WO2010124619A1 - 1,2,3-3h pyridine heterocyclic compounds, their agricultural compositions, their use and their preparation methods - Google Patents

1,2,3-3h pyridine heterocyclic compounds, their agricultural compositions, their use and their preparation methods Download PDF

Info

Publication number
WO2010124619A1
WO2010124619A1 PCT/CN2010/072232 CN2010072232W WO2010124619A1 WO 2010124619 A1 WO2010124619 A1 WO 2010124619A1 CN 2010072232 W CN2010072232 W CN 2010072232W WO 2010124619 A1 WO2010124619 A1 WO 2010124619A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alkyl
compound
formula
substituted
Prior art date
Application number
PCT/CN2010/072232
Other languages
French (fr)
Chinese (zh)
Inventor
李忠
钱旭红
张文文
徐晓勇
邵旭升
陶黎明
宋恭华
Original Assignee
华东理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 华东理工大学 filed Critical 华东理工大学
Publication of WO2010124619A1 publication Critical patent/WO2010124619A1/en

Links

Classifications

    • 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
    • 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
    • A01N43/72—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
    • 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
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • 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
    • 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
    • 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
    • C07D471/02—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 two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the invention relates to a novel neonicotinoid-like 1,2,3-3H pyridine heterocyclic insecticide, a preparation method thereof and a use thereof.
  • Ri is a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a substituted or unsubstituted phenyl group, Wherein the substituent is one or more selected from the group consisting of halogen, d- 4 haloalkyl or d- 4 chloroalkoxy;
  • R 2 are each independently H, d_ 6 alkyl, d_ 6 alkoxy, allyl, benzyl, d_ 4 alkoxy -d_ 4 alkyl, d- 4 alkoxy - carbonyl group, a phenoxycarbonyl group , C 2 - 6 alkynyl group - carbonyl group, C 2 - 3 alkenyl - carbonyl group, a cycloalkyl - carbonyl, benzoyl, or substituted with one or more substituents selected from halogen atoms, d- 4-alkyl, d- 4 haloalkoxy a benzoyl group, a furanylcarbonyl group or a hydrazine, a fluorenyl-dimethylcarbonyl group substituted with a substituent of a d- 4 alkoxy group and an alkyl-carbonyl group;
  • R 2 and R 3 together form -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - or -CH 2 -ZR-CH 2 -, wherein Z is a hetero atom
  • R is a substituent on a hetero atom selected from H, d- 6 alkyl, d- 6 alkoxy, allyl, benzyl, phenyl, d- 4 alkoxy-d- 4 alkyl, d- 4 alkoxy - carbonyl group, a phenoxycarbonyl group, an alkynyl group - carbonyl group, C 2 - 3 alkenyl - carbonyl group, C 3 - 6 cycloalkyl - carbonyl, benzoyl, or substituted with one or more substituents selected from halogen atoms, d a 4- haloalkyl group, a d- 8 saturated or unsaturated alkyl group or a d- 8 alkoxy group and a 4- alkyl-carbonyl substituent substituted with a benzoyl group, a furanylcarbonyl group or a hydrazine, a fluorenyl-dimethylcarbonyl group; I
  • R 5 is phenyl, or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group, a substituted five- or six-membered heterocyclic ring containing nitrogen, oxygen and/or sulfur a substituted or unsubstituted C 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, d- 6 halogenated alkyl, hydroxy d_ 6 alkyl, hydroxy, d- 6 alkoxy, d- 6 haloalkoxy, amine, d- 6 alkylamino, unsubstituted or having 1-3 selected from d- 6 alkyl, nitro, cyano, halogen a substituted phenyl group having a substituent of a hydroxyl group or an amino group;
  • a phenyl group or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group, a substituted five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, Or a substituted or unsubstituted C 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, d- 6 halogenated alkyl, hydroxy d- 6 alkyl Alkyl, hydroxy, d- 6 alkoxy, d- 6 alkoxy, amino, d- 6 alkylamino, unsubstituted or having 1-3 selected from d- 6 alkyl, nitro, cyano, halogen, hydroxy Or a substituted phenyl group of an amine substituent;
  • R 7 and each independently H or d 6 alkyl, d 6 alkoxy, or d 6 alkyl or d 6 alkoxy substituted by F, Cl, Br;
  • X is cyano, nitro, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl
  • ⁇ ⁇ 2 are each independently hydrogen, nitro, cyano, ester, trifluoroacetyl, acetyl, trifluoromethanesulfonyl, amide, trifluoromethyl or R 9 , wherein Where Ri, R 2 , R 3 are as defined above.
  • ⁇ 1 and ⁇ 2 are not equal to 11.
  • Preferred examples are nitro, cyano, ester, trifluoroacetyl, acetyl, trifluoromethanesulfonyl, amide or trifluoromethyl; and Y 2 is hydrogen, cyano, ester, or R 9 .
  • R 2 and R 3 together form -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - ; -CH 2 -ZR-CH 2 -, wherein Z is N, 0 a hetero atom such as S, and R is a d- 6 alkyl group or alkoxy group on a hetero atom.
  • the compound has a structure selected from the group consisting of:
  • Ri R 2 , R 3 , , R 5 , Re, R 7 , R 9 and X are as defined above,
  • ⁇ is 0 or 1.
  • ⁇ is 0.
  • R 2 R 3 is H or d 6 alkyl; allyl, benzyl, alkoxyalkyl having 2 to 4 C, alkoxycarbonyl having 1 to 3 C, phenoxycarbonyl, band 1 -6 C alkynylcarbonyl groups, having 2 to 3 C alkenylcarbonyl groups, having 3 to 6 C cycloalkylcarbonyl groups, benzoyl groups, or substituted benzoyl groups, furanylcarbonyl groups, anthracene, fluorene- Dimethylcarbonyl; or R 2 and R 3 together form -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - - ;
  • X is a nitro group or a cyano group
  • R 5 a phenyl group or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, Or a substituted or unsubstituted c 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, hydroxy d- 6 alkyl, hydroxy, d_ 6 alkoxy, amino, D_ 6 alkyl group, a substituted and unsubstituted phenyl;
  • n 0 or 1
  • R 7 is H or d 6 alkyl and alkoxy, or alkyl and alkoxy substituted by F Cl Br;
  • R 9 is Wherein Ri, R 2 R 3 R4 are as defined above.
  • it is selected from the group consisting of pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, oxazolyl, or a halogenated (halo group) thereof.
  • it is a halogenated pyridyl group, a halogenated thiazolyl group, a halogenated pyrimidinyl group, a halogenated tetrahydrofuranyl group, or a halogenated oxazolyl group, and more preferably, the halogenated substance is Chloride.
  • R is -
  • R 2 and R 3 are independently hydrogen or alkyl, H or d 6 alkyl, and R 7 is hydrogen or d- 6 .
  • R 2 and R 3 are independently hydrogen or d- 3- alkyl, preferably hydrogen, methyl or ethyl.
  • D_ 3 is hydrogen or alkyl, preferably hydrogen, methyl or ethyl,
  • R 7 is hydrogen or d_ 3 alkyl, preferably hydrogen or methyl, more preferably hydrogen.
  • R 5 is selected from the group consisting of: substituted or unsubstituted phenyl, furyl, thienyl, pyrrolyl, imidazolyl, thiazolyl, or oxazolyl.
  • R 5 is a substituted or unsubstituted furyl, thienyl or pyrrolyl group, preferably
  • Ri R 2 R 3 R 5 Re R 7 R 8 R 9 X Yi and/or Y 3 in the formula are specific groups as shown in Tables 1-4.
  • the compound is a compound 1-286 as shown in Tables 1-4.
  • a pesticide composition comprising:
  • component (a) comprises from 0.001 to 99.9% by weight, preferably from 0.05 to 90% by weight, of the insecticidal composition.
  • the agricultural composition is used to kill or prevent agricultural pests, sanitary pests, and pests that are harmful to animal health. More preferably, it is used to kill pests selected from the group consisting of Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Isoptera, or Diptera, preferably Isoptera or Lepidoptera.
  • the pest has a sucking or sucking mouthpart.
  • Representative pests are aphids, planthoppers, whiteflies, spider mites, thrips, cotton bollworm, cabbage caterpillar, diamondback moth, Spodoptera litura, or armyworm.
  • the insecticide further comprises other active substances selected from the group consisting of: insecticides, bait, fungicides, acaricides, nematicides, fungicides or Growth control agent.
  • the invention also provides the use of the agricultural composition described 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.
  • a pesticidal and/or pest control method comprising applying a compound of the invention or a pesticide composition containing the compound to a plant body that suffers or may suffer from pests , the soil around it or the environment.
  • a compound of the invention an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, or a combination thereof, in the preparation of an agricultural composition (especially an insecticide) Use in the composition).
  • a compound of the invention an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, or a combination thereof, for insecticidal and/or pest control.
  • the compound of the formula (a) is subjected to an addition reaction with the compound of the formula (b) in an inert solvent to obtain a compound having the formula (I) or (II); or the addition reaction of the formula (a) itself is carried out.
  • a compound of the general formula (III) or (IV) is obtained.
  • R 2 , R 3 , , R 5 , Re, R 7 , X, n, Yi and Y 3 are as defined above.
  • the compound has a structure represented by the formula (I), ( ⁇ ), ( ⁇ ), or (IV), and the preparation method thereof comprises the following steps:
  • n is 0 or 1.
  • the addition reaction is carried out at 10-50 ° C, preferably 20-30 ° C.
  • the solvent used is selected from the group consisting of: acetonitrile, dichloromethane, preferably dichloromethane.
  • reaction time for the addition reaction of the compound of the formula (I) and ( ⁇ ) is 1-4 hours, and the addition reaction of the compounds of the formula (II) and (IV) is carried out.
  • the reaction time is 2-24 hours.
  • the inventors have introduced an aromatic heterocyclic ring on the nitromethylene group of the existing nitromethylene-based neonicotinoid insecticide by a long-term and in-depth study, and shifted the double bond.
  • a novel 1,2,3-3H pyridine ring was obtained by addition reaction, and a new type of neonicotinoid compound was synthesized by changing the structure common in neonicotinoid compounds.
  • the insecticidal activity of the compound was very good. On this basis, the inventors have completed the present invention.
  • d- 6 hydrocarbyl refers to an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, etc. having from 1 to 6 carbon atoms containing only carbon or hydrogen saturated or unsaturated.
  • a group preferably an alkyl, alkenyl or alkynyl group.
  • alkenyl refers to a straight or branched alkenyl group having 2 to 6 carbon atoms, such as ethenyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butene Or a similar group
  • alkynyl refers to a straight or branched alkynyl group having 2 to 6 carbon atoms, such as ethynyl, propynyl, and the like
  • cycloalkyl refers to cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl
  • 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, sec-butyl, tert
  • d- 6 alkoxy refers to a straight or branched alkoxy group having from 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutylene.
  • 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. "halogenated” includes partially halogenated and Fully halogenated.
  • C 5 -12 aryl refers to a monocyclic to tricyclic aromatic hydrocarbon group such as phenyl, naphthyl, or the like.
  • aralkyl refers to a d- 6 alkyl group substituted by the above aryl group.
  • five- or six-membered heterocyclic group refers to a five- or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, such as pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, or Azolyl and the like.
  • the compounds of the invention can be synthesized by the reaction steps as described previously.
  • the compounds of the present invention may also be conveniently prepared by combining various synthetic methods described in the specification or known in the art, and such combinations are readily made by those skilled in the art to which the present invention pertains.
  • each reaction is usually carried out in an inert solvent at a temperature of from -20 ° C to the reflux temperature of the solvent (preferably from -10 to 80 t.
  • the reaction time is usually from 0.1 to 72 hours, preferably from 0.5 to 1). 48 hours.
  • the compound of formula (I) can be prepared by the following reaction:
  • a compound of the formula ( ⁇ ) can be prepared by the following reaction:
  • the compound of formula (IV) can be prepared by the following reaction:
  • 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, and public health pests.
  • insecticide is a general term for substances having the action of controlling all the pests mentioned above.
  • 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 having 1, 2, 3 A 3 pyridine pyridine heterocyclic structure having significant insecticidal activity, and/or an expanded insecticidal spectrum.
  • agrochemically 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.
  • the acid addition salts formed from the compounds of the formula ( ⁇ ) include salts formed with inorganic acids, such as hydrochlorides, phosphates, sulfates, nitrates; and salts formed from organic acids, such as acetates. , 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, and public health pests.
  • the pests which can be killed by the compounds of the present invention are not particularly limited, and examples of representative pests include, but are not limited to, coleopteran insects such as Sitophilus zeamais, Tribolium castaneum, and potato ladybugs (Henosepilachna vigintioctomaculata).
  • 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 containing the active substance of the present invention
  • 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, in polypolymers Microcapsules, coatings for seeds, and preparations for use with burning devices, such as smoked cans, 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/or A dispersant and/or a foam former.
  • 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 an auxiliary.
  • an organic solvent can also be used as an auxiliary.
  • a liquid solvent When a liquid solvent is used as the diluent or carrier, it is basically suitable, such as: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride Or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffin, such as mineral oil; alcohols such as ethanol or ethylene glycol and their ethers and lipids; ketones such as acetone, methyl ethyl ketone, methyl Butyl ketone or cyclohexanone; or less common polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride Or methylene
  • a diluent or carrier for a liquefied gas it is meant a liquid which will become a gas at normal temperature and pressure, such as an aerosol propellant such as a halogenated hydrocarbon and butane, propane, nitrogen and carbon dioxide.
  • Solid supports can be used on the ground for natural minerals 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 granules, and organic materials such as sawdust, coconut shell, Corn cobs and granules of tobacco stems.
  • Emulsified columns of nonionic and anionic ions can be used as emulsifiers and/or foam formers.
  • 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 added to the formulation.
  • Colorants such as inorganic dyes such as iron oxide, oxidized diamond 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 added. , cobalt, aluminum and zinc salts, etc.
  • active compounds of the invention can be used in admixture with other active compounds.
  • active compounds include insecticides, baits, fungicides, acaricides, nematicides, fungicides, growth control agents and the like.
  • Insecticides include, for example, phosphates, carbamates, pyrethrins, chlorinated hydrocarbons, benzoylureas, nematotoxins, and substances produced by microorganisms such as avermectin.
  • the active compounds of the invention may also be used in admixture with synergists.
  • 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.
  • These formulations usually comprise from 0.0001 to 99.99% by weight, preferably from 0.001 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.
  • the concentration of the active compound in the dosage form prepared from the commercial preparation can be varied within a wide range. move.
  • the concentration of active compound in the dosage form used may range from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1%.
  • Example 14 The procedures of Examples 1-12 were repeated except that different starting materials were selected according to the structure of the compounds shown in Tables 1-4, thereby preparing compounds 1-286 (the compounds which have been prepared in Examples 1-12 are not repeated). preparation;).
  • Example 14 The procedures of Examples 1-12 were repeated except that different starting materials were selected according to the structure of the compounds shown in Tables 1-4, thereby preparing compounds 1-286 (the compounds which have been prepared in Examples 1-12 are not repeated). preparation;).
  • Example 14 Example 14
  • Aphids belong to Homoptera pests and have a sucker, which is a common crop pest.
  • the soybean meal ( / ⁇ craccivora) was used as the test object and tested by the dipping method.
  • Operation process Accurately weigh various samples, add ⁇ , ⁇ -dimethylformamide to make 10g/L mother liquor, and dilute it to 500 ug/mL with 0.2mL/L Triton X-100 aqueous solution. concentration. After the wingless mites are stably sucked on the bean sprouts, they are immersed in the medicinal solution with a concentration of 500 ug/mL together with the bean sprouts, and taken out after 5 s. The excess liquid is sucked up with absorbent paper, and transferred to a clean vessel and kept at a constant temperature of 23 °C. . Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.2 mL/L Triton X-100. After 24 hours of treatment, the number of dead insects tested was counted and the mortality (;%;) was calculated.
  • Mortality (%) (control live number - number of live insects) / number of live insects X 100% (2): Insecticidal activity against armyworm
  • the following components were prepared in proportion: 25% by weight of the compound 1-424; 5% polyoxyethylene sorbitol hexaoleate; 70% higher aliphatic hydrocarbon oil.
  • the components were ground together in a sanding mill until the solid particles fell below about 5 microns.
