosus, Thripsrtsaw Thrips hawaiiensis, Haplothrips kurdjumovi, Thrips coloratus , Lilyripa vaneeckei, and the like.
- mite moths (Leptotrombidium akamushi), Ashinowa spider mite (Tetranychus ludeni), American dock ticks (Dermacentor variabilis), Ichinami spider mite (Tetranychus truncatus), house dust mite (Ornithonyssus bacoti), mite Tetranychus viennensis), ticks (Tetranychus kanzawai), ticks (Rhipicephalus sanguineus) and other ticks (Cheyletus acc malaccensis), stag beetle tick (Tyrophagus putrescent moth) Tick (Dermacentor taiwanicus), Chinese cabbage mite (Acaphylla theavagrans), Chinese dust mite (Polyphagotarsonemus latus), Tomato mite (Aculops lycopersici), Trichoid mite (Ornithonyssus sylvairum), Nami spider mite (
- Amite termites (Reticulitermes miyatakei), American termites (Incisitermes minor), Termites (Coptotermes formosanus), Termites (Hodotermopsis japonica), Common termites (Reticulitermes termm ants) , Glyptotermes , Nakaly termites (Glyptotermes nakajimai), Nitobe termites (Pericapritermes nitobei), Yamato termites (Reticulitermes speratus) and the like.
- cockroach Periplaneta fuliginosa
- German cockroach Blattella germanica
- Great cockroach Blatta orientalis
- Greater cockroach Periplaneta brunnea
- Greater cockroach Blattella lituriplanet (Periplaneta americana) and the like.
- fleas examples include human fleas (Pulex irritans), cat fleas (Ctenocephalides felis), and fleas (Ceratophyllus gallinae).
- Nematodes for example, strawberry nematode (Nothotylenchus acris), rice scallop nematode (Aphelenchoides besseyi), red-footed nematode (Pratylenchus penetrans), red-knot nematode (Meloidogyne hapla), sweet potato nematode (Meloidogyne rostochiensis), Javaloid nematode (Meloidogyne javanica), soybean cyst nematode (Heterodera glycines), southern nematode nematode (Pratylenchus coffeae), and pterolenchus nematode (Pratylenchus neglectus)
- mollusks examples include Pomacea canaliculata, Achatina fulica, slug (Meghimatium bilineatum), Lehmannina valentiana, Limax flavus, and Acusta despecta Is mentioned.
- the agricultural and horticultural insecticide of the present invention has a strong insecticidal effect against tomato kibaga (Tuta absoluta) as other pests.
- animal parasite ticks Boophilus microplus
- black tick ticks Raicephalus sanguineus
- yellow tick ticks Haemaphysalis longicornis
- yellow ticks Haemaphysalis flava
- tsurigane tick ticks Haemaphysata tick
- Tick Haemaphysalis concinna
- tick Haemaphysalis japonica
- tuna Haemaphysalis kitaokai
- tick Haemaphysalis ias
- tick Ixodes ovatus
- tick desmite Ticks Dermanyssus, ticks such as Amblyomma testudinarium, Haemaphysalis megaspinosa, Dermacentor reticulatus, and Dermacentor taiwanesis gallinae
- avian mite Ornithonyssus sylviarum
- fleas to be controlled include, for example, ectoparasite worms belonging to the order Flea (Siphonaptera), more specifically fleas belonging to the family Flea (Pulicidae), Cleaphyllus (Ceratephyllus), etc. .
- Fleas belonging to the family flea family include, for example, dog fleas (Ctenocephalides canis), cat fleas (Ctenocephalides felis), human fleas (Pulex irritans), elephant fleas (Echidnophaga gallinacea), keops mouse fleas (Xenopsylla cheopis), Leptopsylla segnis), European mouse minnow (Nosopsyllus fasciatus), and Yamato mouse minnow (Monopsyllus anisus).
- ectoparasites to be controlled include, for example, bovine lice (Haematopinus eurysternus), foal lice (Haematopinus asini), sheep lice (Dalmalinia ovis), bovine lice (Linognathus vituli), pig lice (Haematopinus suis), hirke us lice And lice like head lice (Pediculus capitis), and lice like dog lice (Trichodectes canis), blood-absorbing diptera like Trichodectes canis, Tabanus trigonus, Culicoides schultzei, and Simulium ornatum Examples include pests.
- endoparasites include nematodes such as pneumoniae, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms, manson cleft worms, broad-headed crest worms, berries Tapeworms such as tapeworms, multi-headed tapeworms, single-banded tapeworms, and multi-banded tapeworms, flukes such as Schistosoma japonicum, and liver fluke, and coccidium, malaria parasites, intestinal granulocysts, toxoplasma And protozoa such as Cryptosporidium.
- administration of the benzoxazole compound or its salt represented by General formula (1) of this invention may be internal administration or external administration.
- the agricultural and horticultural insecticide containing the benzoxazole compound represented by the general formula (1) of the present invention or a salt thereof as an active ingredient damages paddy field crops, field crops, fruit trees, vegetables, other crops, flowers, etc. It has a remarkable control effect against the pests, so that it matches the time when the occurrence of the pests is predicted, before the occurrence of the pests or at the time when the occurrence of the pests is confirmed, seedling facilities, paddy fields, fields, fruit trees, vegetables, etc.
- the desired effect of the agricultural and horticultural insecticide of the present invention can be achieved by treating the seeds such as crops, flower buds, paddy water, stalks and leaves, or soil and other cultivation carriers.
- Useful plants to which the agricultural and horticultural insecticide of the present invention can be used are not particularly limited, and examples thereof include cereals (eg, rice, barley, wheat, rye, oats, corn, etc.), beans (soybean, Red beans, broad beans, green beans, green beans, peanuts, etc.), fruit trees and fruits (apples, citrus fruits, pears, peaches, peaches, plums, cherry peaches, walnuts, chestnuts, almonds, bananas, etc.), leaves and fruit vegetables (cabbage, Tomato, spinach, broccoli, lettuce, onion, green onion (satsuki, parrot), green pepper, eggplant, strawberry, pepper, ladle, leek, etc., root vegetables (carrot, potato, sweet potato, sweet potato, daiko, kabu, lotus root, gobo) , Garlic, raccoon, etc.), crops for processing (crab, hemp, beet, hop, sugar cane, sugar beet, olive, rubber, coffee, tobacco, tea, etc
- the “plant” includes HPPD inhibitors such as isoxaflutol, ALS inhibitors such as imazetapyr and thifensulfuron methyl, EPSP synthase inhibitors such as glyphosate, glutamine synthase inhibitors such as glufosinate, Also included are plants that have been rendered resistant by classical breeding methods or genetic recombination techniques to resistance to herbicides such as acetyl CoA carboxylase inhibitors, bromoxynil, dicamba, 2,4-D.
- HPPD inhibitors such as isoxaflutol
- ALS inhibitors such as imazetapyr and thifensulfuron methyl
- EPSP synthase inhibitors such as glyphosate
- glutamine synthase inhibitors such as glufosinate
- plants that have been rendered resistant by classical breeding methods or genetic recombination techniques to resistance to herbicides such as acetyl CoA carboxylase inhibitors, bromoxynil
- Plants to which tolerance to an acetyl-CoA carboxylase inhibitor has been imparted are Procedures of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci). USA) 87, 7175-7179 (1990).
- a mutant acetyl CoA carboxylase resistant to an acetyl CoA carboxylase inhibitor has been reported in Weed Science 53, 728-746 (2005).
- Introducing a plant resistant to an acetyl-CoA carboxylase inhibitor by introducing a mutation into the plant or introducing a mutation associated with imparting resistance into the plant acetyl-CoA carboxylase, and further, chimeric plastic technology (Gura T. et al. 1999.
- toxins expressed in transgenic plants insecticidal proteins derived from Bacillus cereus and Bacillus popirie; ⁇ - such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C derived from Bacillus thuringiensis Insecticidal proteins such as endotoxin, VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins from nematodes; toxins produced by animals such as scorpion toxin, spider toxin, bee toxin or insect-specific neurotoxin; filamentous fungal toxins; plant lectins; Agglutinin; protease inhibitors such as trypsin inhibitor, serine protease inhibitor, patatin, cystatin, papain inhibitor; ribozo such as lysine, corn-RIP, abrin, ruffin, saporin, bryodin Inactivated protein (RIP); steroid
- toxins expressed in such genetically modified plants Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9C, Cry34Ab or Cry35Ab or the like ⁇ -endotoxin proteins, VIP1, VIP2, VIP3 or VIP3A, etc.
