WO2010069266A1 - 二醛构建的具有杀虫活性的含氮或氧杂环化合物及其制备方法 - Google Patents

二醛构建的具有杀虫活性的含氮或氧杂环化合物及其制备方法 Download PDF

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WO2010069266A1
WO2010069266A1 PCT/CN2009/075693 CN2009075693W WO2010069266A1 WO 2010069266 A1 WO2010069266 A1 WO 2010069266A1 CN 2009075693 W CN2009075693 W CN 2009075693W WO 2010069266 A1 WO2010069266 A1 WO 2010069266A1
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group
alkyl
compound
saturated
unsaturated
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PCT/CN2009/075693
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English (en)
French (fr)
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李忠
钱旭红
邵旭升
徐晓勇
陶黎明
宋恭华
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华东理工大学
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Priority to KR1020117016887A priority Critical patent/KR101392296B1/ko
Priority to EP09832948.5A priority patent/EP2377845B1/en
Priority to JP2011541073A priority patent/JP5771150B2/ja
Priority to US13/140,968 priority patent/US8563546B2/en
Priority to RU2011129408/04A priority patent/RU2495023C2/ru
Priority to BRPI0918359A priority patent/BRPI0918359B1/pt
Priority to AU2009328851A priority patent/AU2009328851C1/en
Publication of WO2010069266A1 publication Critical patent/WO2010069266A1/zh
Priority to IL213656A priority patent/IL213656A/en

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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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • 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
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/62—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms three- or four-membered rings or rings with more than six members
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C07D413/12—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 linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • 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
    • C07D471/12—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 system contains three hetero rings
    • C07D471/14—Ortho-condensed systems
    • 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
    • C07D491/12—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 three hetero rings
    • C07D491/18—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/18—Bridged systems

Definitions

  • Nitrogen-containing or oxygen-containing heterocyclic compound having insecticidal activity and preparation method thereof having insecticidal activity and preparation method thereof
  • the invention relates to a novel neonicotinoid insecticide, a preparation method and application thereof. Background technique
  • the neonicotinoid insecticide represented by imidacloprid has high insecticidal activity, wide insecticidal spectrum, low toxicity to mammals and aquatic animals, good systemic property, appropriate field stability and environmental friendliness. An important hot spot for the creation of new pesticides. Later, a series of nicotinic insecticides such as thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran have been developed (see European patents 247477, 296453, 685477, 235725, 235725, 315826, 192060, 244777, 0386565, 580553, and 1031566, Japanese Patent Nos. 62292965, 8259568, 8291171, and 7242633).
  • the present invention provides a new and more effective insecticide, solves the problem of resistance of neonicotinoid insecticides, expands the insecticidal spectrum, and solves the problems in the prior art.
  • Another object of the invention is to provide protection for growing and harvested crops from insect attack and infestation.
  • the invention provides a compound having the structure of formula (A;), (B), (C) or (D), or an optical isomer, cis-trans isomer or pesticide of said compound Learnably acceptable salt:
  • ⁇ is a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted or unsubstituted phenyl group, Wherein the substituent is one or more selected from the group consisting of halogen, 4-haloalkyl or 4-chloroalkoxy;
  • R 2 is H, CC 8 saturated or unsaturated alkyl, halogenated d 8 saturated or unsaturated alkyl,
  • R 3 and each independently H, d- 6 alkyl, allyl, benzyl, d- 4 alkoxy-C ⁇ alkyl,
  • X is a hetero atom such as N, O, S
  • R is a hetero atom
  • Y is nitro, cyano, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl.
  • it is selected from the group consisting of: pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, Oxazolyl or a halogenated product thereof.
  • a halogenated pyridyl group, a halogenated thiazolyl group, a halogenated pyrimidinyl group, a halogenated tetrahydrofuranyl group, or a halogenated oxazolyl group is preferred, and more preferably the halogenated product is a chlorinated product.
  • the halogenated product is a chlorinated product.
  • R 2 is H, d 4 saturated or unsaturated alkyl, halogenated CC 4 saturated or unsaturated alkyl, d-4 alkyl-carbonyl, substituted or unsubstituted benzyl Wherein the substituent is one or more selected from the group consisting of halogen, 4 haloalkyl or d-4 chloroalkoxy.
  • it is hydrogen or an alkyl group, preferably hydrogen or methyl.
  • R 3 is either hydrogen or ( ⁇ -6 alkyl, or R 3 and together constitute -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -.
  • R 3 is hydrogen or an alkyl group, preferably hydrogen, methyl or ethyl, or R 3 and together constitute -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -.
  • R 5 , R 6 , R 7 , and 11 a saturated or unsaturated d 2 hydrocarbon group, a halogen, a d 4 saturated or unsaturated alkoxy group, a halogenated ( ⁇ 2 saturated or Unsaturated alkoxy, d-4 alkyl-ester (RCOO-), d- 2 alkyl-sulfonyl ester or trifluoromethanesulfonyl ester.
  • R 5 , R 6 , R 7 , R 8 and R 9 are hydrogen, methyl, chloro, bromo, methoxy or ethoxy, preferably hydrogen, methyl, methoxy.
  • Y is a nitro group or a cyano group.
  • Y is preferably a nitro group.
  • the invention provides an agricultural composition comprising:
  • component (a) comprises from 0.01 to 99.9% by weight, preferably from 0.05 to 90% by weight, of the agricultural composition.
  • the agricultural composition is used to kill or prevent pests selected from the group consisting of Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Isoptera or Diptera.
  • the pest has a sucking or sucking mouthpart.
  • the pests are aphids, locusts, whiteflies, spider mites, hummers, cotton bollworms, green buds Insect, Plutella xylostella, Spodoptera litura, or armyworm.
  • the agricultural composition further comprises other active substances selected from the group consisting of: insecticides, baits, fungicides, acaricides, nematicides, fungicides or growth control Agent.
  • the invention relates to the use of the agricultural composition for killing or preventing agricultural pests, sanitary pests and pests that are harmful to animal health; or for killing or preventing agricultural pests, sanitary pests and endangering animal health Insecticide composition.
  • the invention provides a pesticidal and/or pest control method comprising applying the above agricultural composition to a plant body that is or may be subject to pests, soil surrounding it, or the environment.
  • the invention relates to the use of a compound of the above, an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, or a combination thereof, in the preparation of a pesticide composition.
  • the present invention provides a process for the preparation of the above compound, its optical isomer, cis-trans isomer or agrochemically acceptable salt, the method comprising the steps of:
  • the compound of formula (a) is reacted with a compound of formula (b;), (; c) or (; d) in the presence of a catalytic acid at 0-60 ° C to yield formula (A;) a compound of (B), (C) or (D), wherein R 2 is hydrogen,
  • R , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 and Y are as defined above, and n is 0 or 1.
  • the reaction temperature is 15-45 ° C, preferably 20-30 ° C.
  • the solvent used is selected from the group consisting of: acetonitrile or ethanol, preferably acetonitrile.
  • the catalytic amount of acid used is selected from the group consisting of: concentrated hydrochloric acid, concentrated sulfuric acid or benzoic acid, preferably concentrated hydrochloric acid.
  • the method comprises the steps of:
  • the compound of the formula (D) is obtained in acetonitrile in the presence of a catalytic amount of an acid at 10-50 ° C under the following reaction 2-24:
  • the inventors of the present invention have synthesized through a long-term and in-depth study based on the nitromethylene structure of the existing nitromethylene-based neonicotinoid insecticide by reacting a dialdehyde with a nitromethylene compound.
  • a novel neonicotinoid compound having a markedly enhanced insecticidal activity and an expanded insecticidal spectrum On this basis, the inventors have completed the present invention.
  • d- 6 alkyl refers to a straight or branched alkyl group having from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, A sec-butyl group, a tert-butyl group, or the like.
  • ( ⁇ _ 6 alkoxy) refers to straight or branched chain alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, Isobutoxy, sec-butoxy, tert-butoxy, or the like.
  • halogen means fluoro, chloro, bromo, or iodo.
  • halogenated refers to a group substituted with one or more of the above halogen atoms, which may be the same or different, such as a trifluoromethyl group, a pentafluoroethyl group, or the like.
  • five- or six-membered heterocyclic group refers to a five-membered or one containing a hetero atom selected from nitrogen, oxygen or sulfur.
  • a six-membered ring such as pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, or oxazolyl, and the like.
  • the compounds of the invention can be synthesized by the reaction steps described above. Those skilled in the art can synthesize the compound of formula 0) in the reaction step according to the prior art literature, for example, see WO 2006056108 A1, WO 2007101369 A1 and PCT/CN2008/071115.
  • the compound of formula (; A) can be prepared by the following reaction:
  • the compound of formula (B) can be prepared by the following reaction:
  • the compound of formula (C) can be prepared by the following reaction:
  • the reaction is 5-10 hours; the post-treatment removes the diamine under reduced pressure, dissolves with ethyl acetate, and spins the solvent to give the product: N* l *-(6-chloro-3 -methylpyridyl)-diamine;
  • the compound of formula (D) can be prepared by the following reaction:
  • active substance of the invention or “active compound of the invention” means a compound of the invention, an optical isomer, a cis-trans isomer or a pesticide-accepting salt thereof, which has a markedly enhanced insecticidal activity , as well as an expanded insecticidal spectrum.
  • a pesticidally acceptable salt means that the anion of the salt is known and acceptable in forming the pharmaceutically acceptable salt of the pesticide.
  • the salt is preferably water soluble.
  • Suitable acid addition salts formed from the compounds of formula (; A), (; B), (; C) and (D) include salts formed with inorganic acids, such as hydrochlorides, phosphates, sulfates, nitric acid Salt; and salts including organic acids, such as acetate, benzoate.
  • the active material of the present invention can be used for controlling and eliminating a wide range of agricultural and forestry plant pests, storing cereal pests, public health pests, and pests that are harmful to animal health.
  • insecticide is a general term for substances having the action of controlling all the pests mentioned above. Examples of pests include, but are not limited to, Coleoptera: Jade Sitophilus zeamais, Red Stork (7 / ⁇ // w castaneum), Horse Bell, Ladybug
  • Alternatus ⁇ (Echi oc emus squameus), R ⁇ ⁇ Basiprionota bisignata), Anoplophora chinensis, Apripona germari, Sco/yi s schevy ⁇ or fine-breasted gold needle Insects (4g otey fuscicollis); Lepidoptera insects: ⁇ Lymantria dispar), 3 ⁇ 4 ⁇ ⁇ Malacosoma neustria testacea), 3 ⁇ 4 (Diapha ia perspectalis), large bag moth (C7"w/ variegata), Astragalus lj moth ( Cw/i oc m " flauescens), horse
  • Hyalomma anatolicum (Haemaphysalis longicornis ), Hyalomma anatolicum, Coleoptera
  • the compound of the invention has special effects especially for sucking and sucking mouthparts pests, such as aphids, leafhoppers, planthoppers, thrips, whiteflies and the like.
  • Insecticide composition containing the active substance of the present invention is aphids, leafhoppers, planthoppers, thrips, whiteflies and the like.
  • the active substance of the present invention can be prepared into a pesticide composition in a conventional manner.
  • These active compounds can be formulated into conventional preparations such as solutions, emulsions, suspensions, powders, foams, pastes, granules; aerosols, natural and synthetic materials impregnated with active substances, Microcapsules in polymers, coatings for seeds, and preparations for use with combustion devices, such as smoking cartridges, smoked cans and smokers, as well as ULV cold mist and hot fog ( Warm mist) formulation.
  • compositions can be produced by known methods, for example, by mixing the active compound with an extender, which is a liquid or liquefied gas or solid diluent or carrier, and optionally a surfactant, an emulsifier and I or Dispersant and I or foam forming agent.
  • an extender which is a liquid or liquefied gas or solid diluent or carrier
  • a surfactant for example, an organic solvent can also be used as a helper.
  • an organic solvent can also be used as a helper.
  • a liquid solvent as a diluent or a carrier
  • aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or Dichloromethane
  • aliphatic hydrocarbons such as cyclohexane or paraffin, such as mineral oil fractions
  • alcohols such as ethanol or ethylene glycol and their ethers and lipids
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl Ketone or cyclohexanone
  • less common polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • the diluent or carrier for the liquefied gas refers to a liquid which will become a gas at normal temperature and normal pressure, such as an aerosol propellant such as a halogenated hydrocarbon and butane, propane, nitrogen and
  • Solid supports can be used as natural minerals on the ground, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates.
  • the solid carrier for the granules is a ground and graded natural stone, such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic coarse powder synthetic particles, and organic materials such as sawdust, coconut shell, Corn cobs and granules of tobacco stems.
  • Emulsified columns of nonionic and anionic agents can be used as emulsifiers and/or bubble formers.
  • polyoxyethylene-fatty acid esters polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and white Protein hydrolysate.
  • Dispersing agents include, for example, lignin sulfite waste liquid and methyl cellulose.
  • Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions such as gum arabic, polyvinyl alcohol and polyvinyl acetate may be used in the formulation.
  • Colorants such as inorganic dyes such as iron oxide, oxidized diamonds and Prussian blue; organic dyes such as organic dyes such as azo dyes or metal phthalocyanine dyes; and trace nutrients such as iron, lanthanum, boron, copper may be used. , cobalt, aluminum and zinc salts, etc.
  • the active compounds of the present invention may be present in a commercial preparation or in a dosage form prepared from these preparations in combination with other active compounds, including but not limited to: insecticides, baits, bactericides, Acaricides, killing lines, fungicides, growth control agents, etc.
  • Insecticides include, for example, phosphates, carbamates, pyrethroids, chlorinated hydrocarbons, benzoylureas, nematodes, and microbial-derived substances such as avermectin.
  • the active compounds of the present invention may also be formulated as a mixture with synergists in their commercial formulations for use in the dosage forms prepared from these formulations.
  • synergists are compounds which increase the action of the active compound. Since the active compound itself is active, it is not necessary to add a synergist.
  • formulations usually contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight, of the active compound of the invention, of the insecticidal composition.
  • concentration of the active compound in the dosage form prepared from the commercial preparation can be varied within a wide range.
  • concentration of the active compound in the dosage form used may range from 0.000000 l to 100% (g/v), preferably between 0.0001 and 1%.
  • N-(6-chloropyridine-3-methylene)-N-ethyl-1-thiomethyl-2-nitrovinylideneamine 5 g, 0.017 mol
  • a solution of methylamine 1.8 g, 0.017 mol of methylamine
  • absolute ethanol 30 mL
  • the solvent was evaporated under reduced pressure and concentrated to give a syrup.
  • Example 12 10-((6-chloropyridin-3-yl)methyl)-4-nitro-9-oxa-11,12-dihydroimidazo[2,3-abicyclo[3,3 , 1] Synthesis of indole-3-ene (Compound 77) 1.27 g (0.005 mol) of 2-chloro-5-(2-nitromethylene-imidazol-1-ylmethyl)-pyridine, 30 ml of anhydrous acetonitrile, 3 ml of 25% aqueous solution of glutaraldehyde, catalyzed The amount of HC1 was placed in a 50 ml round bottom flask. Stir at room temperature and TLC to follow the reaction. After the completion of the reaction, the solvent was removed, and
  • a 25% aqueous solution of glutaraldehyde and a catalytic amount of HC1 were placed in a 50 ml round bottom flask. Stir at room temperature and TLC is followed by reaction. After the completion of the reaction, the solvent was removed, and the residue was purified by column chromatography to yield pale yellow powdery product.
  • Aphids belong to the homopteran pests and have a sucker, which is a common crop pest. Taking soybean meal O ⁇ s craccivora) as the test object, it was tested by dipping and method.
  • the locust is a homopteran pest with a sputum sucker and is a common crop pest.
  • the brown planthopper (Nilaparvata / wgew was used as the test object and tested by spray method.
  • test compound was accurately prepared into acetone, 500, 250, 100, 50, 25, 12.5, 6.25, 3.13, 1.57, 0.79 ppm solution, and treated with acetone aqueous solution as a blank control. Repeat 3 cups per treatment (ie 3 times;). Spray 2 ml evenly with a small hand sprayer. 10 hours before the application, 10 rice hoppers were taken from each pot. A total of three batches of experiments were conducted. After 24 hours of treatment, the number of dead insects of the test insects was counted, and the mortality (%) was calculated (the formula is the same as above;). The results are shown in Table 1-4 below.
  • test compound is accurately formulated into acetone, 500, 250, 100, 50,
  • Example 15 Preparation of a Pesticide Composition Containing a Compound of the Invention
  • the following components were prepared in proportion: 25% of compound 1-73; 3% hydrate attapulgit; 10% calcium lignosulfonate; 0.5% sodium dihydrogen phosphate; 61.5% water.
  • the components are ground together in a ball mill until the solid particles fall below about 10 microns. This aqueous suspension can be used directly.