  • the resulting viscous suspension can be used as it is, but it can also be used after emulsification in water.
  • the following components were prepared in proportion: 25% of the compound 1-424; 3% hydrate attapulgit; 10% calcium lignosulfonate; 0.5% sodium dihydrogen phosphate; 61.5% water.
  • the components were ground together in a ball mill until the solid particles fell below about 10 microns. This aqueous suspension can be used directly.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Veterinary Medicine (AREA)
  • Tropical Medicine & Parasitology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

N-containing heterocyclic compounds of general formula (A), or optical isomers, cis-trans isomers or agriculturally acceptable salts thereof are disclosed. Meanwhile, the agricultural compositions containing said compounds and the use of the agricultural compositions are also disclosed.

Description

1，2，3-3H吡啶杂环化合物、 其农用组合物、 用途及制备方法 技术领域  1,2,3-3H pyridine heterocyclic compound, agricultural composition thereof, use and preparation method
本发明涉及一种类新烟碱类的 1,2,3-3H吡啶杂环新型杀虫剂、 及其制备方法和用途。 技术背景  The invention relates to a novel neonicotinoid-like 1,2,3-3H pyridine heterocyclic insecticide, a preparation method thereof and a use thereof. technical background
在过去的三十多年， 新烟碱类杀虫剂的发现是杀虫剂研究领域里程碑式的革新。 20世 纪 80年代中期拜耳公司开发出第一个新烟碱类杀虫剂吡虫啉， 成为最成功的新型杀虫剂之 一。 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 (欧洲专利 247477、 296453、 685477、 235725、 235725、 315826、 192060、 244777、 0386565、 580553、和 1031566， 日本专利 62292765、 8259568、 8291 171、和 7242633)。  Over the past three decades, the discovery of neonicotinoid insecticides has been a milestone in the field of pesticide research. In the mid-1980s, Bayer developed the first neonicotinoid insecticide imidacloprid, making it one of the most successful new insecticides. 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 (European patents 247477, 296453, 685477, 235725, 235725). , 315826, 192060, 244777, 0386565, 580553, and 1031566, Japanese Patent Nos. 62229765, 8259568, 8291 171, and 7242633).
但是由于吡虫啉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。 因此， 本领域迫切需要对硝基亚甲基化合物 进行结构改造， 以产生新的、 更有效的杀虫剂， 从而解决新烟碱类杀虫剂的抗性问题。 发明内容  However, due to the resistance problems of imidacloprid and the interaction resistance between neonicotinoid insecticides due to structural similarity, the application of such compounds is limited to some extent. Therefore, there is an urgent need in the art to structurally modify nitromethylene compounds to produce new, more effective insecticides to address the resistance of neonicotinoid insecticides. Summary of the invention
本发明目的在于， 提供一类高效的防治害虫的化合物及其制备方法。 本发明的第一方面，提供了一种具有通式 (A)所示结构的化合物、或所述化合物的光学 构体、 顺反异构体或农药学上可接受的盐：
Figure imgf000003_0001
It is an object of the present invention to provide a class of highly effective pest control compounds and methods for their preparation. According to a first aspect of the invention, there is provided a compound having the structure of the formula (A), or an optical, cis or agrochemically acceptable salt of the compound:
Figure imgf000003_0001
通式 (A)  General formula (A)
式中：  In the formula:
Ri为含氮、 氧和 /或硫的五元或六元杂环基， 或卤代的含氮、 氧和 /或硫的五元或六元 杂环基， 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 d— 4 氯代烷氧基； Ri is a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a substituted or unsubstituted phenyl group, Wherein the substituent is one or more selected from the group consisting of halogen, d- 4 haloalkyl or d- 4 chloroalkoxy;
R2和 各自独立地为 H， d_6烷基， d_6烷氧基， 烯丙基， 苄基， 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， 环烷基-羰基， 苯甲酰基， 或者被一个或多个选自卤原子、 d— 4烷基、 d— 4卤代烷基、 d— 4烷氧基和 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； And R 2 are each independently H, d_ 6 alkyl, d_ 6 alkoxy, allyl, benzyl, d_ 4 alkoxy -d_ 4 alkyl, d- 4 alkoxy - carbonyl group, a phenoxycarbonyl group , C 2 - 6 alkynyl group - carbonyl group, C 2 - 3 alkenyl - carbonyl group, a cycloalkyl - carbonyl, benzoyl, or substituted with one or more substituents selected from halogen atoms, d- 4-alkyl, d- 4 haloalkoxy a benzoyl group, a furanylcarbonyl group or a hydrazine, a fluorenyl-dimethylcarbonyl group substituted with a substituent of a d- 4 alkoxy group and an alkyl-carbonyl group;
或者 R2和 R3共同构成 -CH2-CH2-， -CH2-CH2-CH2-或 -CH2-ZR-CH2-， 式中 Z为杂原子，Or R 2 and R 3 together form -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - or -CH 2 -ZR-CH 2 -, wherein Z is a hetero atom,
R 为杂原子上的取代基， 选自 H， d_6烷基， d_6烷氧基， 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， 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 d_8 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； 为 H， 饱和或不饱和 d_6烃基， 卤代的饱和或不饱和 d_6烃基， 饱和或不饱和 d_6烷 氧基；在在 R is a substituent on a hetero atom selected from H, d- 6 alkyl, d- 6 alkoxy, allyl, benzyl, phenyl, d- 4 alkoxy-d- 4 alkyl, d- 4 alkoxy - carbonyl group, a phenoxycarbonyl group, an alkynyl group - carbonyl group, C 2 - 3 alkenyl - carbonyl group, C 3 - 6 cycloalkyl - carbonyl, benzoyl, or substituted with one or more substituents selected from halogen atoms, d a 4- haloalkyl group, a d- 8 saturated or unsaturated alkyl group or a d- 8 alkoxy group and a 4- alkyl-carbonyl substituent substituted with a benzoyl group, a furanylcarbonyl group or a hydrazine, a fluorenyl-dimethylcarbonyl group; Is H, saturated or unsaturated d- 6 hydrocarbon, halogenated saturated or unsaturated d- 6 hydrocarbon, saturated or unsaturated d- 6 alkoxy;
另另为  Another
R5为苯基， 或为含氮、 氧和 /或硫的五元或六元杂环基， 或取代的苯基， 取代的含氮、 氧和 /或硫的五元或六元杂环基， 或取代或未取代的 C5_12杂芳基， 其中所述取代基为选自下 组中的一个或多个： 卤素、 硝基、 d_6烷基、 d_6卤代烷基、 羟基 d_6烷基、 羟基、 d_6烷氧 基、 d_6卤代烷氧基、 胺基、 d_6烷基胺基、 未取代或具有 1-3个选自 d_6烷基、 硝基、 氰基、 卤素、 羟基或胺基的取代基的取代的苯基； R 5 is phenyl, or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group, a substituted five- or six-membered heterocyclic ring containing nitrogen, oxygen and/or sulfur a substituted or unsubstituted C 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, d- 6 halogenated alkyl, hydroxy d_ 6 alkyl, hydroxy, d- 6 alkoxy, d- 6 haloalkoxy, amine, d- 6 alkylamino, unsubstituted or having 1-3 selected from d- 6 alkyl, nitro, cyano, halogen a substituted phenyl group having a substituent of a hydroxyl group or an amino group;
为苯基， 或为含氮、 氧和 /或硫的五元或六元杂环基， 或取代的苯基， 取代的含氮、 氧和 /或硫的五元或六元杂环基， 或取代或未取代的 C5_12杂芳基， 其中所述取代基为选自下 组中的一个或多个： 卤素、 硝基、 d_6烷基、 d_6卤代烷基、 羟基 d_6烷基、 羟基、 d_6烷氧 基、 d_6卤代烷氧基、 胺基、 d_6烷基胺基、 未取代或具有 1-3个选自 d_6烷基、 硝基、 氰基、 卤素、 羟基或胺基的取代基的取代的苯基； a phenyl group, or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group, a substituted five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, Or a substituted or unsubstituted C 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, d- 6 halogenated alkyl, hydroxy d- 6 alkyl Alkyl, hydroxy, d- 6 alkoxy, d- 6 alkoxy, amino, d- 6 alkylamino, unsubstituted or having 1-3 selected from d- 6 alkyl, nitro, cyano, halogen, hydroxy Or a substituted phenyl group of an amine substituent;
R7和 各自独立地为 H或 d_6烷基， d_6烷氧基， 或者被 F， Cl， Br取代的 d_6烷基或 d_6 烷氧基； R 7 and each independently H or d 6 alkyl, d 6 alkoxy, or d 6 alkyl or d 6 alkoxy substituted by F, Cl, Br;
X为氰基， 硝基， 三氟甲基， 三氟乙酰基或三氟甲磺酰基；  X is cyano, nitro, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl;
Υ ΒΥ2各自独立地为氢、 硝基， 氰基， 酯基， 三氟乙酰基， 乙酰基， 三氟甲磺酰基， 酰胺基、 三氟甲基或 R9， 其中
Figure imgf000004_0001
, 其中 Ri, R2， R3， 如上所定义。 Υ ΒΥ 2 are each independently hydrogen, nitro, cyano, ester, trifluoroacetyl, acetyl, trifluoromethanesulfonyl, amide, trifluoromethyl or R 9 , wherein
Figure imgf000004_0001
Where Ri, R 2 , R 3 are as defined above.
类优选例中 ¥1和¥2不同时为11。 In the preferred example of the class, ¥ 1 and ¥ 2 are not equal to 11.
类优选例中 为硝基， 氰基， 酯基， 三氟乙酰基， 乙酰基， 三氟甲磺酰基， 酰胺基或三氟甲基； 而 Y2为氢， 氰基， 酯基， 或 R9。 Preferred examples are nitro, cyano, ester, trifluoroacetyl, acetyl, trifluoromethanesulfonyl, amide or trifluoromethyl; and Y 2 is hydrogen, cyano, ester, or R 9 .
在另一类优选例中， R2和 R3共同构成 -CH2-CH2-或 -CH2-CH2-CH2-; -CH2-ZR-CH2-, 其 中 Z为 N， 0， S等杂原子， R是杂原子上的 d_6烷基或烷氧基。 In another preferred embodiment, R 2 and R 3 together form -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - ; -CH 2 -ZR-CH 2 -, wherein Z is N, 0 a hetero atom such as S, and R is a d- 6 alkyl group or alkoxy group on a hetero atom.
在另一类优选例中， 所述化合物具有选自以下通式的结构:  In another preferred embodiment, the compound has a structure selected from the group consisting of:
Figure imgf000004_0002
Figure imgf000004_0002
Ri R2、 R3、 、 R5、 Re、 R7、 R9和 X如上所定义， Ri R 2 , R 3 , , R 5 , Re, R 7 , R 9 and X are as defined above,
为硝基， 氰基， 酯基， 三氟乙酰基， 乙酰基， 三氟甲磺酰基， 酰胺基、或三氟甲基; Y3为硝基， 氰基或酯基； Is nitro, cyano, ester, trifluoroacetyl, acetyl, trifluoromethanesulfonyl, amide or trifluoromethyl; Y 3 is nitro, cyano or ester;
η为 0或 1。  η is 0 or 1.
在另一个优选例中， η为 0。  In another preferred embodiment, η is 0.
在另一个优选例中， 为11。  In another preferred embodiment, it is 11.
在另一类优选例中， 所述通式中：  In another preferred embodiment, in the formula:
为未取代或卤代的含氮、 氧和 /或硫的五元或六元杂环基； R2 R3为 H或 d_6烷基； 烯丙基， 苄基， 带 2-4个 C的烷氧基烷基， 带 1-3个 C的烷氧基 羰基， 苯氧羰基， 带 1-6个 C的炔基羰基， 带 2-3个 C的烯基羰基， 带 3-6个 C的环烷基羰基， 苯甲酰基，或取代的苯甲酰基，呋喃羰基， Ν,Ν-二甲基羰基；或者 R2和 R3共同构成 -CH2-CH2- 或 -CH2-CH2-CH2-; An unsubstituted or halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur; R 2 R 3 is H or d 6 alkyl; allyl, benzyl, alkoxyalkyl having 2 to 4 C, alkoxycarbonyl having 1 to 3 C, phenoxycarbonyl, band 1 -6 C alkynylcarbonyl groups, having 2 to 3 C alkenylcarbonyl groups, having 3 to 6 C cycloalkylcarbonyl groups, benzoyl groups, or substituted benzoyl groups, furanylcarbonyl groups, anthracene, fluorene- Dimethylcarbonyl; or R 2 and R 3 together form -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - ;
为 H d_6饱和或不饱和烷基， 卤代的 d_6饱和或不饱和烷基， d_6饱和或不饱和烷 Is H d 6 saturated or unsaturated alkyl, halogenated d 6 saturated or unsaturated alkyl, d 6 saturated or unsaturated alkyl
X为硝基或氰基； X is a nitro group or a cyano group;
R5， 为苯基或为含氮、 氧和 /或硫的五元或六元杂环基， 或取代的苯基或含氮、 氧 和 /或硫的五元或六元杂环基， 或取代或未取代的 c5_12杂芳基， 其中所述取代基为选自下组 中的一个或多个： 卤素、 硝基、 d_6烷基、 羟基 d_6烷基、 羟基、 d_6烷氧基、 胺基、 d_6 烷基胺基、 取代及未取代的苯基； R 5 , a phenyl group or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, Or a substituted or unsubstituted c 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, hydroxy d- 6 alkyl, hydroxy, d_ 6 alkoxy, amino, D_ 6 alkyl group, a substituted and unsubstituted phenyl;
n为 0或 1  n is 0 or 1
R7为 H或 d_6烷基及烷氧基， 或被 F Cl Br取代的烷基及烷氧基； R 7 is H or d 6 alkyl and alkoxy, or alkyl and alkoxy substituted by F Cl Br;
R9为
Figure imgf000005_0001
中 Ri, R2 R3 R4如上所定义。 R 9 is
Figure imgf000005_0001
Wherein Ri, R 2 R 3 R4 are as defined above.
在另一类优选例中， 选自： 吡啶基、 噻唑基、 嘧啶基、 四氢呋喃基、 噁唑基， 或其 卤代物 (卤代基团)。  In another preferred embodiment, it is selected from the group consisting of pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, oxazolyl, or a halogenated (halo group) thereof.
在另一类优选例中， 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， 更优选地， 所述卤代物为氯代物。 在另一类优选例中， R为—
Figure imgf000005_0002
In another preferred embodiment, it is a halogenated pyridyl group, a halogenated thiazolyl group, a halogenated pyrimidinyl group, a halogenated tetrahydrofuranyl group, or a halogenated oxazolyl group, and more preferably, the halogenated substance is Chloride. In another preferred form, R is -
Figure imgf000005_0002
在另一类优选例中， R2和 R3独立地为氢或 烷基， 为 H或 d_6烷基， R7为氢或 d_6 院基。 In another preferred embodiment, R 2 and R 3 are independently hydrogen or alkyl, H or d 6 alkyl, and R 7 is hydrogen or d- 6 .
在另一类优选例中， R2和 R3独立地为氢或 d_3烷基， 优选氢、 甲基或乙基。 为氢或 d_3烷基， 优选氢、 甲基或乙基， R7为氢或 d_3烷基， 优选氢或甲基， 更优选氢。 In another preferred embodiment, R 2 and R 3 are independently hydrogen or d- 3- alkyl, preferably hydrogen, methyl or ethyl. D_ 3 is hydrogen or alkyl, preferably hydrogen, methyl or ethyl, R 7 is hydrogen or d_ 3 alkyl, preferably hydrogen or methyl, more preferably hydrogen.
在另一类优选例中， R5选自： 取代或未取代的苯基， 呋喃基， 噻吩基， 吡咯基， 咪唑 基， 噻唑基， 或噁唑基。 在一个优选例中， R5为取代或未取代的呋喃基、噻吩基或吡咯基，优选
Figure imgf000005_0003
In another preferred embodiment, R 5 is selected from the group consisting of: substituted or unsubstituted phenyl, furyl, thienyl, pyrrolyl, imidazolyl, thiazolyl, or oxazolyl. In a preferred embodiment, R 5 is a substituted or unsubstituted furyl, thienyl or pyrrolyl group, preferably
Figure imgf000005_0003
Figure imgf000005_0004
Figure imgf000005_0004
在另一类优选例中， 所述通式中 Ri R2 R3 R5 Re R7 R8 R9 X Yi和 / 或 Y3是如表 1-4中所示的具体基团。 In another preferred embodiment, Ri R 2 R 3 R 5 Re R 7 R 8 R 9 X Yi and/or Y 3 in the formula are specific groups as shown in Tables 1-4.