- insecticidal protein hybrid toxins partially defective toxins, and modified toxins.
- Hybrid toxins are produced by new combinations of different domains of these proteins using recombinant techniques.
- Cry1Ab lacking a part Cry1Ab lacking a part of the amino acid sequence is known.
- the modified toxin one or more amino acids of the natural toxin are substituted.
- Examples of these toxins and recombinant plants capable of synthesizing these toxins are EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878. , WO 03/052073, and the like.
- Toxins contained in these recombinant plants particularly confer resistance to Coleoptera, Hemiptera pests, Diptera pests, Lepidoptera pests and nematodes.
- the agricultural and horticultural insecticides of the present invention can be used in combination or systematized with these techniques.
- the insecticide for agricultural and horticultural use according to the present invention is used as it is to control various pests, or appropriately diluted with water or the like, or suspended in an amount effective for controlling the pests or nematodes.
- pests and nematodes that occur in fruit trees, cereals, vegetables, etc.
- seed immersion in seeds, seed dressing, calper treatment Etc seed treatment, soil all layer mixing, crop application, floor soil mixing, cell seedling treatment, planting hole treatment, plant root treatment, top dress, rice box treatment, water surface application, etc. It can also be absorbed and used.
- it can be used for nutrient solution in nutrient solution (hydroponics) cultivation, smoke, or trunk injection.
- the agricultural and horticultural insecticide of the present invention may be used as it is, appropriately diluted with water or the like or suspended in an amount effective for pest control in a place where the occurrence of the pest is predicted.
- the agricultural and horticultural insecticide of the present invention may be used as it is, appropriately diluted with water or the like or suspended in an amount effective for pest control in a place where the occurrence of the pest is predicted.
- they can also be used as application to house building materials, smoke, bait and the like.
- Seed treatment methods include, for example, a method in which a liquid or solid preparation is diluted or undiluted and the seed is immersed in a liquid state to infiltrate the drug, a solid preparation or liquid preparation is mixed with the seed, Examples thereof include a method of treating and adhering to the surface of the seed, a method of coating the seed by mixing with an adhesive carrier such as resin and polymer, and a method of spraying around the seed simultaneously with planting.
- the “seed” for performing the seed treatment means a plant body at the initial stage of cultivation used for the propagation of plants, for example, for seeds, bulbs, tubers, seed buds, stock buds, baskets, bulbs, or cuttings. Mention may be made of plants for vegetative propagation.
- the “soil” or “cultivation carrier” of the plant when carrying out the method of use of the present invention refers to a support for cultivating crops, particularly a support for growing roots, and the material is not particularly limited. However, any material that can grow plants may be used, and so-called soil, seedling mats, water, etc. may be used. Specific materials include, for example, sand, pumice, vermiculite, diatomaceous earth, agar, gel material, high It may be a molecular substance, rock wool, glass wool, wood chip, bark or the like.
- a spraying method for crop foliage for crop foliage, stored grain pests, house pests, hygiene pests, forest pests, etc., dilute liquid preparations such as emulsions and flowables or solid preparations such as wettable powders or granular wettable powders with water as appropriate.
- Examples of application methods to soil include, for example, a method in which a liquid preparation is diluted or not diluted with water and applied to a plant stock or seedling nursery, etc.
- a method of spraying to a nursery, etc. a method of spraying powder, wettable powder, granule wettable powder, granule, etc. before sowing or transplanting, and mixing with the whole soil, a planting hole, cropping before sowing or planting a plant body
- Examples thereof include a method of spraying powder, wettable powder, wettable powder, granule, etc. on the strip.
- the dosage form may vary depending on the time of application such as application during sowing, greening period, application during transplantation, etc., but agents such as powder, granule wettable powder, granules, etc. Apply by mold. It can also be applied by mixing with soil, and it can be mixed with soil and powder, granulated wettable powder or granules, for example, mixed with ground soil, mixed with soil covering, mixed with the entire soil. Simply, the soil and the various preparations may be applied alternately in layers.
- solid preparations such as jumbo agents, packs, granules, granule wettable powders, and liquid preparations such as flowables and emulsions are usually sprayed on flooded paddy fields.
- an appropriate formulation can be sprayed and injected into the soil as it is or mixed with fertilizer.
- a chemical solution such as emulsion or flowable as a source of water flowing into a paddy field such as a water mouth or an irrigation device, it can be applied in a labor-saving manner along with the supply of water.
- the plant source of the plant being cultivated In field crops, it can be treated to seeds or a cultivation carrier close to the plant body from sowing to raising seedling.
- treatment on the plant source of the plant being cultivated is suitable.
- a spray treatment using a granule or a irrigation treatment in a liquid of a drug diluted or not diluted with water can be performed. It is also a preferable treatment to mix the granules with the cultivation carrier before sowing and then sow.
- the irrigation treatment of the liquid drug or the granule spraying treatment to the seedling nursery is preferred.
- a granule is treated in a planting hole at the time of planting or is mixed with a cultivation carrier in the vicinity of the transplantation site.
- the agricultural and horticultural insecticide of the present invention is generally used in a form convenient for use according to a conventional method for agricultural chemical preparations. That is, the benzoxazole compound represented by the general formula (1) of the present invention or a salt thereof is dissolved and separated by blending them in a suitable inert carrier, or if necessary, together with an auxiliary agent in a suitable ratio.
- Suspended, mixed, impregnated, adsorbed or adhered, and formulated into appropriate dosage forms such as suspensions, emulsions, solutions, wettable powders, wettable granules, granules, powders, tablets, packs, etc. Use it.
- the composition of the present invention can contain, in addition to the active ingredient, additive components usually used in agricultural chemical formulations or animal parasite control agents as required.
- additive components include a carrier such as a solid carrier and a liquid carrier, a surfactant, a dispersant, a wetting agent, a binder, a tackifier, a thickener, a colorant, a spreading agent, a spreading agent, and an antifreezing agent. , Anti-caking agents, disintegrants, decomposition inhibitors and the like. In addition, you may use a preservative, a plant piece, etc. for an additional component as needed. These additive components may be used alone or in combination of two or more.
- the solid support examples include natural minerals such as quartz, clay, kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, diatomaceous earth, and inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride.
- liquid carrier examples include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin.
- monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol
- polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin.
- Alcohols such as propylene glycol ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, ethyl ether, dioxane, ethylene glycol monoethyl ether, dipropyl ether, tetrahydrofuran, etc.
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, ethyl ether, dioxane, ethylene glycol monoethyl ether, dipropyl ether, tetrahydrofuran, etc.
- Ethers normal paraffins, naphthenes, isoparaffins, kerosene, mineral oils and other aliphatic hydrocarbons
- Aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, dimethyl adipate, etc.
- Esters lactones such as ⁇ -butyrolactone, amides such as dimethylformamide, diethylformamide, dimethylacetamide, N-alkylpyrrolidinone, nitriles such as acetonitrile, sulfur compounds such as dimethylsulfoxide, soybean oil, rapeseed oil, Examples thereof include vegetable oils such as cottonseed oil and castor oil, and water. These may be used alone or in combination of two or more.
- surfactants used as dispersants and wetting agents include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene fatty acid diesters, Polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether, polyoxyethylene alkyl phenyl ether formalin condensate, polyoxyethylene polyoxypropylene block copolymer, polystyrene polyoxyethylene Block polymer, alkyl polyoxyethylene polypropylene block copolymer ether, polyoxye Lenalkylamine, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, acetylene dio
- binders and tackifiers include carboxymethyl cellulose and salts thereof, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinyl pyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, and an average molecular weight of 6000 to 20000.
- Polyethylene glycol polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, phospholipid (for example, cephalin, lecithin, etc.) cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compound, cross-linked polyvinylpyrrolidone, maleic acid and styrenes Polymers, (meth) acrylic acid copolymers, half-esters of polycarboxylic alcohol polymers and dicarboxylic acid anhydrides, water soluble salts of polystyrene sulfonic acid, para Fin, terpene, polyamide resins, polyacrylate, polyoxyethylene, wax, polyvinyl alkyl ethers, alkylphenol-formalin condensates, synthetic resin emulsions, and the like.
