WO2010071219A1 - 16-ケトアスペルギルイミド類およびそれを有効成分として含有する有害生物防除剤 - Google Patents
16-ケトアスペルギルイミド類およびそれを有効成分として含有する有害生物防除剤 Download PDFInfo
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- WO2010071219A1 WO2010071219A1 PCT/JP2009/071257 JP2009071257W WO2010071219A1 WO 2010071219 A1 WO2010071219 A1 WO 2010071219A1 JP 2009071257 W JP2009071257 W JP 2009071257W WO 2010071219 A1 WO2010071219 A1 WO 2010071219A1
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- 0 CCC(*)(C(C*)(C*(*1C(C)(*2)C=C)C2=O)C(*(C2)C3)*2(C)*1=O)[C@]3(C1)*C*(C)(*)C1(**=C)IC Chemical compound CCC(*)(C(C*)(C*(*1C(C)(*2)C=C)C2=O)C(*(C2)C3)*2(C)*1=O)[C@]3(C1)*C*(C)(*)C1(**=C)IC 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
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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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/14—Ectoparasiticides, e.g. scabicides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/22—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains four or more hetero rings
Definitions
- the present invention relates to 16-ketoaspergylimides having excellent insecticidal activity and ectoparasite control compositions containing them as active ingredients.
- 16-keto aspergillimide is a compound having the following structure, reported as a metabolite produced by filamentous fungi of the genus Aspergillus, and is a mammalian gastrointestinal parasitic nematode It is known as an anthelmintic active substance against the third instar larva of Haemonchus contortus (The Journal of Antibiotics, 1997, 50 (10), 840-846 (Non-patent Document 1)). However, there is no report on the activity of this substance against ectoparasites.
- Patent Document 1 reports that asperparaline, an analog of 16-ketoaspergylimide, has a paralytic activity against silkworms or an insecticidal activity against white spiders, leafhoppers, and cockroaches (Non-patent Documents 2 and 3, Patent Document 1). However, there is no report on the activity of this substance against ectoparasites. Moreover, there was no report about the new compound obtained by the chemical conversion based on this structure mother nucleus, and it was interested in the novel derivative and its pest control effect.
- paraherquamides having a structure similar to that of 16-ketoaspergylimide and asperparaline A show control effects on mammalian endoparasites, but are not known to be effective against ectoparasites. (Journal of veterinary pharmacology and therapeutics, 2002, 25 (4), 241-250 (Non-patent Document 4)).
- Non-patent Document 5 a novel ectoparasite control agent having high safety for mammals is desired.
- the present inventors now have an excellent ectoparasite control effect and a high effect by using one or more of compounds represented by the following formula (I) or formula (III) or salts thereof as active ingredients. It has been found that it has safety, in particular, has an ectoparasite-controlling effect on thermostatic animals.
- the present inventors as an active ingredient, by using one or more of the compounds represented by the following formula (I) or salts thereof, an excellent pest control effect, osmotic transfer insecticidal effect And a high level of safety, particularly a pest control effect on thermostatic animals.
- the present invention is based on such knowledge.
- an object of the present invention is to provide a composition for controlling ectoparasites, a compound having a pest control effect or a salt thereof that can be used safely.
- R 1 is Hydrogen atom, Hydroxyl group, An optionally substituted C 1-10 alkyloxy group (preferably a methoxy group), An optionally substituted C 7-15 aralkyloxy group (preferably a benzyloxy group), An optionally substituted C 1-10 (preferably C 1-6 , more preferably C 1-4 ) alkylcarbonyloxy group (more preferably an acetyloxy group), or an optionally substituted C 7- 15 represents an aralkylcarbonyloxy group, R 2 represents a hydrogen atom, or R 1 and R 2 together represent an oxo group, R 3 is Hydrogen atom, Hydroxyl group, Represents an optionally substituted C 1-5 alkyl group, or an optionally substituted C 7-15 aralkyl group, R 4 represents a hydrogen atom, Or R 1 and R 3 are bonded to each other to represent a double bond, and when R 2
- the method comprises applying an effective amount of one or more compounds represented by the above formula (I) or formula (III) or a salt thereof to an animal.
- Methods for controlling ectoparasites are provided.
- a pest control composition comprising one or more compounds represented by the above formula (I) or a salt thereof as an active ingredient.
- an agricultural and horticultural pest composition comprising, as an active ingredient, one or more of the compounds represented by the above formula (I) or a salt thereof.
- the effective amount of the composition is selected from the following: water surface, soil, nutrient solution in hydroponics, solid medium in hydroponics, plant seeds, roots, tubers, bulbs, and rhizomes.
- a method for controlling agricultural and horticultural pests comprising applying to a subject selected from the group consisting of:
- a method for controlling agricultural and horticultural pests which comprises applying an effective amount of the composition to a plant.
- the carbon number of the alkylcarbonyloxy group and the aralkylcarbonyloxy group is represented by the carbon number of the alkyl group and aralkyl group part excluding the carbonyloxy structure.
- Me means a methyl group.
- the alkyl part of the alkyl group and the substituent containing the alkyl group part preferably has 1 to 6 carbon atoms (C 1-6 ).
- Aralkyl group represents an arylalkyl group.
- the aryl group means a 6 to 14 membered (monocyclic to tricyclic) aromatic ring not containing a hetero atom such as a phenyl group, a naphthyl group, a biphenylyl group, and a phenanthryl group.
- a 6-14 membered aryl group has 6-14 carbon atoms in its ring system.
- examples of preferable substituents for each group described as “optionally substituted” include halogen and a C 1-4 alkyl group which may be substituted with halogen (provided that A C 1-4 alkyloxy group, a nitro group, and a cyano group, which may be substituted with a halogen, except for the case where the group may be an alkyl group.
- the salts of 16-ketoaspergylimide and related compounds represented by the above formulas (I) and (III) are A pharmaceutically acceptable acid addition salt, for example, hydrochloride, nitrate, sulfate, phosphate or acetate.
- R 5 is Hydrogen atom, Hydroxyl group, An optionally substituted C 1-10 alkyloxy group (preferably a methoxy group), An optionally substituted C 7-15 aralkyloxy group (preferably a benzyloxy group), An optionally substituted C 1-10 (preferably C 1-6 , more preferably C 1-4 ) alkylcarbonyloxy group (more preferably an acetyloxy group), or an optionally substituted C 7- 15 represents an aralkylcarbonyloxy group)
- R 5 is Hydrogen atom, Hydroxyl group, An optionally substituted C 1-10 alkyloxy group (preferably a methoxy group), An optionally substituted C 7-15 aralkyloxy group (preferably a benzyloxy group), An optionally substituted C 1-10 (preferably C 1-6 , more preferably C 1-4 ) alkylcarbonyloxy group (more preferably an acetyloxy group), or an optionally substituted C 7- 15 represents an aralkylcarbony
- R 1 , R 2 , R 3 , and R 4 represent a hydrogen atom
- R 1 represents a hydroxyl group
- R 2 , R 3 , and R 4 represent a hydrogen atom
- R 1 and R 2 together represent an oxo group
- R 3 represents a hydroxyl group
- R 4 represents a hydrogen atom
- R 1 and R 2 together represent an oxo group
- R 3 represents a benzyl group
- R 4 represents a hydrogen atom
- R 1 represents a methoxy group
- R 2 , R 3 , and R 4 represent a hydrogen atom
- R 1 represents a benzyloxy group
- R 2 , R 3 , and R 4 represent a hydrogen atom
- R 1 represents a methylcarbonyloxy group
- R 2 , R 3 , and R 4 represent a hydrogen atom
- R 1 and R 3 combine with each other to represent a double bond
- R 2 represents a hydrogen atom
- R 1 and R 3 combine
- Compound A (16-ketoaspergylimide) is a culture of 16-ketoaspergylimide-producing bacteria according to the method described in, for example, The Journal of Antibiotics, 1997, 50 (10), 840-846 (Non-patent Document 1). Can get more. Furthermore, for example, the derivatives shown in Table 1 can be produced using Compound A as a starting material.
- Compound B (asperparaline A) can be obtained from a culture of asperparaline A-producing bacteria, for example, according to the method described in JP-A-10-245383 (Patent Document 1).
- Compound 1 can be obtained by subjecting 16-ketoaspergylimide to a reduction reaction.
- the reagent used in this reduction reaction is a hydride reducing agent such as sodium borohydride (NaBH 4 ), lithium borohydride, tetrabutylammonium borohydride, preferably sodium borohydride, preferably 16-ketoaspergylimide. It is recommended to use 1 to 5 equivalents.