Description

二醛构建的具有杀虫活性的含氮或氧杂环化合物及其制备方法 技术领域
本发明涉及新型新烟碱类的杀虫剂、 及其制备方法和应用。 背景技术
以吡虫啉为代表的新烟碱类杀虫剂因杀虫活性高， 杀虫谱广，对哺乳动物和水 生动物毒性低，且有良好的系统物性及适当的田间稳定性和环境友好性， 成为新农 药创制的重要热点领域。 后来又相继开发出噻虫啉、 噻虫胺、 噻虫嗪、 啶虫脒、 烯 啶虫胺、 呋虫胺等一系列烟碱类杀虫剂 (参见欧洲专利 247477、 296453、 685477、 235725、 235725、 315826、 192060、 244777、 0386565、 580553和 1031566， 日本 专利 62292765、 8259568、 8291171和 7242633)。
但是由于吡虫啉过量频繁使用造成较为严重的抗性问题以及由于结构相似性 带来的新烟碱杀虫剂之间的交互抗性，在一定程度上限制了该类化合物的应用， 制 约了此类化合物发展， 同时新烟碱类杀虫剂主要对同翅目和鞘翅目害虫高效，其相 对较窄的杀虫谱也限制了虫害防治方面的用药选择性。
因此， 如何对具有高活性的硝基亚甲基化合物进行结构改造， 以产生新的、 更有效的杀虫剂， 解决新烟碱类杀虫剂的抗性问题， 扩大杀虫谱， 使其应用于杀虫 剂组合物就成为本领域迫切需要解决的技术问题。 发明内容
本发明提供了新的、更有效的杀虫剂， 解决了新烟碱类杀虫剂的抗性问题， 扩大 了杀虫谱， 解决了现有技术中存在的问题。
本发明目的在于， 提供一类高效防治害虫的化合物及其制备方法。
本发明的另一个目的是为生长中的和收获的作物不受昆虫攻击和侵扰而提供 保护。
一方面， 本发明提供了一种具有式 (A；)、 (B), (C)或 (D)所示结构的化合物、 或者 所述化合物的光学异构体、 顺反异构体或农药学上可接受的盐：
Figure imgf000004_0001
式中：
！^为含氮、 氧和 /或硫的五元或六元杂环基， ¾代的含氮、 氧和 /或硫的五元或 六元杂环基， 或者取代或未取代的苯基， 其中， 所述取代基为选自下组中的一个或 多个： 卤素， 4卤代烷基或 4氯代烷氧基；
R2为 H， C C8饱和或不饱和烷基， 卤代的 d_8饱和或不饱和烷基，
-CH2CH2OCH2CH3， -CH2CH2OCH3， C1-8饱和或不饱和烷氧基， 苯基， 苄基， d_4 烷基-羰基或 d— 4烷基-磺酰基；
R3和 各自独立地为 H， d_6烷基， 烯丙基， 苄基， d_4烷氧基 -C^烷基，
4烷氧基-羰基， 苯氧羰基， C2— 6炔基-羰基， C2— 3烯基-羰基， C3— 6环烷基-羰基， 苯甲酰基， 或者被一个或多个选自卤原子、 4烷基、 d— 4卤代烷基、 d— 4烷氧基 和 (^— 4烷基-羰基的取代基所取代的苯甲酰基， 呋喃羰基或 Ν,Ν-二甲基羰基， 或者
R3和 共同构成 -CH2-CH2-， -CH2-CH2-CH2-或 CH2-XR-CH2-， 式中 X为 N、 O、 S 等杂原子， R是杂原子上的取代基， 选自 H， d_6烷基， 烯丙基， 苄基， 苯基， d— 4 烷氧基 4烷基， d— 4烷氧基-羰基， 苯氧羰基， C2— 6炔基-羰基， C2— 3烯基-羰基，
C3— 6环烷基-羰基， 苯甲酰基， 或者被一个或多个选自卤原子、 d— 4卤代烷基、 d_8 饱和或不饱和烷基或烷氧基和 d— 4烷基-羰基的取代基所取代的苯甲酰基， 呋喃羰 基或 Ν,Ν-二甲基羰基；
R5， R6， R7， 和 为 11， 饱和或不饱和 d_4烷基， 卤素， （^_8饱和或不饱 和烷氧基， 卤代 d_4饱和或不饱和烷氧基， 4烷基-羰基， 8烷基-酯基， d— 4 烷基 -磺酸酯基， 苯基或苄基；
Y为硝基， 氰基， 三氟甲基， 三氟乙酰基或三氟甲磺酰基。
在一个优选的实施方式中， 选自： 吡啶基、 噻唑基、 嘧啶基、 四氢呋喃基、 噁唑基或其卤代物。
在一个优选例中， 优选 为卤代的吡啶基、 卤代的噻唑基、 卤代的嘧啶基、 卤代的四氢呋喃基、 或卤代的噁唑基， 更优选所述卤代物为氯代物。 在另一优选例中， ！^为。1^^， α ^^或 。
在另一个优选的实施方式中， R2为 H， d_4饱和或不饱和烷基， 卤代的 C C4 饱和或不饱和烷基， d— 4烷基-羰基， 取代或未取代的苄基， 其中， 所述取代基为 选自下组中的一个或多个： 卤素， 4卤代烷基或 d— 4氯代烷氧基。
在一个优选例中， 为氢或 烷基， 优选氢或甲基。
在另一个优选的实施方式中， R3和 为氢或（^_6烷基， 或者 R3和 共同构 成 -CH2-CH2-或 -CH2-CH2-CH2-。
在一个优选例中， R3和 为氢或 烷基， 优选氢、 甲基或乙基， 或者 R3 和 共同构成 -CH2-CH2-或 -CH2-CH2-CH2-。
在另一个优选的实施方式中， R5， R6， R7， 和 为 11， 饱和或不饱和 d_2 烃基， 卤素， d_4饱和或不饱和烷氧基， 卤代 (^_2饱和或不饱和烷氧基， d— 4烷基- 酯基 （RCOO-) ， d_2烷基-磺酰酯基或三氟甲磺酰酯。
在一个优选例中， R5， R6， R7， R8和 R9为氢， 甲基， 氯， 溴， 甲氧基或乙氧 基， 优选氢， 甲基， 甲氧基。
在另一个优选的实施方式中， Y为硝基或氰基。
在一个优选例中， Y优选硝基。
另一方面， 本发明提供了一种农用组合物， 它包含：
(a) 0.001-99.99重量％的上述化合物、 其光学异构体、 顺反异构体或农药学上 可接受的盐、 或者它们的组合； 以及
(b) 农药学上可接受的载体和 /或赋形剂。
在一个优选例中， 组分 (a)占所述农用组合物的 0.01-99.9重量％， 优选 0.05-90 重量％。
在一个优选的实施方式中， 所述农用组合物用于杀灭或预防选自下组的害虫： 鞘翅目、 鳞翅目、 半翅目、 直翅目、 等翅目或双翅目昆虫。
在一个优选例中， 所述害虫具有剌吸式或锉吸式口器。
在另一优选例中， 所述害虫为蚜虫、 飞虱、 粉虱、 叶蝉、 蓟马、 棉铃虫、 菜青 虫、 小菜蛾、 斜纹夜蛾、 或粘虫。
在另一优选例中，所述农用组合物还包含其它活性物质， 所述其它活性物质选 自： 杀虫剂、 饵剂、 杀菌剂、 杀螨剂、 杀线虫剂、 杀真菌剂或生长控制剂。
另一方面， 本发明涉及所述农用组合物的用途， 用于杀灭或预防农业害虫、 卫 生害虫和危害动物健康的害虫； 或用作用于杀灭或预防农业害虫、卫生害虫和危害 动物健康的杀虫剂组合物。
另一方面， 本发明提供了一种杀虫和 /或防虫方法， 所述方法包括将上述农用 组合物施加于遭受或可能遭受虫害的植物体、 其周围的土壤或环境中。
另一方面， 本发明涉及上述化合物、 其光学异构体、 顺反异构体或农药学上可 接受的盐、 或它们的组合在制备杀虫剂组合物中的用途。
再一方面， 本发明提供了上述化合物、其光学异构体、顺反异构体或农药学上 可接受的盐的制备方法， 所述方法包括步骤：
在催化量酸的存在下， 于 0-60°C下， 使式 (a)化合物与式 (b；)、 （； c)或 (； d)化合物反 应， 从而制得具有式 (A；)、 (B), (C)或 (D)的化合物， 式中 R2为氢，
Figure imgf000006_0001
式中， R 、 R3、 、 R5、 R6， R7， R8， R9和 Y如上文中所定义， n为 0或 1。
在一个优选例中， 所述反应温度为 15-45°C， 优选 20-30°C。
在另一优选例中， 所用的溶剂选自： 乙腈或乙醇， 优选乙腈。
在另一优选例中， 所用的催化量的酸选自： 浓盐酸、 浓硫酸或苯甲酸， 优选浓 盐酸。
在一个优选的实施方式中， 所述方法包括步骤：
在乙腈中， 于催化量的酸存在下， 于 20-30°C下， 进行如下反应 2-24小时， 从 而获得式 (A)的化合物， 式中 R2为氢：
Figure imgf000006_0002
在乙腈中， 于催化量的酸存在下， 于 20-30°C下， 进行如下反应 2-24小时， 从 而获得式 (B)的化合物：
Figure imgf000007_0001
(B).
在乙腈中， 于催化量的酸存在下， 于 10-50°C下， 进行如下反应 2-24小时， 从 而获得式 (C)的化合物：
Figure imgf000007_0002
在乙腈中， 于催化量的酸存在下， 于 10-50°C下， 进行如下反应 2-24 时， 从 而获得式 (D)的化合物：
Figure imgf000007_0003
(D 具体实施方式
本发明的发明人通过长期而深入的研究，基于现有的硝基亚甲基类新烟碱杀虫 剂的硝基亚甲基结构，通过二醛与硝基亚甲基类化合物反应， 合成了一种新型的新 烟碱化合物， 该化合物的杀虫活性显著提高， 并具有扩大的杀虫谱。 在此基础上， 发明人完成了本发明。 基团定义
如本文所用， 术语 " d _6烷基"指具有 1-6个碳原子的直链或支链烷基， 例如 甲基、 乙基、 丙基、 异丙基、 丁基、 异丁基、 仲丁基、 叔丁基、 或类似基团。
术语 " (^_6烷氧基" 指具有 1-6个碳原子的直链或支链烷氧基， 例如甲氧基、 乙氧基、 丙氧基、 异丙氧基、 丁氧基、 异丁氧基、 仲丁氧基、 叔丁氧基、 或类似基 团。
术语 "卤素"指氟、 氯、 溴、 或碘。 术语 "卤代的"指被相同或不同的一个或 多个上述卤原子取代的基团， 例如三氟甲基、 五氟乙基、 或类似基团。
术语"五元或六元杂环基"指含一个或多个选自氮、氧或硫的杂原子的五元或 六元环， 例如吡啶基、 噻唑基、 嘧啶基、 四氢呋喃基、 或噁唑基等。 本发明化合物的制备方法
本发明化合物可通过上文所描述的反应步骤合成。本领域技术人员可按照现有 技术文献合成反应步骤中的式 0)化合物， 例如可参照 WO 2006056108A1, WO 2007101369A1和 PCT/CN2008/071115。
在本发明的一个具体实施方式中， 式 (A)化合物的合成方法如下：
Figure imgf000008_0001
(A) ( R2为氢） 。 在 发明的一个具体实施方式 ， 式 (B)化合物的合成方法如下：
Figure imgf000008_0002
在本发明的一个具体实施方式中， 式 (C)化合物的合成方法如下:
Figure imgf000008_0003
(C)。
在本发明的一个具体实施方式中， 式 (C)化合物的合成方法如下:
R
|
Figure imgf000008_0004
(D)o
在本发明的一个实施方式中， 式 (； A)的化合物可通过下列反应制备：
(1) 将 2-氯 -5-氯甲基吡啶的乙腈溶液滴加到 5-10倍摩尔量的二胺溶液中， 在 0-50°C之间， 反应 5-10小时。 后处理将二胺在减压条件下除去， 用乙酸乙酯溶解， 旋干溶剂， 得到产品： N* l *-(6-氯 -3-甲基吡啶基) -二胺；
(2) Ν* 1 *-(6-氯 -3-甲基吡啶基) -二胺与 1, 1-二硫甲基 -2-硝基乙烯， 以乙醇作溶 剂， 回流 4-8个小时， 得到产品： 硝基亚甲基类化合物；
(3) 硝基亚甲基类化合物与乙二醛在酸 (盐酸、 硫酸、 杂多酸等；)催化条件下， 得到所述通式的化合物 (A；)。
在另一个实施方式中， 式 (B)的化合物可通过下列反应制备：
(1) 乙胺水溶液中加入适量乙腈，在冰浴下滴加 6-氯 -3-氯甲基吡啶的乙腈溶解 液， TLC跟踪反应进程， 反应结束后， 向反应混合液中加入大量的水， 二氯甲烷 萃取， 干燥， 抽滤， 蒸去溶剂， 得到油状液体 N-(6-氯吡啶 -3-亚甲基)乙胺；
(2) N-(6-氯吡啶 -3-亚甲基)乙胺与 1, 1-二硫甲基 -2-硝基乙烯， 以乙醇作溶剂， 回流 4-8个小时， 浓缩， 柱层析分离得到产物 N-(6-氯吡啶 -3-亚甲基;) -N-乙基 -1-硫 甲基 -2-硝基亚乙烯基胺；