- phospholipid for example, cephalin, lecithin, etc.
- cellulose powder dextrin
- polyaminocarboxylic acid chelate compound cross-linked polyviny
- thickener examples include xanthan gum, guar gum, diyutane gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch compound, water-soluble polymer such as polysaccharide, high-purity bentonite, fumed silica (fumed Inorganic fine powders such as silica and white carbon.
- the colorant examples include inorganic pigments such as iron oxide, titanium oxide and Prussian blue, organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes.
- antifreezing agent examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
- Adjuvants for preventing caking and promoting disintegration include, for example, polysaccharides such as starch, alginic acid, mannose, galactose, polyvinylpyrrolidone, fumed silica (fumed silica), ester gum, petroleum resin, sodium tripolyphosphate, Sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, methacrylate copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, sulfonated styrene / isobutylene / maleic anhydride copolymer, starch / polyacrylonitrile graft copolymer A polymer etc. are mentioned.
- the decomposition inhibitor examples include desiccants such as zeolite, quicklime and magnesium oxide, antioxidants such as phenolic compounds, amine compounds, sulfur compounds and phosphoric acid compounds, and ultraviolet absorbers such as salicylic acid compounds and benzophenone compounds. It is done.
- desiccants such as zeolite, quicklime and magnesium oxide
- antioxidants such as phenolic compounds, amine compounds, sulfur compounds and phosphoric acid compounds
- ultraviolet absorbers such as salicylic acid compounds and benzophenone compounds. It is done.
- preservative examples include potassium sorbate, 1,2-benzothiazolin-3-one, and the like.
- functional aids such as metabolic degradation inhibitors such as piperonyl butoxide, antifreezing agents such as propylene glycol, antioxidants such as BHT, UV absorbers and other supplements as necessary Agents can also be used.
- the blending ratio of the active ingredient compound can be adjusted as necessary, and may be appropriately selected from the range of 0.01 to 90 parts by weight in 100 parts by weight of the agricultural and horticultural insecticide of the present invention.
- 0.01 to 50 parts by weight 0.01 to 50% by weight based on the total weight of the agricultural and horticultural insecticide
- the amount of the agricultural and horticultural insecticide of the present invention depends on various factors such as purpose, target pests, crop growth status, pest occurrence tendency, weather, environmental conditions, dosage form, application method, application location, application time, etc. Although it varies, the active ingredient compound may be suitably selected from the range of 0.001 g to 10 kg per 10 ares, preferably 0.01 g to 1 kg depending on the purpose.
- Agricultural and horticultural insecticides of the present invention are pests to be controlled, other agricultural and horticultural insecticides, acaricides, nematicides, fungicides, for the purpose of expanding the appropriate period of control or reducing the dose. It can also be used by mixing with biological pesticides, etc., and can also be used by mixing with herbicides, plant growth regulators, fertilizers, etc., depending on the usage situation.
- Examples of agricultural and horticultural fungicides used for similar purposes include aureofungin, azaconazole, azithiram, acipetacs, acibenzolar, acibenzolar-S-methyl. ), Azoxystrobin, anilazine, amisulbrom, ampropylfos, ametoctradin, allyl alcohol, aldimorph, amobam, isothianyl (Isotianil), isovaledione, isopyrazam, isoprothiolane, ipconazole, iprodione, iprovalicarb, iprobenfos, imazalil Iminoctadine, iminoctadine-albesilate, iminoctadine-triacetate, imibenconazole, uniconazole, uniconazole-P, eclomeole, echlomez Edifenphos, etaconazole, ethaboxam, e
- herbicides for example, 1-naphthylacetamide, 2,4-PA, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, 2,4-D, 2, 4-DB, 2,4-DEB, 2,4-DEP, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, MCP, MCPA, MCPA thioethyl, MCPB, ioxynil, aclonifen, azafenidin, acifluorfen, aziprotryne, azimsulfuron, aslam, acetochlor, Atrazine, atraton, anisuron, anilofos, abiglycine, abscisic acid, amicarbazone, amidosulfuron, amitrole, amino Cyclopyrachlor (aminocyclopyrachlor), aminopyralid (aminopyralid), Amibu Gin (amibuzin), amiprophos-methyl,
- biological pesticides include nuclear polyhedrosis virus (NPV), granulosis virus (GV), cytoplasmic polyhedrosis virus (CPV), insect pox virus (Entomopoxivirus, EPV) ) Virus preparations, Monocrosporium ⁇ ⁇ phymatophagum, Steinernema ⁇ carpocapsae, Steinernema kushidai, Pasturia ⁇ pene insecticides, and Pasturia pene insecticides Sterilization of microbial pesticides, Trichoderma lignorum, Agrobacterium radiobactor, non-pathogenic Erwinia carotovora, Bacillus subtilis, etc.
- microbial pesticide to be used by using mixed such as biological pesticides utilized as herbicides, such as Xanthomonas campestris (Xanthomonas campestris), the same effect can be expected.
- examples of biological pesticides include Encarsia formosa, Aphidius colemani, Aphidoletes aphidimyza, Diglyphus isaea, Dacnusahysrica persimilis), natural enemies such as Amblyseius cucumeris, Orius sauteri, microbial pesticides such as Beauveria brongniartii, (Z) -10-tetradecenyl acetate, (E, Z) ) -4,10-tetradecadinyl acetate, (Z) -8-dodecenyl acetate, (Z) -11-tetradecenyl acetate, (Z) -13-icosen-10-one, 14-methyl-1 - May also be used in combination with pheromone agents such as octadecene It is a function.
- pheromone agents such as octadecene It is a function.
- Reference example 2 Process for producing 5-chloro-6-ethoxycarbonylnicotinic acid t-butyl ester
- 5-Chloro-6-ethoxycarbonylnicotinic acid (10.9 g, 47.6 mmol) obtained in Reference Example 1 was dissolved in toluene (30 mL), and DMF (N, N-dimethylformamide) (4 mL) was added. It was. Subsequently, thionyl chloride (11 g, 2 equivalents) was added, and the mixture was heated with stirring at 90 ° C. for 3 hours. The reaction solution was returned to room temperature and concentrated.
- Formulation Example 1 Compound of the present invention 10 parts Xylene 70 parts N-methylpyrrolidone 10 parts Equal weight mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 10 parts The above is uniformly mixed and dissolved to prepare an emulsion.
- Formulation Example 2 Compound of the present invention 3 parts Clay powder 82 parts Diatomaceous earth powder 15 parts The above is mixed and ground uniformly to obtain a powder.
- Formulation Example 3 Compound of the present invention 5 parts Mixed powder of bentonite and clay 90 parts lignin sulfonate 5 parts The above is uniformly mixed, kneaded with an appropriate amount of water, granulated and dried to give granules.
- Formulation Example 4 Compound of the present invention 20 parts Kaolin, synthetic highly dispersed silicic acid 75 parts Polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 parts The above mixture is uniformly mixed and ground to obtain a wettable powder.
- test example of this invention is shown, it is not limited to these. .
- Control value test against peach aphid (Myzus persicae) Chinese cabbage was planted in a plastic pot having a diameter of 8 cm and a height of 8 cm to breed a peach aphid, and the number of parasites in each pot was investigated.
- the benzoxazole compound represented by the general formula (1) of the present invention or a salt thereof is dispersed in water and diluted to a chemical solution of 500 ppm, the chemical solution is sprayed on the stems and leaves of potted Chinese cabbage, air-dried, and then the pot is placed in a greenhouse.
- the number of parasites of the peach aphid parasitizing each Chinese cabbage was stored on the sixth day after spraying the drug, the control value was calculated from the following formula, and the determination was made according to the following criteria.
- Ta Number of parasites before spraying in the treated zone
- Ca Number of parasites before spraying in the untreated zone
- C Number of parasites after spraying in the untreated zone
- Test Example 2 Insecticidal test against Japanese brown planthopper (Laodelphax striatella)
- the benzoxazole compound represented by the general formula (1) of the present invention or a salt thereof is dispersed in water and diluted to a chemical solution of 500 ppm, and rice seedlings (variety: Nipponbare) are added to the chemical solution.
- the death rate was calculated according to the following criteria.
- Test Example 3 Insecticidal test against Plutella xylostella Benzoxazole represented by the general formula (1) of the present invention is prepared by releasing adult moths by laying eggs on the cypress seedlings, and laying eggs laid two weeks after the release.