- the reaction solvent may be an alcoholic solvent such as methanol or ethanol. However, if it is not soluble in an alcoholic solvent such as this reaction substrate, it may be dissolved in tetrahydrofuran (THF) or the like to form a 1: 1 mixed solution.
- the reaction temperature proceeds in the range of -10 ° C to 50 ° C, and the reaction time is 1 minute to 3 hours.
- Compound 3 in which the elimination reaction has progressed can be obtained via Compound 2 in which the hydroxyl group of Compound 1 is modified with an appropriate substituent.
- the hydroxyl group in this reaction is suitably modified with a substituent having appropriate stability and leaving ability, and preferably an acyl group such as acetyl.
- the reagent used in this acylation reaction may be an acyl halide such as acetyl chloride, or an acid anhydride such as acetic anhydride, and is preferably used in an amount of 1 to 10 equivalents.
- the base used in this reaction may be an organic base such as collidine, lutidine, diethylamine, triethylamine, isopropylamine, in addition to pyridine.
- reaction is promoted by adding a catalytic amount of 4-dimethylaminopyridine (4-DMAP).
- the reaction solvent may be an aprotic solvent such as methylene chloride or chloroform used in ordinary acylation reactions.
- the reaction temperature proceeds in a good yield in the range of 0 ° C. to 60 ° C., and the reaction time is 1 hour to 24 hours.
- the subsequent elimination reaction proceeds in silica gel in the purification.
- compound 5 can be obtained by using trifluoromethanesulfonic anhydride as an activator for the hydroxyl group of compound 1.
- the tolylfluoromethanesulfonic anhydride used in this reaction is preferably used in an amount of 1 to 5 equivalents relative to Compound 1.
- organic bases such as collidine, lutidine, diethylamine, triethylamine and isopropylamine may be used in addition to pyridine.
- the reaction solvent may be an aprotic solvent such as methylene chloride or chloroform.
- the reaction temperature proceeds in a good yield in the range of -10 ° C to 50 ° C, and the reaction time is 1 minute to 12 hours.
- Compound 4 can be obtained by subjecting compound 3 to catalytic reduction in the presence of a palladium catalyst, in a hydrogen atmosphere, under pressure or at normal pressure.
- the catalyst in this reaction may be supported palladium, and it is preferable to use 1 to 100 mol% of palladium carbon (Pd-C) containing 1 to 100% in a hydrogen atmosphere or by bubbling in a solvent.
- the reaction solvent may be an alcohol solvent such as methanol or ethanol, the reaction temperature proceeds in a yield range of 10 ° C. to 60 ° C., and the reaction time is 1 hour to 2 days.
- Compound 6 can be obtained by subjecting Compound 3 to an epoxidation reaction with an oxidizing reagent.
- the oxidizing agent used in this reaction may be a peroxide such as hydrogen peroxide or peracetic acid in addition to metachloroperbenzoic acid (m-CPBA).
- reaction may be accelerated
- a reaction solvent in addition to methylene chloride and chloroform, alcohol solvents such as methanol may be used, and water may be added.
- the reaction temperature proceeds in the range of -10 ° C to 60 ° C, and the reaction time is 1 hour to 2 days.
- compound 7 can also be obtained by reacting compound 3 with potassium permanganate in the presence of metaperiodic acid.
- the metaperiodic acid and potassium permanganate used in this reaction may be 1 to 20 equivalents relative to compound 3.
- acetone may be t-butanol or the like, and the same amount of water may be added.
- the reaction proceeds in the range of ⁇ 10 ° C. to 60 ° C., and the reaction time is 1 hour to 3 days.
- Some of the new basic skeletons or 16-ketoaspergylimides that can be produced as described above can be modified by the method described below.
- the hydroxyl group of Compound 1 can be modified with a substituent such as alkylation or acylation, and 16-ketoaspergylimide can introduce an alkyl group at the ⁇ -position of its succinimide carbonyl group. (Compounds 2, 8, 9, 10).
- Alkylation may be performed by reacting with an alkyl halide or aralkyl halide having a desired alkyl group in the presence of a base.
- a reagent used in this alkylation reaction for example, 1 to 10 equivalents of alkyl halide or aralkyl halide such as methyl iodide and benzyl bromide may be used.
- metal alkoxide bases such as sodium methoxide and sodium ethoxide may be used in addition to sodium hydride and lithium hydride.
- the reaction solvent may be an aprotic polar solvent such as tetrahydrofuran and dimethylformamide (DMF) in addition to methylene chloride and chloroform.
- DMF dimethylformamide
- an acyl halide having a desired alkyl group may be reacted in the presence of a base.
- the reagent used in the acylation reaction may be, for example, an alkyl carbonyl halide such as acetyl chloride or benzoyl chloride or an aralkyl carbonyl halide, or an acid anhydride such as acetic anhydride, and 1 to 10 equivalents are preferably used.
- the base used in this reaction may be an organic base such as collidine, lutidine, diethylamine, triethylamine, isopropylamine, in addition to pyridine.
- the reaction may be promoted by adding a catalytic amount of 4-DMAP.
- the reaction solvent may be an aprotic solvent such as methylene chloride and chloroform used in ordinary acylation reactions in addition to pyridine which also serves as a base.
- the reaction temperature proceeds in the range of 10 ° C to 80 ° C, and the reaction time is 1 hour to 2 days.
- composition for controlling ectoparasites comprises, as an active ingredient, one or more compounds represented by the above formula (I) or formula (III) or salts thereof. Is.
- the composition for controlling ectoparasites according to the present invention has an excellent ectoparasite control effect and high safety, in particular, an ectoparasite control effect on a thermostat animal.
- the composition for controlling ectoparasites according to the present invention comprises, as an active ingredient, one or more compounds represented by the above formula (III) or salts thereof. .
- insects for example, cat fleas, human fleas, etc.
- lice For example, human lice, white lice, etc.
- mites for example, mites, staghorn mites, mites, mites, sword mites, spider mites, birds, mites, mites, etc.
- moths flies (eg, fly flies), mosquitoes (E.g., Aedes albopictus, Culex mosquito, etc.), blackfishes, nutkas, and the like, more preferably fleas and mites.
- Preferred examples of other ectoparasite control agents that can be mixed with the ectoparasite control composition according to the present invention include pyrethroid compounds, neonicotinoid compounds, avermectin compounds, macrolide compounds, and phenylpyrazole compounds.
- Phenylpyrrole compounds Phenylpyrrole compounds, organophosphate compounds, carbamate compounds, nereistoxin derivatives, organochlorine compounds, benzoylurea compounds, juvenile hormone-like compounds, molting hormone-like compounds, spinosyn-based compounds, cyclodepsipeptide compounds , Neuronal sodium channel blockers, insecticidal macrocyclic lactones, ⁇ -aminobutyric acid (GABA) antagonists, ryanodine receptor-acting compounds, and the like.
- GABA ⁇ -aminobutyric acid
- More preferred specific examples include ivermectin, ceramectin ( selamectin), Moxidectin, doramectin, eprinomectin, milbemycin oxime, maduramycin, imidacloprid, dinotefuran, nitenpyram (nitenpyrid), acetampyrid, acetampyram ), Thiamethoxam, clothianidin, sulfoxaflor, fipronil, ethiprole, pyriprole, allethrin, d ⁇ dT-allethrin ), Dl ⁇ d-T80 allethrin, pyrethrin (pyrethrins), permethrin, phenothrin, flumethrin, cyfluthrin, d ⁇ d-T80 plastic Retrin (d ⁇ d-T80 prarethrin), phthalthrin, transfluthrine, resmeth
- Further preferred examples include ivermectin, imidacloprid, nitenpyram, acetamiprid, acetamiprid, thiamethoxam, clothianidin, dinotefuran, and sulfoxaflor. It is done.
- composition for controlling ectoparasites includes liquids, sprays, foam preparations, tablets, granules, fine granules, powders, capsules, tablets, chewables, injections, suppositories, creams, shampoos. It is provided in various dosage forms acceptable as an ectoparasite control agent such as an agent, a rinse agent, a resin agent, a smoke agent, and a poison bait. Among these, a liquid agent is particularly preferable.
- Examples of the carrier that can be used for preparing the composition for controlling ectoparasites according to the present invention include a liquid carrier, a solid carrier, a gaseous carrier, a surfactant, a dispersant, and other formulation adjuvants.
- liquid carrier examples include alcohols (methanol, ethanol, isopropanol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzyl).
- alcohols methanol, ethanol, isopropanol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, etc.