在另一类优选例中， 所述的化合物是表 1-4中所示的化合物 1-286  In another preferred embodiment, the compound is a compound 1-286 as shown in Tables 1-4.
应理解， 上述优选基团可相互组合以形成本发明的各种优选化合物。  It will be understood that the above preferred groups may be combined with one another to form the various preferred compounds of the invention.
在本发明的第二方面， 提供了一种杀虫剂组合物， 其包含：  In a second aspect of the invention, there is provided a pesticide composition comprising:
(a)0.00001-99.99 重量％本发明第一方面的化合物、其光学异构体、顺反异构体或农药 学上可接受的盐、 或它们的组合； 以及 (b)农药学上可接受的载体和 /或赋形剂。  (a) 0.00001 to 99.99% by weight of the compound of the first aspect of the invention, an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, or a combination thereof; and (b) an agrochemically acceptable Carrier and / or excipient.
在一个优选例中， 组分 (a)占杀虫剂组合物的 0.001-99.9重量％， 优选 0.05-90重量％。 在另一类优选例中， 所述农用组合物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。 更佳地， 用于杀灭选自下组的害虫： 鞘翅目、 鳞翅目、 半翅目、 直翅目、 等 翅目、 或双翅目昆虫， 优选等翅目或鳞翅目昆虫。 In a preferred embodiment, component (a) comprises from 0.001 to 99.9% by weight, preferably from 0.05 to 90% by weight, of the insecticidal composition. In another preferred embodiment, the agricultural composition is used to kill or prevent agricultural pests, sanitary pests, and pests that are harmful to animal health. More preferably, it is used to kill pests selected from the group consisting of Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Isoptera, or Diptera, preferably Isoptera or Lepidoptera.
在另一类优选例中， 所述害虫具有剌吸式或锉吸式口器。代表性的害虫为蚜虫、飞虱、 粉虱、 叶蝉、 蓟马、 棉铃虫、 菜青虫、 小菜蛾、 斜纹夜蛾、 或粘虫。  In another preferred embodiment, the pest has a sucking or sucking mouthpart. Representative pests are aphids, planthoppers, whiteflies, spider mites, thrips, cotton bollworm, cabbage caterpillar, diamondback moth, Spodoptera litura, or armyworm.
在另一类优选例中， 所述杀虫剂还包含其它活性物质， 所述其它活性物质选自： 杀虫 齐 u、 合饵、 杀菌剂、 杀螨剂、 杀线虫剂、 杀真菌剂或生长控制剂。  In another preferred embodiment, the insecticide further comprises other active substances selected from the group consisting of: insecticides, bait, fungicides, acaricides, nematicides, fungicides or Growth control agent.
本发明还提供了所述的农用组合物的用途， 它被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。  The invention also provides the use of the agricultural composition described 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.
在本发明的第三方面中， 提供了一种杀虫和 /或防虫方法， 所述方法包括将本发明化合 物或含有所述化合物的杀虫剂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。  In a third aspect of the invention, there is provided a pesticidal and/or pest control method, the method comprising applying a compound of the invention or a pesticide composition containing the compound to a plant body that suffers or may suffer from pests , the soil around it or the environment.
在本发明的第四方面中， 提供了本发明化合物、 其光学异构体、 顺反异构体或农药学 上可接受的盐、 或它们的组合在制备农用组合物 (尤其是杀虫剂组合物)中的用途。  In a fourth aspect of the invention, there is provided a compound of the invention, an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, or a combination thereof, in the preparation of an agricultural composition (especially an insecticide) Use in the composition).
还提供了本发明化合物、 其光学异构体、 顺反异构体或农药学上可接受的盐、 或它们 的组合在杀虫和 /或防虫中的用途。  Also provided is the use of a compound of the invention, an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, or a combination thereof, for insecticidal and/or pest control.
在本发明的第五方面， 提供了本发明化合物、 其光学异构体、 顺反异构体或农药学上 可接受的盐的制备方法， 所述方法包括步骤：  In a fifth aspect of the invention, there is provided a process for the preparation of a compound of the invention, an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, the process comprising the steps of:
在惰性溶剂中， 使式 (a)的化合物与式 (b)的化合物发生加成反应从而制得具有通式 (I) 或 (II)的化合物； 或者使式 (a)自身发生加成反应从而制得具有通式 (III)或 (IV)的化合物.  The compound of the formula (a) is subjected to an addition reaction with the compound of the formula (b) in an inert solvent to obtain a compound having the formula (I) or (II); or the addition reaction of the formula (a) itself is carried out. Thus to obtain a compound of the general formula (III) or (IV).
Figure imgf000006_0001
式 (a) 式 (b)，
Figure imgf000006_0001
Formula (a), formula (b),
式中， R2、 R3、 、 R5、 Re、 R7、 X、 n、 Yi 和 Y3如上所定义。 Wherein R 2 , R 3 , , R 5 , Re, R 7 , X, n, Yi and Y 3 are as defined above.
在另一类优选例中， 所述化合物具有通式 (I), (Π), (ΙΠ)， 或 (IV)所示的结构， 且其制备 方法包括以下步骤：  In another preferred embodiment, the compound has a structure represented by the formula (I), (Π), (ΙΠ), or (IV), and the preparation method thereof comprises the following steps:
在二氯甲烷中， 进行如下反应， 从而获得通式 (I)的化合物：  In dichloromethane, the following reaction is carried out to obtain a compound of the formula (I):
Figure imgf000006_0002
通式 (I) 在二氯甲烷中， 进行如下反应， 从而获得通式 (Π)的化合物：
Figure imgf000006_0002
The compound of the formula (I) is subjected to the following reaction in dichloromethane to obtain a compound of the formula (Π):
Figure imgf000006_0003
通式 (II) 在二氯甲烷中 进行如下反应， 从而获得通式 (III)的化合物:
Figure imgf000006_0003
General formula (II) The following reaction is carried out in dichloromethane to obtain a compound of the formula (III):
Figure imgf000007_0001
Figure imgf000007_0001
在二氯甲烷中 ， 进行如下反应， 从而获得通式 (IV)的化合物:  In dichloromethane, the following reaction is carried out to obtain a compound of the formula (IV):
Figure imgf000007_0002
Figure imgf000007_0002
通式 (IV)。  General formula (IV).
在另一类优选例中， n为 0或 1。  In another preferred embodiment, n is 0 or 1.
在另一类优选例中， 所述的加成反应在 10-50°C， 较佳地 20-30°C下进行。  In another preferred embodiment, the addition reaction is carried out at 10-50 ° C, preferably 20-30 ° C.
在另一类优选例中， 所用的溶剂选自： 乙腈， 二氯甲烷， 优选二氯甲烷。  In another preferred embodiment, the solvent used is selected from the group consisting of: acetonitrile, dichloromethane, preferably dichloromethane.
在另一类优选例中， 制得通式化合物 (I)和 (Π)的加成反应的反应时间为 1-4小时， 而制 得通式化合物 (II)和 (IV)的加成反应的反应时间为 2-24小时。  In another preferred embodiment, the reaction time for the addition reaction of the compound of the formula (I) and (Π) is 1-4 hours, and the addition reaction of the compounds of the formula (II) and (IV) is carried out. The reaction time is 2-24 hours.
应理解， 在本发明范围内中， 本发明的上述各技术特征和在下文 (如实施例)中具体描 述的各技术特征可以互相组合， 从而构成新的或优选的技术方案。 限于篇幅， 在此不再一 一累述。 具体实施方式  It is to be understood that within the scope of the present invention, the above various technical features of the present invention and the technical features specifically described hereinafter (as in the embodiments) may be combined with each other to constitute a new or preferred technical solution. Due to space limitations, we will not repeat them here. detailed description
本发明人通过长期而深入的研究， 在现有的硝基亚甲基类新烟碱杀虫剂的硝基亚甲基 上引入芳杂环， 并使双键移位， 在此基础之上通过加成反应得到新的 1,2,3-3H吡啶环， 改 变新烟碱类化合物中常见的结构， 合成了一类新型的类新烟碱化合物， 该化合物的杀虫活 性非常良好。 在此基础上， 发明人完成了本发明。 基团定义  The inventors have introduced an aromatic heterocyclic ring on the nitromethylene group of the existing nitromethylene-based neonicotinoid insecticide by a long-term and in-depth study, and shifted the double bond. A novel 1,2,3-3H pyridine ring was obtained by addition reaction, and a new type of neonicotinoid compound was synthesized by changing the structure common in neonicotinoid compounds. The insecticidal activity of the compound was very good. On this basis, the inventors have completed the present invention. Group definition
如本文所用， 术语 "d_6烃基"是指具有 1-6个碳原子的烷基、 烯基、 炔基、 环烷基、 环烯基、 芳基等仅含碳、 氢的饱和或不饱和基团， 优选烷基、 烯基或炔基。 术语 "烯基" 指具有 2-6个碳原子的直链或支链的烯基， 例如乙烯基、 烯丙基、 1-丙烯基、 异丙烯基、 1- 丁烯基、 2-丁烯基、或类似基团； 术语"炔基"是指具有 2-6个碳原子的直链或支链的炔基， 例如乙炔基、 丙炔基等； 术语 "环烷基"指环丙基、 环丁基、 环戊基、 环己基、 或环庚基 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。 As used herein, the term "d- 6 hydrocarbyl" refers to an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, etc. having from 1 to 6 carbon atoms containing only carbon or hydrogen saturated or unsaturated. A group, preferably an alkyl, alkenyl or alkynyl group. The term "alkenyl" refers to a straight or branched alkenyl group having 2 to 6 carbon atoms, such as ethenyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butene Or a similar group; the term "alkynyl" refers to a straight or branched alkynyl group having 2 to 6 carbon atoms, such as ethynyl, propynyl, and the like; the term "cycloalkyl" refers to cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl As used herein, the term "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, sec-butyl, tert-butyl, or the like.
术语 " d_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。 The term "d- 6 alkoxy" refers to a straight or branched alkoxy group having from 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutylene. An oxy group, a sec-butoxy group, a tert-butoxy group, or the like.
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。 "卤代 "包括部分卤代和 全卤代。 The term "halogen" means fluoro, chloro, bromo, or iodo. The term "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. "halogenated" includes partially halogenated and Fully halogenated.
术语" C5_12芳基"指单环至三环的芳族烃基， 例如苯基、 萘基、 或类似基团。 术语"芳 烷基"指被上述芳基取代的 d_6烷基。 The term "C 5 -12 aryl" refers to a monocyclic to tricyclic aromatic hydrocarbon group such as phenyl, naphthyl, or the like. The term "aralkyl" refers to a d- 6 alkyl group substituted by the above aryl group.
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  The term "five- or six-membered heterocyclic group" refers to a five- or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, such as pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, or Azolyl and the like. Method for preparing compounds of the invention
本发明化合物可通过如前所描述的反应步骤合成。本发明化合物还可以任选将在本说 明书中描述的或本领域已知的各种合成方法组合起来而方便的制得， 这样的组合可由本发 明所属领域的技术人员容易的进行。  The compounds of the invention can be synthesized by the reaction steps as described previously. The compounds of the present invention may also be conveniently prepared by combining various synthetic methods described in the specification or known in the art, and such combinations are readily made by those skilled in the art to which the present invention pertains.
在本发明的制备方法中， 各反应通常在惰性溶剂中， 在 -20°C至溶剂回流温度 (优选 -10 至 80t 下进行。 反应时间通常为 0.1小时〜 72小时， 较佳地为 0.5〜48小时。  In the production method of the present invention, each reaction is usually carried out in an inert solvent at a temperature of from -20 ° C to the reflux temperature of the solvent (preferably from -10 to 80 t. The reaction time is usually from 0.1 to 72 hours, preferably from 0.5 to 1). 48 hours.
在本发明的一个具体实施方式中， 通式 (I)化合物的合成方法如下：  In a specific embodiment of the invention, the synthesis of the compound of formula (I) is as follows:
Figure imgf000008_0001
Figure imgf000008_0001
在本发明其它具体实施方式中， 通式 (II)化合物的合成方法如下:  In other embodiments of the invention, the synthesis of the compound of formula (II) is as follows:
Figure imgf000008_0002
Figure imgf000008_0002
在本发明其它具体实施方式中， 通式 (II)化合物的合成方法如下：
Figure imgf000009_0001
In other embodiments of the invention, the synthesis of the compound of formula (II) is as follows:
Figure imgf000009_0001
在本发明其它具体实施万式中， 通式 (IV)化合物的合成万法如下:  In other specific embodiments of the present invention, the synthesis of the compound of the formula (IV) is as follows:
Figure imgf000009_0002
Figure imgf000009_0002
在上述反应流程中的式 (a)和式 (b)的化合物， 可按文献或专利中的现有方法制得。 The compounds of the formula (a) and the formula (b) in the above reaction scheme can be obtained by a conventional method in the literature or the patent.
在一个具体实施方式中， 通式 (I)的化合物可通过下列反应制备：  In a specific embodiment, the compound of formula (I) can be prepared by the following reaction:
(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；  (1) Add an appropriate amount of acetonitrile to the aqueous solution of acetamine, add 6-chloro-3-chloromethylpyridine in acetonitrile to the ice bath, and follow the progress of TLC. After the reaction, add a large amount of water to the reaction mixture. Extracting with dichloromethane, drying, suction filtration, evaporation of solvent to give an oily liquid N-(6-chloropyridine-3-methylene;
(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；  (2) N-(6-chloropyridine-3-methylene)ethylamine and 1,1-dithiomethyl-2-nitroethylene, using ethanol as solvent, refluxing for 4-8 hours, concentration, column Chromatographic separation of the product N-(6-chloropyridine-3-methylene;)-N-ethyl-1-thiomethyl-2-nitrovinylideneamine;
(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 4-8h， 浓缩， 柱层析分离得到得到 N-(6-氯吡啶 -3-亚甲基;) -N-乙基 -Ν'- 甲基 -2-硝基亚乙烯基二胺；  (3) N-(6-chloropyridine-3-methylene)-N-ethyl-1-thiomethyl-2-nitrovinylideneamine and methylamine solution, using ethanol as solvent, in ice The reaction is carried out in a bath for 4-8 h, concentrated, and separated by column chromatography to give N-(6-chloropyridine-3-methylene;)-N-ethyl-indole-methyl-2-nitrovinylidene Amine
(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糠醛在酸 (盐酸、 硫 酸、 杂多酸等)催化条件下， 得到 Ν-(6-氯吡啶 -3-亚甲基) -Ν-乙基 -3- (呋喃 -2-基) -Ν'-甲基 -2- 硝基亚乙烯基二胺。  (4) Ν-(6-chloropyridine-3-methylene)-Ν-ethyl-Ν'-methyl-2-nitrovinylidene diamine and furfural in acid (hydrochloric acid, sulfuric acid, heteropolyacid Under the catalytic conditions, Ν-(6-chloropyridine-3-methylene)-fluorenyl-ethyl-3-(furan-2-yl)-Ν'-methyl-2-nitrovinylidene Diamine.
(5)丙二腈与醛， 以乙醇作溶剂， 加入哌啶作催化剂， 室温反应， 过滤得到化合物 (b) (5) Malononitrile and aldehyde, using ethanol as solvent, adding piperidine as a catalyst, reacting at room temperature, and filtering to obtain compound (b)
(6) N-(6-氯吡啶 -3-亚甲基) -N-乙基 -3- (呋喃 -2-基) -Ν'-甲基 -2-硝基亚乙烯基二胺 (a)与化 合物 (b)在二氯甲烷中反应， 柱层析得到所述通式的化合物 (1)。 (6) N-(6-chloropyridine-3-methylene)-N-ethyl-3-(furan-2-yl)-indole-methyl-2-nitrovinylidene diamine (a Reaction with compound (b) in dichloromethane, column chromatography to give compound (1) of the formula.