- medical agent which uses a compound as an active ingredient was immersed in the chemical
- the compound according to the present invention has an excellent control effect against various pests that are problematic in the field of agriculture and horticulture, and is useful.
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Abstract
Description
即ち、本発明は、
[1]一般式(1)
R2は 、水素原子;又はシアノ基を示す。mは、0;1;又は2を示す。}で表されるベンゾオキサゾール化合物又はその塩類、
[2]R1が、ハロ(C1-C3)アルコキシ基である[1]に記載のベンゾオキサゾール化合物又はその塩類、
[3]R1が、ハロ(C1-C3)アルキルスルフィニル基である[1]に記載のベンゾオキサゾール化合物又はその塩類、
[4][1]~[3]の何れかに記載のベンゾオキサゾール化合物又はその塩類を有効成分として含有することを特徴とする農園芸用殺虫剤、
[5][1]~[3]の何れかに記載のベンゾオキサゾール化合物又はその塩類の有効量で植物又は土壌を処理することを特徴とする[4]に記載の農園芸用殺虫剤の使用方法、
[6][1]~[3]の何れかに記載のベンゾオキサゾール化合物又はその塩類を有効成分として含有することを特徴とする動物用外部寄生虫防除剤、
[7]
R2は、(b)水素原子;又は (b2)シアノ基;を示す。mは0、1、又は2を示す。}で示される縮合複素環化合物、
[8]R1が、(a1) ハロ(C1-C6)アルコキシ基である[7]に記載の縮合複素環化合物、
[9]R1が、(a2) ハロ(C1-C6)アルキルスルフィニル基である[7]に記載の縮合複素環化合物、
[10][7]~[9]の何れかに記載の縮合複素環化合物を有効成分として含有することを特徴とする農園芸用殺虫剤、
[11][7]~[9]の何れかに記載の縮合複素環化合物の有効量を植物又は土壌に処理することを特徴とする農園芸用殺虫剤の使用方法、
[12][7]~[9]の何れかに記載の縮合複素環化合物の有効量を有効成分として含有することを特徴とする外部寄生虫防除剤、
に関する。
更に好ましくは、R1が、ハロ(C1-C3)アルキルスルフィニル基であり、R2が、 水素原子であり、mが、2である。
工程[a] 一般式(2)で表される化合物と、アミノフェノール化合物を反応させることにより、一般式(2-1)で表される化合物を製造する工程。
工程[b] 一般式(2-1)で表される化合物を分子内環化させることにより、一般式(1-1)で表される化合物を製造する工程。
工程[c] 一般式(1-1)で表される化合物を酸化することにより、一般式(1a)で表されるベンゾオキサゾール化合物を製造する工程。
一般式(2‐1)で表される化合物は、一般式(2)で表される化合物から有機合成における通常の方法によって誘導したカルボン酸クロリドと、市販されており容易に入手することができるアミノフェノール化合物とを塩基及び不活性溶媒の存在下、反応させることにより製造することができる。
一般式(1‐1)で表される化合物は、一般式(2‐1)で表される化合物を不活性溶媒の存在下、Synthesis 1981, 1‐28に記載された方法に従って(好ましくはアゾジカルボン酸ジエステル類、及びトリフェニルホスフィン(PPh3)を使用して)製造することができる。
一般式(1a)で表されるベンゾオキサゾール化合物は、一般式(1‐1)で表される化合物を、不活性溶媒中、酸化剤と反応させることにより製造することができる。
工程[d] ジクロロピリジンカルボン酸(2’-i)の2位のハロゲン原子をエステル基へと変換することで、一般式(2’-h)で表される化合物を製造する工程。
工程[e] 一般式(2’-h)で表される化合物のカルボキシル基を、ターシャリーブチルエステルとして保護することにより、一般式(2’-g)で表される化合物を製造する工程。
工程[f] 一般式(2’-g)で表される化合物を、一般式(5)で表される化合物と反応させることにより、一般式(2’-f)で表される化合物を製造する工程。
工程[g] 一般式(2’-f)で表される化合物のターシャリーブチルエステルとして保護されたカルボキシル基を脱保護することにより、一般式(2’-e)で表される化合物を製造する工程。
工程[h] 一般式(2’-e)で表される化合物に対して、Crutius転移反応を行うことにより、一般式(2’-d)で表される化合物を製造する工程。
工程[i] 一般式(2’-d)で表される化合物の、Bocで保護されたアミノ基を脱保護することにより、一般式(2’-c)で表される化合物を製造する工程。
工程[j] 一般式(2’-c)で表される化合物のアミノ基をSandmeyer反応によりハロゲン原子に変換することで、一般式(2’-b)で表される化合物を製造する工程。
工程[k] 一般式(2’-b)で表される化合物のハロゲン原子を、クロスカップリング反応によりシクロプロピル基へと変換することで、一般式(2’-a)で表される化合物を製造する工程。
工程[l] 一般式(2’-a)で表される化合物のエステル基を加水分解することにより、一般式(2’)で表される中間体を製造する工程。
一般式(2’‐h)で表される化合物は、市販で入手可能なジクロロピリジンカルボン酸(2’‐i)を特開2005-272338号に記載された方法に従って反応させることにより、製造することができる。
一般式(2’‐h)で表される化合物と塩素化剤等とを不活性溶媒の存在下、反応させることにより、対応するカルボン酸クロリドを製造することができる。
一般式(2’‐f)で表される化合物は、一般式(2’‐g)で表される化合物と一般式(5)で表される化合物とを不活性溶媒の存在下、反応させることにより、製造することができる。
一般式(2’‐e)で表される化合物は、一般式(2’‐f)で表される化合物を酸及び/又は不活性溶媒の存在下、反応させることにより製造することができる。
反応終了後、目的物を含む反応系から目的物を常法により単離すれば良く、必要に応じて再結晶、カラムクロマトグラフィー等で精製することにより目的物を製造することができる。
一般式(2’‐d)で表される化合物は、一般式(2’‐e)で表される化合物を、J.A.Chem.Soc.1972, 94, 6203‐6205に記載の方法に従い、DPPA(ジフェニルリン酸アジド)とターシャリーブチルアルコールの存在下反応させることにより、製造することができる。
一般式(2’‐c)で表される化合物は、一般式(2’‐d)で表される化合物を、酸、及び不活性溶媒の存在下、反応させることにより製造することができる。
一般式(2’-b)で表される化合物は、一般式(2’‐c)で表される化合物を、Sandmeyer反応(Chem. Rev. 1988, 88, 765)に記載された方法に従ってハロゲン化した後、有機合成において通常用いられる方法によりエステル化することにより製造することができる。
一般式(2’-a)で表される化合物は、一般式(2’-b)で表される化合物とシクロプロピルボロン酸を、遷移金属触媒、塩基、不活性溶媒存在下、クロスカップリング反応を行うことにより、製造することができる。
一般式(2’-a)で表される化合物のエステル基を、有機合成において通常用いられる方法により加水分解することにより、一般式(2’)で表される化合物を製造することができる。
鱗翅目(チョウ目)害虫として例えば、アオイラガ(Parasa consocia)、アカキリバ(Anomis mesogona)、アゲハ(Papilio xuthus)、アズキサヤムシガ(Matsumuraeses azukivora)、アズキノメイガ(Ostrinia scapulalis)、アフリカヨトウ(Spodoptera exempta)、アメリカシロヒトリ(Hyphantria cunea)、アワノメイガ(Ostrinia furnacalis)、アワヨトウ(Pseudaletia separata)、イガ(Tinea translucens)、イグサシンムシガ(Bactra furfuryla)、イチモンジセセリ(Parnara guttata)、イネタテハマキ(Marasmia exigua)、イネツトムシ(Parnara guttata)、イネヨトウ(Sesamia inferens)、イモキバガ(Brachmia triannulella)、イラガ(Monema flavescens)、イラクサギンウワバ(Trichoplusia ni)、ウコンノメイガ(Pleuroptya ruralis)、ウメエダシャク(Cystidia couaggaria)、ウラナミシジミ(Lampides boeticus)、オオスカシバ(Cephonodes hylas)、オオタバコガ(Helicoverpa armigera)、オオトビモンシャチホコ(Phalerodonta manleyi)、オオミノガ(Eumeta japonica)、オオモンシロチョウ(Pieris brassicae)、オビカレハ(Malacosoma neustria testacea)、カキノヘタムシガ(Stathmopoda masinissa)、カキホソガ(Cuphodes diospyrosella)、カクモンハマキ(Archips xylosteanus)、カブラヤガ(Agrotis