- ketones acetone, methyl ethyl ketone, etc.
- aromatic hydrocarbons benzyl
- Alcohol Alcohol, benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (paraffin, n-hexane, cyclohexane, kerosene, kerosene, etc.), ethers (diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diisopropyl ether, Diethyl ether, dioxane, tetrahydrofuran, etc.), esters (propylene carbonate, ethyl acetate, butyl acetate, benzyl benzoate, Isopropyl styrene, fatty acid esters of propylene glycol, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), amides (dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.),
- solid carriers examples include clays (carion clay, diatomaceous earth, bentonite, acidic clay), synthetic hydrous silicon oxide, talc, ceramic, and other inorganic minerals (selinite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica). Etc.) and other synthetic polymers such as starch, lactose, vinyl chloride polymers and polyurethane.
- the liquid preparation can further contain formulation emulsifiers such as ordinary emulsifiers, dispersants, spreading agents, wetting agents, suspending agents, preservatives, propellants, etc.
- a forming agent can also be blended.
- surfactants for emulsification, dispersion, spreading, etc. include soaps, polyoxyalkylene alkyl (aryl) ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, higher alcohols, alkylaryls A sulfonate or the like is used.
- the dispersant include casein, gelatin, polysaccharides, lignin derivatives, saccharides, and synthetic water-soluble polymers.
- Examples of spreading / wetting agents include glycerin and polyethylene glycol.
- Examples of the suspending agent include casein, gelatin, hydroxypropyl cellulose, gum arabic and the like.
- Examples of the stabilizing agent include phenolic antioxidants (BHT, BHA, etc.) and amine antioxidants (diphenylamine, etc.). ), Organic sulfur-based antioxidants and the like.
- Examples of the preservative include methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, and butyl paraoxybenzoate.
- the above carriers, surfactants, dispersants, and adjuvants may be used alone or in combination as necessary. Furthermore, you may contain a fragrance
- the content of the active ingredient in the composition for controlling ectoparasites of the present invention is usually 1 to 75% by weight as a liquid.
- Examples of the carrier used for preparing the cream include non-volatile hydrocarbons (such as liquid paraffin), lanolin-added oils and fats, higher fatty acids, fatty acid esters, animal and vegetable oils, silicone oils, and water. , Emulsifiers, moisturizers, antioxidants, fragrances, borax, and ultraviolet absorbers may be used alone or in combination as required.
- Examples of the emulsifier include fatty acid sorbitan, polyoxyethylene alkyl ether, and fatty acid polyoxyethylene.
- the content of the active ingredient in the composition for controlling ectoparasites of the present invention is usually 0.5 to 70% by weight for creams.
- Capsules, pills, or tablets are appropriately divided into active ingredients in the composition of the present invention, mixed with a diluent or a carrier such as starch, lactose, talc, and the like, and further disintegrating agents such as magnesium stearate and It can be used by adding a binder and / or tableting as necessary.
- a diluent or a carrier such as starch, lactose, talc, and the like
- further disintegrating agents such as magnesium stearate and It can be used by adding a binder and / or tableting as necessary.
- Carriers for preparing injections must be prepared as sterile solutions, which contain other substances, for example enough salt or glucose to make the solution isotonic with blood. May be.
- Usable carriers include glycerides, benzyl benzoate, isopropyl myristate, and esters such as fatty acid derivatives of propylene glycol, and organic solvents such as N-methylpyrrolidone and glycerol formal.
- the content of the active ingredient in the composition for controlling ectoparasites of the present invention is suitably 0.01 to 10% by weight for injections.
- Examples of the carrier for preparing the resin agent include vinyl chloride polymers and polyurethane. If necessary, plasticizers such as phthalates, adipic esters, and stearic acid can be added to these substrates.
- the active ingredient is kneaded in the base material and then molded by injection molding, extrusion molding, press molding or the like. Furthermore, it can be made into an animal ear tag and an animal insect repellent collar through processes such as proper molding and cutting.
- Carriers for poisonous baits include food and attractants (flours such as wheat flour and corn flour, starches such as corn starch and potato starch, sugars such as granulated sugar, maltose and honey, foods such as glycerin, onion flavor and milk flavor) Examples include animal powders such as flavors, rice bran powder, fish meal, various pheromones, etc.
- the content of active ingredients in the composition for controlling ectoparasites of the present invention is usually 0.0001-90% by weight for poison baits. is there.
- composition for controlling ectoparasites according to the present invention is expected to be administered orally or by injection into the body of an applied animal, administered to all or part of the body surface of the applied animal, and invasion, parasitism, and migration of ectoparasites. It is possible to control ectoparasites by covering the place to be treated and applying it to a breeding house.
- composition for controlling ectoparasites according to the present invention may be used as it is, but depending on the case, it can be diluted with water, a liquid carrier, a commercially available shampoo, rinse, bait, a breeding house underlay or the like. *
- the compound represented by the above formula (I) or formula (III) or a salt thereof may be used as one or more ectoparasite control agents.
- an external parasite comprising applying an effective amount of one or more of the compounds represented by the above formula (I) or formula (III) or a salt thereof to an animal.
- Insect control methods are provided.
- the animal to which the composition for controlling ectoparasites according to the present invention is not particularly limited, but is preferably a thermostatic animal, more preferably a pig, horse, cow, sheep, goat, rabbit, chicken, duck, turkey, Examples include mice, rats, guinea pigs, monkeys, dogs, cats, and small birds.
- composition for controlling pests comprises, as an active ingredient, one or more of the compounds represented by the above formula (I) or salts thereof.
- the composition for controlling pests according to the present invention has an excellent pest control effect, an osmotic transfer insecticidal effect, and high safety, in particular, a pest control effect on a thermostat animal.
- insect species in which the pest control composition comprising one or more compounds represented by the above formula (I) or a salt thereof according to the present invention as an active ingredient exhibits a controlling effect is not particularly limited. Although there are no agricultural and horticultural pests, there are lepidopterous pests (for example, Spodoptera spp.
- Hemiptera pests eg, peach aphid, cotton aphid, Aphisfabae, corn aphid, pea aphid, potato aphid, bean aphid, tulip genus
- Aphids Ma crosiphum avenae, Methopolophium dirhodum, wheat beetle aphids, barley aphids, radish aphids, falcon aphids, snowy aphids, Rosy apple aphid, apple aphids, aphids such as Adelida, Aphid, ephiidae
- Leafhoppers such as leafhoppers, leafhoppers, leafhoppers, leafhoppers, leafhoppers such as white planthoppers, white stink bugs, white stink bugs, stink bugs, red leaf whitefly, whitefly whitefly
- Scale insects such as scale insects and citrus scale insects (Diaspididae, Margarodidae, Ortheziidae, Ac1erdiae, Dacty1opiidae, Kerridae, Pseudococcidae, Cocc idae, Eriococcidae, Asterolecaniidae, Beesonidae, Lecanodiaspididae, Cerococcidae) Potato beetles, rice beetles, beetles, beetles, etc.), mites (for example, urticae, kanzawa spider mites, citrus mites), hymenopterous insects (for example, wasps), straight insects (for example, grasshoppers), diptera (For example, house flies and leafhoppers), thrips pests (for example, southern thrips, citrus thrips, etc.), plant parasitic nematodes (for example, root-knot nemato
- Insects tapeworms, nematodes, protozoa, sporeworms, and the like, more preferably, Hemiptera pests, Thripidae pests, Diptera pests, Coleoptera pests, animal parasitic fleas, Examples include mites, more preferably hemiptera pests, and particularly preferably fleas and mites.
- pest control agents that can be mixed with the compound represented by the formula (I) or their salts according to the present invention include insecticides, fungicides, acaricides, herbicides, plant growth regulators, Examples of such drugs include those described in the Pesticide Manual (The Pesticide Manual, 14th edition published by The British Crop Protection Council) and Shibuya Index (SHIBUYA INDEX 13th edition, 2008, issued by SHIBUYA INDEX RESEARCH GROUP). .
- Other pest control agents that can be mixed with the compounds of the present invention include preferably insecticides and / or fungicides, more preferably insecticides, and may further include mixing fungicides with the insecticides.
- Preferred examples of the other pest control agent that can be mixed with the compound represented by the formula (I) or a salt thereof according to the present invention include an organophosphate ester compound, a carbamate compound, and a nereistoxin derivative.