(3) N-(6-氯吡啶 -3-亚甲基) -N-乙基 -1-硫甲基 -2-硝基亚乙烯基胺与甲胺醇溶液， 以乙醇作溶剂， 在冰浴下反应 4-8个小时， 浓缩， 柱层析分离得到 N-(6-氯吡啶 -3- 亚甲基) -N-乙基 -Ν'-甲基 -2-硝基亚乙烯基二胺；
(4) Ν-(6-氯吡啶 -3-亚甲基) -Ν-乙基 -Ν'-甲基 -2-硝基亚乙烯基二胺与丙二醛在酸 (盐酸、 硫酸、 杂多酸等;)催化条件下， 得到所述式的化合物 (Β)。
在另一个实施方式中， 式 (C)的化合物可通过下列反应制备：
(1) 将 2-氯 -5-氯甲基吡啶的乙腈溶液滴加到 5-10倍摩尔量的二胺溶液中， 在
0-50°C之间， 反应 5-10小时； 后处理将二胺在减压条件下除去， 用乙酸乙酯溶解， 旋干溶剂， 得到产品： N* l *-(6-氯 -3-甲基吡啶基) -二胺；
(2) Ν* 1 *-(6-氯 -3-甲基吡啶基) -二胺与 1, 1-二硫甲基 -2-硝基乙烯， 以乙醇作溶 剂， 回流 4-8个小时， 得到产品： 硝基亚甲基类化合物；
(3) 硝基亚甲基类化合物 （2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶） 与 丁二醛在酸 (盐酸、 硫酸、 杂多酸等;)催化条件下， 得到所述通式的化合物 (C)。
在另一个实施方式中， 式 (D)的化合物可通过下列反应制备：
(1) 将 2-氯 -5-氯甲基吡啶的乙腈溶液滴加到 5-10倍摩尔量的二胺溶液中， 在 0-50°C之间， 反应 5-10小时。 后处理将二胺在减压条件下除去， 用乙酸乙酯溶解， 旋干溶剂， 得到产品 N* l *-(6-氯 -3-甲基吡啶基) -二胺；
(2) Ν* 1 *-(6-氯 -3-甲基吡啶基) -二胺与 1, 1-二硫甲基 -2-硝基乙烯， 以乙醇作溶 剂， 回流 4-8个小时， 得到产品： 硝基亚甲基类化合物；
(3) 硝基亚甲基类化合物 （2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶） 与 戊二醛在酸 (盐酸、 硫酸、 杂多酸等;)催化条件下， 得到所述通式的化合物 (D)。 本发明活性物质的杀虫活性
术语 "本发明的活性物质"或 "本发明的活性化合物"是指本发明化合物、 其 光学异构体、顺反异构体或农药学上可接受的盐， 其具有显著提高的杀虫活性， 以 及扩大的杀虫谱。
术语"农药学上可接受的盐"意指该盐的阴离子在形成杀虫剂药学上可接受的 盐时为已了解的和可接受的。 该盐较好的为水溶性的。 合适的、 由式 (； A), (； B), (； C) 和 (D)化合物形成的酸加成盐包括有无机酸形成的盐， 例如盐酸盐、 磷酸盐、 硫酸 盐、 硝酸盐； 及包括有机酸形成的盐， 如醋酸盐， 苯甲酸盐。
本发明的活性物质能用作控制和消灭广泛的农林植物害虫、 贮藏谷类的害虫、 公共卫生害虫以及危害动物健康的害虫等。在本说明书中， "杀虫剂"是具有防治 上述提到的所有害虫的作用的物质的统称。害虫的例子包括但不限于：鞘翅目昆虫： 玉 象 Sitophilus zeamais) , 赤拟谷盗 (7 / < // w castaneum), 马铃暮,瓢虫
(Henosepilachna vigintioctomaculata) , ^† 7 Ι]ϋ. (Henosepilachna sparsa) , 田月匈 口口头虫 ( Ig /ofey fuscicollis), 红月却绿金龟 ( 4 worn"/" cupripes), 四纹丽金龟 (尸0 /〃/+" quadri guttata) 马铃暮口十甲 (Mo < e hieroglyphica),
Figure imgf000010_0001
alternatus)， ^^(Echi oc emus squameus), R† {Basiprionota bisignata)， 星天牛 (Anoplophora chinensis), 桑天牛 (Apripona germari)， 腹小蠹 (Sco/yi s schevy) ^或细胸金针虫 ( 4g otey fuscicollis);鳞翅目昆虫： ^^^{Lymantria dispar), ¾ ^ {Malacosoma neustria testacea), ¾ (Diapha ia perspectalis), 大 袋蛾 (C7"w/ variegata) , 黄朿 lj蛾 (Cw/i oc m " flauescens), 马
Figure imgf000010_0002
punctatus)， 古毒蛾 gono stigma), 白杨透翅蛾 (尸 ra r^ ^ tabaniformis), 斜 ¾ 4¾ (Spodoptera litura), 二化蟆 (CTn/o suppressalis), 玉米蟆 nubilalis), ¾ ¾ (Ephes tia cautella), IS ¾ 4¾ {A doxophyes or ana), 栗子小卷娥 (/ s^yrra/ splendana) 小地老虎 (ylgroto fucosa) , {Gal I e via mellonella), ^^ Plutella xylostella), †p ^{Phyllocnistis citrella), 或东方粘虫 separata)-, 同翅目 昆虫： 黑尾叶虫单 (A¾p 70fe«/'j
Figure imgf000010_0003
稻褐飞 H(V/7op" v"to /tgew ， 康氏粉虫介 {Pseudococcus comstocki), 矢尖 (U aspis yanonensis), 桃虫牙 (Afymy persicae), 棉 ^Aphis gossydii), 萝卜虫牙 ( p pto erysimi pseudobrassicae) , ^{Stephanitis nashi) , 或粉風 tabaci)； 直翅目昆虫： 德国小蠊 germanica), 美国
Figure imgf000010_0004
¾ W (Gry / / o tal pa africana) , 或亚洲飞虫皇 ( migratoria) ; 等翅目昆虫： 入侵红火蚁 (So/ewo/w/s /«v/cta)， 或家白蚁
(Coptotermes formosanus)； 双翅目昆虫： ^^{Musca domestica) , 埃及伊絞 (ylecfes aegypti) , ^ (Delia platura) , 库紋 (CWex 5 λ)， W ^ ^^.^.{Anopheles sinensis) a 危害动物健康的害虫包括微小牛蜱 (Boophilus microplus )， 长角血蜱
(Haemaphysalis longicornis )， 小亚璃目艮婢 (Hyalomma anatolicum )， 牛皮虫黾
(Hypoderma spp. )， 肝片吸虫 (Fasciola hepatica )， 贝氏莫尼茨绦虫 (Moniezia blanchard)， 奧斯特线虫 (Ostertagia spp. )， J¾ i¾, Trypanosoma enansi, Babesia bigemina爭。
本发明涉及的化合物尤其对剌吸式、 锉吸式口器害虫， 如蚜虫、 叶蝉、 飞虱、 蓟马、 粉虱等农林害虫有特效。 含本发明活性物质的杀虫剂组合物
可将本发明的活性物质以常规的方法制备成杀虫剂组合物。这些活性化合物可 做成常规的制剂， 例如溶液剂， 乳剂， 混悬剂， 粉剂， 泡沬剂， 糊剂， 颗粒剂； 气 雾剂， 用活性物质浸渍的天然的和合成的材料， 在多聚物中的微胶囊， 用于种子的 包衣复方， 和与燃烧装置一起使用的制剂， 例如烟熏药筒， 烟熏罐和烟熏盘， 以及 ULV冷雾 (Cold mist)和热雾 (Warm mist)制剂。
这些制剂可用已知的方法生产， 例如， 将活性化合物与扩充剂混合， 这些扩充 剂就是液体的或液化气的或固体的稀释剂或载体，并可任意选用表面活性剂即乳化 剂和 I或分散剂和 I或泡沬形成剂。例如在用水作扩充剂时，有机溶剂也可用作助 剂。
用液体溶剂作稀释剂或载体时基本上是合适的， 如： 芳香烃类， 例如二甲苯， 甲苯或烷基萘； 氯化的芳香或氯化的脂肪烃类， 例如氯苯， 氯乙烯或二氯甲烷； 脂 肪烃类， 例如环己烷或石蜡， 例如矿物油馏分； 醇类， 例如乙醇或乙二醇以及它们 的醚和脂类； 酮类， 例如丙酮， 甲乙酮， 甲基异丁基酮或环已酮； 或不常用的极性 溶剂， 例如二甲基甲酰胺和二甲基亚砜， 以及水。 液化气的稀释剂或载体是指在常 温常压下将成为气体的液体， 例如气溶胶推进剂， 如卤化的烃类以及丁烷， 丙烷， 氮气和二氧化碳。
固体载体可用地面天然的矿物质， 例如高岭土， 粘土， 滑石， 石英， 活性白土， 蒙脱土，或硅藻土，和地面合成的矿物质，例如高度分散的硅酸，氧化铝和硅酸盐。 供颗粒用的固体载体是碾碎的和分级的天然告石， 例如方解石， 大理石， 浮石， 海 泡石和白云石，以及无机和有机粗粉合成的颗粒，和有机材料例如锯木屑，椰子壳， 玉米棒子和烟草梗的颗粒等。
非离子的和阴离子的乳化列可用作乳化剂和 /或泡沬形成剂。 例如聚氧乙烯- 脂肪酸酯类， 聚氧乙烯-脂肪醇醚类， 例如烷芳基聚乙二醇醚类， 烷基磺酸酯类， 烷基硫酸酯类， 芳基磺酸酯类以及白蛋白水解产物。 分散剂包括， 例如木质素亚硫 酸盐废液和甲基纤维素。
在制剂中可以用粘合剂， 例如羧甲基纤维素和以粉末， 颗粒或乳液形式的天然 和合成的多聚物， 例如阿拉伯胶， 聚乙烯基醇和聚乙烯醋酸酯。 可以用着色剂例如 无机染料， 如氧化铁， 氧化钻和普鲁士蓝； 有机染料， 如有机染料， 如偶氯染料或 金属钛菁染料； 和用痕量营养剂， 如铁， 猛， 硼， 铜， 钴， 铝和锌的盐等。
本发明的这些活性化合物可与其它活性化合物制成混合物存在于商品制剂中 或从这些制剂制备的使用剂型中， 所述其它的活性化合物包括但不限于： 杀虫剂， 合饵， 杀菌剂， 杀螨剂， 杀线， 杀真菌剂， 生长控制剂等。 杀虫剂包括， 例如磷酸 酯类， 氨基甲酸酯类， 除虫菊酯类， 氯化烃类， 苯甲酰脲类， 沙蚕毒素类以及由微 生物产生的物质， 如阿维菌素。
此外，本发明的这些活性化合物也可与增效剂制成一种混合物存在于它们的商 品制剂中成从这些制剂制备的使用剂型中。 增效剂是提高活性化合物作用的化合 物， 由于活性化合物本身有活性， 也可不必加增效剂。
这些制剂通常含有占所述杀虫剂组合物 0.001-99.99重量％， 优选 0.01-99.9重 量％， 更优选 0.05-90重量％的本发明的活性化合物。 从商品制剂制成使用剂型中 的活性化合物的浓度可在广阔的范围内变动。使用剂型中的活性化合物的浓度可从 0.000000 l-100%(g/v) , 最好在 0.0001与 1%之间。 实施例
下面结合具体实施例， 进一步阐述本发明。应理解， 这些实施例仅用于说明本 发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常 按照常规条件， 或按照制造厂商所建议的条件。 除非另外说明， 否则百分比和份数 按重量计算。 其中， r. t.代表室温。 实施例 1 : 4-(l-((6-氯吡啶 -3-基）甲基) -4,5-二氢 -1H-咪唑烷 -2-基) -l-(l-((6-氯吡 啶 -3-基)甲基)咪唑烷 -2-基) -1,4-二硝基 -3-丁烯 -2-醇 (化合物 13)的合成
以 0.03mol的 2-氯 -5-氯甲基吡啶为起始原料， 按照 WO 2006056108A1和 WO 2007101369A1所述的方法制备 2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶， 产 率为 56% ; Rf = 0.46(石油醚：乙酸乙酯 = l: l ) ; mp= 156.9°C -161.8°C。GC MS(m/s) 220(25)， 126(100)， 90(9)。