segetum)、カンショシンクイハマキ(Tetramoera schistaceana)、キアゲハ(Papilio machaon hippocrates)、キマダラコウモリ(Endoclyta sinensis)、ギンモンハモグリガ(Lyonetia prunifoliella)、キンモンホソガ(Phyllonorycter ringoneella)、クリミガ(Cydia kurokoi)、クリミドリシンクイガ(Eucoenogenes aestuosa)、グレープベリーモス(Lobesia botrana)、クロシタアオイラガ(Latoia sinica)、クロフタモンマダラメイガ(Euzophera batangensis)、クワイホソハマキ(Phalonidia mesotypa)、クワゴマダラヒトリ(Spilosoma imparilis)、クワノメイガ(Glyphodes pyloalis)、クワヒメハマキ(Olethreutes mori)、コイガ(Tineola bisselliella)、コウモリガ(Endoclyta excrescens)、コクガ(Nemapogon granellus)、コスカシバ(Synanthedon hector)、コドリンガ(Cydia pomonella)、コナガ(Plutella xylostella)、コブノメイガ(Cnaphalocrocis medinalis)、サザンピンクボーラー(Sesamia calamistis)、サンカメイガ(Scirpophaga incertulas)、シバツトガ(Pediasia teterrellus)、ジャガイモガ(Phthorimaea operculella)、シャチホコガ(Stauropus fagi persimilis)、シロイチモジマダラメイガ(Etiella zinckenella)、シロイチモジヨトウ(Spodoptera exigua)、シロテンコウモリ(Palpifer sexnotata)、シロナヨトウ(Spodoptera mauritia)、イネシロオオメイガ(Scirpophaga innotata)、シロモンヤガ(Xestia c-nigrum)、スジキリヨトウ(Spodoptera depravata)、スジコナマダラメイガ(Ephestia kuehniella)、スモモエダシャク(Angerona prunaria)、セグロシャチホコ(Clostera anastomosis)、ソイビーンルーパー(Pseudoplusia includens)、ダイズサヤムシガ(Matsumuraeses falcana)、タバコガ(Helicoverpa assulta)、タマナギンウワバ(Autographa nigrisigna)、タマナヤガ(Agrotis ipsilon)、チャドクガ(Euproctis pseudoconspersa)、チャノコカクモンハマキ(Adoxophyes orana)、チャノホソガ(Caloptilia theivora)、チャハマキ(Homona magnanima)、チャマダラメイガ(Ephestia elutella)、チャミノガ(Eumeta minuscula)、ツマアカシャチホコ(Clostera anachoreta)、ツメクサガ(Heliothis maritima)、テングハマキ(Sparganothis pilleriana)、トウモロコシメイガ(Busseola fusca)、ドクガ(Euproctis subflava)、トビモンオオエダシャク(Biston robustum)、トマトフルーツワーム(Heliothis zea)、ナカジロシタバ(Aedia leucomelas)、ナシイラガ(Narosoideus flavidorsalis)、ナシケンモン(Viminia rumicis)、ナシチビガ(Bucculatrix pyrivorella)、ナシヒメシンクイ(Grapholita molesta)、ナシホソガ(Spulerina astaurota)、ナシマダラメイガ(Ectomyelois pyrivorella)、ニカメイガ(Chilo suppressalis)、ネギコガ(Acrolepiopsis sapporensis)、ノシメマダラメイガ(Plodia interpunctella)、ハイマダラノメイガ(Hellula undalis)、バクガ(Sitotroga cerealella)、ハスモンヨトウ(Spodoptera litura)、ハマキガの一種(Eucosma aporema)、バラハマキ(Acleris comariana)、ヒメクロイラガ(Scopelodes contractus)、ヒメシロモンドクガ(Orgyia thyellina)、フォールアーミーワーム(Spodoptera frugiperda)、フキノメイガ(Ostrinia zaguliaevi)、フタオビコヤガ(Naranga aenescens)、フタテンカギバモドキ(Andraca bipunctata)、ブドウスカシバ(Paranthrene regalis)、ブドウスズメ(Acosmeryx castanea)、ブドウハモグリガ(Phyllocnistis toparcha)、ブドウヒメハマキ(Endopiza viteana)、ブドウホソハマキ(Eupoecillia ambiguella)、ベルベットビーンキャタピラー(Anticarsia gemmatalis)、ホソバハイイロハマキ(Cnephasia cinereipalpana)、マイマイガ(Lymantria dispar)、マツカレハ(Dendrolimus spectabilis)、マメシンクイガ(Leguminivora glycinivorella)、マメノメイガ(Maruca testulalis)、マメヒメサヤムシガ(Matsumuraeses phaseoli)、マメホソガ(Caloptilia soyella)、ミカンハモグリガ(Phyllocnistis citrella)、マエウスキノメイガ(Omiodes indicate)、ミダレカクモンハマキ(Archips fuscocupreanus)、ミツモンキンウワバ(Acanthoplusia agnata)、ミノガ(Bambalina sp.)、モモシンクイガ(Carposina niponensis)、モモノゴマダラノメイガ(Conogethes punctiferalis)、モモスカシバ類(Synanthedon sp.)、モモハモグリガ(Lyonetia clerkella)、モンキアゲハ(Papilio helenus)、モンキチョウ(Colias erate poliographus)、モンクロシャチホコ(Phalera flavescens)、モンシロチョウ(Pieris rapae crucivora)、モンシロチョウ(Pieris rapae)等のシロチョウ類、モンシロドクガ(Euproctis similis)、ヤマノイモコガ(Acrolepiopsis suzukiella)、ヨーロピアンコーンボーラー(Ostrinia nubilalis)、ヨトウガ(Mamestra brassicae)、ヨモギエダシャク(Ascotis selenaria)、ヨモギオオホソハマキ(Phtheochroides clandestina)、リンゴオオハマキ(Hoshinoa adumbratana)、リンゴカレハ(Odonestis pruni japonensis)、リンゴケンモン(Triaena intermedia)、リンゴコカクモンハマキ(Adoxophyes orana fasciata)、リンゴコシンクイ(Grapholita inopinata)、リンゴシロヒメハマキ(Spilonota ocellana)、リンゴハイイロハマキ(Spilonota lechriaspis)、リンゴハマキクロバ(Illiberis pruni)、リンゴヒメシンクイ(Argyresthia conjugella)、リンゴホソガ(Caloptilia zachrysa)、リンゴモンハマキ(Archips breviplicanus)、ワタアカキリバ(Anomis flava)、ワタアカミムシ(Pectinophora gossypiella)、ワタノメイガ(Notarcha derogata)、ワタヘリクロノメイガ(Diaphania indica)、ニセアメリカタバコガ(Heliothis virescens)、及びワタリンガ(Earias cupreoviridis)等が挙げられる。
なお、本発明の一般式(1)で表されるベンゾオキサゾール化合物又はその塩類の投与は体内投与であっても体外投与であってもよい。
またアセチルCoAカルボキシラーゼ阻害剤に耐性が付与された植物はプロシーディングズ・オブ・ザ・ナショナル・アカデミー・オブ・サイエンシーズ・オブ・ザ・ユナイテッド・ステーツ・オブ・アメリカ(Proc.Natl.Acad.Sci.USA)87巻、7175~7179頁(1990年)等に記載されている。またアセチルCoAカルボキシラーゼ阻害剤に耐性の変異アセチルCoAカルボキシラーゼがウィード・サイエンス(Weed Science)53巻、728~746頁(2005年)等に報告されており、こうした変異アセチルCoAカルボキシラーゼ遺伝子を遺伝子組換え技術により植物に導入するか若しくは抵抗性付与に関わる変異を植物アセチルCoAカルボキシラーゼに導入することにより、アセチルCoAカルボキシラーゼ阻害剤に耐性の植物を作出することができ、さらに、キメラプラスティ技術(Gura T. 1999. Repairing the Genome’s Spelling Mistakes. Science 285: 316-318.)に代表される塩基置換変異導入核酸を植物細胞内に導入して植物のアセチルCoAカルボキシラーゼ遺伝子やALS遺伝子等に部位特異的アミノ酸置換変異を導入することにより、アセチルCoAカルボキシラーゼ阻害剤やALS阻害剤等に耐性の植物を作出することができ、これらの植物に対しても本発明の農園芸用殺虫剤を使用することができる。