- GABA ⁇ -aminobutyric acid
- More preferred specific examples include acephate, dichlorvos, EPN, fenitrothion. (Fenitrothion), fenamifos, prothiofos, Lofenofos, pyraclofos, chlorpyrifos-methyl, chlorfenvinphos, demeton, ethion, malathion, coumaphos, isoxathion , Fenthion, diazinon, thiodicarb, aldicarb, oxamyl, propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb , Pirimicarb, carbofuran, carbosulfan, furathiocarb, hyquincarb, alanycarb, metomyl, benfuracarb, cartap, thiocyclam thiocy clam), bensultap, dicofol, tetradifon, a
- Het 1 represents a 3-pyridyl group
- R 9 represents a hydroxyl group
- R 10 and R 11 represent a cyclopropylcarbonyloxy group
- R 12 represents a hydrogen atom or a hydroxyl group
- the compound of the said formula (VII) is mentioned.
- strobilurin compounds such as (orysastrobin), picoxystrobin, floxastrobin, ananilinopyrimidine compounds such as mepanipyrim, pyrimethanil, cyprodinil, triadimefon ), Bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole, tebuconazole tebuconazole), hexaconazo Azole compounds such as hexaconazole, prochloraz, simeconazole, quinoxaline compounds such as quinomethionate, maneb, zineb, mancozeb, polycarbamate
- Sulfenic acid-based compounds such as dichlofluanid, copper-based compounds such as cupric hydroxide, oxine-copper, isoxazole-based compounds such as hydroxyisoxazole, fosetyl aluminum (fosetyl-aluminium), organophosphorus compounds such as tolclofos-methyl, N-halogenothioalkyl compounds such as captan, captafol and folpet, procymidone , Iprodione, dicarboximide compounds such as vinchlozolin, thifluzamide, acid amide compounds such as furametpyr, benzanilide compounds such as flutolanil, mepronil, phen Morphs such as fenpropimorph and dimethomorph Folin compounds, organotin compounds such as triphenyltin hydroxide, phenthin acetate, cyanopyrrole compounds such as fludioxonil, fenpiclonil,
- More preferred examples of other fungicides that can be mixed with the compound represented by formula (I) or a salt thereof according to the present invention include orysastrobin, thifluzamide, furametpyr, furthatpyr, fthalide, Probenazole, acibenzolar-S-methyl, thiadinyl, isothianyl, carpropamid, diclocymet, fenoxanil, tricyclazole, quilrolone (pyroxylone) Tebufloquine, ferimzonezone), and more preferred examples include probenazole.
- a pest control composition comprising one or more compounds according to the present invention or salts thereof as an active ingredient.
- the pest control composition according to the present invention is for agricultural and horticultural pests.
- Preferred examples of other pesticides that can be mixed with at least one of 16-ketoaspergylimide, its enantiomers, mixtures thereof, or acid addition salts thereof include, for example, organophosphate compounds, carbamate compounds , Nereistoxin derivatives, organochlorine compounds, pyrethroid compounds, benzoyl urea compounds, juvenile hormone-like compounds, molting hormone-like compounds, neonicotinoid compounds, neuronal sodium channel blockers, insecticidal macrocyclic lactones, ⁇ -aminobutyric acid (GABA) antagonists, ryanodine receptor agonist compounds, insecticidal ureas, BT agents, entomopathogenic virus agents, polyether antibiotics, thiamine antagonists, sulfa drugs and folic acid antagonist combinations, etc.
- organophosphate compounds carbamate compounds
- Nereistoxin derivatives organochlorine compounds
- pyrethroid compounds benzoyl urea compounds
- More preferred specific examples include AS Acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenofos, pyraclofos, chlorpyrifos-methyl, haloxon, haloxon Coumaphos, malathion, dimpylate, naled, tetradifon, diazinon, mesomy1, thiodicarb, aldicarb, oxamyl, Propoxur, carbaryl, fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran, benfuracarb, cartap, thiosi Thiocyclam, dicofol, tetradifon, permethrin, tefluthrin, cypermethrin, deltamethrin, cyhalothrin, fenvalerate, fulvalinate fluvalinate
- a pest control composition further comprising a suitable agricultural and veterinary acceptable carrier.
- the forms are emulsion, liquid, suspension, wettable powder, granular wettable powder, flowable powder, powder, DL powder, granule, fine granule F, tablet, oil, aerosol, smoke, microcapsule It is provided to be formulated into any dosage form such as an agent.
- These various dosage forms can be produced by the method described in, for example, “Agricultural Chemicals Formulation Guide” (edited by the Japanese Agricultural Chemical Society, Application Method Research Group, published by the Japan Plant Protection Association, 1997).
- carriers examples include solid carriers, liquid carriers, gaseous carriers, surfactants, dispersants, and other formulation adjuvants.
- solid carrier examples include talc, bennite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, calcium carbonate and the like.
- liquid carrier examples include alcohols such as methanol, n-hexanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aliphatic hydrocarbons such as n-hexane, kerosene and kerosene, toluene, xylene and methyl Aromatic hydrocarbons such as naphthalene, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, soybean Examples include oils, vegetable oils such as cotton seed drops, dimethyl sulfoxide, and water.
- alcohols such as methanol, n-hexanol and ethylene glycol
- ketones such as acetone, methyl ethyl ket
- gaseous carrier examples include LPG, air, nitrogen, carbon dioxide gas, dimethyl ether and the like.
- Surfactants and dispersants for emulsification, dispersion, spreading, etc. include, for example, alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyhydric alcohol esters, lignin A sulfonate or the like is used.
- an adjuvant for improving the properties of the preparation for example, carboxymethylcellulose, gum arabic, polyethylene glycol, calcium stearate and the like are used.
- the above carriers, surfactants, dispersants, and adjuvants may be used alone or in combination as necessary.
- the amount of the active ingredient in the composition of the present invention is such that the content of the active ingredient in these preparations is usually 1-75% by weight in the emulsion, usually 0.3-25% by weight in the powder, and usually 1-90 in the wettable powder.
- Appropriate weight is 0.5-10% by weight for granules.
- the preparation may be used as it is, but may be diluted in some cases and applied directly to the target pest or applied to plants, seeds, soil, etc. Can be applied.
- an effective amount of the pest control composition according to the present invention in particular, a pest control composition for agricultural and horticultural pests is applied to the water surface, soil, nutrient solution in hydroponic culture, hydroponic culture.
- a method for controlling pests on agriculture and horticulture comprising applying to a target selected from the group consisting of solid medium, plant seeds, roots, tubers, bulbs, and rhizomes.
- agricultural and horticultural horticulture comprising applying an effective amount of the pesticidal composition according to the present invention, particularly a pesticidal composition for agricultural and horticultural pests, to a plant.
- an effective amount of the pesticidal composition according to the present invention particularly a pesticidal composition for agricultural and horticultural pests.
- a pest control composition for agricultural and horticultural pests
- a spraying treatment preferably a soil treatment (mixing, irrigation, etc.)
- Surface treatment coating, powder coating, coating
- fumigation treatment may be mentioned.
- Synthesis Example 2 (Compound 2 (1: 4)) 15.0 mg of compound 1 obtained in Synthesis Example 1 was dissolved in 1.0 ml of methylene chloride, 33.0 ⁇ l of pyridine and 15.0 mg of 4-DMAP were added, 7.0 ⁇ l of acetyl chloride was added, and the mixture was stirred at room temperature for 1 hour. Furthermore, 7.0 ⁇ l of acetyl chloride was added and stirred overnight at room temperature. Aqueous ammonia chloride was added to the reaction solution, followed by extraction with chloroform. The organic layer was washed with aqueous sodium bicarbonate and brine and then dried over anhydrous sodium sulfate.
- Synthesis Example 3 (Compound 3) 20 mg of the compound 1 obtained in Synthesis Example 1 was dissolved in 1 ml of methylene chloride, 44 ⁇ l of pyridine and 20 mg of 4-DMAP were added, 14 ⁇ l of acetyl chloride was added, and the mixture was stirred at room temperature for 1 hour. Furthermore, 14 ⁇ l of acetyl chloride was added and stirred overnight at room temperature. Aqueous ammonia chloride was added to the reaction solution, followed by extraction with chloroform. The organic layer was washed with aqueous sodium hydrogen carbonate and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure.
- Synthesis Example 4 (Compound 4) Compound 3 (13.0 mg) obtained in Synthesis Example 3 was dissolved in ethanol (1.0 ml) and 10% Pd-C (5.0 mg) was added. A balloon filled with hydrogen gas was attached and the mixture was stirred overnight at room temperature. The reaction solution was filtered to remove 10% Pd-C. The obtained reaction solution was distilled off under reduced pressure to obtain 13.0 mg (100%) of Compound 4.