4-(1-((6-氯吡啶 -3-基）甲基) -4,5-二氢 -1H-咪唑垸 -2-基) -1-(1-((6-氯吡啶 -3-基）甲 基)咪唑垸 -2-基) -1.4-二硝基 -3-丁烯 -2-醇的合成
Figure imgf000013_0001
将 1.27g(0.005mol)的 2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶， 30ml的无 水乙腈， 3ml 30%的乙二醛水溶液加入 50ml的圆底烧瓶中， 搅拌半个小时， 然后 加入催化量的浓盐酸催化， 继续搅拌， TLC跟踪反应至原料全部反应完全， 然后 抽滤得白色粉末状固体。 重结晶得到化合物 13的纯品， 为白色粉末状固体 1.05g， 产率约 76%。
mp = 164.6-165.3。C; 1H NMR (400 Mz, DMSO-d6): δ 9.01 (s, 1H), 8.41 (d, J = 2.0 Hz, 1H), 8.38 (d, J = 2.0 Hz, 1H), 7.80-7.86 (m, 2H), 7.51-7.54 (m, 2H), 6.50 (d, J = 7.2 Hz, 1H), 5.34 (d, J = 15.2 Hz, 1H), 5.18 (d, J = 15.2 Hz, 1H), 4.84 (dd, Ji = 2.4 Hz, J2 = 7.2 Hz, 1H), 4.77 (d, J = 16.8 Hz, 1H), 4.67 (d, J = 16.8 Hz, 1H), 3.98 (d, J = 2.4 Hz, 1H), 3.86-3.95 (m, 2H), 3.61-3.80 (m, 5H), 3.40-3.47 (m, 1H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 162.7, 158.7, 148.3, 148.2, 148.0, 147.7, 138.1, 137.7, 130.9, 130.2, 123.1, 123.0, 102.5, 101.4, 81.4, 53.8, 52.6, 49.4, 48.8, 46.4, 41.2, 41.0 ppm; HRMS (ES+) 计算值 C22H23N8O5 35Cl2 (M+H)+, 549.1168; 测得值， 549.1178; 计算 值 C22H23N8O5 35Cl37Cl (M+H)+, 551.1139; 测得值， 551.1152; 计算值
C22H23N8O5 37Cl2 (M+H)+, 553.1109; 测得值， 553.1108。 实施例 2: 2-氯 -5-((-2-(-4-(1-((6-氯吡啶 -3-基）甲基) - 4,5-二氢 -1H-咪唑烷 -2- 基) -2-甲氧基 -1,4-二硝基 -3-丁烯基)咪唑烷 -1-基)甲基)吡啶 (化合物 14)的合成
Figure imgf000014_0001
将 0.549g (O.OOlmol) 的化合物 1加入到 50ml的圆底烧瓶中， 再加入 10ml 的甲醇， 50ml二氯甲烷和催化量的浓盐酸， 回流， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到黄色粉末状纯品， 产率为 62%。
mp = 151.6-153.1 °C; 1H NMR (400 Mz, DMSO-d6): δ 9.03 (s, 1H), 8.38 (d, J = 2.0 Hz, 1H), 8.36 (d, J = 2.0 Hz, 1H), 7.81-7.85 (m, 2H), 7.49-7.51 (m, 2H), 6.50 (d, J = 7.2 Hz, 1H), 5.35 (d, J = 15.2 Hz, 1H), 5.19 (d, J = 15.2 Hz, 1H), 4.80 (d, Ji = 7.2 Hz; 1H), 4.77 (d, J = 16.8 Hz, 1H), 4.69 (d, J = 16.8 Hz, 1H), 3.68 (s, 3H), 3.88-3.95 (m, 2H), 3.61-3.85 (m, 5H), 3.38-3.41 (m, 1H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 162.6, 158.7, 148.9, 148.3, 148.1, 147.6, 138.1, 137.8, 130.9, 129.9, 122.8, 123.1, 102.2, 101.6, 81.6, 58.7, 53.8, 52.6, 49.6, 48.9, 46.4, 41.3, 41.0 ppm; HRMS (ES+) 计 算值 C23H25N8O5 35Cl2 (M+H)+, 563.1325; 测得值， 563.1311. 计算值
C23H25N8O5 35Cl37Cl (M+H)+, 565.1295。 实施例 3: N1,N7-二 ((6-氯吡啶 -3-基）甲基) N1,N7-二乙基 -N，1,N，7-二甲基 -2,6- 二硝基 -2,5-庚二亚胺 (；化合物 37)的合成
(1)Ν-(6-氯吡啶 -3-亚甲基)乙胺的合成
Figure imgf000014_0002
在带有恒压滴液漏斗、温度计的 300mL三口圆底烧瓶中，加入 65-70%乙胺水溶 液 (70g, l mol)， 乙腈 50mL， 在冰浴下搅拌 15分钟， 使溶液温度稳定在 0°C附近， 在恒压滴液漏斗中加入 6-氯 -3-氯甲基吡啶（16.10 g， O.lOmol)的乙腈 (25 mL)溶液， 控制滴加速度在 3滴 /分钟， 滴加时间在 3.5小时， 反应结束后， 加水， 二氯甲烷萃 取， 收集有机相， 得油状液体 N-(6-氯吡啶 -3-亚甲基)乙胺 14g， 收率 70%。 GC-MS: m/z (%) = 170 (岡+, 20), 155 (80), 126 (100), 114 (10), 90 (12)。
(2) N-(6-氯吡啶 -3-亚甲基) -N-乙基 -1-硫甲基 -2-硝基亚乙烯基胺的合成
Figure imgf000014_0003
在 100毫升三口圆底烧瓶中， 加入 N-(6-氯吡啶 -3-亚甲基)乙胺 (17.0 g, O. l mol), 1, 1-二硫甲基 -2-硝基乙烯（15.0 g, 0.09 mol)， 无水乙醇 (50 mL)， 回流。 反应结束后， 冷却至室温， 减压浓缩得到浓稠状液体， 柱层析分离得 N-(6-氯吡啶 -3-亚甲基;) -N- 乙基 -1-硫甲基 -2-硝基亚乙烯基胺 5.3 g，收率 18.5%。 GC-MS: m/z (%) = 242 ([M]+-46 53), 227 (15), 213 (100), 169 (45), 155 (28), 141 (29), 126 (91), 90 (12)。
(3) Ν-(6-氯吡啶 -3-亚甲基) -N-乙基 -Ν'-甲基 -2-硝基亚乙烯基二胺的合成
Figure imgf000015_0001
向 100 mL单口圆底烧瓶中， 加入 N-(6-氯吡啶 -3-亚甲基) -N-乙基 -1-硫甲基 -2- 硝基亚乙烯基胺 (5 g, 0.017 mol)， 甲胺醇溶液 (1.8 g, 0.017 mol甲胺)， 无水乙醇 (30 mL), 在冰浴下搅拌使温度降至 0°C， 继续反应直至结束。 再减压旋转蒸去溶剂， 浓缩得浆状物， 将此浆状物用适量二氯甲烷溶解， 以硅胶为填料， 用二氯甲烷:乙 醇 = 25: 1为展开剂进行柱分， 收集产品， 浓缩得到 N-(6-氯吡啶 -3-亚甲基;) -N-乙基 -N，-甲基 -2-硝基亚乙烯基二胺 0.9 g，收率 19.1%。 TLC: 二氯甲烷:丙酮 = 5: 1, Rf = 0.23. 熔点： 78-80 oC. (lit[67] 79-81 °C) GC-MS: m/z (%) =236 ([M]+— 34, 32), 207 (49), 169 (52), 126 (49), 110 (20), 90 (16), 67 (100). 16.65
(4) Nl, N7-二 (Ϊ6-氯吡啶 -3-基）甲基) Nl, N7-二乙基 -N，l, N，7-二甲基 -2,6-二 -2.5-庚二亚胺 (化合物 37)的合成
Figure imgf000015_0002
将 1.35g(0.005mol)的 N-(6-氯吡啶 -3-亚甲基) -N-乙基 -N，-甲基 -2-硝基亚乙烯基 二胺， 30ml的无水乙腈， 0. 72g(0.01mol)的丙二醛， 催化量的 HC1置于 50ml的圆 底烧瓶中。 常温下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离 得到淡黄色粉末状纯品， 产率为 56%。
mp = 117.3-118.7°C ; 1H NMR (400 Mz, DMSO-d6): δ 8.36 (d, J = 2.4 Hz, 2H), 7.88 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 2H), 4.97 (t, J = 2.8 Hz, 2H), 4.86 (d, J = 15.2 Hz, 2H), 4.49 (d, J = 15.2 Hz, 2H), 3.95-3.99 (m, 4H), 3.66-3.78 (m, 6H), 3.12-3.21 (m, 2H), 1.91-1.93 (m, 6H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 156.3, 148.5, 148.1, 137.3, 131.9, 122.5, 104.8, 49.2, 48.9, 48.0, 48.5, 28.1, 20.2 ppm; HRMS (EI+) 计算值 C25H3QN8O4 35C12 (M+), 576. 1767; 测得值， 576. 1751 , 实施例 4: 1,5-二（l-((6-氯吡啶 -3-基）甲基) -4,5-二氢 -1H-咪唑烷 -2-基) -1,5-二硝 基 -1,4-戊二烯 (；化合物 39)的合成
Figure imgf000016_0001
将 1.27g(0.005mol)的 2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶， 30ml的无 水乙腈， 0.720g(0.01mol)的丙二醛， 催化量的 HC1置于 50ml的圆底烧瓶中。 常温 下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉末 状纯品， 产率为 52%。
mp = 136.5-137.8。C; 1H NMR (400 Mz, DMSO-d6): δ 8.34 (d, J = 2.4 Hz, 2H),
7.82 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 2H), 7.47 (d, J = 8.4 Hz, 2H), 4.96 (t, J = 2.8 Hz, 2H), 4.81 (d, J = 15.8 Hz, 2H), 4.44 (d, J = 15.8 Hz, 2H), 3.92-3.97 (m, 4H), 3.65-3.72 (m, 2H), 3.49-3.56 (m, 2H), 1.92-1.93 (m, 2H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 155.3, 147.9, 147.8, 138.0, 130.9, 122.7, 104.8, 50.2, 48.9, 48.5, 48.5, 28.1 ppm;