これら毒素の例及びこれら毒素を合成することができる組換え植物は、EP-A-0 374 753、WO 93/07278、WO 95/34656、EP-A-0 427 529、EP-A-451 878、WO 03/052073等に記載されている。
更に、本発明の農園芸用殺虫剤は、そのまま、又は水等で適宜希釈し、若しくは懸濁させた形で害虫防除に有効な量を当該害虫の発生が予測される場所に使用すればよく、例えば貯穀害虫、家屋害虫、衛生害虫、森林害虫等に散布する他に、家屋建材への塗布、くん煙、ベイト等として使用することもできる。
当該種子処理を行う「種子」とは、植物の繁殖に用いられる栽培初期の植物体を意味し、例えば、種子の他、球根、塊茎、種芋、株芽、むかご、鱗茎、あるいは挿し木栽培用の栄養繁殖用の植物体を挙げることができる。
本発明の使用方法を実施する場合の植物の「土壌」又は「栽培担体」とは、作物を栽培するための支持体、特に根を生えさせる支持体を示すものであり、材質は特に制限されないが、植物が生育しうる材質であれば良く、いわゆる土壌、育苗マット、水等であっても良く、具体的な素材としては例えば、砂、軽石、バーミキュライト、珪藻土、寒天、ゲル状物質、高分子物質、ロックウール、グラスウール、木材チップ、バーク等であっても良い。
土壌への施用方法としては、例えば、液体製剤を水に希釈又は希釈せずして植物体の株元又は育苗用苗床等に施用する方法、粒剤を植物体の株元又は育苗のための苗床等に散布する方法、播種前又は移植前に粉剤、水和剤、顆粒水和剤、粒剤等を散布し土壌全体と混和する方法、播種前又は植物体を植える前に植え穴、作条等に粉剤、水和剤、顆粒水和剤、粒剤等を散布する方法等が挙げられる。
水田への施用方法としては、ジャンボ剤、パック剤、粒剤、顆粒水和剤等の固形製剤、フロアブル、乳剤等の液体状製剤を、通常は、湛水状態の水田に散布する。その他、田植え時には、適当な製剤をそのまま、あるいは、肥料に混和して土壌に散布、注入することもできる。また、水口や灌漑装置等の水田への水の流入元に乳剤、フロアブル等の薬液を利用することにより、水の供給に伴い省力的に施用することもできる。
移植を行う栽培植物の播種、育苗期の処理としては、種子への直接処理の他、育苗用苗床への、液状とした薬剤の潅注処理又は粒剤の散布処理が好ましい。また、定植時に粒剤を植え穴に処理をしたり、移植場所近辺の栽培担体に混和することも好ましい処理である。
本発明の農園芸用殺虫剤は、農薬製剤上の常法に従い使用上都合の良い形状に製剤して使用するのが一般的である。
即ち、本発明の一般式(1)で表されるベンゾオキサゾール化合物又はその塩類はこれらを適当な不活性担体に、又は必要に応じて補助剤と一緒に適当な割合に配合して溶解、分離、懸濁、混合、含浸、吸着若しくは付着させて適宜の剤型、例えば懸濁剤、乳剤、液剤、水和剤、顆粒水和剤、粒剤、粉剤、錠剤、パック剤等に製剤して使用すれば良い。
更に必要に応じて機能性展着剤、ピペロニルブトキサイド等の代謝分解阻害剤等の活性増強剤、プロピレングリコール等の凍結防止剤、BHT等の酸化防止剤、紫外線吸収剤等その他の補助剤も使用することができる。
本発明の農園芸用殺虫剤は、防除対象病害虫、防除適期の拡大のため、或いは薬量の低減をはかる目的で他の農園芸用殺虫剤、殺ダニ剤、殺線虫剤、殺菌剤、生物農薬等と混合して使用することも可能であり、また、使用場面に応じて除草剤、植物成長調節剤、肥料等と混合して使用することも可能である。
化メチル(iodomethane)、ラベンザゾール(rabenzazole)、塩化ベンザルコニウム(benzalkonium chloride)、塩基性塩化銅(basic copper chloride)、塩基性硫酸銅(basic copper sulfate)、金属銀(silver)等の無機殺菌剤、次亜塩素酸ナトリウム(sodium hypochlorote)、水酸化第二銅(cupric hydroxide)、水和硫黄剤(wettable sulfur)、石灰硫黄合剤(calcium polysulfide)、炭酸水素カリウム(potassium hydrogen carbonate)、炭酸水素ナトリウム(sodium hydrogen carbonate)、無機硫黄(sulfur)、無水硫酸銅(copper sulfate anhydride)、ジメチルジチオカルバミド酸ニッケル(nickel dimethyldithiocarbamate)、8-ヒドロキシキノリン銅(oxine copper)のような銅系化合物、硫酸亜鉛(zinc sulfate)、硫酸銅五水塩(copper sulfate pentahydrate)等を例示することができる。
ール(fenteracol)、フェントラザミド(fentrazamide)、フェンメディファム(phenmedipham)、フェンメディファムエチル(phenmedipham-ethyl)、ブタクロール(butachlor)、ブタフェナシル(butafenacil)、ブタミホス(butamifos)、ブチウロン(buthiuron)、ブチダゾール(buthidazole)、ブチレート(butylate)、ブツロン(buturon)、ブテナクロール(butenachlor)、ブトキシジム(butroxydim)、ブトラリン(butralin)、フラザスルフロン(flazasulfuron)、フラムプロップ(flamprop)、フリロオキシフェン(furyloxyfen)、プリナクロール(prynachlor)、プリミスルフロンメチル(primisulfuron-methyl)、フルアジホップ(fluazifop)、フルアジホップ-P(fluazifop-P)、フルアジホップブチル(fluazifop-butyl)、フルアゾレート(fluazolate)、フルロキシピル(fluroxypyr)、フルオチウロン(fluothiuron)、フルオメツロン(fluometuron)、フルオログリコフェン(fluoroglycofen)、フルロクロリドン(flurochloridone)、フルオロジフェン(fluorodifen)、フルオロニトロフェン(fluoronitrofen)、フルオロミジン(fluoromidine)、フルカルバゾン(flucarbazone)、フルカルバゾンナトリウム(flucarbazone-sodium)、フルクロラリン(fluchloralin)、フルセトスルフロン(flucetosulfuron)、フルチアセット(fluthiacet)、フルチアセットメチル(fluthiacet-methyl)、フルピルスルフロン(flupyrsulfuron)、フルフェナセット(flufenacet)、フルフェニカン(flufenican)、フルフェンピル(flufenpyr)、フルプロパシル(flupropacil)、フルプロパナート(flupropanate)、フルポキサム(flupoxam)、フルミオキサジン(flumioxazin)、フルミクロラック(flumiclorac)、フルミクロラックペンチル(flumiclorac-pentyl)、フルミプロピン(flumipropyn)、フルメジン(flumezin)、フルオメツロン(fluometuron)、フルメトスラム(flumetsulam)、フルリドン(fluridone)、フルルタモン(flurtamone)、フルロキシピル(fluroxypyr)、プレチラクロール(pretilachlor)、プロキサン(proxan)、プログリナジン(proglinazine)、プロシアジン(procyazine)、プロジアミン(prodiamine)、プロスルファリン(prosulfalin)、プロスルフロン(prosulfuron)、プロスルホカルブ(prosulfocarb)、プロパキザホップ(propaquizafop)、プロパクロール(propachlor)、プロパジン(propazine)、プロパニル(propanil)、プロピザミド(propyzamide)、プロピソクロール(propisochlor)、プロヒドロジャスモン(prohydrojasmon)、プロピリスルフロン(propyrisulfuron)、プロファム(propham)、プロフルアゾール(profluazol)、プロフルラリン(profluralin)、プロヘキサジオンカルシウム(prohexadione-calcium)、プロポキシカルバゾン(propoxycarbazone)、プロポキシカルバゾンナトリウム(propoxycarbazone-sodium)、プロホキシジム(profoxydim)、ブロマシル(bromacil)、ブロムピラゾン(brompyrazon)、プロメトリン(prometryn)、プロメトン(prometon)、ブロモキシニル(bromoxynil)、ブロモフェノキシム(bromofenoxim)、ブロモブチド(bromobutide)、ブロモボニル(bromobonil)、フロラスラム(florasulam)、ヘキサクロロアセトン(hexachloroacetone)、ヘキサジノン(hexazinone)、ペトキサミド(pethoxamid)、ベナゾリン(benazolin)、ペノクスラム(penoxsulam)、ペブレート(pebulate)、ベフルブタミド(beflubutamid)、ベルノレート(vernolate)、ペルフルイドン(perfluidone)、ベンカルバゾン(bencarbazone)、ベンザドックス(benzadox)、ベンジプラム(benzipram)、ベンジルアミノプリン(benzylaminopurine)、ベンズチアズロン(benzthiazuron)、ベンズフェンジゾン(benzfendizone)、ベンスリド(bensulide)、ベンスルフロンメチル(bensulfuron-methyl)、ベンゾイルプロップ(benzoylprop)、ベンゾビシクロン(benzobicyclon)、ベンゾフェナップ(benzofenap)、ベンゾフルオール(benzofluor)、ベンタゾン(bentazone)、ペンタノクロール(pentanochlor)、ベンチオカーブ(benthiocarb)、ペンディメタリン(pendimethalin)、ペントキサゾン(pentoxazone)、ベンフラリン(benfluralin)、ベンフレセート(benfuresate)、ホサミン(fosamine)、ホメサフェン(fomesafen)、ホラムスルフロン(foramsulfuron)、ホルクロルフェニュロン(forchlorfenuron)、マレイン酸ヒドラジド(maleic