- Synthesis Example 5 (Compound 5) 10 mg of the compound 1 obtained in Synthesis Example 1 was dissolved in 500 ⁇ l of methylene chloride, and 10 mg of 4-DMAP was added. After stirring at 0 ° C. for 10 minutes, 5.5 ⁇ l of trifluoromethanesulfonic anhydride was added and stirred at room temperature for 1 hour. Further, 5.5 ⁇ l of trifluoromethanesulfonic anhydride was added and stirred overnight at room temperature. Aqueous ammonia chloride was added to the reaction solution, followed by extraction with chloroform. The organic layer was washed with aqueous sodium hydrogen carbonate and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure.
- Synthesis Example 6 (Compound 6) After dissolving 9.0 mg of compound 3 obtained in Synthesis Example 3 in 1.0 ml of methylene chloride, 8.7 mg of m-CPBA was added and stirred at 60 ° C. overnight. A 10% hypo aqueous solution was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was washed with aqueous sodium bicarbonate and brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain Compound 6 9.0 mg (96%).
- Synthesis Example 7 (Compound 7) Dissolve Compound 3 9.0 mg obtained in Synthesis Example 3 in acetone 1.0 ml and water 0.5 ml and add metaperiodic acid 22.0 mg, then add 0.02 mol aqueous solution of potassium permanganate 0.5 ml dropwise at room temperature overnight. Stir. A 10% hypo aqueous solution was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was washed with aqueous sodium bicarbonate and brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3.5 mg (36%) of Compound 7.
- Synthesis Example 8 (Compound 8 (1: 1)) 8.0 mg of the compound 1 obtained in Synthesis Example 1 was dissolved in 500 ⁇ l of THF, 2.5 mg of sodium hydride was added, 6.5 ⁇ l of methyl iodide was added, and the mixture was stirred at room temperature for 1 hour. Aqueous ammonia chloride was added to the reaction solution, followed by extraction with chloroform. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 8.0 mg (94%) of Compound 8 (isomer ratio 1: 1).
- Formulation Examples 1 to 8 represent formulation examples for controlling agricultural and horticultural pests
- Formulation Example 9 represents a formulation example for controlling ectoparasites.
- Formulation Example 1 [Granule] Compound 8 5% by weight Bentonite 40% by weight Talc 10% by weight 43% by weight of clay 2% by weight calcium lignin sulfonate The above components were pulverized and mixed uniformly, kneaded well with water, and granulated and dried to obtain granules.
- Formulation Example 2 [wettable powder] Compound 8 30% by weight 50% by weight of clay 2% white carbon Diatomaceous earth 13% by weight Calcium lignin sulfonate 4% by weight Sodium lauryl sulfate 1% by weight The above ingredients were mixed uniformly and pulverized to obtain a wettable powder.
- Formulation Example 3 [Granule wettable powder] Compound 8 30% by weight 60% clay Dextrin 5% by weight Alkyl maleic acid copolymer 4% by weight Sodium lauryl sulfate 1% by weight The above ingredients were uniformly pulverized and mixed, mixed well with water, then granulated and dried to obtain a granulated wettable powder
- Formulation Example 4 Compound 8 25% by weight POE polystyryl phenyl ether sulfate 5% by weight Propylene glycol 6% by weight Bentonite 1% by weight Xanthan gum 1% aqueous solution 3% by weight PRONAL EX-300 (Toho Chemical Industry Co., Ltd.) 0.05% by weight ADDAC 827 (Kay Kasei Co., Ltd.) 0.02% by weight 100% by weight of water The whole amount except for the 1% aqueous solution of xanthan gum and an appropriate amount of water from the above blend was premixed and then pulverized with a wet pulverizer. Thereafter, 1% aqueous solution of xanthan gum and the remaining water were added to obtain a flowable agent at 100% by weight.
- Formulation Example 6 [powder] Compound 8 2% by weight 60% clay Talc 37% by weight Calcium stearate 1% by weight The said component was mixed uniformly and the powder agent was obtained.
- Formulation Example 7 [DL powder] Compound 8 2% by weight DL clay 94.5% by weight 2% white carbon Calcium stearate 1% by weight Light liquid paraffin 0.5% by weight The said component was mixed uniformly and the powder agent was obtained.
- Formulation Example 8 [Fine Granule F] Compound 8 2% by weight Carrier 94% by weight 2% white carbon Hyzol SAS-296 2% by weight The said component was mixed uniformly and the powder agent was obtained.
- Test example 2 (cat flea control test) 200 ⁇ L of a 6.3 ppm acetone solution of Compound A was dropped onto a 4.0 cm diameter filter paper, and acetone was air-dried at room temperature.
- the filter paper treated with the chemical was fitted into the lid (diameter 3.7 cm) of a 200 mL vial without any gap.
- About 25 adult cat fleas 1 to 3 days after emergence were released in a 200 mL vial and sealed with a vial lid fitted with a filter paper treated with a drug.
- the vial was inverted and allowed to stand so that the cat fleas contacted the filter paper. Life and death were observed 3 days after release, and the death rate was calculated according to the following formula.
- the test was conducted by a triple system.
- Mortality rate (%) ⁇ Number of dead insects / (Number of living insects tens of dead insects) ⁇ x 100 The results are shown in Table 4.
- the compounds A and B are more effective than the insecticidal activity of the compound B against agricultural pests and sanitary pests described in JP-A-10-245383 (Patent Document 1), for example. Effects on ectoparasites were observed at low concentrations.
- Test Example 3 Single oral acute toxicity test on rats
- Compound A was prepared as a suspension with a concentration of 100 mg / mL using 0.5% methylcellulose.
- the drug solution was forcibly orally administered to rats (Jcl: Wistar, female, 8 weeks old) using a sonde and a disposable syringe.
- the dose of administration was 2000 mg / kg. Life and death were observed up to 6 hours after administration and from 1 to 15 days after administration.
- the results were as shown in Table 5 below.
- the LD 50 value of Compound A for rats is 2000 mg / kg or more, indicating that Compound A has low toxicity to rats.
- Test example 4 (cotton aphid control test) A leaf disc having a diameter of 2.0 cm was cut out from a pot-grown cucumber and sprayed with 200 ppm of a chemical solution prepared to be 50% acetone water (added with 0.05% Tween 20). After air drying, the first instar larvae were released. Thereafter, this was left in a constant temperature room at 25 ° C. (16 hours light period 18 hours dark period). The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
- Mortality rate (%) ⁇ Number of dead insects / (Number of living insects tens of dead insects) ⁇ x 100 Compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 showed insecticidal activity with a mortality rate of 80% or more against cotton aphids.
- Test Example 6 (Prunus carp control test) A hydroponic wheat seedling was treated with 200 ⁇ L of a chemical solution prepared to 100 ppm with 10% acetone water. After the drug was absorbed from the root for 3 days, 10 second-instar larvae were released. Thereafter, it was left in a constant temperature room at 25 ° C. (16 hours light period 18 hours dark period). The insects were observed for life and death 3 days after the release, and the death rate was calculated according to the following formula. The test was conducted by a two-run system.
- Mortality rate (%) ⁇ Number of dead insects / (Number of living insects tens of dead insects) ⁇ x 100 Compounds 1, 2, 3, 4, 6, 7, 8, and 9 showed an insecticidal activity with a mortality rate of 100% against the brown planthopper.
- Test Example 7 Spot mite control test on mouse surface
- the back body hair of a mouse ICR, male, 5 weeks old
- a 15 mL polystyrene conical tube cut to a height of about 1.5 cm was bonded thereto using an instantaneous adhesive.
- 10 or more larva mites were released in the tube and capped. Three days after the release, the dead and dead ticks were observed, and the death rate was calculated according to the following formula.