HRMS (ES+) 计算值 C23H23N8O4 35Cl2 (M+H)+, 545.1219; 测得值， 545.1201。计算值 C23H23N8O4 35Cl37Cl (M+H)+, 547.1190; 测得值， 547.1178. 计算值 C23H23N8O4 37Cl2 (M+H)+, 549.1160; 测得值， 549.1181。
Figure imgf000016_0002
1 :(1-((2-氯噻唑 -5-基）甲基) -4,5-二氢 -1H-咪唑烷 -2-基) -1,5-二硝 基 -1,4-戊二烯 (化合物 41)的合成
按照实施例 1所述的方法， 以 0.03mol 2-氯 -5-氯甲基噻唑代替 2-氯 -5-氯甲基 吡啶作为起始原料制备 1-( 2-氯噻唑 -5-基)甲基; )-2- (；硝基亚甲基; )-1-咪唑烷， 产率为 56% ; GC MS(m/s) 226(24), 132(100)， 77(9)。
1,5-二 (1-((2-氯噻唑 -5-基）甲基) -4,5-二氢 -1H-咪唑垸 -2-基) -1,5-二硝基 -1,4-戊二 烯的合成
Figure imgf000016_0003
将 1.30g(0.005mol)的 l-((2-氯噻唑 -5-基）甲基) -2- (硝基亚甲基 )-1-咪唑烷， 30ml 的无水乙腈， 0. 720g(0.01mol)的丙二醛， 催化量的 HCl置于 50ml的圆底烧瓶中。 常温下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色 粉末状纯品， 产率为 44%。
mp = 138.6-139.9°C; 1H NMR (400 Mz, DMSO-d6): δ 7.63 (s, 1H), 4.98 (t, J = 2.8 Hz, 2H), 4.85 (d, J = 15.8 Hz, 2H), 4.43 (d, J = 15.8 Hz, 2H), 3.96-3.99 (m, 4H), 3.67-3.71 (m, 2H), 3.51-3.56 (m, 2H), 1.95-1.97 (m, 2H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 157.6, 149.3, 138.3, 105.8, 50.6, 48.9, 48.4, 48.1, 29.1 ppm; HRMS (ES+) 计算值 C19H19N8O4S2 35Cl2 (M+H)+, 557.0348; 测得值， 557.0363. 计算值
C19H19N8O4S2 35Cl37Cl (M+H)+, 559.0318; 测得值， 559.0620。 实施例 6: 1,5-二 (1-((6-氯吡啶 -3-基)甲基) -1,4,5,6-四氢嘧啶 -2-基) -1,5-二硝基 -1,4-戊二烯 (；化合物 43)的合成
以 2.42g(0.015mol)的对氯吡啶为起始原料， 按照 WO 2006056108A1和 WO 2007101369A1所述的方法制备 1-(6-氯 -3-甲基吡啶基) -2-硝基亚甲基六氢嘧啶， 产 率为 56% ; Rf=0.19 (乙醇： 二氯甲烷 = 1 : 1)； mp= 175.7-182.6°C。 GC MS(m/s) 225(100)， 196(9)， 154(10)， 139(11)， 126(31)， 113(10)， 90(31)。
1,5-二 (1-((6-氯吡啶 -3-基）甲基) -4,5-二氢 -1Η-咪唑垸 2-基) -1,5-二硝基 -1,4-戊二 烯的合成
Figure imgf000017_0001
将 1.34g(0.005mol)的 1-(6-氯 -3-甲基吡啶基； )-2-硝基亚甲基六氢嘧啶， 30ml的 无水乙腈， 0. 720g(0.01mol)的丙二醛， 催化量的 HC1置于 50ml的圆底烧瓶中。 常 温下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉 末状纯品， 产率为 55%。
mp = 133.7-134.9°C; 1H NMR (400 Mz, DMSO-d6): δ 8.32 (d, J = 2.4 Hz, 2H), 7.81 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 4.93 (t, J = 2.8 Hz,
2H), 4.78 (d, J = 15.8 Hz, 2H), 4.40 (d, J = 15.8 Hz, 2H), 3.91-3.96 (m, 4H), 3.63-3.71 (m, 2H), 3.49-3.53 (m, 2H), 2.32-2.37 (m, 2H), 1.92-1.93 (m, 2H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 155.6, 148.3, 147.9, 138.0, 130.7, 122.7, 105.1, 50.2, 48.8, 48.5, 48.1, 36.2, 28.0 ppm; HRMS (ES+) 计算值 C25H27N8O4 35Cl2 (M+H)+, 572.1454; 测得 值， 572.1468。 计算值 C25H27N8O4 35Cl37Cl (M+H)+, 574.1425; 测得值， 574.1416。 实施例 7: Ν-((6-氯吡啶 -3-基）甲基) -Ν-乙基 -2-甲基 -4-硝基 -8-氧杂 -2-氮杂双环 [3,2, 1]辛 -3-烯 -3-胺 (化合物 46)的合成
Figure imgf000018_0001
将 1.35g(0.005mol)的 N-(6-氯吡啶 -3-亚甲基) -N-乙基 -N，-甲基 -2-硝基亚乙烯基 二胺， 30ml的无水乙腈， 0. 860g(0.01mol)的丁二醛， 催化量的 HC1置于 50ml的圆 底烧瓶中。 常温下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离 得到淡黄色粉末状纯品， 产率为 40%。
mp = 125.3-125.7°C ; 1H NMR (400 Mz, DMSO-d6): δ 8.72 (s, 1H), 8.27 (d, J = 2.4 Hz, 1H), 7.75 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.58 (d, J = 8.4 Hz, 1H), 5.25-5.30 (s, 2H), 4.41-4.50 (m, 2H), 2.96-3.26 (m, 2H), 2.86 (s, 3H), 2.36-2.41 (m, 2H),
1.81-1.5 (m, 4H), 1.16-1.26 (m, 3H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 158.5, 154.4, 151.6, 150.8, 148.1, 139.3, 137.1, 107.8, 89.5, 65.8, 49.8, 46.9, 40.6, 21.9, 20.3 ppm; HRMS (EI+) 计算值 C15H21N4O3 35Cl (M+), 339.1224; 测得值， 339.1257。 计算 值 C15H21N4O3 37Cl (M+), 341.1194; 测得值， 341.1213。 实施例 8: 9-((6-氯吡啶 -3-基）甲基) -4-硝基 -8-氧杂 -10, 11-二氢咪唑并 [2,3-a]双环 [3,2, 1]辛 -3-烯 (化合物 52)的合成
Figure imgf000018_0002
将 1.27g(0.005mol)的 2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶， 30ml的无 水乙腈， 0. 860g(0.01mol)的丁二醛， 催化量的 HC1置于 50ml的圆底烧瓶中。 常温 下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉末 状纯品， 产率为 71%。
mp = 149.0-150.0。C; 1H NMR (400 Mz, DMSO-d6): δ 8.35 (d, J = 2.4 Hz, 1H), 7.81 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.51 (d, J = 8.4 Hz, 1H), 5.36-5.39 (s, 2H), 5.00 (d, J = 15.6 Hz, 1H), 4.68 (d, J = 15.6 Hz, 1H), 3.57-3.73 (m, 4H), 1.94-2.04 (m, 4H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 155.6, 149.7, 149.6, 139.7, 132.6, 124.5, 109.6, 87.0, 75.1, 51.2, 50.3, 46.6, 31.9, 31.7 ppm; HRMS (ES+) 计算值 C14H16N4O3 35Cl (M+H)+, 323.0911; 测得值， 323.0912。计算值 C14H16N4O3 37Cl (M+H)+, 325.0811; 测 得值， 325.0895。 计算值 C14H15N4O3 35ClNa (M+Na)+, 345.0730; 测得值， 345.0722。 计算值 C14H15N4O3 37ClNa (M+Na)++, 347.0701; 测得值， 347.0692。 实施例 9: 9-((2-氯噻唑 -5-基）甲基) -4-硝基 -8-氧杂 -10, 11-二氢咪唑并 [2,3-a]双环 [3,2, 1]辛 -3-烯 (化合物 53)的合成
Figure imgf000019_0001
将 1.30g(0.005mol)的 2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶， 30ml的无 水乙腈， 0. 860g(0.01mol)的丁二醛， 催化量的 HC1置于 50ml的圆底烧瓶中。 常温 下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉末 状纯品， 产率为 63%。
mp = 151.7-152.1 °C; 1H NMR (400 Mz, DMSO-d6): δ 7.65 (s, 1H), 5.33-5.37 (s, 2H), 5.01 (d, J = 15.6 Hz, 1H), 4.69 (d, J = 15.6 Hz, 1H), 3.52-3.70 (m, 4H), 1.90-2.01 (m, 4H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 155.2, 149.6, 139.1, 124.5, 110.6, 87.1 75.6, 51.3, 50.6, 46.9, 31.9, 31.2 ppm; HRMS (ES+) 计算值 C12H15N4O3S35Cl (M+H)+ 329.0475; 测得值， 329.0412. 计算值 C12H15N4O3S37Cl (M+H)+, 331.0446; 测得值， 331.0423。 实施例 10: 9-((6-氯吡啶 -3-基）甲基) -4-硝基 -8-氧杂 -10, 11, 12- 双环 [3,2, 1]辛 -3-烯 (化合物 61)的合成
Figure imgf000019_0002
将 1.34g(0.005mol)的 1-(6-氯 -3-甲基吡啶基； )-2-硝基亚甲基六氢嘧啶， 30ml的 无水乙腈， 0. 860g(0.01mol)的丁二醛， 催化量的 HC1置于 50ml的圆底烧瓶中。 常 温下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉 末状纯品， 产率为 38%。