hydrazide)、メコプロップ(mecoprop)、メコプロップ-P(mecoprop-P)、メジノテルブ(medinoterb)、メソスルフロン(mesosulfuron)、メソスルフロンメチル(mesosulfuron-methyl)、メソトリオン(mesotrione)、メソプラジン(mesoprazine)、メソプロトリン(methoprotryne)、メタザクロール(metazachlor)、メタゾール(methazole)、メタゾスルフロン(metazosulfuron)、メタベンズチアズロン(methabenzthiazuron)、メタミトロン(metamitron)、メタミホップ(metamifop)、メタム(metam)、メタルプロパリン(methalpropalin)、メチウロン(methiuron)、メチオゾリン(methiozolin)、メチオベンカルブ(methiobencarb)、メチルダイムロン(methyldymron)、メトクスロン(metoxuron)、メトスラム(metosulam)、メトスルフロン(metsulfuron)、メトスルフロンメチル(metsu1furon-methy1)、メトフラゾン(metflurazon)、メトブロムロン(metobromuron)、メトベンズロン(metobenzuron)、メトメトン(methometon)、メトラクロール(metolachlor)、メトリブジン(metribuzin)、メピコートクロリド(mepiquat-chloride)、メフェナセット(mefenacet)、メフルイジド(mefluidide)、モナリド(monalide)、モニソウロン(monisouron)、モニュヌロン(monuron)、モノクロル酢酸(monochloroacetic acid)、モノリニュヌロン(monolinuron)、モリネート(molinate)、モルファムコート(morfamquat)、ヨードスルフロン(iodosulfuron)、ヨードスルフロンメチルナトリウム(iodosulfuron-methyl-sodium)、ヨードボニル(iodobonil)、ヨードメタン(iodomethane)、ラクトフェン(lactofen)、リヌロン(linuron)、リムスルフロン(rimsulfuron)、レナシル(lenacil)、ローデタニル(rhodethanil)、過酸化カルシウム(calcium peroxide)、臭化メチル(methyl bromide)等を例示することができる。
5‐シクロプロピル‐3‐エチルチオ‐N‐(2‐ヒドロキシ‐5‐(トリフルオロメチルチオ)フェニル)‐2‐ピリジンカルボン酸アミドの製造方法
収率:77%(2工程)
2‐(5‐シクロプロピル‐3‐エチルチオピリジン‐2‐イル)‐5‐(トリフルオロメチルチオ)ベンゾ[d]オキサゾールの製造方法
収率:78%
2‐(5‐シクロプロピル‐3‐エチルスルホニルピリジン‐2‐イル)‐5‐(トリフルオロメチルスルフィニル)ベンゾ[d]オキサゾール(化合物番号1-12)の製造方法
収率:37%
物性:融点58~60℃
2‐(5‐シクロプロピル‐3‐エチルスルホニルピリジン‐2‐イル)‐5‐(トリフルオロメチメトキシ)ベンゾ[d]オキサゾール(化合物番号1-3)の製造方法
2‐アミノ‐4‐(トリフルオロメチルチオ)フェノールに代えて、2‐アミノ‐4‐(トリフルオロメトキシ)フェノールを使用して、前記製造実施例1-1乃至1-3と同様の製造方法により、表題のの化合物を得た。
物性:融点113~114℃
5-クロロ-6-エトキシカルボニルニコチン酸の製造方法
収率:76%
物性:1H‐NMR(CDCl3) δ 9.02(d、1H)、8.44(d、1H)、4.42(dd、2H)、1.33(t、3H)
5‐クロロ‐6‐エトキシカルボニルニコチン酸 t‐ブチルエステルの製造方法
収率:62%
物性:1H‐NMR(CDCl3) δ 9.05(d、1H)、8.30(d、1H)、4.50(dd、2H)、1.61(s、9H)、1.44(t、3H)
5-エチルチオ-6-エトキシカルボニルニコチン酸 t-ブチルエステルの製造方法
収率:92%
物性:1H‐NMR(CDCl3) δ 8.91(d、1H)、8.22(d、1H)、4.49(dd、2H)、2.99(dd、2H)、1.61(s、9H)、1.45(t、3H)、1.40(t、3H)
3-エチルチオ-5-t‐ブトキシカルボニルアミノピコリン酸 エチルエステルの製造方法
収率:未精製
物性:1H‐NMR(CDCl3) δ 9.06(d、1H)、8.33(d、1H)、4.52(q、2H)、3.03(q、2H)、1.50‐1.41(m、6H)
収率:56%(2工程)
物性:1H‐NMR(CDCl3) δ 8.25(d、1H)、8.09(d、1H)、6.74(s、1H)、4.46(dd、2H)、2.97(dd、2H)、1.53(s、9H)、1.44(t、3H)、1.41(t、3H)
5-アミノ-3-エチルチオピコリン酸 エチルエステルの製造方法
収率:77%
物性:1H‐NMR(CDCl3) δ 7.89(d、1H)、6.80(s、1H)、4.43(dd、2H)、4.08(s、2H)、2.88(dd、2H)、1.56(s、9H)、1.42(t、3H)、1.40(t、3H)
3‐エチルチオ‐5‐ヨードピコリン酸 エチルエステルの製造方法
収率:51%
物性:1H‐NMR(CDCl3) δ 8.61(s、1H)、7.95(s、1H)、4.45(dd、2H)、2.91(dd、2H)、1.43(t、3H)、1.39(t、3H)
3‐エチルチオ‐5‐シクロプロピルピコリン酸の製造方法
収率:89%
物性:1H-NMR δ 8.19(d、1H)、7.27(d、1H)、4.46(q、2H)、2.92(q、2H)、1.97-1.90(m、1H)、1.46-1.37(m、6H)、1.13-1.10(m、2H)、0.82-0.78(m、2H)
収率:91%
物性:1H‐NMR δ 8.01(d、1H)、7.31(d、1H)、2.95(q、2H)、2.00-1.94(m、1H)、1.42(t、3H)、1.21-1.16(m、2H)、0.87-0.84(m、2H)
本発明化合物 10部
キシレン 70部
N-メチルピロリドン 10部
ポリオキシエチレンノニルフェニルエーテルと
アルキルベンゼンスルホン酸カルシウムとの等重量混合物 10部
以上を均一に混合溶解して乳剤とする。
本発明化合物 3部
クレー粉末 82部
珪藻土粉末 15部
以上を均一に混合粉砕して粉剤とする。
本発明化合物 5部
ベントナイトとクレーの混合粉末 90部
リグニンスルホン酸カルシウム 5部
以上を均一に混合し、適量の水を加えて混練し、造粒、乾燥して粒剤とする。
本発明化合物 20部
カオリンと合成高分散珪酸 75部
ポリオキシエチレンノニルフェニルエーテルと
アルキルベンゼンスルホン酸カルシウムとの等重量混合物 5部
以上を均一に混合粉砕して水和剤とする。
モモアカアブラムシ(Myzus persicae)に対する防除価試験
直径8cm、高さ8cmのプラスチックポットにハクサイを植えてモモアカアブラムシを繁殖させ、それぞれのポットの寄生虫数を調査した。本発明の一般式(1)で表されるベンゾオキサゾール化合物又はその塩類を水に分散させて500ppmの薬液に希釈し、該薬液をポット植えハクサイの茎葉に散布して風乾後、ポットを温室に保管し、薬剤散布後6日目にそれぞれのハクサイに寄生しているモモアカアブラムシの寄生虫数を調査し、下記の式より防除価を算出し、下記判定基準に従って判定した。
T :処理区の散布後寄生虫数
Ca:無処理区の散布前寄生虫数
C:無処理区の散布後寄生虫数
A・・・防除価100%
B・・・防除価99%~90%
C・・・防除価89%~80%
D・・・防除価79%~50%
本発明の一般式(1)で表されるベンゾオキサゾール化合物又はその塩類を水に分散させて500ppmの薬液に希釈し、該薬液にイネ実生(品種:日本晴)を30秒間浸漬し、風乾した後にガラス試験管に入れ、ヒメトビウンカ3令を各10頭ずつ接種した後に綿栓をし、接種8日後に生死虫数を調査し、補正死虫率を下記の式より算出し、下記の判定基準に従って死虫率判定を行った。
A・・・補正死虫率100%
B・・・補正死虫率99%~90%
C・・・補正死虫率89%~80%