在另一实施方式中， 通式 (Π)的化合物可通过下列反应制备：  In another embodiment, a compound of the formula (Π) can be prepared by the following reaction:
2-氯 -5-《2-(2- (呋喃 -2-基) -1-硝基乙烯基) -4,5-二氢咪唑烷 -1-基)甲基)吡啶与化合物 (b)在 二氯甲烷中反应得到所述通式的化合物 (11)。 在另一实施方式中， 通式 (in)的化合物可通过下列反应制备： 2-Chloro-5-"2-(2-(furan-2-yl)-1-nitrovinyl)-4,5-dihydroimidazolidine-1-yl)methyl)pyridine and compound (b) The compound (11) of the above formula is obtained by reaction in dichloromethane. In another embodiment, the compound of formula (in) can be prepared by the following reaction:
N-(6-氯吡啶 -3-亚甲基) -N-乙基 -3- (呋喃 -2-基) -Ν'-甲基 -2-硝基亚乙烯基二胺在二氯甲烷 中反应得到所述通式的化合物 (III)。  N-(6-chloropyridine-3-methylene)-N-ethyl-3-(furan-2-yl)-indole-methyl-2-nitrovinylidene diamine in dichloromethane The reaction gives the compound (III) of the above formula.
在另一实施方式中， 通式 (IV)的化合物可通过下列反应制备：  In another embodiment, the compound of formula (IV) can be prepared by the following reaction:
-氯 -5-((2-(2- (呋喃 -2-基) -1-硝基乙烯基) -4,5-二氢咪唑烷 -1-基)甲基)吡啶在二氯甲烷中 反应得到所述通式的化合物 (IV；)。 本发明活性物质的杀虫活性  -Chloro-5-((2-(2-(furan-2-yl)-1-nitrovinyl)-4,5-dihydroimidazolidine-1-yl)methyl)pyridine in dichloromethane The reaction gives the compound of the formula (IV;). Insecticidal activity of the active substance of the present invention
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、 以及公 共卫生害虫等。  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, and public health pests.
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。 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 1,2,3-3Η吡啶杂环结构， 其具有显著的 杀虫活性， 和 /或扩大的杀虫谱。  In the present specification, "insecticide" is a general term for substances having the action of controlling all the pests mentioned above. The term "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 having 1, 2, 3 A 3 pyridine pyridine heterocyclic structure having significant insecticidal activity, and/or an expanded insecticidal spectrum.
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 (Α)的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、 以及公共卫生害虫等。  The term "agrochemically 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. Suitably, the acid addition salts formed from the compounds of the formula (Α) include salts formed with inorganic acids, such as hydrochlorides, phosphates, sulfates, nitrates; and salts formed from organic acids, such as acetates. , 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, and public health pests.
可用本发明化合物杀灭的害虫没有特别限制， 代表性的害虫的例子包括但不限于： 鞘 翅目昆虫， 如玉米象 (Sitophilus zeamais) , 赤拟谷盗 (Tribolium castaneum), 马铃薯瓢虫 (Henosepilachna vigintioctomaculata)， 二十 、星票瓜虫 (Henosepilachna sparsa) , 细月匈叩头虫 (Agriotes fuscicollis), 红 HP绿金龟 (Anomala cupripes), 四纹丽金龟 (Popillia quadriguttata), 马铃薯叶甲 (Monolepta hieroglyphica)， 松天牛 (Monochamus alternatus)， 稻根象 20 (Echinocnemus squameus),泡桐叶甲 (Basiprionota bisignata),星天牛 (Anoplophora chinensis), 桑天牛 (Apripona germari), 脐腹小蠹 (Scolytus schevy), 或细胸金针虫 (Agriotes fhscicollis); 鳞翅目昆虫， 如舞毒娥 (Lymantria dispar), 天幕毛虫 (Malacosoma neustria testacea), 黄杨绢 里予螟 (Diaphania perspectalis), 大袋蛾 (Clania variegata), 黄朿 lj蛾 (Cnidocampa flauescens), 马 尾松毛虫 (Dendrolimus punctatus)， 古毒蛾 (Orgyia gono stigma)， 白杨透翅蛾 (Paranthrenetabaniformis) , 斜纹夜蛾 (Spodoptera litura), 二化螟 (Chilo suppressalis), 玉米螟 (Ostrinia nubilalis) , 粉斑螟 (Ephestia cautella) , 棉卷蛾 (Adoxophyes orana) , 栗子小卷蛾 (laspyresia splendana), 小地老虎 (Agrotis fUcosa), 大錯螟 (Galleriamellonella), 菜蛾 (Plutella xylostella), 桔潜蛾 (Phyllocnistis citrella), 或东方粘虫 (Mythimna separata); 同翅目昆虫， 如 黑尾叶蝉 (Nephotettix cincticeps), 稻褐飞 H(Nilaparvata lugens), 康氏粉蚧 (Pseudococcus comstocki), 矢尖阶 (Unaspisyanonensis), 桃虫牙 (Myzus persicae), 棉虫牙 (Aphis gossydii), 萝卜 虫牙 (Lipaphis erysimipseudobrassicae), 梨班网蝽 (Stephanitis nashi), 或粉風 (Bemisia tabaci); 直翅目昆虫， 如德国小蠊 (Blattella germanica), 美国大蠊 (Periplaneta american), 非洲蝼蛄 (Gryllotalpa africana) , 或亚洲飞蝗 (Locus migratoria) ; 5 ； 等翅目昆虫， 如入侵红火蚁 (Solenopsis invicta) , 或家白蚁 (Coptotermes formosanus)； 双翅目昆虫， 如家螞 (Musca domestica), 埃及伊蚊 (Aedes aegypti), 种蝇 (Delia platura), 库蚊 (Culex sp.)， 或中华按蚊 (Anopheles sinensis); 危害动物健康的害虫， 如微小牛蜱 (Boophilus microplus), 长角血蜱 (Haemaphysalis longicornis) , 小亚璃目艮蜱 10 (Hyalomma anatolicum) , 牛皮 !fe黾 (Hypoderma spp.)， 肝片吸虫 (Fasciola hepatica) , 贝氏莫尼茨绦虫 (Moniezia blanchard) , 奥斯特线虫 (Ostertagia spp.), 原虫 (Trypanosoma enansi, Babesia bigemina)等。 The pests which can be killed by the compounds of the present invention are not particularly limited, and examples of representative pests include, but are not limited to, coleopteran insects such as Sitophilus zeamais, Tribolium castaneum, and potato ladybugs (Henosepilachna vigintioctomaculata). ), 20, Henosepilachna sparsa, Agriotes fuscicollis, Anomala cupripes, Popillia quadriguttata, Monolepta hieroglyphica, Monochamus alternatus, Echinocnemus squameus, Basiprionota bisignata, Anoplophora chinensis, Apripona germari, Scolytus schevy, Or Agopiaes fhscicollis; Lepidoptera, such as Lymantria dispar, Malacosoma neustria testacea, Diaphania perspectalis, Clania variegata, yellow Nilj moth (Cnidocampa flauescens), Dendrolimus punctatus, Orgyia gono stigma, white poplar (Paranthrenetabaniformis), Spodoptera litura, Chilo suppressalis, Ostrinia nubilalis, Ephestia cautella, Adoxophyes orana, laspyresia splendana ), Agrotis fUcosa, Galleriamellonella, Plutella xylostella, Phyllocnistis citrella, or Mythimna separata; Homoptera, such as the black-tailed leaf Pho (Nephotettix cincticeps), Nilaparvata lugens, Pseudococcus comstocki, Unaspisyanonensis, Myzus persicae, Aphis gossydii, Lipaphis erysimipseudobrassicae ), Stephanitis nashi, or Bemisia tabaci; Orthoptera, such as Blattella germanica, Periplaneta american, Gryllotalpa africana, or Asia Locus migratoria; 5; Isoptera, such as Solenopsis invicta, or Coptotermes formosanus; Diptera, House ant (Musca domestica), Aedes aegypti (Aedes aegypti), species of flies (Delia platura), mosquitoes (Culex sp.), Or Anopheles (Anopheles sinensis); pests that are harmful to animal health, such as Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, cowhide! fe黾 (Hypoderma spp.) , Fasciola hepatica, Moniezia blanchard, Ostertagia spp., Trypanosoma enansi, Babesia bigemina, and the like.
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  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
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， 泡沫剂， 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 装置一块使用的制剂， 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 /或分散剂和 /或泡沫形成剂。 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， 例如矿物油熘分； 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 30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。就液化气的稀释剂或载体说， 指的是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 /或泡沫形成剂。 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。  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, in polypolymers Microcapsules, coatings for seeds, and preparations for use with burning devices, such as smoked cans, smoked cans and smokers, as well as ULV cold mist and hot fog (Warm Mist) formulation. These preparations 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/or A dispersant and/or a foam former. For example, when water is used as an extender, an organic solvent can also be used as an auxiliary. When a liquid solvent is used as the diluent or carrier, it is basically suitable, such as: aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride Or methylene chloride; aliphatic hydrocarbons such as cyclohexane or paraffin, such as mineral oil; alcohols such as ethanol or ethylene glycol and their ethers and lipids; ketones such as acetone, methyl ethyl ketone, methyl Butyl ketone or cyclohexanone; or less common polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. In the case of a diluent or carrier for a liquefied gas, it is meant a liquid which will become a gas at normal temperature and pressure, such as an aerosol propellant such as a halogenated hydrocarbon and butane, propane, nitrogen and carbon dioxide. Solid supports can be used on the ground for natural minerals 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 granules, and organic materials such as sawdust, coconut shell, Corn cobs and granules of tobacco stems. Emulsified columns of nonionic and anionic ions can be used as emulsifiers and/or foam formers. For example, polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and white Protein hydrolysate. Dispersing agents include, for example, lignin sulfite waste liquid and methyl cellulose.
在制剂中可以添加粘合剂， 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。可以添加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。  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 added to the formulation. Colorants such as inorganic dyes such as iron oxide, oxidized diamond 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 added. , cobalt, aluminum and zinc salts, etc.
本发明的这些活性化合物可与其他活性化合物混合使用。 这些其他的活性化合物包括 杀虫剂， 合饵， 杀菌剂， 杀螨剂， 杀线虫剂， 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。  These active compounds of the invention can be used in admixture with other active compounds. These other active compounds include insecticides, baits, fungicides, acaricides, nematicides, fungicides, growth control agents and the like. Insecticides include, for example, phosphates, carbamates, pyrethrins, chlorinated hydrocarbons, benzoylureas, nematotoxins, and substances produced by microorganisms such as avermectin.
此外， 本发明的这些活性化合物也可与增效剂混合使用。 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 0.0001-99.99 重量％， 优选 0.001-99.9重量％， 更优选 0.05-90 重量％的本发明 的活性化合物。 从商品制剂制成的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 0.0000001-100%(g/v)， 最好在 0.0001 与 1%之间。 实施例 Furthermore, the active compounds of the invention may also be used in admixture with synergists. 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. These formulations usually comprise from 0.0001 to 99.99% by weight, preferably from 0.001 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. The concentration of the active compound in the dosage form prepared from the commercial preparation can be varied within a wide range. move. The concentration of active compound in the dosage form used may range from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1%. Example
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。  The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually in accordance with conventional conditions or according to the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated.
实施例 1. 6-(((6-氯吡啶 -3-基)甲基) (乙基)氨基) -4- (呋喃 -2-基) -1-甲基 -5-硝基 -2-(4-硝基 苯基) -1,2-二氢吡啶 -3,3(4H)-二腈 (化合物 31 )的合成  Example 1. 6-(((6-chloropyridin-3-yl)methyl)(ethyl)amino)-4-(furan-2-yl)-1-methyl-5-nitro-2- Synthesis of (4-Nitrophenyl)-1,2-dihydropyridine-3,3(4H)-dicarbonitrile (Compound 31)
Figure imgf000012_0001
Figure imgf000012_0001
将 0.766g(0.0022mol)的 N-((6-氯吡啶 -3-基）甲基) -N-乙基 -3- (呋喃 -2-基) -Ν'-甲基 -2-硝基 丙烯脒， 20ml的二氯甲烷， 0.398g(0.002mol)的 2-(4-硝基苯乙烯基)丙二腈置于 50ml的圆底 烧瓶中。 常温下搅拌 2h后， 停止反应， 将溶剂旋干， 柱层析得到化合物 31的纯品， 为淡黄 色固体 0.590g， 产率约 50.7%。  0.766 g (0.0022 mol) of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-3-(furan-2-yl)-indole-methyl-2-nitro Propylene oxime, 20 ml of dichloromethane, 0.398 g (0.002 mol) of 2-(4-nitrostyryl)malononitrile were placed in a 50 ml round bottom flask. After stirring at room temperature for 2 hours, the reaction was quenched, and the solvent was evaporated to dryness to give crystals of compound 31 as a pale yellow solid, 0.590 g, yield: 50.7%.
1H MR (400 Mz, OMSO-d6): δ 8.38 (d, J= 2.4 Hz ,2H), 8.37 (s, 1H), 7.89 (d, J= 8.4 Hz, 2H), 7.85 (m , 1H), 7.71 (d, J = 1.2 Hz, 1H), 7.51 (d, J= 8.0Hz, 1H), 6.55 (dd, Ji= 1.6 Hz, J2 = 3.2 Hz, 1H), 6.49(d, J= 3.6 Hz, 1H), 5.70 (s, 1H), 5.11 (s, 1H), 4.52 (q, Ji= 7.2 Hz, J2 = 14.0Hz, 1H), 4.45 (d, J = 14.0 Hz, 1H), 4.10 (d, J = 14.0 Hz, 1H), 3.31(q, Ji= 7.2 Hz, J2 = 14.0Hz, 1H), 3.16 (s, 3H), 1.20 (t, J= 7.2 Hz, 3H) ppm; 13C NMR (100 Mz, DMSO- 6): δ 157.4, 149.9, 149.5, 149.2, 148.1 144.8, 139.8, 139.0, 131.7, 130.8, 124.7, 124.5, 112.6, 112.6, 111.4, 111.3, 99.2, 55.6, 49.0, 48.2, 46.3, 43.8, 42.1, 13.9ppm; HRMS (ES+) 计算值 C26H23N705 35C1 (M+H)+, 548.1392; 测得值， 548.1401. 计算值 C26H23N705 37C1 (M+H)+, 550.1363; 测得值， 550.1347。 实施例 2. 6-(((6-氯吡啶 -3-基)甲基) (乙基)氨基) -1-甲基 -5-硝基 -2-(4-硝基苯基) -4-(1Η-吡 咯 -2-基) -1,2,二氢吡啶 -3,3(4Η)-二腈 (化合物 32 )的合成 1H MR (400 Mz, OMSO-d 6 ): δ 8.38 (d, J = 2.4 Hz , 2H), 8.37 (s, 1H), 7.89 (d, J = 8.4 Hz, 2H), 7.85 (m , 1H) , 7.71 (d, J = 1.2 Hz, 1H), 7.51 (d, J= 8.0Hz, 1H), 6.55 (dd, Ji= 1.6 Hz, J 2 = 3.2 Hz, 1H), 6.49(d, J= 3.6 Hz, 1H), 5.70 (s, 1H), 5.11 (s, 1H), 4.52 (q, Ji= 7.2 Hz, J 2 = 14.0 Hz, 1H), 4.45 (d, J = 14.0 Hz, 1H), 4.10 (d, J = 14.0 Hz, 1H), 3.31 (q, Ji = 7.2 Hz, J 2 = 14.0 Hz, 1H), 3.16 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H) ppm; 13 C NMR (100 Mz, DMSO- 6 ): δ 157.4, 149.9, 149.5, 149.2, 148.1 144.8, 139.8, 139.0, 131.7, 130.8, 124.7, 124.5, 112.6, 112.6, 111.4, 111.3, 99.2, 55.6, 49.0, 48.2 , 46.3, 43.8, 42.1, 13.9ppm; HRMS (ES+) calcd for C 2 6H 23 N 7 0 5 35 C1 (M+H) + , 548.1392; Measured value, 548.1401. Calculated value C 2 6H 23 N 7 0 5 37 C1 (M+H) + , 550.1363; measured value, 550.1347. Example 2. 6-(((6-chloropyridin-3-yl)methyl)(ethyl)amino)-1-methyl-5-nitro-2-(4-nitrophenyl)-4 Synthesis of -(1Η-pyrrol-2-yl)-1,2,dihydropyridine-3,3(4Η)-dicarbonitrile (Compound 32)
Figure imgf000012_0002
Figure imgf000012_0002
将 0.763g(0.0022mol)的 Ν-((6-氯吡啶 -3-基）甲基) -Ν-乙基 -Ν'-甲基 -2-硝基 -3-(1Η-吡咯 -2-基)丙 烯脒， 20ml的二氯甲烷， 0.398g(0.002mol)的 2-(4-硝基苯乙烯基)丙二腈置于 50ml的圆底烧 瓶中。 常温下搅拌 2h后， 停止反应， 将溶剂旋干， 柱层析得到化合物 32的纯品， 为淡黄色 固体 0.563g， 产率约 48.5%。 0.763 g (0.0022 mol) of ruthenium-((6-chloropyridin-3-yl)methyl)-indole-ethyl-oxime-methyl-2-nitro-3-(1Η-pyrrole-2- Acrylhydrazine, 20 ml of dichloromethane, 0.398 g (0.002 mol) of 2-(4-nitrostyryl)malononitrile were placed in a 50 ml round bottom flask. After stirring at room temperature for 2 hours, the reaction was quenched, the solvent was evaporated, and then purified to afford crystals of compound 32 as a pale yellow solid.