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Abstract
Description
本発明は、優れた殺虫活性を有した16-ケトアスペルギルイミド類およびのそれらを有効成分として含有する外部寄生虫防除用組成物に関するものである。
16-ケトアスペルギルイミド(16-keto aspergillimide)は、下記構造を有する化合物であり、アスペルギルス(Aspergillus)属の糸状菌が生産する代謝産物として報告され、哺乳類の消化管寄生線虫であるHaemonchus contortusの3令幼虫に対する駆虫活性物質として知られている(The Journal of Antibiotics、1997、50(10)、840-846(非特許文献1))。しかしながら、この物質の外部寄生虫に対する活性については、何ら報告されていない。
R1は、
水素原子、
水酸基、
置換されていてもよいC1-10アルキルオキシ基(好ましくは、メトキシ基)、
置換されていてもよいC7-15アラルキルオキシ基(好ましくは、ベンジルオキシ基)、
置換されていてもよいC1-10(好ましくはC1-6、より好ましくはC1-4)アルキルカルボニルオキシ基(さらに好ましくは、アセチルオキシ基)、または
置換されていてもよいC7-15アラルキルカルボニルオキシ基を表し、
R2は、水素原子を表すか、または
R1と、R2とは一緒になってオキソ基を表し、
R3は、
水素原子、
水酸基、
置換されていてもよいC1-5アルキル基、または
置換されていてもよいC7-15アラルキル基を表し、
R4は、水素原子を表し、
またはR1と、R3とは互いに結合して二重結合を表し、かつR2が水素原子を表す場合、R4は下記式(II)を表し、
ただし、
R1が、水酸基、
置換されていてもよいC1-10アルキルオキシ基、
置換されていてもよいC7-15アラルキルオキシ基、
置換されていてもよいC1-10アルキルカルボニルオキシ基、または
置換されていてもよいC7-15アラルキルカルボニルオキシ基を表す場合、
R2、R3、およびR4は共に水素原子を表し、または
R1と、R2とが一緒になってオキソ基を表す場合、R3は、水酸基、置換されていてもよいC1-5アルキル基、または置換されていてもよいC7-15アラルキル基(好ましくは、ベンジル基)を表す)
で表される化合物または
下記式(III):
で表される化合物もしくはそれら塩の一種またはそれ以上を含んでなる外部寄生虫防除用組成物が提供される。
本明細書において、アルキルカルボニルオキシ基、アラルキルカルボニルオキシ基の炭素数は、カルボニルオキシ構造を除いたアルキル基、アラルキル基部分の炭素数で表す。Meはメチル基を意味する。
上記式(I)および式(III)で表される16-ケトアスペルギルイミドおよびその類縁化合物の塩とは、農畜薬上許容可能な酸付加塩であり、例えば、塩酸塩、硝酸塩、硫酸塩、リン酸塩または酢酸塩などが挙げられる。
R5は、
水素原子、
水酸基、
置換されていてもよいC1-10アルキルオキシ基(好ましくは、メトキシ基)、
置換されていてもよいC7-15アラルキルオキシ基(好ましくは、ベンジルオキシ基)、
置換されていてもよいC1-10(好ましくはC1-6、より好ましくはC1-4)アルキルカルボニルオキシ基(さらに好ましくは、アセチルオキシ基)、または
置換されていてもよいC7-15アラルキルカルボニルオキシ基を表す)
で表される化合物が挙げられる。
置換されていてもよいC7-15アラルキル基(好ましくは、ベンジル基)を表す)
で表される化合物が挙げられる。
で表される化合物が挙げられる。
R1、R2、R3、およびR4が共に水素原子を表すか、
R1が水酸基、R2、R3、およびR4が水素原子を表すか、
R1と、R2とが一緒になってオキソ基、R3が水酸基、R4が水素原子を表すか、
R1と、R2とが一緒になってオキソ基、R3がベンジル基、R4が水素原子を表すか、
R1がメトキシ基、R2、R3、およびR4が水素原子を表すか、
R1がベンジルオキシ基、R2、R3、およびR4が水素原子を表すか、
R1がメチルカルボニルオキシ基、R2、R3、およびR4が水素原子を表すか、または
R1およびR3が互いに結合して二重結合を表し、R2が水素原子を表し、R4が上記式(IV)で表される基を表される化合物が挙げられる。
本発明による外部寄生虫防除用組成物は、有効成分として、上記式(I)または式(III)で表される化合物もしくはそれら塩を一種またはそれ以上を含んでなるものである。本発明による外部寄生虫防除用組成物は、優れた外部寄生虫防除効果および高い安全性、特には恒温動物に対する外部寄生虫防除効果を有するものである。
本発明による有害生物防除用組成物は、有効成分として、上記式(I)で表される化合物またはそれらの塩の一種またはそれ以上を含んでなるものである。本発明による有害生物防除用組成物は、優れた有害生物防除効果、浸透移行性殺虫効果、および高い安全性、特には恒温動物に対する有害生物防除効果を有するものである。
において表される化合物が挙げられる。
合成例1(化合物1)
1H NMR(CDCl3) 0.93 (3H, s), 0.95 (3H, s), 1.45 (3H, d, J = 6.5 Hz), 1.45 (1H, m), 1.53 (1H, d, J = 6.5 Hz), 2.04-2.16 (2H, m), 2.20-2.32 (2H, m), 2.43 (1H, dd,J= 7.5, 16.0 Hz), 2.66 (1H, d, J = 15.0 Hz), 2.76(1H, d, J = 16.5 Hz), 2.80 (3H,s), 2.87 (3H, s), 2.93 (1H, br t, J = 9.5 Hz), 3.26(1H, d, J = 12.5 Hz), 3.30(1H, d, J = 12.0 Hz), 3.90 (1H, br s), 5.00 (1H, br s).;
MS (FAB) m/z 376 (M+H)+
1H NMR(CDCl3) 0.88, 0.92, 0.99 & 1.00 (6H, each s), 1.50 (3H, d, J = 6.4 Hz), 1.58 (1H, d, J = 15.1Hz), 1.70 & 1.82 (1H, each d, J = 15.8Hz), 2.10 (3H, s), 2.05-2.60 (4H, m), 2.62-3.00 (6H, m), 6.02 & 6.10 (1H, each br d, J = 6.1 Hz).;
MS (FAB) m/z 418 (M+H)+
1H NMR (CDCl3) 0.82 (3H, s), 1.01 (3H, s), 1.49(1H, m) 1.51 (3H, d, J = 7.0 Hz), 1.85 (1H, d, J = 15.5 Hz), 2.08-2.18 (1H, m), 2.25-2.35 (1H, m), 2.38(1H, dd,J = 11.5, 16.0 Hz), 2.47 (1H, d, J = 15.5 Hz), 2.50 (1H, dd, J = 8.0 Hz, 16.0 Hz), 2.95 (3H, s), 2.98 (3H, s), 3.08 (1H, br t, J = 10.0 Hz), 3.33-3.47 (1H, m), 5.23 (1H, d, J = 4.8 Hz), 6.42 (1H, d, J = 4.8 Hz).;
MS (FAB) m/z 358(M+H)+
1H NMR(CDCl3) 0.90 (3H, s), 1.00 (3H, s), 1.46(1H, dd, J = 10.2, 13.0 Hz)1.49(3H, d, J = 6.8 Hz), 1.55 (1H, d, J = 15.0 Hz), 1.86 (1H, t, J = 8.3 Hz), 1.90 (1H, t, J = 8.3 Hz), 2.10 (1H, dd, J = 10.7, 12.7 Hz), 2.30 (1H, m), 2.35(1H, dd,J = 10.7, 16.1 Hz), 2.48 (1H, dd, J = 7.8 Hz, 16.1 Hz), 2.73 (1H, d, J = 15.1 Hz), 2.85 (3H, s), 2.93 (3H, s), 3.17-3.32 (2H, m), 3.32 (1H, d, J = 12.0 Hz), 3.36 (1H, d, J = 12.0 Hz).; MS (FAB) m/z 360(M+H)+
1H NMR(CDCl3) 0.84 (3H, s), 0.97 (3H, s), 1.05 (3H, s), 1.09 (3H, s), 1.51 (3H,d, J = 7.0 Hz), 1.55 (3H, d, J = 7.0 Hz), 1.80 (1H, dd, J = 9.0, 13.5 Hz), 1.87(1H, d, J = 15.5 Hz), 2.13 (1H, dd, J = 10.6, 12.9 Hz), 2.16 (1H, dd, J = 10.6,12.9 Hz), 2.25-2.43 (4H, m), 2.47-2.55 (3H, m), 2.65 (3H, s), 2.79 (1H, br t, J= 10.0 Hz), 2.88 (1H, dd, J = 5.5, 13.5 Hz), 2.95 (1H, d, J = 15.5 Hz), 3.00 (3H, s), 3.01 (3H, s), 3.27 (3H, s), 3.29 (1H, br t, J = 10.0 Hz), 3.35 (1H, s), 3.48 (1H, dd, J = 12.0, 18.0 Hz), 3.90 (1H, dd, J = 6.0, 9.0 Hz).;