D・・・補正死虫率79%~50%
ハクサイ実生にコナガの成虫を放飼して産卵させ、放飼2日後に産下卵の付いたハクサイ実生を本発明の一般式(1)で表されるベンゾオキサゾール化合物を有効成分とする薬剤を水で500ppmに希釈した薬液に約30秒間浸漬し、風乾後に25℃の恒温室に静置した。薬液浸漬6日後に孵化虫数を調査し、下記の式により死虫率を算出し、試験例2の判定基準に従って判定を行った。1区10頭3連制。
Claims (6)
- R1が、ハロ(C1-C3)アルコキシ基である請求項1に記載のベンゾオキサゾール化合物又はその塩類。
- R1が、ハロ(C1-C3)アルキルスルフィニル基である請求項1に記載のベンゾオキサゾール化合物又はその塩類。
- 請求項1~3の何れか一項に記載のベンゾオキサゾール化合物又はその塩類を有効成分として含有することを特徴とする農園芸用殺虫剤。
- 請求項1~3の何れか一項に記載のベンゾオキサゾール化合物又はその塩類の有効量で植物又は土壌を処理することを特徴とする請求項4に記載の農園芸用殺虫剤の使用方法。
- 請求項1~3の何れか一項に記載のベンゾオキサゾール化合物又はその塩類を有効成分として含有することを特徴とする動物用外部寄生虫防除剤。
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RU2018133694A RU2709615C1 (ru) | 2016-02-26 | 2017-02-24 | Соединение бензоксазола или его соль, сельскохозяйственный и садовый инсектицид, содержащий соединение, и способ применения инсектицида |
US16/077,978 US10575525B2 (en) | 2016-02-26 | 2017-02-24 | Benzoxazole compound or salt thereof, agricultural and horticultural insecticide comprising the compound, and method for using the insecticide |
CONC2018/0009134A CO2018009134A2 (es) | 2016-02-26 | 2017-02-24 | Compuesto de benzoxazol o su sal, insecticida agrícola y hortícola que comprende el compuesto y método para usar el insecticida |
BR112018014512-2A BR112018014512B1 (pt) | 2016-02-26 | 2017-02-24 | Composto de benzoxazol, método para usá-lo, composição inseticida agrícola e hortícola e para controle de ectoparasitas |
AU2017221988A AU2017221988B2 (en) | 2016-02-26 | 2017-02-24 | Benzoxazole compound or salt thereof, agricultural and horticultural insecticide comprising the compound, and method for using the insecticide |
CN201780006638.8A CN108699050B (zh) | 2016-02-26 | 2017-02-24 | 苯并噁唑化合物或其盐类及含有该化合物的农业园艺用杀虫剂及其使用方法 |
JP2018501804A JP6581284B2 (ja) | 2016-02-26 | 2017-02-24 | ベンゾオキサゾール化合物又はその塩類及び該化合物を含有する農園芸用殺虫剤並びにその使用方法 |
CA3013564A CA3013564C (en) | 2016-02-26 | 2017-02-24 | Benzoxazole compound or salt thereof, agricultural and horticultural insecticide comprising the compound, and method for using the insecticide |
MX2018010188A MX2018010188A (es) | 2016-02-26 | 2017-02-24 | Compuesto de benzoxazol o su sal, insecticida agricola y horticola que comprende el compuesto y metodo para usar el insecticida. |
KR1020187020373A KR102066901B1 (ko) | 2016-02-26 | 2017-02-24 | 벤즈옥사졸 화합물 또는 그의 염류 및 상기 화합물을 함유하는 농원예용 살충제 및 그 사용 방법 |
EP17756660.1A EP3421466B1 (en) | 2016-02-26 | 2017-02-24 | Benzoxazole compound or salt thereof, agricultural/horticultural insecticide containing said compound, and method for using same |
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KR (1) | KR102066901B1 (ja) |
CN (1) | CN108699050B (ja) |
AU (1) | AU2017221988B2 (ja) |
BR (1) | BR112018014512B1 (ja) |
CA (1) | CA3013564C (ja) |
CL (1) | CL2018002440A1 (ja) |
CO (1) | CO2018009134A2 (ja) |
MX (1) | MX2018010188A (ja) |
RU (1) | RU2709615C1 (ja) |
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WO2024085225A1 (ja) * | 2022-10-20 | 2024-04-25 | 住友化学株式会社 | 2-(5-シクロプロピル-3-(エチルスルホニル)ピリジン-2-イル)-5-((トリフルオロメチル)スルフィニル)ベンゾ[d]オキサゾールの結晶 |
WO2024085224A1 (ja) * | 2022-10-20 | 2024-04-25 | 住友化学株式会社 | 2-(5-シクロプロピル-3-(エチルスルホニル)ピリジン-2-イル)-5-((トリフルオロメチル)スルホニル)ベンゾ[d]オキサゾールの結晶 |
JP7489564B1 (ja) | 2022-10-20 | 2024-05-23 | 住友化学株式会社 | 2-(5-シクロプロピル-3-(エチルスルホニル)ピリジン-2-イル)-5-((トリフルオロメチル)スルフィニル)ベンゾ[d]オキサゾールの結晶 |
JP7489565B1 (ja) | 2022-10-20 | 2024-05-23 | 住友化学株式会社 | 2-(5-シクロプロピル-3-(エチルスルホニル)ピリジン-2-イル)-5-((トリフルオロメチル)スルホニル)ベンゾ[d]オキサゾールの結晶 |
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CA3013564A1 (en) | 2017-08-31 |
AU2017221988B2 (en) | 2019-02-14 |
BR112018014512A2 (ja) | 2018-12-11 |
RU2709615C1 (ru) | 2019-12-19 |
KR102066901B1 (ko) | 2020-01-16 |
EP3421466A1 (en) | 2019-01-02 |
CN108699050A (zh) | 2018-10-23 |
CO2018009134A2 (es) | 2018-09-20 |
AU2017221988A1 (en) | 2018-08-30 |
MX2018010188A (es) | 2019-01-14 |
US20190045786A1 (en) | 2019-02-14 |
EP3421466A4 (en) | 2019-07-24 |
JP6581284B2 (ja) | 2019-09-25 |
KR20180095024A (ko) | 2018-08-24 |
US10575525B2 (en) | 2020-03-03 |
CA3013564C (en) | 2020-08-25 |
CN108699050B (zh) | 2021-06-11 |
BR112018014512B1 (pt) | 2022-06-14 |
CL2018002440A1 (es) | 2018-12-21 |
EP3421466B1 (en) | 2021-10-27 |
JPWO2017146226A1 (ja) | 2018-12-13 |
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