1H MR (400 Mz, DMSO-i ): δ 8.43 (d, J= 2.4 Hz ,2H), 8.42 (s, 1H), 7.96 (d, J= 8.4 Hz, 2H), 7.90 (m , 1H), 7.72 (d, J = 1.2 Hz, 1H), 7.55 (d, J= 8.0Hz, 1H), 6.58 (dd, Ji= 1.6 Hz, J2 = 3.2 Hz, 1H), 6.50(d, J = 3.6 Hz, 1H), 5.98(s, lH), 5.76 (s, 1H), 5.19 (s, 1H), 4.57 (q, Ji= 7.2 Hz, J2 = 14.0Hz, 1H), 4.50 (d, J = 15.6Hz, 1H), 4.14 (d, J = 15.6 Hz, 1H), 3.33(q, Ji= 7.2 Hz, J2 = 14.0Hz, 1H), 3.19 (s, 3H), 1.25 (t, J = 7.2 Hz, 3H) ppm; 13C MR (100 Mz, OMSO-d6): δ 157.5, 150.1, 149.8, 149.5, 148.9 145.8, 140.2, 139.7, 131.9, 131.5, 125.0, 124.7, 1 12.7, 1 12.5, 1 1 1.8, 1 1 1.6, 99.7, 55.8, 49.3, 48.5, 46.5, 44.0, 42.3, 14.3ppm; HRMS (ES+) 计算值 C26H24N804 35C1 (M+H)+, 547.1579; 测得值， 547.1561. 计算值 C26H24N804 37C1 (M+H)+, 549.1550; 测得值, 549.1562。 1H MR (400 Mz, DMSO-i ): δ 8.43 (d, J = 2.4 Hz , 2H), 8.42 (s, 1H), 7.96 (d, J = 8.4 Hz, 2H), 7.90 (m , 1H), 7.72 (d, J = 1.2 Hz, 1H), 7.55 (d, J= 8.0Hz, 1H), 6.58 (dd, Ji= 1.6 Hz, J 2 = 3.2 Hz, 1H), 6.50 (d, J = 3.6 Hz, 1H), 5.98(s, lH), 5.76 (s, 1H), 5.19 (s, 1H), 4.57 (q, Ji= 7.2 Hz, J 2 = 14.0 Hz, 1H), 4.50 (d, J = 15.6 Hz, 1H), 4.14 (d, J = 15.6 Hz, 1H), 3.33 (q, Ji = 7.2 Hz, J 2 = 14.0 Hz, 1H), 3.19 (s, 3H), 1.25 (t, J = 7.2 Hz, 3H) ppm; 13 C MR (100 Mz, OMSO-d 6 ): δ 157.5, 150.1, 149.8, 149.5, 148.9 145.8, 140.2, 139.7, 131.9, 131.5, 125.0, 124.7, 1 12.7, 1 12.5, 1 1 1.8, 1 1 1.6, 99.7, 55.8, 49.3, 48.5, 46.5, 44.0, 42.3, 14.3ppm; HRMS (ES+) Calculated value C 2 6H 24 N 8 0 4 35 C1 (M + H) +, 547.1579; Found, 547.1561 calcd for C 26 H 24 N 8 0 4 37 C1 (M + H) +, 549.1550;. Found, 549.1562.
实施例 3. 1-((6-氯吡啶 -3-基)甲基) -7- (呋喃 -2-基) -8-硝基 -5-(4-硝基苯基) -2,3-二氢咪唑垸  Example 3. 1-((6-chloropyridin-3-yl)methyl)-7-(furan-2-yl)-8-nitro-5-(4-nitrophenyl)-2,3 - dihydroimidazolium
[1,2-a]吡啶 -6,6(1H,5H,7H)-二甲腈 (化合物 105)的合成 Synthesis of [1,2-a]pyridine-6,6(1H,5H,7H)-dicarbonitrile (Compound 105)
Figure imgf000013_0001
Figure imgf000013_0001
将 0.730g(0.0022mol)的 2-氯 -5-((2-(2- (呋喃 -2-基) -1-硝基乙烯基) -4,5-二氢咪唑烷 -1-基） 甲基)吡啶， 20ml的二氯甲烷， 0.398g(0.002mol)的 2-(4-硝基苯乙烯基)丙二腈置于 50ml的圆 底烧瓶中。 常温下搅拌 2h后， 停止反应， 将溶剂旋干， 柱层析得到化合物 105的纯品， 为 淡黄色固体 0.703g， 产率约 62.3%。  0.730 g (0.0022 mol) of 2-chloro-5-((2-(2-(furan-2-yl)-1-nitrovinyl)-4,5-dihydroimidazolidine-1-yl) Methyl)pyridine, 20 ml of dichloromethane, 0.398 g (0.002 mol) of 2-(4-nitrostyryl)malononitrile were placed in a 50 ml round bottom flask. After stirring at room temperature for 2 hours, the reaction was quenched, and the solvent was evaporated to dryness to give crystals of compound 105 as a pale yellow solid (yield: 0.703 g).
mp =179.4°C ; 1H NMR (400 Mz, DMSO-i¾): δ 8.39 (d, J= 2.4 Hz ,2H), 8.36 (s, 1H), 7.87 (d, J = 8.8 Hz, 2H), 7.83 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz , 1H), 7.69 (d, J = 1.2 Hz, 1H), 7.50 (d, J= 8.4Hz, 1H), 6.53 (dd, J= 2 Hz, J2 = 3.2 Hz, 1H), 6.47(d, J = 3.6 Hz, 1H), 5.74 (s, 1H), 5.15 (s, 1H), 4.92 (d, J = 15.6 Hz, 1H), 4.82 (d, J = 15.6 Hz, 1H), 3.98-4.06 (m, 1H), 3.84-3.90 (m, 1H), 3.37-3.53 (m, 2H) ppm; 13C NMR (100 Mz, DMSO- 6): δ 157.3, 149.9, 149.7, 149.2, 148.2 144.8, 139.6, 139.0, 131.6, 130.8, 124.5, 124.4, 1 12.6, 1 12.4, 1 1 1.4, 1 1 1.3, 99.1, 60.4, 55.3, 51.3: 49.5, 48.2, 43.6, 42.0 ppm; IR (KBr) 1578, 1519, 1389, 1291, 1209, 1 142, 1021, 844, 754, cm"1; HRMS (ES+) 计算值 C25H19N705 35C1 (M+H)+, 532.1 136; 测得值， 532.1 133. 计算值 C25H19N705 37C1 (M+H)+, 534.1 107; 测得值， 534.1 127。 实施例 4. 1-((6-氯吡啶 -3-基)甲基) -5-(4-氰基苯基) -8-硝基 -7- (噻吩 -2-基) -2,3-二氢咪唑垸 Mp = 179.4 ° C ; 1H NMR (400 Mz, DMSO-i3⁄4): δ 8.39 (d, J = 2.4 Hz, 2H), 8.36 (s, 1H), 7.87 (d, J = 8.8 Hz, 2H), 7.83 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.69 (d, J = 1.2 Hz, 1H), 7.50 (d, J = 8.4Hz, 1H), 6.53 (dd, J= 2 Hz, J 2 = 3.2 Hz, 1H), 6.47 (d, J = 3.6 Hz, 1H), 5.74 (s, 1H), 5.15 (s, 1H), 4.92 (d, J = 15.6 Hz, 1H), 4.82 (d , J = 15.6 Hz, 1H), 3.98-4.06 (m, 1H), 3.84-3.90 (m, 1H), 3.37-3.53 (m, 2H) ppm; 13 C NMR (100 Mz, DMSO- 6 ): δ 157.3, 149.9, 149.7, 149.2, 148.2 144.8, 139.6, 139.0, 131.6, 130.8, 124.5, 124.4, 1 12.6, 1 12.4, 1 1 1.4, 1 1 1.3, 99.1, 60.4, 55.3, 51.3: 49.5, 48.2, 43.6 , 42.0 ppm; IR (KBr) 1578, 1519, 1389, 1291, 1209, 1 142, 1021, 844, 754, cm"1; HRMS (ES+) Calculated C 25 H 19 N 7 0 5 35 C1 (M+ H) + , 532.1 136; Measured value, 532.1 133. Calculated C 2 5H 19 N 7 0 5 37 C1 (M+H) + , 534.1 107; Measured value, 534.1 127. Example 4. 1-( (6-chloropyridin-3-yl)methyl)-5-(4-cyanophenyl)-8-nitro-7-(thiophen-2-yl)-2,3-dihydroimidazolium
[1,2-a]吡啶 -6,6(1H,5H,7H)-二甲腈 (化合物 143)的合成 Synthesis of [1,2-a]pyridine-6,6(1H,5H,7H)-dicarbonitrile (Compound 143)
Figure imgf000013_0002
Figure imgf000013_0002
将 0.766g(0.0022mol)的 2-氯 -5-((2-(1-硝基 -2- (噻吩 -2-基)乙烯基 )-4,5-二氢咪唑烷 -1-基） 甲基)吡啶， 20ml的二氯甲烷， 0.358g(0.002mol)的 4-(2,2-二氰基乙烯基)苯甲腈置于 50ml的 圆底烧瓶中。 常温下搅拌 2h后， 停止反应， 将溶剂旋干， 柱层析得到化合物 143的纯品， -9's>'i-(¾ ^¾i4-i-(¾-2-Sd¥dHH-(¾i(¾-e-¾¾tiB-9))-i^(iOUI^ooO)§i9^O¾ 0.766 g (0.0022 mol) of 2-chloro-5-((2-(1-nitro-2-(thiophen-2-yl)vinyl)-4,5-dihydroimidazolidine-1-yl) Methyl)pyridine, 20 ml of dichloromethane, 0.358 g (0.002 mol) of 4-(2,2-dicyanovinyl)benzonitrile were placed in a 50 ml round bottom flask. After stirring at room temperature for 2 h, the reaction was stopped, the solvent was spin-dried, and the residue was purified by column chromatography. -9's>'i-(3⁄4 ^3⁄4i4-i-(3⁄4-2-Sd¥dHH-(3⁄4i(3⁄4-e-3⁄43⁄4tiB-9))-i^(i OUI ^ooO)§i9^O3⁄4
Figure imgf000014_0001
Figure imgf000014_0001
蓄 0-1^'∑；'1-(¾¾¾鼬寸) -9-¾ϋ-6-(¾-∑;-¾¾ι)-8- (¾i (¾-ε-¾ ¾-9))-ι ·9\ Μ^ 0-11^'∑; '1-(3⁄43⁄43⁄4鼬 inch) -9-3⁄4ϋ-6-(3⁄4-∑;-3⁄43⁄4ι)-8- (3⁄4i (3⁄4-ε-3⁄4 3⁄4-9))-ι · 9\ Μ^
°εΔε 8 'i} p -99eri8s '+(Η+Μ)
Figure imgf000014_0002
°εΔε 8 'i} p -99eri8s ' + (Η+Μ)
Figure imgf000014_0002
Μ-¥ 69£νβίξ ' U P -ξβίνβίξ
Figure imgf000014_0003
1}葛 4 (+sa) svmi uidd o n '9 i7 '081 ' 6ΐ 'I IS 'I CS '6'8S '17 9 'ΓΟΟΐ 'ΓΟΠ ' Πΐ '6 sn 'r½t Lv z\ ' ΐεΐ '8 ΐεΐ '9·6£ΐ '6Όΐ7ΐ lW '9.8W乙 6H '6.6W 'ε'乙 ' 9ΐ？ (9p-OSWQ '^ i 00l)¾RN 3εΐ -radd (κε 'ZH ZL = Γ Ί) 911 '(HI ¾ LZ'£-\Z£ '(HI ¾ 09 £-^ £ '(Ηΐ ¾ ζ^£-6ί £Μ-¥ 69£νβίξ ' UP -ξβίνβίξ
Figure imgf000014_0003
1}Ge 4 (+sa) svmi uidd on '9 i7 '081 ' 6ΐ 'I IS 'I CS '6'8S '17 9 'ΓΟΟΐ 'ΓΟΠ ' Πΐ '6 sn 'r1⁄2t L vz\ ' ΐεΐ '8 ΐεΐ '9·6£ΐ '6Όΐ7ΐ lW '9.8W B 6H '6.6W 'ε'B' 9ΐ? ( 9 p-OSWQ '^ i 00l) 3⁄4RN 3 εΐ -radd (κε 'ZH ZL = Γ Ί) 911 '(HI 3⁄4 LZ'£-\Z£ '(HI 3⁄4 09 £-^ £ '(Ηΐ 3⁄4 ζ ^£-6ί £
'(HI ΐο'ΐ-ε6'ε Xuz ¾ 6i -90 '(HI m 9 si =r 'p) is '(HI m 9 si =r v) 68 '(HI'(HI ΐο'ΐ-ε6'ε Xuz 3⁄4 6i -90 '(HI m 9 si =r 'p) is '(HI m 9 si =r v) 68 '(HI
's) SI S '(HI 'S) L ' (HI 'ZH =f 'Ρ) 9Z.9 '(Ηΐ' i = zf ¾i O Z=lf 'ΡΡ 17·9 '(HI ¾i 0.8 =f 'P) LVL '(HI 'ζΗ .ΐ =f 'P) £9 L ΧϊίΖ ¾i 16 =f 'P) L L '(Ηΐ' m 0.8 = zf ¾i VZ = lf 'PP) 08'乙 XliZ ZH 16 =f 'P) 61% '(Ηΐ' ¾ O Z =f 'P) 8£ 8 ? (9p-OSWQ OOI7) ¾RN HT 's) SI S '(HI 'S) L ' (HI 'ZH =f 'Ρ) 9Z.9 '(Ηΐ' i = z f 3⁄4i OZ= l f 'ΡΡ 17·9 '(HI 3⁄4i 0.8 =f 'P) LVL '(HI 'ζΗ .ΐ =f 'P) £9 L ΧϊίΖ 3⁄4i 16 =f 'P) LL '(Ηΐ' m 0.8 = z f 3⁄4i VZ = l f 'PP) 08'B XliZ ZH 16 =f 'P) 61% '(Ηΐ' 3⁄4 OZ =f 'P) 8£ 8 ? ( 9 p-OSWQ OOI7) 3⁄4RN H T
'
Figure imgf000014_0004
'
Figure imgf000014_0004
Figure imgf000014_0005
Figure imgf000014_0005
* ¾ ^)-5- ¾ 14 -8-( ¾ -Z- ¾l - ¾ ϋ -9-( ¾i (¾"€-¾ ¾tiB -9))-I  * 3⁄4 ^)-5- 3⁄4 14 -8-( 3⁄4 -Z- 3⁄4l - 3⁄4 ϋ -9-( 3⁄4i (3⁄4"€-3⁄4 3⁄4tiB -9))-I
°S00r0£S 'l} p -0860OeS '+(H+ i) 13Αε8¾ΑΜ6ΐΗ9Ζ31}^ °S00r0£S 'l} p -0860OeS ' + (H+ i) 13 Αε 83⁄4 Α Μ 6ΐ Η 9Ζ 31}^
P
Figure imgf000014_0006
's isP
Figure imgf000014_0006
's is
'6.6S '1X01 '8X11 '6X11 'Δ'εΐΐ 8II 'S ½t LV LZ\ LZ%Z\ '0'6 £0£l 'S lCl 'ε εεΐ VL£l 6'8εΐ '6'6εΐ '6.6W 'O'OSl '69S1 ? (9p-OSWQ OOl) ¾RN 3εΐ dd (γ[Ζ ¾ ^ £-6£ £ '(HI 乙 8'ε-ΐ/;ε '(HI Μ)'ΐ-96'ε Xuz 's) 98 '(HI 'S) ors '(HI 'S) 68 S '(HI m o =f 'ρ) '乙'6.6S '1X01 '8X11 '6X11 'Δ'εΐΐ 8II 'S 1⁄2t L V LZ\ L Z%Z\ '0'6 £0£l 'S lCl 'ε εεΐ VL£l 6'8εΐ '6'6εΐ '6.6W 'O'OSl '69S1 ? ( 9 p-OSWQ OOl) 3⁄4RN 3 εΐ dd (γ[Ζ 3⁄4 ^ £-6£ £ '(HI B 8'ε-ΐ/;ε '(HI Μ)'Ϊ́-96'ε Xuz 's) 98 '(HI 'S) ors '(HI 'S) 68 S '(HI mo =f 'ρ) 'B
'(HI 'S) S17. '(HI 'ZH0.8 =f V) £ξ'ί '(Ηΐ ¾i 8 'Ρ) 19 L ΧϊίΖ ¾i 0.8 =f 'P) 9 L '(HI ZH 1·8 =f 'P) Z6 L X Z ¾i 0.8 =f 'P) £08 '(HI 's) / ·8？ :(9p-OSMI '^ i OOI7) ^vm HT '(HI 'S) S17. '(HI 'ZH0.8 =f V) £ξ'ί '(Ηΐ 3⁄4i 8 'Ρ) 19 L ΧϊίΖ 3⁄4i 0.8 =f 'P) 9 L '(HI ZH 1·8 =f 'P) Z6 LXZ 3⁄4i 0.8 =f 'P) £08 '(HI 's) / ·8? :( 9 p-OSMI '^ i OOI7) ^vm H T
。％乙 9^ ^ '§8e^O#@ ^¥. %乙 9^ ^ '§8e^O#@ ^¥
Z£ZZLOIOlOZSi3l∑3d 6Ϊ9 0Ϊ0Ζ OAV 四氢嘧啶， 20ml的二氯甲烷， 0.398g(0.002mol)的 2-(4-硝基苯乙烯基)丙二腈置于 50ml的圆 底烧瓶中。 常温下搅拌 2h后， 停止反应， 将溶剂旋干， 柱层析得到化合物 209的纯品， 为 淡黄色固体 0.693g， 产率约 59.8%。 Z£ZZLOIOlOZSi3l∑3d 6Ϊ9 0Ϊ0Ζ OAV Tetrahydropyrimidine, 20 ml of dichloromethane, 0.398 g (0.002 mol) of 2-(4-nitrostyryl)malononitrile were placed in a 50 ml round bottom flask. After stirring at room temperature for 2 h, the reaction was quenched, and the solvent was evaporated to dryness to afford crystals of compound 209 as a pale yellow solid.