MS (FAB) m/z 715(M+H)+
1H NMR(CDCl3) 0.86 (3H, s), 1.02 (3H, s), 1.48 and 1.51 (3H, each s), 2.92 (3H,s), 2.97 (3H, s), 5.03 and 5.07 (1H, each m).;
MS (FAB) m/z 374 (M+H)+
1H NMR(CDCl3) 0.99 (3H, s), 1.12 (3H, s), 1.55 (3H, d, J = 6.5 Hz), 2.15-2.25 (2H, m), 2.26-2.80 (4H, m), 2.90 (3H, s) , 3.02 (3H, s), 3.11 (1H, m), 3.44(1H, br s), 4.42(1H, br s).; MS (FAB) m/z 390 (M+H)+
1H NMR(CDCl3) 0.85, 0.92, 0.95 & 0.98 (6H, each s), 1.42-1.55 (4H, m), 1.63-1.70(1H, m), 1.78(0.5H, dd, J = 1.4, 13.9 Hz), 1.95(0.5H, dd, J = 6.1, 14.4 Hz), 2.07-2.17(1H, m), 2.22-2.53(4H, m), 2.68 & 2.77 (1H, each d, J = 15.0 Hz), 2.83-2.95 (6.5H, m), 3.20 (0.5H, br t, J = 10.5 Hz), 3.35 & 3.39 (3H, each s), 4.54(0.5H, br d, J = 5.4 Hz), 4.63(0.5H, dd, J = 1.7, 6.0 Hz).; MS (FAB) m/z 390 (M+H)+
1H NMR (CDCl3) 0.86 (3H, s), 0.91 (3H, s), 1.46 (3H, dd, J = 10.2 Hz, 12.2 Hz), 1.50 (1H, d, J = 6.4 Hz), 1.68 (1H, d, J = 16.1 Hz), 1.82 (1H, dd, J = 1.5, 14.2Hz), 2.12 (1H, dd, J = 9.3, 11.7 Hz), 2.22-2.32 (2H, m), 2.36 (1H, dd, J = 12.2Hz, 15.6 Hz), 2.48 (1H, dd, J = 7.8 Hz, 15.6 Hz), 2.73 (1H, d, J = 15.6 Hz), 2.83 (3H, s) , 2.89 (3H, s), 3.20 (1H, br t, J = 10.5 Hz), 4.59(1H, dd, J = 12.0,17.1 Hz), 4.82(1H, dd, J = 1.7, 5.6 Hz), 7.26-7.28(5H, m).; MS (FAB) m/z 466(M+H)+
1H NMR (CDCl3) 0.78 (3H, s), 0.80 (3H, s), 1.41 (1H, dd, J = 12.5 Hz, 15.5 Hz),1.50 (3H, d, J = 7.0 Hz), 2.02 (1H, d, J = 15.5 Hz), 2.09 (1H, dd, J = 10.6, 12.9Hz), 2.20-2.27 (1H, m), 2.35 (1H, dd, J = 11.8 Hz, 16.5 Hz), 2.47 (1H, dd, J = 7.9, 16.5 Hz), 2.52 (1H, d, J = 15.5 Hz), 2.83(1H, dd, J = 8.6, 14.5 Hz), 2.88-2.96 (2H, m), 2.97 (3H, s), 2.99 (3H, s), 3.13-3.17 (1H, m), 3.20-3.24 (2H, m),7.19-7.35 (5H, m).;
MS (FAB) m/z 464(M+H)+
製剤例1~8は農園芸用害虫防除用製剤例を表し、製剤例9は外部寄生虫防除用製剤例を表す。
化合物8 5重量%
ベントナイト 40重量%
タルク 10重量%
クレー 43重量%
リグニンスルホン酸カルシウム 2重量%
上記成分を均一に粉砕混合し、水を加えてよく練合した後、造粒乾燥して粒剤を得た。
化合物8 30重量%
クレー 50重量%
ホワイトカーボン 2重量%
ケイソウ土 13重量%
リグニンスルホン酸カルシウム 4重量%
ラウリル硫酸ナトリウム 1重量%
上記成分を均一に混合し、粉砕して水和剤を得た。
化合物8 30重量%
クレー 60重量%
デキストリン 5重量%
アルキルマレイン酸共重合物 4重量%
ラウリル硫酸ナトリウム 1重量%
上記成分を均一に粉砕混合し、水を加えてよく練合した後、造粒乾燥して顆粒水和剤を得た
化合物8 25重量%
POEポリスチリルフェニルエーテル硫酸塩 5重量%
プロピレングリコール 6重量%
ベントナイト 1重量%
キサンタンガム1%水溶液 3重量%
PRONAL EX-300(東邦化学工業株式会社) 0.05重量%
ADDAC 827(ケイ・アイ化成株式会社) 0.02重量%
水 加えて100重量%
上記配合からキサンタンガム1%水溶液と適当量の水を除いた全量を予備混合した後、湿式粉砕機にて粉砕した。その後、キサンタンガム1%水溶液と残りの水を加え100重量%としてフロアブル剤を得た。
化合物8 15重量%
N,N-ジメチルホルムアミド 20重量%
ソルベッソ150(エクソンモービル有限会社) 55重量%
ポリオキシエチレンアルキルアリールエーテル 10重量%
上記成分を均一に混合、溶解して乳剤を得た。
化合物8 2重量%
クレー 60重量%
タルク 37重量%
ステアリン酸カルシウム 1重量%
上記成分を均一に混合して粉剤を得た。
化合物8 2重量%
DLクレー 94.5重量%
ホワイトカーボン 2重量%
ステアリン酸カルシウム 1重量%
軽質流動パラフィン 0.5重量%
上記成分を均一に混合して粉剤を得た。
化合物8 2重量%
キャリヤー 94重量%
ホワイトカーボン 2重量%
ハイゾールSAS-296 2重量%
上記成分を均一に混合して粉剤を得た。
化合物A 20重量%
ジエチレングリコールモノエチルエーテル 66.7重量%
エタノール 13.3重量%
上記成分を均一に混合して液化滴剤を得た。
化合物1~9の200ppm、化合物AおよびBの20ppmのアセトン溶液30μLを、4mL容ガラスバイアルに入れた。これをシェーカーに載せて、バイアル内壁に化合物のドライフィルムを形成させた。24時間以上、バイアルを乾燥させた後、これにフタトゲチマダニ幼ダニ10頭を放飼して、蓋をした。バイアルは、25℃、湿度85%、全暗条件の恒温室に静置した。放飼1日後に生死を観察し、次式に従って死虫率を算出した。
試験は、2連制により行った。
死虫率(%)={死亡虫数 /(生存虫数十死亡虫数)}×100
結果は表3の通りであった。
化合物Aの6.3ppmのアセトン溶液200μLを、直径4.0cm濾紙に滴下、室温にてアセトンを風乾した。薬剤処理した濾紙を200mL容バイアルの蓋(直径3.7cm)に隙間なく嵌め込んだ。200mL容バイアルに羽化1から3日後のネコノミ成虫を約25匹放飼し、薬剤処理をした濾紙を嵌め込んだバイアル蓋にて封をした。バイアルは、ネコノミが濾紙に接触するように倒立させ、静置した。放飼3日後に生死を観察し、次式に従って死虫率を算出した。試験は、3連制により行った。
死虫率(%)={死亡虫数 /(生存虫数十死亡虫数)}×100
結果は表4の通りであった。
化合物Aを、0.5%メチルセルロースを用いて100mg/mLの濃度に懸濁調製した。薬液をゾンデおよびディスポーザブルシリンジを用いて、ラット(Jcl:Wistar、雌、8週齢)に強制経口投与した。投与薬量は2000mg/kgとした。投与6時間までを経時的に、投与1から15日後まで生死を観察した。結果は下記表5の通りであった。
ポット栽培のキュウリから直径2.0cmのリーフディスクを切り抜き、これに50%アセトン水(0.05%Tween20加用)となるように調製した200ppmの薬液を散布した。風乾後、これに1令幼虫を放飼した。その後、これを25℃の恒温室(16時間明期一8時間暗期)に放置した。放飼3日後に虫の生死を観察し、次式に従って死虫率を算出した。試験は、2連制により行った。
死虫率(%)={死亡虫数 /(生存虫数十死亡虫数)}×100
化合物1、2、3、4、5、6、7、8、9、10は、ワタアブラムシに対して、死虫率80%以上の殺虫活性を示した。
ポット栽培のインゲンから直径2.8cmのリーフディスクを切り抜き、これに50%アセトン水(0.05%Tween20加用)となるように調製した100ppmの薬液を散布した。風乾後、これに1令幼虫を放飼した。その後、これを25℃の恒温室(16時間明期一8時間暗期)に放置した。放飼6日後に虫の生死を観察し、次式に従って死虫率を算出した。試験は、2連制により行った。
死虫率(%)={死亡虫数 /(生存虫数十死亡虫数)}×100
化合物8は、ミカンキイロアザミウマに対して、死虫率80%以上の殺虫活性を示した。
水耕栽培のコムギ苗根部に、10%アセトン水にて100ppmに調製した薬液200μLを処理した。3日間根部より薬剤を吸収させた後、これにヒメトビウンカ2令幼虫を10頭放飼した。その後、25℃の恒温室(16時間明期一8時間暗期)に放置した。放飼3日後に虫の生死を観察し、次式に従って死虫率を算出した。試験は、2連制により行った。