mp = 143.2-144.9。C; 1H NMR (400 Mz, DMSO-d6): δ 8.33 (d, J = 2.4 Hz, 1H), 7.80 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.49 (d, J = 8.4 Hz, 1H), 5.32-5.35 (s, 2H), 5.00 (d, J = 15.6 Hz, 1H), 4.66 (d, J = 15.6 Hz, 1H), 3.51-3.68 (m, 4H), 2.33-2.41 (m, 2H), 1.89-2.00 (m, 4H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 155.5, 149.6, 149.3, 139.7, 132.6, 124.1, 109.3, 86.6, 75.1, 51.2, 50.7, 46.6, 32.1, 31.7, 26.9 ppm; HRMS (ES+) 计算值 C15H19N4O3 35Cl (M+H)+, 337.1067; 测得值， 337.1015。计算值(315111(^403 37(：1 (M+H)+, 339.1038; 测得值， 339.0995。 实施例 11 : 9-((6-氯吡啶 -3-基）甲基) -4-氰基 -8-氧杂 -10, 11-二氢咪唑并 [2,3-a]双 环 [3,2, 1]辛 -3-烯 (化合物 64)的合成
Figure imgf000020_0001
将 1.17g(0.005mol)的 2-氯 -5-(2-氰基亚甲基-咪唑烷 -1-基甲基) -吡啶， 30ml的无 水乙腈， 0. 860g(0.01mol)的丁二醛， 催化量的 HC1置于 50ml的圆底烧瓶中。 常温 下搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉末 状纯品， 产率为 66%。
mp = 125.1-126.8。C; 1H NMR (400 Mz, DMSO-d6): δ 8.34 (d, J = 2.4 Hz, 1H), 7.82 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.55 (d, J = 8.4 Hz, 1H), 5.33 (s, 1H), 5.25 (s, 1H), 5.00 (d, J = 15.6 Hz, 1H), 4.78 (d, J = 15.6 Hz, 1H), 3.56-3.78 (m, 4H), 1.91-2.00 (m, 4H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 153.6, 149.0, 148.6, 139.7, 132.3, 121.5, 99.6, 87.3, 75.7, 51.3, 50.2, 46.6, 31.5, 29.7 ppm; HRMS (ES+) 计算值
C15H16N4O35Cl (M+H)+, 303.1013; 测得值， 303.0992。计算值 C15H16N4O37Cl (M+H)+, 305.0983; 测得值， 305.0957。 实施例 12: 10-((6-氯吡啶 -3-基）甲基) -4-硝基 -9-氧杂 -11, 12-二氢咪唑并 [2,3-a 双环 [3,3, 1]壬 -3-烯 (化合物 77)的合成
Figure imgf000020_0002
将 1.27g(0.005mol)的 2-氯 -5-(2-硝基亚甲基-咪唑烷 -1-基甲基) -吡啶， 30ml的无 水乙腈， 3ml 25%戊二醛水溶液， 催化量的 HC1置于 50ml的圆底烧瓶中。 常温下 搅拌， TLC跟踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉末状 纯品， 产率为 86%。
mp = 174.7-175.4。C; 1H NMR (400 Mz, DMSO-d6): δ 8.38 (dd, Ji = 0.6 Hz, J2 =
2.4 Hz, 1H), 7.84 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.52 (dd, Ji = 0.6 Hz, J2 = 8.4 Hz, 1H), 5.12 (s, 1H), 5.04-5.05 (m, 1H), 4.97 (d, J = 15.6 Hz, 1H), 4.71 (d, J = 15.6 Hz, 1H), 3.62-3.74 (m, 4H), 1.66-1.81 (m, 4H), 1.51-1.55 (m, 1H), 1.32-1.44 (m, 1H) ppm; 13C NMR (100 Mz, DMSO-d6): δ 156.6, 149.7, 149.6, 139.7, 132.9, 124.5, 105.8, 81.7, 68.9, 51.7, 50.0, 46.3, 28.8, 27.2, 14.8 ppm; HRMS (EI+) 计算值 C15H17N4O3 35Cl (M+) 336.0989; 测得值， 336.0988。 计算值 C15H17N4O3 37Cl (M+), 338.0960; 测得值， 338.0968。 实施例 13 : 10- ((四氢呋喃 -3-基)甲基) -4-硝基 -9-氧杂 -11, 12-二氢咪唑并 [2,3-a] 双环 [3,3, 1]壬 -3-烯 (化合物 80)的合成
按照实施例 1所述的方法， 以 0.2mol 3-氯甲基四氢呋喃代替 2-氯 -5-氯甲基吡 啶作为起始原料制备 1- 四氢呋喃 -3-基)甲基; )-2- (；-硝基亚甲基; )-1-咪唑啉， 产率为 51 % ; GC MS(m/s) 177(29), 99(100)， 56(9)。
10- ((四氢呋喃 -3-基）甲基) -4-硝基 -9-氧杂 -11, 12-二氢咪唑并「2,3-al双环「3,3, 11壬 -3-烯
Figure imgf000021_0001
将 1.065g(0.005mol)的 1- ((四氢呋喃 -3-基）甲基) -2- (-硝基亚甲基) -1-咪唑啉， 3ml
25%戊二醛水溶液， 催化量的 HC1置于 50ml的圆底烧瓶中。 常温下搅拌， TLC跟 踪反应。 待反应结束后， 除去溶剂， 柱层析分离得到淡黄色粉末状纯品， 产率为 36%。
mp = 115.3-116.9°C ; 1H NMR (400 Mz, DMSO-d6): δ 5.11 (s, 1H), 5.00-5.03 (m, 1H), 4.18 (d, J = 3.2 Hz, 2H), 4.05-4.25 (m, 2H), 3.85-3.96 (m, 4H), 2.25 (m, 1H), 1.66-1.81 (m, 4H), 1.63 -1.64 (m, 2H), 1.57-1.59 (m, 2H), 1.51-1.55 (m, 1H), 1.32- 1.44 (m, 1H) ppm; "C NMR (100 Mz, DMSO-d6): δ 81.7, 80.6, 78.5, 68.9, 50.0, 49.7, 46.9, 44.6, 36.8, 33.9, 28.8, 27.2, 17.8, 14.8ppm; HRMS (EI+) 计算值
C14H21N3O4 (M+), 295. 1532; 测得值， 295. 1598。 实施例 14 : 本发明化合物的杀虫活性测试
(1) 对蚜虫的杀虫活性
蚜虫属于同翅目害虫，具有剌吸口器，是一种常见的农作物害虫。以豆蚜 O^ s craccivora)为测试对象， 采用浸渍、法测试。
操作过程： 准确称量各种样品， 分别加入 Ν,Ν-二甲基甲酰胺配制成 10g/L母 液， 实验时用含 0.2mL/L Triton X- 100的水溶液将其稀释至 500ppm的浓度。 待无 翅成蚜在豆芽上稳定吸食后， 连同豆芽一起浸入浓度为 500ppm的药液中， 5秒后 取出， 用吸水纸吸去多余药液， 移入干净器皿中于 23 °C恒温饲养。 每浓度设 3次 重复， 对照组为含 0.2mL/L Triton X- 100的水溶液。 处理 24小时后， 统计试蚜的 死亡虫数， 并根据公式计算死亡率 (％；): 死亡率 (％) = (；对照活虫数 -处理活虫数 y对 照活虫数 X 100%。 结果见下表 1-4。
(2) 对飞虱的杀虫活性
飞虱属于同翅目害虫， 具有剌吸口器， 是一种常见的农作物害虫。 以褐飞虱 (Nilaparvata /wgew 为测试对象， 采用喷雾法测试。
操作过程： 将待测化合物以丙酮为溶剂准确配制成 500、 250、 100、 50、 25、 12.5、 6.25、 3. 13、 1.57、 0.79 ppm溶液， 并以丙酮水溶液处理作空白对照。 每个 处理重复 3杯 (即重复 3次；)。 用小型手动喷雾器每杯均匀喷雾 2 ml。 施药前 6小时 每盆接稻飞虱 10头。 先后共进行了 3批次试验。 处理 24小时后， 统计试虫的死 亡虫数， 并计算死亡率 (％)(；公式同上；)。 结果见下表 1-4。
(3) 对粘虫的杀虫活性
采用浸叶饲喂法。将待测化合物以丙酮为溶剂准确配制成 500、 250、 100、 50、
25、 12.5、 6.25、 3. 13、 1.57 ppm溶液， 并以丙酮水溶液处理作空白对照。 将新鲜 的玉米叶片在溶液中浸渍 3秒， 然后在室温下凉干， 供试虫取食， 24h后检査并计 算试虫的死亡率 (％， 公式同上；)， 每处理使用 10试虫， 设 3次重复。 。 结果见表 1-4。
(4) 对小菜蛾的杀虫活性 采用浸叶饲喂法。 将新鲜的卷心菜叶片在上述溶液中浸渍 3秒， 然后在室温 下凉干， 供试虫取食， 24小时后检査并计算试虫的死亡率 (％， 公式同上；)， 每处理 使用 10试虫， 设 3次重复。 以清水处理作空白对照。 结果见下表 1-4。
Figure imgf000024_0001
Figure imgf000025_0001
表 2: 式 (B)化合物的杀虫活性
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
实施例 15 : 含有本发明化合物的杀虫剂组合物的制备
(a) 油状悬浮液
按比例准备以下组分： 25% (重量百分比， 下同） 化合物 1-73中任一种化合物；
5 %聚氧乙烯山梨醇六油酸酯； 70 %高级脂肪族烃油。 将各组分在沙磨中一起研磨， 直到固体颗粒降至约 5微米以下为止。 所得的粘稠悬浮液可直接使用， 但也可在水中 乳化后使用。
(b) 水悬浮液
按比例准备以下组分： 25%化合物 1-73中任一种化合物； 3%水合硅镁土 (hydrate attapulgit) ; 10%木质素磺酸钙； 0.5%磷酸二氢钠； 61.5%水。 将各组分在球磨机中一 起研磨， 直到固体颗粒降至约 10微米以下为止。 该水悬浮液可直接使用。
(c) 饵剂
按比例准备以下组分： 0.1-10%化合物 1-73 中任一种化合物； 80%小麦面粉； 19.9-10%糖蜜。 将这些组分完全混合， 按需要形成饵形状。 可食用饵可以分散到卫生 害虫所侵染的场所， 例如家居或工业场所， 诸如厨房、 医院或商店或户外区域， 以通 过口服摄入来防治害虫。 本发明提及的所有文献都在本申请中引用作为参考， 就如同每一篇文献被单 独引用作为参考那样。 此外应理解， 在阅读了本发明的上述讲授内容之后， 本领域 技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利 要求书所限定的范围。