1H MR (400 Mz, OMSO-d6): δ 8.41 (d, J= 2.4 Hz ,2H), 8.39 (s, 1H), 7.89 (d, J= 8.8 Hz, 2H), 7.86 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz , 1H), 7.70 (d, J = 1.2 Hz, 1H), 7.50 (d, J= 8.4Hz, 1H), 6.63 (dd, Ji= 2 Hz, J2 = 3.2 Hz, 1H), 6.50(d, J = 3.6 Hz, 1H), 5.78 (s, 1H), 5.19 (s, 1H), 4.93 (d, J = 15.6 Hz, 1H), 4.83 (d, J= 15.6 Hz, 1H), 3.50-4.08 (m, 1H), 3.86-3.92 (m, 1H), 3.40-3.62 (m, 4H) ppm; 13C NMR (100 Mz, DMSO- 6): δ 157.3, 149.9, 149.7, 149.2, 148.2 144.8, 139.6, 139.0, 131.6, 130.8, 124.5, 124.4, 112.6, 112.4, 111.4, 111.3, 99.1, 60.4, 55.3, 51.3, 49.5, 48.2, 43.6, 42.0, 37.8 ppm; HRMS (ES+) 计算值 C26H2。N705 35C1 (M+H)+, 546.1214; 测得值, 546.1203. 计算值 C25H18N705 37C1 (M+H)+, 548.1185; 测得值， 548.1200。 实施例 7. 1-((2-氯噻唑 -5-基)甲基) - 7- (呋喃 -2-基) -8-硝基 -5-(4-硝基苯基) -2,3-二氢咪唑 并 [1,2-a]吡啶 -6,6(1Η,5Η,7Η)-二腈 (化合物 175)的合成 1H MR (400 Mz, OMSO-d 6 ): δ 8.41 (d, J = 2.4 Hz , 2H), 8.39 (s, 1H), 7.89 (d, J = 8.8 Hz, 2H), 7.86 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz , 1H), 7.70 (d, J = 1.2 Hz, 1H), 7.50 (d, J = 8.4Hz, 1H), 6.63 (dd, Ji= 2 Hz, J 2 = 3.2 Hz , 1H), 6.50 (d, J = 3.6 Hz, 1H), 5.78 (s, 1H), 5.19 (s, 1H), 4.93 (d, J = 15.6 Hz, 1H), 4.83 (d, J = 15.6 Hz , 1H), 3.50-4.08 (m, 1H), 3.86-3.92 (m, 1H), 3.40-3.62 (m, 4H) ppm; 13 C NMR (100 Mz, DMSO- 6 ): δ 157.3, 149.9, 149.7 , 149.2, 148.2 144.8, 139.6, 139.0, 131.6, 130.8, 124.5, 124.4, 112.6, 112.4, 111.4, 111.3, 99.1, 60.4, 55.3, 51.3, 49.5, 48.2, 43.6, 42.0, 37.8 ppm; HRMS (ES+) calculation Value C 26 H 2 . N 7 0 5 35 C1 (M + H) +, 546.1214; Found, 546.1203 calcd for C 2 5H 18 N 7 0 5 37 C1 (M + H) +, 548.1185;. Found, 548.1200. Example 7. 1-((2-Chlorothothazo-5-yl)methyl)-7-(furan-2-yl)-8-nitro-5-(4-nitrophenyl)-2,3 Synthesis of dihydroimidazo[1,2-a]pyridine-6,6(1Η,5Η,7Η)-dicarbonitrile (Compound 175)
Figure imgf000015_0001
Figure imgf000015_0001
将 0.744g(0.0022mol)的 1-((2-氯噻唑 -5-基)甲基) -2-(2- (呋喃 -2-基) -1-硝基乙烯基) -4,5-二氢 -1H-咪唑烷， 20ml的二氯甲烷， 0.398g(0.002mol)的 2-(4-硝基苯乙烯基)丙二腈置于 50ml的 圆底烧瓶中。 常温下搅拌 2h后， 停止反应， 将溶剂旋干， 柱层析得到化合物 175的纯品， 为淡黄色固体 0.736g， 产率约 64.5%。  0.744 g (0.0022 mol) of 1-((2-chlorothiazol-5-yl)methyl)-2-(2-(furan-2-yl)-1-nitrovinyl)-4,5- Dihydro-1H-imidazolidine, 20 ml of dichloromethane, 0.398 g (0.002 mol) of 2-(4-nitrostyryl)malononitrile were placed in a 50 ml round bottom flask. After stirring at room temperature for 2 hours, the reaction was quenched, and the solvent was evaporated to dryness to afford crystals of compound 175 as a pale yellow solid (yield: 0.736 g,
1H MR (400 Mz, DMSO-i ) : δ 8.40 (d, J= 2.4 Hz ,2H), 8.37 (s, 1H), 7.82 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz , 1H), 7.70 (d, J = 1.2 Hz, 1H), 7.31 (d, J= 8.4Hz, 1H), 6.55 (dd, Ji= 2 Hz, J2 = 3.2 Hz, 1H), 6.50(d, J = 3.6 Hz, 1H), 5.77 (s, 1H), 5.16 (s, 1H), 4.95 (d, J = 15.6 Hz, 1H), 4.85 (d, J = 15.6 Hz, 1H), 4.00-4.05 (m, 1H), 3.84-3.90 (m, 1H), 3.39-3.55 (m, 2H) ppm; 13C NMR (100 Mz, DMSO-i¾) : δ 157.3, 149.7, 148.7, 146.8, 143.6, 131.6, 130.8, 124.5, 124.4, 112.6, 112.4, 111.4, 111.3, 108.7, 99.1, 60.4, 55.3, 51.3, 49.5, 48.2, 43.6, 42.0 ppm; HRMS (ES+) 计算值 C23H16N705S35C1 (M+H)+, 538.0625; 测得值， 538.0638. 计算值 C23H16N705S37C1 (M+H)+, 540.0596; 测得值， 540.0589。 实施例 8. 7- (呋喃 -2-基) -8-硝基 -5-(4-硝基苯基) -1- ((四氢呋喃 -3-基)甲基) -2,3-二氢咪唑 并 [1,2-a]吡啶 -6,6(1H,5H,7H)-二腈 (化合物 185)的合成
Figure imgf000016_0001
1H MR (400 Mz, DMSO-i) : δ 8.40 (d, J = 2.4 Hz , 2H), 8.37 (s, 1H), 7.82 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz , 1H), 7.70 (d, J = 1.2 Hz, 1H), 7.31 (d, J = 8.4Hz, 1H), 6.55 (dd, Ji= 2 Hz, J 2 = 3.2 Hz, 1H), 6.50 (d, J = 3.6 Hz, 1H), 5.77 (s, 1H), 5.16 (s, 1H), 4.95 (d, J = 15.6 Hz, 1H), 4.85 (d, J = 15.6 Hz, 1H), 4.00-4.05 (m, 1H), 3.84-3.90 (m, 1H), 3.39-3.55 (m, 2H) ppm; 13 C NMR (100 Mz, DMSO-i3⁄4): δ 157.3, 149.7, 148.7, 146.8, 143.6, 131.6, 130.8, 124.5, 124.4, 112.6, 112.4, 111.4, 111.3, 108.7, 99.1, 60.4, 55.3, 51.3, 49.5, 48.2, 43.6, 42.0 ppm; HRMS (ES+) Calculated C 23 H 16 N 7 0 5 S 35 C1 (M+H) + , 538.0625; Found, 538.0638 Calcd 37 C1 (M + H) + , 540.0596 C 23 H 16 N 7 0 5 S;. Found, 540.0589. Example 8. 7-(Furan-2-yl)-8-nitro-5-(4-nitrophenyl)-1-((tetrahydrofuran-3-yl)methyl)-2,3-dihydro Synthesis of Imidazo[1,2-a]pyridine-6,6(1H,5H,7H)-dicarbonitrile (Compound 185)
Figure imgf000016_0001
将 0.640g(0.0022mol)2-(2- (呋喃 -2-基) -1-硝基乙烯基) -1- ((四氢呋喃 -3-基)甲基) -4,5-二氢 -1H-咪唑烷， 20ml的二氯甲烷， 0.398g(0.002mol)的 2-(4-硝基苯乙烯基)丙二腈置于 50ml的 圆底烧瓶中。 常温下搅拌 2h后， 停止反应， 将溶剂旋干， 柱层析得到化合物 185的纯品， 为淡黄色固体 0.630g， 产率约 60.7%。  0.640 g (0.0022 mol) of 2-(2-(furan-2-yl)-1-nitrovinyl)-1-((tetrahydrofuran-3-yl)methyl)-4,5-dihydro-1H - Imidazolium, 20 ml of dichloromethane, 0.398 g (0.002 mol) of 2-(4-nitrostyryl)malononitrile were placed in a 50 ml round bottom flask. After stirring at room temperature for 2 hours, the reaction was quenched, and the solvent was evaporated to dryness to afford crystals of Compound 185 as a pale yellow solid.
1H MR (400 Mz, OMSO-d6): δ 8.56 (d, J= 2.4 Hz ,2H), 8.45 (s, 1H), 7.89 (d, J= 1.2 Hz, 1H), 7.31 (d, J=7.2Hz, 1H), 6.71 (dd, Ji= 1.2 Hz, J2 = 3.2 Hz, 1H), 6.60(d, J = 3.6 Hz, 1H), 5.91(s, 1H), 5.20 (s, 1H), 4.97 (d, J= 15.6 Hz, 1H), 4.87 (d, J= 15.6 Hz, 1H), 4.00-4.25 (m, 2H), 3.84-3.98 (m, 6H), 2.27 (s, 1H), 1.69(s, 2H) ppm; 13C NMR (100 Mz, OMSO-d6). δ 157.3, 148.9: 144.0, 131.3, 124.7, 124.1, 112.8, 112.5, 111.6, 99.7, 80.6, 78.5, 60.4, 55.3, 51.3, 49.5, 48.2, 43.6, 42.0, 36.8, 33.9 ppm; HRMS (ES+) 计算值 C24H22N606 (M+H)+, 491.1617; 测得值, 491.1623. 实施例 9. N-((6-氯吡啶 -3-基)甲基) -6-(((6-氯吡啶 -3-基)甲基) (乙基)氨基) -N-乙基 -2,4二 (呋喃 -2-基) -N',1-二甲基 -3,5-二硝基 -1,2,3,4-四氢吡啶 -3-甲脒 (化合物 227-1, 227-2)的合成 1H MR (400 Mz, OMSO-d 6 ): δ 8.56 (d, J = 2.4 Hz , 2H), 8.45 (s, 1H), 7.89 (d, J = 1.2 Hz, 1H), 7.31 (d, J= 7.2 Hz, 1H), 6.71 (dd, Ji= 1.2 Hz, J 2 = 3.2 Hz, 1H), 6.60 (d, J = 3.6 Hz, 1H), 5.91(s, 1H), 5.20 (s, 1H), 4.97 (d, J= 15.6 Hz, 1H), 4.87 (d, J= 15.6 Hz, 1H), 4.00-4.25 (m, 2H), 3.84-3.98 (m, 6H), 2.27 (s, 1H), 1.69 (s, 2H) ppm; 13 C NMR (100 Mz, OMSO-d 6 ). δ 157.3, 148.9 : 144.0, 131.3, 124.7, 124.1, 112.8, 112.5, 111.6, 99.7, 80.6, 78.5, 60.4, 55.3, 51.3 , 49.5, 48.2, 43.6, 42.0, 36.8, 33.9 ppm; HRMS (ES+) calcd for C 24 H 22 N 6 0 6 (M+H) + , 491.1617; measured value, 491.1623. Example 9. N-( (6-chloropyridin-3-yl)methyl)-6-(((6-chloropyridin-3-yl)methyl)(ethyl)amino)-N-ethyl-2,4 bis(furan- Synthesis of 2-yl)-N',1-dimethyl-3,5-dinitro-1,2,3,4-tetrahydropyridine-3-carboxamide (Compound 227-1, 227-2)
Figure imgf000016_0002
Figure imgf000016_0002
将 1.392g(0.004mol)的 N-((6-氯吡啶 -3-基）甲基 -N-乙基 -3- (噻吩 -2-基) -Ν'-甲基 -2-硝基丙 烯脒， 50ml的二氯甲烷置于 50ml的圆底烧瓶中。 常温下搅拌 10h后， 停止反应， 将溶剂旋 干， 柱层析得到化合物 227-1, 227-2的纯品， 为淡黄色固体 0.451g, 0.438g， 产率约 32.4%, 31.5% 。  1.392 g (0.004 mol) of N-((6-chloropyridin-3-yl)methyl-N-ethyl-3-(thiophen-2-yl)-indole-methyl-2-nitropropene脒, 50 ml of methylene chloride was placed in a 50 ml round bottom flask. After stirring at normal temperature for 10 h, the reaction was stopped, the solvent was spun and the residue was purified by column chromatography to give the product as a pale yellow solid. 0.451 g, 0.438 g, yield about 32.4%, 31.5%.