死虫率(%)={死亡虫数 /(生存虫数十死亡虫数)}×100
化合物1、2、3、4、6、7、8、9は、ヒメトビウンカに対して、死虫率100%の殺虫活性を示した。
マウス(ICR、雄、5週令)の背面体毛を直径約2cm刈り、そこに高さ約1.5cmに切取った15mLポリスチレンコニカルチューブを瞬間接着剤を用いて接着した。溶剤(ジエチレングリコールモノエチルエーテル:エタノール=75:15)を用いて調整した薬液20μLを接着したチューブ内のマウス体表に滴下した。十分に乾燥させた後、フタトゲチマダニ幼ダニ 10頭以上をチューブ内に放飼して蓋をした。放飼3日後にフタトゲチマダニの生死を観察し、次式に従って死虫率を算出した。試験は6連制により行った。
死虫率(%)={死亡虫数 /(生存虫数十死亡虫数)}×100
結果は表6の通りであった。
Claims (19)
- 有効成分として、下記式(I):
R1は、
水素原子、
水酸基、
置換されていてもよいC1-10アルキルオキシ基、
置換されていてもよいC7-15アラルキルオキシ基、
置換されていてもよいC1-10アルキルカルボニルオキシ基、または
置換されていてもよいC7-15アラルキルカルボニルオキシ基を表し、
R2は、水素原子を表すか、または
R1と、R2とは一緒になってオキソ基を表し、
R3は、
水素原子、
水酸基、
置換されていてもよいC1-5アルキル基、または
置換されていてもよいC7-15アラルキル基を表し、
R4は、水素原子を表し、
またはR1と、R3とは互いに結合して二重結合を表し、かつR2が水素原子を表す場合、R4は下記式(II)を表し、
ただし、
R1が、水酸基、
置換されていてもよいC1-10アルキルオキシ基、
置換されていてもよいC7-15アラルキルオキシ基、
置換されていてもよいC1-10アルキルカルボニルオキシ基、または
置換されていてもよいC7-15アラルキルカルボニルオキシ基を表す場合、
R2、R3、およびR4は共に水素原子を表し、または
R1と、R2とが一緒になってオキソ基を表す場合、R3は、水酸基、置換されていてもよいC1-5アルキル基、または置換されていてもよいC7-15アラルキル基を表す)
で表される化合物または
下記式(III):
で表される化合物もしくはそれら塩の一種またはそれ以上を含んでなる、外部寄生虫防除用組成物。 - 有効成分として、前記式(I)中、
R1、R2、R3、およびR4が共に水素原子を表すか、
R1が水酸基、R2、R3、およびR4が水素原子を表すか、
R1と、R2とが一緒になってオキソ基、R3が水酸基、R4が水素原子を表すか、
R1と、R2とが一緒になってオキソ基、R3がベンジル基、R4が水素原子を表すか、
R1がメトキシ基、R2、R3、およびR4が水素原子を表すか、
R1がベンジルオキシ基、R2、R3、およびR4が水素原子を表すか、
R1がメチルカルボニルオキシ基、R2、R3、およびR4が水素原子を表すか、または
R1およびR3が互いに結合して二重結合を表し、R2が水素原子、R4が前記式(II)で表される基を表す
化合物もしくはそれら塩の一種またはそれ以上を含んでなる、請求項1に記載の組成物。 - 有効成分として、前記式(III)で表される化合物またはそれらの塩の一種またはそれ以上を含んでなる、請求項1に記載の組成物。
- 請求項1において定義される式(I)もしくは式(III)で表される化合物またはそれらの塩の一種またはそれ以上の、外部寄生虫防除剤としての使用。
- 請求項1において定義される式(I)もしくは式(III)で表される化合物またはそれらの塩の一種またはそれ以上の有効量を、動物に適用することを含んでなる、外部寄生虫の防除方法。
- 請求項1において定義される式(I)で表される化合物またはそれらの塩。
- 請求項2において定義される式(IV)で表される化合物またはそれらの塩。
- 請求項3において定義される式(V)で表される化合物またはそれらの塩。
- 請求項4において定義される式(VI)で表される化合物またはそれらの塩。
- 請求項1において定義される式(I)中、
R1、R2、R3、およびR4が共に水素原子を表すか、
R1が水酸基、R2、R3、およびR4が水素原子を表すか、
R1と、R2とが一緒になってオキソ基、R3が水酸基、R4が水素原子を表すか、
R1と、R2とが一緒になってオキソ基、R3がベンジル基、R4が水素原子を表すか、
R1がメトキシ基、R2、R3、およびR4が水素原子を表すか、
R1がベンジルオキシ基、R2、R3、およびR4が水素原子を表すか、
R1がメチルカルボニルオキシ基、R2、R3、およびR4が水素原子を表すか、または
R1およびR3が互いに結合して二重結合を表し、R4が請求項1において定義される式(II)で表される基を表す
化合物またはそれらの塩である、請求項9に記載の化合物。 - 有効成分として、請求項9~13のいずれか一項に記載の化合物またはそれらの塩を一種またはそれ以上を含んでなる、有害生物防除用組成物。
- 農業園芸害虫用である、請求項14に記載の組成物。
- 有害生物防除剤としての、請求項9~13のいずれか一項に記載の化合物またはそれらの塩の一種またはそれ以上の使用。
- 農業園芸害虫防除剤としての、請求項9~13のいずれか一項に記載の化合物またはそれらの塩の一種またはそれ以上の使用。
- 請求項14または15に記載の組成物の有効量を、水面、土壌、養液栽培における養液、養液栽培における固形培地、植物の種子、根、塊茎、球根、および根茎からなる群から選択される対象に適用することを含んでなる、農園芸上の害虫の防除方法。
- 請求項14または15に記載の組成物の有効量を、植物に適用することを含んでなる、農園芸上の害虫の防除方法。
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BRPI0922930A BRPI0922930A8 (pt) | 2008-12-19 | 2009-12-21 | composição, uso de pelo menos um dos compostos, método para controlar ectoparasitas, composto, e, método para controlar pestes de inseto agrícolas e hortícolas |
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US10842154B2 (en) | 2013-05-17 | 2020-11-24 | Synexis Llc | Methods for the control of arthropods using near-ideal gas phase hydrogen peroxide |
WO2020241702A1 (ja) | 2019-05-27 | 2020-12-03 | Meiji Seikaファルマ株式会社 | 植物寄生性センチュウ防除剤及び植物寄生性センチュウの防除方法 |
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See also references of EP2377398A4 * |
TENNEN YUKI KAGOBUTSU TORONKAI KOEN YOSHISYU, vol. 39, 1997, pages 541 - 546 * |
TETRAHEDRON LETT., vol. 45, no. 23, 2004, pages 4489 - 4493, XP004508285 * |
TETRAHEDRON LETTERS, vol. 38, no. 32, 1997, pages 5655 - 5658 |
THE JOURNAL OF ANTIBIOTICS, vol. 50, no. 10, 1997, pages 840 - 846 |
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US11751569B2 (en) | 2013-05-17 | 2023-09-12 | Synexis Llc | Methods for the control of arthropods using near-ideal gas phase hydrogen peroxide |
WO2020241702A1 (ja) | 2019-05-27 | 2020-12-03 | Meiji Seikaファルマ株式会社 | 植物寄生性センチュウ防除剤及び植物寄生性センチュウの防除方法 |
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BRPI0922930A2 (ja) | 2018-06-05 |
US20110263608A1 (en) | 2011-10-27 |
JPWO2010071219A1 (ja) | 2012-05-31 |
KR20110132318A (ko) | 2011-12-07 |
EP2377398A4 (en) | 2012-06-06 |
BRPI0922930A8 (pt) | 2018-09-18 |
EP2377398A1 (en) | 2011-10-19 |
CN102325452A (zh) | 2012-01-18 |
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