Claims

权 利 要 求
1. 具有式 (A；)、 (B), (C)或 (D)所示结构的化合物、 或者所述化合物的光学异构 体、 顺反异构体或农药学上可接受的盐：
Figure imgf000031_0001
式中：
！^为含氮、 氧和 /或硫的五元或六元杂环基， ¾代的含氮、 氧和 /或硫的五元或 六元杂环基， 或者取代或未取代的苯基， 其中， 所述取代基为选自下组中的一个或 多个： 卤素， d— 4卤代烷基或 4氯代烷氧基；
R2为 H， C C8饱和或不饱和烷基， 卤代的 d_8饱和或不饱和烷基， -CH2CH2OCH2CH3， -CH2CH2OCH3， C1-8饱和或不饱和烷氧基， 苯基， 苄基， d_4 烷基-羰基或 d— 4烷基-磺酰基；
R3和 各自独立地为 H， d_6烷基， 烯丙基， 苄基， d_4烷氧基 -C^烷基， d— 4烷氧基-羰基， 苯氧羰基， C2— 6炔基-羰基， C2— 3烯基-羰基， C3— 6环烷基-羰基， 苯甲酰基， 或者被一个或多个选自卤原子、 4烷基、 d— 4卤代烷基、 d— 4烷氧基 和 (^— 4烷基-羰基的取代基所取代的苯甲酰基， 呋喃羰基或 Ν,Ν-二甲基羰基， 或者 R3和 共同构成 -CH2-CH2-， -CH2-CH2-CH2-或 -CH2-XR-CH2-， 式中 X为杂原子，
R为杂原子上的取代基， 选自 H， d_6烷基， 烯丙基， 苄基， 苯基， d— 4烷氧基 -d— 4 烷基， d— 4烷氧基-羰基， 苯氧羰基， C2— 6炔基-羰基， C2— 3烯基-羰基， C3— 6环烷基- 羰基， 苯甲酰基， 或者被一个或多个选自卤原子、 d— 4卤代烷基、 d_8饱和或不饱 和烷基或烷氧基和 4烷基-羰基的取代基所取代的苯甲酰基， 呋喃羰基或 Ν,Ν- 二甲基羰基；
R5， R6， R7， 和 为 11， 饱和或不饱和 d_4烷基， 卤素， d_8饱和或不饱 和烷氧基， 卤代 d_4饱和或不饱和烷氧基， 4烷基-羰基， 8烷基-酯基， d— 4 烷基 -磺酸酯基， 苯基或苄基；
Y为硝基， 氰基， 三氟甲基， 三氟乙酰基或三氟甲磺酰基。
2. 如权利要求 1所述的化合物、 或者所述化合物的光学异构体、 顺反异构体 或农药学上可接受的盐， 其特征在于， 选自： 吡啶基、 噻唑基、 嘧啶基、 四氢 呋喃基、 噁唑基或其卤代物。
3. 如权利要求 1所述的化合物、 或者所述化合物的光学异构体、 顺反异构体 或农药学上可接受的盐， 其特征在于， R2为 H， d_4饱和或不饱和烷基， 卤代的 C C4饱和或不饱和烷基， 4烷基-羰基， 取代或未取代的苄基， 其中， 所述取代 基为选自下组中的一个或多个： 卤素， d— 4卤代烷基或 d— 4氯代烷氧基。
4. 如权利要求 1所述的化合物、 或者所述化合物的光学异构体、 顺反异构体 或农药学上可接受的盐， 其特征在于， R3和 为氢或 d_6烷基， 或者 R3和 共 同构成 -CH2-CH2-或 -CH2-CH2-CH2-。
5. 如权利要求 1所述的化合物、 或者所述化合物的光学异构体、 顺反异构体 或农药学上可接受的盐， 其特征在于， R5， R6， R7， 和 为 11， 饱和或不饱和 d_2烃基， 卤素， d_4饱和或不饱和烷氧基， 卤代 饱和或不饱和烷氧基， d— 4 烷基 -酯基 （RCOO-) ， d— 2烷基-磺酰酯基或三氟甲磺酰酯。
6. 如权利要求 1所述的化合物、 或者所述化合物的光学异构体、 顺反异构体 或农药学上可接受的盐， 其特征在于， Y为硝基或氰基。
7. 一种农用组合物， 它包含：
(a) 0.001-99.99重量％的权利要求 1-6中任一项所述的化合物、其光学异构体、 顺反异构体或农药学上可接受的盐、 或者它们的组合； 以及
(b) 农药学上可接受的载体和 /或赋形剂。
8. 权利要求 7所述的农用组合物的用途， 其特征在于， 用于杀灭或预防农业 害虫、 卫生害虫和危害动物健康的害虫； 或用作用于杀灭或预防农业害虫、 卫生害 虫和危害动物健康的杀虫剂组合物。
9. 权利要求 1-6中任一项所述的化合物、 其光学异构体、 顺反异构体或农药 学上可接受的盐的制备方法， 所述方法包括步骤：
在催化量酸的存在下， 于 0-60°C下， 使式 (a)化合物与式 (b；)、 （； c)或 (； d)化合物反 应， 从而制得具有式 (A；)、 (B), (C)或 (D)的化合物， 式中 R2为氢，
Figure imgf000033_0001
式中， R 、 R3、 、 R5、 R6， R7， R8， R9和 Y如权利要求 1中所定义， n为 0或 1 ,
10. 如权利要求 9所述的方法， 其特征在于， 所述方法包括步骤：
在乙腈中， 于催化量的酸存在下， 于 20-30°C下， 进行如下反应 2-24 /」 时， 从 而获得式 (A)的化合物， 式中 R2为氢：
Figure imgf000033_0002
时， 从 而获得式 (B)的化合物:
Figure imgf000033_0003
(B).
在乙腈中， 于催化量的酸存在下， 于 10-50°C下， 进行如下反应 2-24小时， 从 而获得式 (C)的化合物：
Figure imgf000033_0004
在乙腈中， 于催化量的酸存在下， 于 10-50°C下， 进行如下反应 2-24 时， 从 而获得式 (D)的化合物：
Figure imgf000033_0005
(D)。
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Cited By (108)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120245126A1 (en) * 2009-12-09 2012-09-27 East China University Of Science And Technology Divalent and oxabridged heterocyclic neonicotinoid compounds and preparation methods thereof
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WO2015091649A1 (en) 2013-12-18 2015-06-25 Basf Se N-substituted imino heterocyclic compounds
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WO2015107133A1 (de) 2014-01-20 2015-07-23 Bayer Cropscience Ag Chinolinderivate als insektizide und akarizide
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EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
US11053175B2 (en) 2015-05-12 2021-07-06 Basf Se Thioether compounds as nitrification inhibitors
US11142514B2 (en) 2015-10-02 2021-10-12 Basf Se Imino compounds with a 2-chloropyrimidin-5-yl substituent as pest-control agents
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WO2022243521A1 (en) 2021-05-21 2022-11-24 Basf Se Use of ethynylpyridine compounds as nitrification inhibitors
WO2022243523A1 (en) 2021-05-21 2022-11-24 Basf Se Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor
WO2022268810A1 (en) 2021-06-21 2022-12-29 Basf Se Metal-organic frameworks with pyrazole-based building blocks
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
WO2024028243A1 (en) 2022-08-02 2024-02-08 Basf Se Pyrazolo pesticidal compounds

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192060A1 (de) 1985-02-04 1986-08-27 Nihon Bayer Agrochem K.K. Heterocyclische Verbindungen
EP0235725A2 (de) 1986-03-07 1987-09-09 Nihon Bayer Agrochem K.K. Heterocyclische Verbindungen
EP0244777A2 (en) 1986-05-09 1987-11-11 General Electric Company Fluorescent lamp operating circuit
EP0247477A1 (de) 1986-05-30 1987-12-02 Bayer Ag 1,2,3,6-Tetrahydro-5-nitro-pyrimidin-Derivate
EP0296453A2 (de) 1987-06-26 1988-12-28 Nihon Bayer Agrochem K.K. Nitro-substituierte heterocyclische Verbindungen
EP0315826A1 (de) 1987-11-06 1989-05-17 Nihon Bayer Agrochem K.K. Imidazoline
EP0386565A1 (en) 1989-03-09 1990-09-12 Nihon Bayer Agrochem K.K. Heterocyclic compounds
EP0580553A2 (de) 1992-07-22 1994-01-26 Ciba-Geigy Ag Oxadiazinderivate
JPH07242633A (ja) 1994-03-03 1995-09-19 Ishihara Sangyo Kaisha Ltd ５−アミノエチルアミノメチル−２−クロロピリジンの製造方法
EP0685477A1 (en) 1994-06-03 1995-12-06 MITSUI TOATSU CHEMICALS, Inc. Insecticidal tetrahydrofuran-compound
JPH08259568A (ja) 1995-03-27 1996-10-08 Mitsui Toatsu Chem Inc 殺虫性テトラヒドロピリミジン誘導体
JPH08291171A (ja) 1995-04-20 1996-11-05 Mitsui Toatsu Chem Inc 殺虫性５−｛（テトラヒドロ−３−フラニル）メチル｝−４−ニトロイミノパーヒドロ−１，３，５−オキサジアジン誘導体
EP1031566A1 (de) 1999-02-26 2000-08-30 Bayer Aktiengesellschaft Verfahren zur Herstellung von 2-Chlor-5-chlormethylthiazol
WO2004056178A2 (en) * 2002-12-19 2004-07-08 Dow Agrosciences Llc Compounds useful as pesticides
WO2006056108A1 (fr) 2004-11-23 2006-06-01 East China University Of Science And Technology Derives de nitromethylene et leur utilisation
WO2007101369A1 (fr) 2006-03-09 2007-09-13 East China University Of Science And Technology Méthode de préparation et utilisation de composés présentant une action biocide

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4819934B1 (zh) * 1968-10-08 1973-06-18
UA79571C2 (en) * 2003-12-04 2007-06-25 Basf Ag Metod for the protection of seeds from soil pests comprising
CN100503585C (zh) * 2007-02-12 2009-06-24 江苏天容集团股份有限公司 第二代新烟碱类杀虫剂jt-l001及其化学合成方法
CN101492444B (zh) 2008-01-23 2012-07-04 华东理工大学 具有杀虫活性的含氮杂环化合物、其制备及用途
CN102093389B (zh) * 2009-12-09 2014-11-19 华东理工大学 双联和氧桥杂环新烟碱化合物及其制备方法

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0192060A1 (de) 1985-02-04 1986-08-27 Nihon Bayer Agrochem K.K. Heterocyclische Verbindungen
EP0235725A2 (de) 1986-03-07 1987-09-09 Nihon Bayer Agrochem K.K. Heterocyclische Verbindungen
EP0244777A2 (en) 1986-05-09 1987-11-11 General Electric Company Fluorescent lamp operating circuit
EP0247477A1 (de) 1986-05-30 1987-12-02 Bayer Ag 1,2,3,6-Tetrahydro-5-nitro-pyrimidin-Derivate
JPS62292765A (ja) 1986-05-30 1987-12-19 バイエル・アクチエンゲゼルシヤフト １，２，３，６−テトラヒドロ−５−ニトロ−ピリミジン誘導体
EP0296453A2 (de) 1987-06-26 1988-12-28 Nihon Bayer Agrochem K.K. Nitro-substituierte heterocyclische Verbindungen
EP0315826A1 (de) 1987-11-06 1989-05-17 Nihon Bayer Agrochem K.K. Imidazoline
EP0386565A1 (en) 1989-03-09 1990-09-12 Nihon Bayer Agrochem K.K. Heterocyclic compounds
EP0580553A2 (de) 1992-07-22 1994-01-26 Ciba-Geigy Ag Oxadiazinderivate
JPH07242633A (ja) 1994-03-03 1995-09-19 Ishihara Sangyo Kaisha Ltd ５−アミノエチルアミノメチル−２−クロロピリジンの製造方法
EP0685477A1 (en) 1994-06-03 1995-12-06 MITSUI TOATSU CHEMICALS, Inc. Insecticidal tetrahydrofuran-compound
JPH08259568A (ja) 1995-03-27 1996-10-08 Mitsui Toatsu Chem Inc 殺虫性テトラヒドロピリミジン誘導体
JPH08291171A (ja) 1995-04-20 1996-11-05 Mitsui Toatsu Chem Inc 殺虫性５−｛（テトラヒドロ−３−フラニル）メチル｝−４−ニトロイミノパーヒドロ−１，３，５−オキサジアジン誘導体
EP1031566A1 (de) 1999-02-26 2000-08-30 Bayer Aktiengesellschaft Verfahren zur Herstellung von 2-Chlor-5-chlormethylthiazol
WO2004056178A2 (en) * 2002-12-19 2004-07-08 Dow Agrosciences Llc Compounds useful as pesticides
WO2006056108A1 (fr) 2004-11-23 2006-06-01 East China University Of Science And Technology Derives de nitromethylene et leur utilisation
WO2007101369A1 (fr) 2006-03-09 2007-09-13 East China University Of Science And Technology Méthode de préparation et utilisation de composés présentant une action biocide

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
MICHIHIKO N. ET AL.: "Chirality Transfer in the Ene-reactions of 3-{2-(2S)- [2-(Substituted) vinyl]pyrrolidin-1-yl}-2-(sustituted)acrolein Derivatives.", TETRAHEDRON LETTERS, vol. 41, no. 44, 2000, pages 8489 - 8493, XP004236108 *
MICHIHIKO N. ET AL.: "Thermal Ene Reactions of3-(Alk-2-enyl)benzylamino -2-(methoxycarbonyl)acrolein Derivatives Leading to 4,5-Dihydro -1H- azepines.", TETRAHEDRON, vol. 56, no. 10, 2000, pages 1299 - 1307, XP004190786 *
See also references of EP2377845A4
SHAO XUSHENG ET AL.: "Divalent and Oxabridged Neonicotinoids Constructed by Dialdehydes and Nitromethylene Analogues of Imidacloprid: Design, Synthesis, Crystal Structure, and Insecticidal Activities.", J. AGRICULTURAL AND FOOD CHEMISTRY, vol. 58, no. 5, 2010, pages 2696 - 2702, XP008140274 *