227-1 :  227-1:
mp = 120.1-121.6 °C; 1H NMR (400 Mz, OMSO-d6). δ 8.32 (d, J= 2.4 Hz, 1H), 8.27 (d, J= 2.4 Hz, 1H), 7.73 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.66 (dd, Ji = 2.4 Hz, J2 = 8.0 Hz, 1H), 7.63 (d, J= 1.2 Hz, 1H), 7.55 (d, J= 1.2 Hz, 1H), 7.50 (d, J= 8.4 Hz, 1H), 7.42 (d, J= 8.0 Hz, 1H), 6.50 (d, J= 3.2 Hz, 1H), 6.41 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, 1H), 6.37 (dd, Ji = 2.0 Hz, J2 = 3.0 Hz, 1H), 6.20 (d, J= 3.2 Hz, 1H), 5.98 (s, 1H), 5.58 (s, 1H), 4.79 (d, J = 15.6 Hz, 1H), 4.68 (d, J = 15.6 Hz, 1H), 4.15 (d, J = 15.2 Hz, 1H), 4.01 (d, J = 14.8 Hz, 1H), 3.33-3.37 (m, 4H)3.17 (s, 3H), 3.15 (s, 3H), 1.21-1.24 (m, 6H) ppm; 13C NMR (100 Mz, OMSO-d6). δ 157.7, 156.5, 150.2, 149.9， 149.7, 149.5, 149.3, 145.9, 145.0, 143.9, 139.7, 139.6, 132.4, 132.2, 125.0, 124.7, 115.1, 112.2, 111.9, 109.8, 102.4, 89.7, 58.3, 56.5, 55.9, 53.1, 52.8, 50.3, 45.0, 44.7, 20.5, 13.1 ppm; HRMS (ES+) 计算值 C32H34N806 35Cl2Na (M+Na)+, 719.1995; 测得值， 719.1987. 计算值 C3oH26N806 35Cl37ClNa (M+Na)+, 721.1977; 测得值， 721.1990. 计算值 C30H26N8O6 37Cl2Na (M+Na)+, 723.1959; 测得值， 723.1972. Mp = 120.1-121.6 °C; 1H NMR (400 Mz, OMSO-d 6 ). δ 8.32 (d, J = 2.4 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 7.73 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.66 (dd, Ji = 2.4 Hz, J 2 = 8.0 Hz, 1H), 7.63 (d, J = 1.2 Hz, 1H), 7.55 (d, J= 1.2 Hz, 1H), 7.50 (d, J= 8.4 Hz, 1H), 7.42 (d, J= 8.0 Hz, 1H), 6.50 (d, J= 3.2 Hz, 1H), 6.41 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, 1H), 6.37 (dd, Ji = 2.0 Hz, J 2 = 3.0 Hz, 1H), 6.20 (d, J = 3.2 Hz, 1H), 5.98 (s, 1H), 5.58 (s, 1H), 4.79 (d, J = 15.6 Hz, 1H), 4.68 (d, J = 15.6 Hz, 1H), 4.15 (d, J = 15.2 Hz, 1H), 4.01 (d, J = 14.8 Hz, 1H) , 3.33-3.37 (m, 4H) 3.17 (s, 3H), 3.15 (s, 3H), 1.21-1.24 (m, 6H) ppm; 13 C NMR (100 Mz, OMSO-d 6 ). δ 157.7, 156.5 , 150.2, 149.9, 149.7, 149.5, 149.3, 145.9, 145.0, 143.9, 139.7, 139.6, 132.4, 132.2, 125.0, 124.7, 115.1, 112.2, 111.9, 109.8, 102.4, 89.7, 58.3, 56.5, 55.9, 53.1, 52.8, 50.3, 45.0, 44.7, 20.5, 13.1 ppm; HRMS (ES+) Calculated C 32 H 34 N 8 0 6 35 Cl 2 Na ( M+Na) + , 719.1995; Measured value, 719.1987. Calculated C3oH 26 N 8 0 6 35 Cl 37 ClNa (M+Na) + , 721.1977; Measured value, 721.1990. Calculated C 30 H 26 N 8 O 6 37 Cl 2 Na (M+Na) + , 723.1959; measured value, 723.1972.
227-2:  227-2:
mp = 177.5-178.0 °C; 1H MR (400 Mz, OMSO-d6): δ 8.38 (d, J= 2.4 Hz, 1H), 8.30 (d, J= 2.4 Hz, 1H), 7.85 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.72 (d, J= 1.2 Hz, 1H), 7.60 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.48-7.46 (m, 2H), 7.33 (d, J= 0.8 Hz, 1H), 6.48 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, 1H), 6.37 (d, J= 3.2 Hz, 1H), 6.36(s, 1H), 6.27 (dd, J = 2.0 Hz, J2 = 3.2 Hz, 1H), 6.00 (d, J = 3.2 Hz, 1H), 5.97 (s, 1H), 4.81 (d, J = 15.6 Hz, 1H), 4.75 (d, J = 15.6 Hz, 1H), 4.13 (d, J = 14.8 Hz, 1H), 3.15 (s, 3H), 3.13 (s, 3H), 1.20-1.22 (m, 6H) ppm; 13C NMR (100 Mz, OMSO-d6). δ 158.5, 156.8, 150.1, 149.7, 149.6， 149.5, 141.0, 139.9, 139.5, 135.8, 132.2, 131.8, 129.9, 129.1, 127.6, 127.4, 127.2, 126.7, 124.9, 124.3, 104.7, 95.1, 58.0, 57.6, 52.9, 52.5, 51.9, 51.4, 47.8, 47.4, 25.4, 15.3 ppm; HRMS (ES+) 计算值 C32H35N806 35C12 (M+H)+, 697.2176; 测得值， 697.2159. 计算值 C32H35N806 35C137C1 (M+H)+, 699.2158; 测得值， 699.2137. 计算值 C32H35N806 37C12 (M+H)+, 701.2140; 测得值， 701.2151. 实施例 10. 1-((6-氯吡啶 -3-基）甲基) -6-(1-((6-氯吡啶 -3-基）甲基) -4,5-二氢 -1H-咪唑 -2- 基) -5,7-二 (呋喃 -2-基) -6,8-二硝基 -1,2,3,5,6,7-六氢咪唑并 [1,2-a]吡啶 (化合物 244-1, 244-2) 的合成 Mp = 177.5-178.0 °C; 1H MR (400 Mz, OMSO-d 6 ): δ 8.38 (d, J = 2.4 Hz, 1H), 8.30 (d, J = 2.4 Hz, 1H), 7.85 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.72 (d, J = 1.2 Hz, 1H), 7.60 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.48-7.46 (m, 2H ), 7.33 (d, J = 0.8 Hz, 1H), 6.48 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, 1H), 6.37 (d, J = 3.2 Hz, 1H), 6.36(s, 1H) , 6.27 (dd, J = 2.0 Hz, J 2 = 3.2 Hz, 1H), 6.00 (d, J = 3.2 Hz, 1H), 5.97 (s, 1H), 4.81 (d, J = 15.6 Hz, 1H), 4.75 (d, J = 15.6 Hz, 1H), 4.13 (d, J = 14.8 Hz, 1H), 3.15 (s, 3H), 3.13 (s, 3H), 1.20-1.22 (m, 6H) ppm; 13 C NMR (100 Mz, OMSO-d 6 ). δ 158.5, 156.8, 150.1, 149.7, 149.6, 149.5, 141.0, 139.9, 139.5, 135.8, 132.2, 131.8, 129.9, 129.1, 127.6, 127.4, 127.2, 126.7, 124.9, 124.3, 104.7, 95.1, 58.0, 57.6, 52.9, 52.5, 51.9, 51.4, 47.8, 47.4, 25.4, 15.3 ppm; HRMS (ES+) Calculated C 32 H 35 N 8 0 6 35 C1 2 (M+H) + , 697.2176; Measured value, calculated for C 32 H 35 N 8 0 6 35 C1 37 C1 (M+H) + , 699.2158; Measured value, 699.2137. Calculated value C 32 H 35 N 8 0 6 37 . C1 2 (M + H) +, 701.2140; Found, 701.2151 Example 10.1 - ((6-chloro-3-yl) methyl) -6- (1 - ((6-chloro-pyridin - 3-yl)methyl)-4,5-dihydro-1H-imidazol-2-yl)-5,7-bis(furan-2-yl)-6,8-dinitro-1,2,3 Synthesis of 5,6,7-hexahydroimidazo[1,2-a]pyridine (Compound 244-1, 244-2)
Figure imgf000017_0001
Figure imgf000017_0001
将 1.328g(0.004mol)的 2-氯 -5-((2-(2- (呋喃 -2-基) -1-硝基乙烯基) -4,5-二氢咪唑烷 -1-基）甲 基；)吡啶， 50ml的二氯甲烷置于 50ml的圆底烧瓶中。 常温下搅拌 10h后， 停止反应， 将溶剂 旋干， 柱层析得到化合物 244-1, 244-2的纯品， 为淡黄色固体 0.516g, 0.488g， 产率约 38.9%, 36.7% 。  1.328 g (0.004 mol) of 2-chloro-5-((2-(2-(furan-2-yl)-1-nitrovinyl)-4,5-dihydroimidazolidine-1-yl) Methyl;)pyridine, 50 ml of dichloromethane was placed in a 50 ml round bottom flask. After stirring at normal temperature for 10 hours, the reaction was quenched, and the solvent was evaporated to dryness. mjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
244-1 :  244-1:
mp = 120.1-121.6 °C; 1H NMR (400 Mz, OMSO-d6). δ 8.34 (d, J= 2.4 Hz, 1H), 8.29 (d, J= 2.4 Hz, 1H), 7.76 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.69 (dd, Ji = 2.4 Hz, J2 = 8.0 Hz, 1H), 7.66 (d, J= 1.2 Hz, 1H), 7.57 (d, J= 1.2 Hz, 1H), 7.52 (d, J= 8.4 Hz, 1H), 7.44 (d, J= 8.0 Hz, 1H), 6.52 (d, J= 3.2 Hz, 1H), 6.45 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, 1H), 6.38 (dd, Ji = 2.0 Hz, J2 = 3.0 Hz, 1H), 6.23 (d, J= 3.2 Hz, 1H), 6.01 (s, 1H), 5.68 (s, 1H), 4.86 (d, J = 15.6 Hz, 1H), 4.75 (d, J = 15.6 Hz, 1H), 4.16 (d, J = 15.2 Hz, 1H), 4.04 (d, J = 14.8 Hz, 1H), 3.66-3.87 (m, 3H), 3.48-3.56 (m, 1H), 3.19-3.28 (m, 1H), 3.07-3.17 (m, 2H), 2.64-3.03 (m, 1H) ppm; 13C NMR (100 Mz, DMSO-i¾): δ 157.5, 156.5, 150.0, 149.9, 149.8, 149.7, 149.6, 145.9, 144.9, 143.6, 139.6, 139.6, 132.2, 132.0, 124.8, 124.5, 113.9, 111.2, 111.1, 109.1, 101.6, 89.1, 57.3, 52.1, 51.4, 51.1, 48.9, 48.2, 48.1, 41.8 ppm; HRMS (ES+) 计算值 C30H26N8O6 35Cl2Na (M+Na)+, 687.1250; 测得值， 687.1256. 计算值 C3QH26N806 35Cl37ClNa (M+Na)+, 689.1221; 测得值， 689.1217. 计 算值 C30H26N8O6 37Cl2Na (M+Na)+, 691.1191; 测得值， 691.1221. Mp = 120.1-121.6 °C; 1H NMR (400 Mz, OMSO-d 6 ). δ 8.34 (d, J = 2.4 Hz, 1H), 8.29 (d, J = 2.4 Hz, 1H), 7.76 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.69 (dd, Ji = 2.4 Hz, J 2 = 8.0 Hz, 1H), 7.66 (d, J = 1.2 Hz, 1H), 7.57 (d, J= 1.2 Hz, 1H), 7.52 (d, J= 8.4 Hz, 1H), 7.44 (d, J= 8.0 Hz, 1H), 6.52 (d, J= 3.2 Hz, 1H), 6.45 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, 1H), 6.38 (dd, Ji = 2.0 Hz, J 2 = 3.0 Hz, 1H), 6.23 (d, J = 3.2 Hz, 1H), 6.01 (s, 1H), 5.68 (s, 1H), 4.86 (d, J = 15.6 Hz, 1H), 4.75 (d, J = 15.6 Hz, 1H), 4.16 (d, J = 15.2 Hz, 1H), 4.04 (d, J = 14.8 Hz, 1H) , 3.66-3.87 (m, 3H), 3.48-3.56 (m, 1H), 3.19-3.28 (m, 1H), 3.07-3.17 (m, 2H), 2.64-3.03 (m, 1H) ppm; 13 C NMR (100 Mz, DMSO-i3⁄4): δ 157.5, 156.5, 150.0, 149.9, 149.8, 149.7, 149.6, 145.9, 144.9, 143.6, 139.6, 139.6, 132.2, 132.0, 124.8, 124.5, 113.9, 111.2, 111.1, 109.1, 101.6, 89.1, 57.3, 52.1, 51.4, 51.1, 48.9, 48.2, 48.1, 41.8 ppm; HRMS (ES+) Calculated value C 30 H For the value of C 3Q H 26 N 8 0 6 35 Cl 37 ClNa (M+Na) + , 689.1221; measured value: 26 N 8 O 6 35 Cl 2 Na (M+Na) + , 687.1250; , 689.1217. Calculated C 30 H 26 N 8 O 6 37 Cl 2 Na (M+Na) + , 691.1191; measured value, 691.1221.
244-2:  244-2:
mp = 177.5-178.0 °C; 1H MR (400 Mz, OMSO-d6): δ 8.40 (d, J= 2.4 Hz, 1H), 8.25 (d, J= 2.4 Hz, 1H), 7.86 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.73 (d, J= 1.2 Hz, 1H), 7.65 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.50-7.54 (m, 2H), 7.36 (d, J= 0.8 Hz, 1H), 6.50 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, 1H), 6.40 (d, J= 3.2 Hz, 1H), 6.38 (s, 1H), 6.27 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, 1H), 6.02 (d, J = 3.2 Hz, 1H), 5.99 (s, 1H), 4.84 (d, J = 15.6 Hz, 1H), 4.78 (d, J = 15.6 Hz, 1H), 4.15 (d, J = 14.8 Hz, 1H), 4.00-4.07 (m, 1H), 3.84-3.91 (m, 3H), 3.62-3.70 (m, 2H), 3.21-3.31 (m, 1H), 3.00-3.12 (m, 2H) ppm; 13C NMR (100 Mz, OMSO-d6). δ 158.3, 156.7, 150.0, 149.9, 149.9,Mp = 177.5-178.0 °C; 1H MR (400 Mz, OMSO-d 6 ): δ 8.40 (d, J = 2.4 Hz, 1H), 8.25 (d, J = 2.4 Hz, 1H), 7.86 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.73 (d, J = 1.2 Hz, 1H), 7.65 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.50-7.54 (m, 2H ), 7.36 (d, J= 0.8 Hz, 1H), 6.50 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, 1H), 6.40 (d, J= 3.2 Hz, 1H), 6.38 (s, 1H) , 6.27 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, 1H), 6.02 (d, J = 3.2 Hz, 1H), 5.99 (s, 1H), 4.84 (d, J = 15.6 Hz, 1H), 4.78 (d, J = 15.6 Hz, 1H), 4.15 (d, J = 14.8 Hz, 1H), 4.00-4.07 (m, 1H), 3.84-3.91 (m, 3H), 3.62-3.70 (m, 2H) , 3.21-3.31 (m, 1H), 3.00-3.12 (m, 2H) ppm; 13 C NMR (100 Mz, OMSO-d 6 ). δ 158.3, 156.7, 150.0, 149.9, 149.9,
149.5, 140.8, 139.8, 139.5, 135.6, 132.0, 131.8, 129.8, 129.1, 127.6, 127.2, 127.0, 126.3, 124.7,149.5, 140.8, 139.8, 139.5, 135.6, 132.0, 131.8, 129.8, 129.1, 127.6, 127.2, 127.0, 126.3, 124.7,
124.6, 104.6, 94.5, 54.6, 52.4, 52.0, 50.9, 49.4, 48.4, 47.3, 42.8 ppm; HRMS (ES+) 计算值 C30H27N8O6 35Cl2 (M+H)+, 665.1431; 测得值， 665.1423. 计算值 C30H27N8O6 35Cl37Cl (M+H)+, 667.1401; 测得值， 667.1400. 计算值 C3QH27N806 37C12 (M+H)+, 669.1372; 测得值， 669.1397. 实施例 11. l-((6-氯吡啶 -3-基）甲基) -6-(l-((6-氯吡啶 -3-基）甲基) -4,5-二氢 -1H-咪唑 -2- 基) - 6,8-二硝基 -5,7-二 (噻吩 -2-基) -1,2,3,5,6,7-六氢咪唑并 [1,2-a]吡啶 (化合物 259-1, 259-2) 的合成 124.6, 104.6, 94.5, 54.6, 52.4, 52.0, 50.9, 49.4, 48.4, 47.3, 42.8 ppm; HRMS (ES+) calculated C 30 H 27 N 8 O 6 35 Cl 2 (M+H) + , 665.1431; Value, 665.1423. Calculated C 30 H 27 N 8 O 6 35 Cl 37 Cl (M+H) + , 667.1401; Measured, 667.1400. Calculated C 3Q H 27 N 8 0 6 37 C1 2 (M+ H) + , 669.1372; Measured value, 669.1397. Example 11. l-((6-Chloropyridin-3-yl)methyl)-6-(l-((6-chloropyridin-3-yl)) -4,5-Dihydro-1H-imidazol-2-yl)-6,8-dinitro-5,7-bis(thiophen-2-yl)-1,2,3,5,6, Synthesis of 7-Hexahydroimidazo[1,2-a]pyridine (Compounds 259-1, 259-2)
Figure imgf000018_0001
将 1.392g(0.004mol)的 2-氯 -5-((2-(1-硝基 -2- (噻吩 -2-基)乙烯基 )-4,5-二氢咪唑烷 -1-基）甲 基；)吡啶， 50ml的二氯甲烷置于 50ml的圆底烧瓶中。 常温下搅拌 10h后， 停止反应， 将溶剂 旋干， 柱层析得到化合物 259-1, 259-2的纯品， 为淡黄色固体 0.470g, 0.462g， 产率约 33.8%, 33.2% 。
Figure imgf000018_0001
1.392 g (0.004 mol) of 2-chloro-5-((2-(1-nitro-2-(thiophen-2-yl)vinyl)-4,5-dihydroimidazolidine-1-yl) Methyl;)pyridine, 50 ml of dichloromethane was placed in a 50 ml round bottom flask. After stirring at normal temperature for 10 h, the reaction was quenched, and the solvent was evaporated to dryness to afford crystals of compound 259-1, 259-2 as pale yellow solid, 0.470 g, 0.462 g, yield 33.8%, 33.2%.