Cited By (122)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2010330474B2 (en) * 2009-12-09 2015-01-29 East China University Of Science And Technology Divalent and oxabridged heterocyclic neonicotinoid compounds and preparation methods thereof
EP2511279A4 (en) * 2009-12-09 2013-05-01 Univ East China Science & Tech HETEROCOTINIC BIVALENT AND OXAPONTATED NEONICOTINIC COMPOUNDS AND PROCESSES FOR PREPARING THE SAME
US20120245126A1 (en) * 2009-12-09 2012-09-27 East China University Of Science And Technology Divalent and oxabridged heterocyclic neonicotinoid compounds and preparation methods thereof
US8809319B2 (en) * 2009-12-09 2014-08-19 East China University Of Science And Technology Substituted 8-oxa-10,11-dihydroimidazo[2,3-a]bicyclo[3.2.1]oct-3-enes and use thereof as an insecticide
WO2013156331A1 (en) 2012-04-16 2013-10-24 Basf Se Synergistic compositions comprising pyraclostrobin and an insecticidal compound
WO2014005982A1 (de) 2012-07-05 2014-01-09 Bayer Cropscience Ag Insektizide und fungizide wirkstoffkombinationen
WO2014053405A1 (en) 2012-10-01 2014-04-10 Basf Se Pesticidally active mixtures comprising anthranilamide compounds
WO2014053404A1 (en) 2012-10-01 2014-04-10 Basf Se Pesticidally active mixtures comprising anthranilamide compounds
WO2014053407A1 (en) 2012-10-01 2014-04-10 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2014053395A1 (en) 2012-10-01 2014-04-10 Basf Se Use of n-thio-anthranilamide compounds on cultivated plants
WO2014053401A2 (en) 2012-10-01 2014-04-10 Basf Se Method of improving plant health
WO2014053403A1 (en) 2012-10-01 2014-04-10 Basf Se Method of controlling insecticide resistant insects
WO2014053406A1 (en) 2012-10-01 2014-04-10 Basf Se Method of controlling ryanodine-modulator insecticide resistant insects
WO2014079820A1 (en) 2012-11-22 2014-05-30 Basf Se Use of anthranilamide compounds for reducing insect-vectored viral infections
WO2014090700A1 (en) 2012-12-14 2014-06-19 Basf Se Malononitrile compounds for controlling animal pests
US10117430B2 (en) 2012-12-14 2018-11-06 Basf Se Malononitrile compounds for controlling animal pests
WO2014102244A1 (en) 2012-12-27 2014-07-03 Basf Se 2-(pyridin-3-yl)-5-hetaryl-thiazole compounds carrying an imine or imine-derived substituent for combating invertebrate pests
CN104054726A (zh) * 2013-03-20 2014-09-24 上海生农生化制品有限公司 苯氧威和环氧虫啶杀虫组合物
CN104054726B (zh) * 2013-03-20 2018-10-26 上海生农生化制品股份有限公司 苯氧威和环氧虫啶杀虫组合物
WO2014170300A1 (en) 2013-04-19 2014-10-23 Basf Se N-substituted acyl-imino-pyridine compounds and derivatives for combating animal pests
WO2014202751A1 (en) 2013-06-21 2014-12-24 Basf Se Methods for controlling pests in soybean
WO2015007682A1 (en) 2013-07-15 2015-01-22 Basf Se Pesticide compounds
WO2015040116A1 (en) 2013-09-19 2015-03-26 Basf Se N-acylimino heterocyclic compounds
WO2015055554A1 (de) 2013-10-14 2015-04-23 Bayer Cropscience Ag Wirkstoff für die saatgut- und bodenbehandlung
US9776967B2 (en) 2013-10-14 2017-10-03 Bayer Animal Health Gmbh Carboxamide derivatives as pesticidal compounds
WO2015055497A1 (en) 2013-10-16 2015-04-23 Basf Se Substituted pesticidal pyrazole compounds
EP3456201A1 (en) 2013-10-18 2019-03-20 BASF Agrochemical Products B.V. Use of pesticidal active carboxamide derivative in soil and seed application and treatment meth-ods
WO2015055757A1 (en) 2013-10-18 2015-04-23 Basf Se Use of pesticidal active carboxamide derivative in soil and seed application and treatment methods
WO2015059088A1 (de) 2013-10-23 2015-04-30 Bayer Cropscience Ag Substituierte chinoxalin-derivate als schädlingsbekämpfungsmittel
WO2015091649A1 (en) 2013-12-18 2015-06-25 Basf Se N-substituted imino heterocyclic compounds
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WO2015104422A1 (en) 2014-01-13 2015-07-16 Basf Se Dihydrothiophene compounds for controlling invertebrate pests
WO2015107133A1 (de) 2014-01-20 2015-07-23 Bayer Cropscience Ag Chinolinderivate als insektizide und akarizide
WO2015169776A1 (en) 2014-05-08 2015-11-12 Bayer Cropscience Ag Pyrazolopyridine sulfonamides as nematicides
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WO2016008830A1 (de) 2014-07-15 2016-01-21 Bayer Cropscience Aktiengesellschaft Aryl-triazolyl-pyridine als schädlingsbekämpfungsmittel
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WO2016071499A1 (en) 2014-11-06 2016-05-12 Basf Se 3-pyridyl heterobicyclic compound for controlling invertebrate pests
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US10701937B2 (en) 2015-02-11 2020-07-07 Basf Se Pesticidal mixture comprising a pyrazole compound, an insecticide and a fungicide
WO2016128261A2 (en) 2015-02-11 2016-08-18 Basf Se Pesticidal mixture comprising a pyrazole compound, an insecticide and a fungicide
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US11053175B2 (en) 2015-05-12 2021-07-06 Basf Se Thioether compounds as nitrification inhibitors
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WO2017016883A1 (en) 2015-07-24 2017-02-02 Basf Se Process for preparation of cyclopentene compounds
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WO2017198588A1 (en) 2016-05-18 2017-11-23 Basf Se Capsules comprising benzylpropargylethers for use as nitrification inhibitors
WO2018013381A1 (en) 2016-07-11 2018-01-18 Covestro Llc, Et Al. Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds
WO2018013380A1 (en) 2016-07-11 2018-01-18 Covestro Llc, Et Al. Methods for treating seeds with an aqueous compostion and seeds treated therewith
WO2018013382A1 (en) 2016-07-11 2018-01-18 Covestro Llc, Et Al Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds
WO2018108671A1 (en) 2016-12-16 2018-06-21 Basf Se Pesticidal compounds
WO2018162312A1 (en) 2017-03-10 2018-09-13 Basf Se Spirocyclic derivatives
WO2018166855A1 (en) 2017-03-16 2018-09-20 Basf Se Heterobicyclic substituted dihydroisoxazoles
WO2018177781A1 (en) 2017-03-28 2018-10-04 Basf Se Pesticidal compounds
EP3978504A1 (en) 2017-03-31 2022-04-06 Basf Se Chiral 2,3-dihydrothiazolo[3,2-a]pyrimidine derivatives for combating animal pests
WO2018177970A1 (en) 2017-03-31 2018-10-04 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
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WO2018197466A1 (en) 2017-04-26 2018-11-01 Basf Se Substituted succinimide derivatives as pesticides
WO2018206479A1 (en) 2017-05-10 2018-11-15 Basf Se Bicyclic pesticidal compounds
WO2018224455A1 (en) 2017-06-07 2018-12-13 Basf Se Substituted cyclopropyl derivatives
WO2018229202A1 (en) 2017-06-16 2018-12-20 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2018234202A1 (en) 2017-06-19 2018-12-27 Basf Se SUBSTITUTED PYRIMIDINIUM COMPOUNDS AND DERIVATIVES FOR CONTROLLING HARMFUL ANIMALS
WO2018234488A1 (en) 2017-06-23 2018-12-27 Basf Se SUBSTITUTED CYCLOPROPYL DERIVATIVES
WO2019007888A1 (de) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Insektizide wirkstoffkombinationen
WO2019007891A1 (de) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Insektizide wirkstoffkombinationen
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se METHOD FOR CONTROLLING RICE PARASITES IN RICE
WO2019043183A1 (en) 2017-08-31 2019-03-07 Basf Se METHOD FOR CONTROLLING PESTS OF RICE IN RICE
EP3453706A1 (en) 2017-09-08 2019-03-13 Basf Se Pesticidal imidazole compounds
WO2019072906A1 (en) 2017-10-13 2019-04-18 Basf Se IMIDAZOLIDINE PYRIMIDINIUM COMPOUNDS FOR CONTROL OF HARMFUL ANIMALS
US11401271B2 (en) 2017-11-03 2022-08-02 South China Agricultural University Fused heterocyclic compound, pyrazole-ring-containing fused heterocyclic compound, agricultural composition containing thereof, and method of using the composition
WO2019086009A1 (zh) 2017-11-03 2019-05-09 华南农业大学 含氮稠合三环化合物及其作为农林业杀虫剂的应用
WO2019121143A1 (en) 2017-12-20 2019-06-27 Basf Se Substituted cyclopropyl derivatives
WO2019121159A1 (en) 2017-12-21 2019-06-27 Basf Se Pesticidal compounds
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WO2019145140A1 (en) 2018-01-09 2019-08-01 Basf Se Silylethynyl hetaryl compounds as nitrification inhibitors
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WO2019175713A1 (en) 2018-03-14 2019-09-19 Basf Corporation New catechol molecules and their use as inhibitors to p450 related metabolic pathways
WO2019185413A1 (en) 2018-03-27 2019-10-03 Basf Se Pesticidal substituted cyclopropyl derivatives
WO2019211106A1 (en) 2018-04-30 2019-11-07 Basf Se Control of pests of soybean plants with mesoionic compounds
WO2019219529A1 (en) 2018-05-15 2019-11-21 Basf Se Mixtures comprising benzpyrimoxan and oxazosulfyl and uses and methods of applying them
WO2019224092A1 (en) 2018-05-22 2019-11-28 Basf Se Pesticidally active c15-derivatives of ginkgolides
WO2020002472A1 (en) 2018-06-28 2020-01-02 Basf Se Use of alkynylthiophenes as nitrification inhibitors
WO2020020765A1 (en) 2018-07-23 2020-01-30 Basf Se Use of a substituted thiazolidine compound as nitrification inhibitor
WO2020020777A1 (en) 2018-07-23 2020-01-30 Basf Se Use of substituted 2-thiazolines as nitrification inhibitors
EP3613736A1 (en) 2018-08-22 2020-02-26 Basf Se Substituted glutarimide derivatives
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
WO2020064408A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
WO2020064492A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof
WO2020064480A1 (en) 2018-09-28 2020-04-02 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
EP3643705A1 (en) 2018-10-24 2020-04-29 Basf Se Pesticidal compounds
WO2020083733A1 (en) 2018-10-24 2020-04-30 Basf Se Pesticidal compounds
WO2020109039A1 (en) 2018-11-28 2020-06-04 Basf Se Pesticidal compounds
WO2020126591A1 (en) 2018-12-18 2020-06-25 Basf Se Substituted pyrimidinium compounds for combating animal pests
EP3696177A1 (en) 2019-02-12 2020-08-19 Basf Se Heterocyclic compounds for the control of invertebrate pests
WO2020239517A1 (en) 2019-05-29 2020-12-03 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3766879A1 (en) 2019-07-19 2021-01-20 Basf Se Pesticidal pyrazole derivatives
WO2021013561A1 (en) 2019-07-19 2021-01-28 Basf Se Pesticidal pyrazole and triazole derivatives
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2022162129A1 (en) 2021-01-28 2022-08-04 Rhodia Operations Method for treating rice seed with improved retention of agrochemical, micronutrient and colorant
WO2022167488A1 (en) 2021-02-02 2022-08-11 Basf Se Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors
WO2022243521A1 (en) 2021-05-21 2022-11-24 Basf Se Use of ethynylpyridine compounds as nitrification inhibitors
WO2022243523A1 (en) 2021-05-21 2022-11-24 Basf Se Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor
WO2022268810A1 (en) 2021-06-21 2022-12-29 Basf Se Metal-organic frameworks with pyrazole-based building blocks
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
WO2024028243A1 (en) 2022-08-02 2024-02-08 Basf Se Pyrazolo pesticidal compounds

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US8563546B2 (en) 2013-10-22
RU2011129408A (ru) 2013-01-27
BRPI0918359B1 (pt) 2018-11-06
AU2009328851C1 (en) 2012-12-06
IL213656A0 (en) 2011-07-31
KR101392296B1 (ko) 2014-05-07
US20110269751A1 (en) 2011-11-03
EP2377845B1 (en) 2015-01-28
EP2377845A4 (en) 2012-12-26
JP5771150B2 (ja) 2015-08-26
EP2377845A1 (en) 2011-10-19
RU2495023C2 (ru) 2013-10-10
IL213656A (en) 2015-11-30
JP2012512191A (ja) 2012-05-31
KR20110097970A (ko) 2011-08-31
AU2009328851B2 (en) 2012-04-05
BRPI0918359A2 (pt) 2015-12-15
AU2009328851A1 (en) 2011-08-04
CN101747320A (zh) 2010-06-23

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