259-1 :  259-1 :
mp = 169.7-170.4 °C; 1H NMR (400 Mz, OMSO-d6). δ 8.40 (d, J= 2.4 Hz, 1H), 8.18 (d, J= 2.4 Hz, 1H), 7.79 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.56-7.59 (m, 2H), 7.43-7.51 (m, 3H), 7.06 (d, J= 2.8 Hz, 1H), 6.99 (dd, Ji = 3.6 Hz, J2 = 5.2 Hz, 1H), 6.93-6.95 (m, 1H), 6.89 (d, J= 3.6 Hz: 1H), 6.21 (s, 1H), 5.89 (s, 1H), 4.85 (d, J= 15.6 Hz, 1H), 4.76 (d, J= 15.6 Hz, 1H), 3.74-3.91 (m， 5H), 3.62-3.71 (m, 1H), 3.38-3.57 (m, 2H), 3.13-3.20 (m, 1H), 2.93-2.96 (m, 1H) ppm; 13C NMR (100 Mz, DMSO-i¾): δ 158.1, 157.8, 151.2, 150.0, 149.9, 149.8, 149.6, 146.8, 144.9, 142.6, 139.9, 139.7, 132.8, 131.9, 124.6, 111.4, 111.1, 110.8, 109.2, 102.6, 94.3, 59.3, 51.8, 51.3, 50.7, 48.7, 48.6, 47.8, 42.1 ppm; HRMS (ES+) 计算值 C30H26N8O4S2 35Cl2Na (M+Na)+, 719.0793; 测得值， 719.0781. 计算值 C30H26N8O4S2 35Cl37ClNa (M+Na)+, 721.0764; 测得值， 721.0771. 计算值 C30H26N8O6 37Cl2Na (M+Na)+, 723.0734; 测得值， 723.0739. Mp = 169.7-170.4 °C; 1H NMR (400 Mz, OMSO-d 6 ). δ 8.40 (d, J = 2.4 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.79 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.56-7.59 (m, 2H), 7.43-7.51 (m, 3H), 7.06 (d, J= 2.8 Hz, 1H), 6.99 (dd, Ji = 3.6 Hz, J 2 = 5.2 Hz, 1H), 6.93-6.95 (m, 1H), 6.89 (d, J= 3.6 Hz : 1H), 6.21 (s, 1H), 5.89 (s, 1H), 4.85 (d, J= 15.6 Hz, 1H), 4.76 (d, J= 15.6 Hz, 1H), 3.74-3.91 (m, 5H), 3.62-3.71 (m, 1H), 3.38-3.57 (m, 2H), 3.13-3.20 (m, 1H), 2.93-2.96 (m, 1H) ppm; 13 C NMR (100 Mz, DMSO-i3⁄4): δ 158.1, 157.8, 151.2, 150.0, 149.9, 149.8, 149.6, 146.8, 144.9, 142.6, 139.9, 139.7, 132.8, 131.9, 124.6, 111.4, 111.1, 110.8, 109.2, 102.6, 94.3, 59.3, 51.8, 51.3, 50.7, 48.7, 48.6, 47.8, 42.1 ppm; HRMS (ES+) Calculated C 30 H 26 N 8 O 4 S 2 35 Cl 2 Na (M + Na) +, 719.0793; Found, 719.0781 calcd for C 30 H 26 N 8 O 4 S 2 35 Cl 37 ClNa (M + Na) +, 721.0764;. measured Calcd for C 30 H 26 N 8 O 6 37 Cl 2 Na (M+Na) + , 723.0734; found, 723.0739.
259-2：  259-2:
mp = 150.3.7-151.3。C; 1H MR (400 Mz, OMSO-d6): δ 8.44 (d, J= 2.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 7.90 (dd, Ji = 2.0 Hz, J2 = 8.4 Hz, 1H), 7.70 (dd, J = 2.0 Hz, J2 = 8.4 Hz, 1H), 7.63 (d, J= 5.0 Hz, 1H), 7.52-7.56 (m, 2H), 7.24-7.26 (m, 1H), 7.15 (d, J= 3.0 Hz, 1H), 7.05 (dd, Ji = 3.6 Hz, J2 = 5.0 Hz, 1H), 6.78 (dd, Ji = 3.6 Hz, J2 = 5.0 Hz, 1H), 6.55 (d, J= 3.2 Hz, 1H), 6.53 (s, 1H), 6.25 (s, 1H), 4.92 (d, J = 15.6 Hz, 1H), 4.79 (d, J = 15.6 Hz, 1H), 4.37 (d, J = 14.4 Hz, 1H), 4.05-4.12 (m, 1H), 3.97 (d, J = 14.4 Hz, 1H), 3.78-3.92 (m, 2H), 3.65-3.73 (m, 2H), 3.13-3.22 (m, 1H), 2.99-3.09 (m, 2H) ppm; 13C NMR (100 Mz, DMSO-i¾): 3156.8, 155.8, 148.5, 148.4, 148.4, 148.3, 141.3, 138.4, 138.3, 133.7, 131.1, 130.3, 128.0, 127.7, 125.2, 124.7, 124.1, 123.2, 123.1, 102.8, 98.5, 95.6, 54.5, 50.8, 50.0, 49.5, 47.9, 47.4, 45.4, 41.0 ppm; HRMS (ES+) 计 算 值 C3QH27N804S2 35C12 (M+H)+, 697.0974; 测 得 值 ， 697.0972. 计 算 值 C30H27N8O4S2 35Cl37Cl (M+H)+, 699.0944; 测得值， 699.0949. 计算值 C30H27N8O6 37Cl2 (M+H)+, 701.0948; 测得值， 701.0972. 计算值 C3QH26N804S2 35Cl2Na (M+Na)+, 719.0793; 测 得值， 719.0798. 计算值 C30H26N8O4S2 35Cl37ClNa (M+Na)+, 721.0764; 测得值， 721.0781. 计 算值 C30H26N8O6 37Cl2Na (M+Na)+, 723.0734; 测得值， 723.0765. 实施例 12. 1-((6-氯吡啶 -3-基）甲基) -7-(1-((6-氯吡啶 -3-基）甲基) -1,4,5,6-四氢嘧啶 -2- 基) -6,8-二（呋喃 -2-基) -7,9-二硝基 -2,3,4,6,7,8-四氢 -1H-吡啶并 [1,2-a]嘧啶（化合物 282-1, 282-2)的合成 Mp = 150.3.7-151.3. C; 1H MR (400 Mz, OMSO-d 6 ): δ 8.44 (d, J = 2.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 7.90 (dd, Ji = 2.0 Hz, J 2 = 8.4 Hz, 1H), 7.70 (dd, J = 2.0 Hz, J 2 = 8.4 Hz, 1H), 7.63 (d, J= 5.0 Hz, 1H), 7.52-7.56 (m, 2H), 7.24-7.26 ( m, 1H), 7.15 (d, J= 3.0 Hz, 1H), 7.05 (dd, Ji = 3.6 Hz, J 2 = 5.0 Hz, 1H), 6.78 (dd, Ji = 3.6 Hz, J 2 = 5.0 Hz, 1H), 6.55 (d, J = 3.2 Hz, 1H), 6.53 (s, 1H), 6.25 (s, 1H), 4.92 (d, J = 15.6 Hz, 1H), 4.79 (d, J = 15.6 Hz, 1H), 4.37 (d, J = 14.4 Hz, 1H), 4.05-4.12 (m, 1H), 3.97 (d, J = 14.4 Hz, 1H), 3.78-3.92 (m, 2H), 3.65-3.73 (m , 2H), 3.13-3.22 (m, 1H), 2.99-3.09 (m, 2H) ppm; 13 C NMR (100 Mz, DMSO-i3⁄4): 3156.8, 155.8, 148.5, 148.4, 148.4, 148.3, 141.3, 138.4 , 138.3, 133.7, 131.1, 130.3, 128.0, 127.7, 125.2, 124.7, 124.1, 123.2, 123.1, 102.8, 98.5, 95.6, 54.5, 50.8, 50.0, 49.5, 47.9, 47.4, 45.4, 41.0 ppm; HRMS (ES+) Calcd C 3Q H 27 N 8 0 4 S 2 35 C1 2 (M + H) +, 697.0974; Found, 697.0972 calcd for C 30 H 27 N 8 O 4 S 2 35 Cl 37 Cl (M + H. ) +, 699.0944; Found . 699.0949 calcd for C 30 H 27 N 8 O 6 37 Cl 2 (M + H) +, 701.0948; Found, 701.0972 Calcd C 3Q H 26 N 8 0 4 S 2 35 Cl 2 Na (M + Na. ) +, 719.0793; Found, 719.0798 calcd for C 30 H 26 N 8 O 4 S 2 35 Cl 37 ClNa (M + Na) +, 721.0764;. Found, 721.0781 calcd for C 30 H 26 N 8. O 6 37 Cl 2 Na (M+Na) + , 723.0734; found, 723.0765. Example 12. 1-((6-chloropyridin-3-yl)methyl)-7-(1-((6) -chloropyridin-3-yl)methyl)-1,4,5,6-tetrahydropyrimidin-2-yl)-6,8-di(furan-2-yl)-7,9-dinitro- Synthesis of 2,3,4,6,7,8-tetrahydro-1H-pyrido[1,2-a]pyrimidine (Compound 282-1, 282-2)
Figure imgf000019_0001
Figure imgf000019_0001
将 1.384g(0.004mol)的 1-((6-氯吡啶 -3-基）甲基) -2-(2- (呋喃 -2-基) -1-硝基乙烯基) -1,4,5,6- 四氢嘧啶， 50ml的二氯甲烷置于 50ml的圆底烧瓶中。 常温下搅拌 10h后， 停止反应， 将溶 剂旋干，柱层析得到化合物 282-1, 282-2的纯品，为淡黄色固体 0.397g, 0.360g，产率约 28.7%, 26.0% 。  1.384 g (0.004 mol) of 1-((6-chloropyridin-3-yl)methyl)-2-(2-(furan-2-yl)-1-nitrovinyl)-1,4, 5,6-tetrahydropyrimidine, 50 ml of dichloromethane was placed in a 50 ml round bottom flask. After stirring at normal temperature for 10 hours, the reaction was quenched, and the solvent was evaporated to dryness to give crystals of compound 282-1, 282-2 as a pale yellow solid, 0.397 g, 0.360 g, yield: 28.7%, 26.0%.
282-1：  282-1:
mp = 120.1-121.6 °C; 1H NMR (400 Mz, DMSO-i¾): δ 8.35 (d, J= 2.4 Hz, 1H), 8.19 (d, J= 2.4 Hz, 1H), 7.70 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, 1H), 7.63 (dd, Ji = 2.4 Hz, J2 = 8.0 Hz, 1H), 7.60 (d, J= 1.2 Hz, 1H), 7.55 (d, J= 1.2 Hz, 1H), 7.49 (d, J= 8.4 Hz, 1H), 7.41 (d, J= 8.0 Hz, 1H), 6.42 (d, J= 3.2 Hz, 1H), 6.35 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, 1H), 6.28 (dd, Ji = 2.0 Hz, J2 = 3.0 Hz, IH), 6.19 (d, J= 3.2 Hz, IH), 6.01 (s, IH), 5.60 (s, IH), 4.81 (d, J = 15.6 Hz, IH), 4.77 (d, J = 15.6 Hz, IH), 4.18 (d, J = 15.2 Hz, IH), 4.06 (d, J = 14.8 Hz, IH), 3.69-3.87 (m, 3H), 3.43-3.58 (m, IH), 3.41-3.58 (m, 2H), 3.17-3.24 (m, IH), 3.02-3.15 (m, 2H), 2.61-2.95 (m, IH) ppm; 13C MR (100 Mz, DMSO- 6): δ 157.5, 156.1, 150.3, 149.9, 149.8, 149.7, 149.6, 146.2, 145.1, 143.7, 139.7, 139.6, 132.5, 132.3, 124.9, 124.7, 114.9, 111.1, 111.0, 109.5, 101.6, 89.3, 57.4, 52.1, 51.5, 51.0, 48.9, 48.1, 48.0, 41.9, 38.0 ppm; HRMS (ES+) 计算值 C32H30N8O6 35Cl2Na (M+Na)+, 715.1678; 测得值， 715.1651. 计算值 C32H30N8O6 35Cl37ClNa (M+Na)+, 717.1660; 测得值， 717.1663. 计算值 C32H30N8O6 37Cl2Na (M+Na)+,719.1642; 测得 值， 719.1638. Mp = 120.1-121.6 °C; 1H NMR (400 Mz, DMSO-i3⁄4): δ 8.35 (d, J = 2.4 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.70 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, 1H), 7.63 (dd, Ji = 2.4 Hz, J 2 = 8.0 Hz, 1H), 7.60 (d, J = 1.2 Hz, 1H), 7.55 (d, J = 1.2 Hz , 1H), 7.49 (d, J= 8.4 Hz, 1H), 7.41 (d, J= 8.0 Hz, 1H), 6.42 (d, J= 3.2 Hz, 1H), 6.35 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, 1H), 6.28 (dd, Ji = 2.0 Hz, J 2 = 3.0 Hz, IH), 6.19 (d, J = 3.2 Hz, IH), 6.01 (s, IH), 5.60 (s, IH), 4.81 (d, J = 15.6 Hz, IH), 4.77 (d, J = 15.6 Hz, IH), 4.18 (d, J = 15.2 Hz, IH), 4.06 (d, J = 14.8 Hz, IH), 3.69-3.87 (m, 3H), 3.43-3.58 (m, IH), 3.41-3.58 (m, 2H), 3.17-3.24 (m, IH), 3.02-3.15 (m, 2H), 2.61-2.95 (m, IH) ppm; 13 C MR (100 Mz, DMSO- 6 ): δ 157.5, 156.1 , 150.3, 149.9, 149.8, 149.7, 149.6, 146.2, 145.1, 143.7, 139.7, 139.6, 132.5, 132.3, 124.9, 124.7, 114.9, 111.1, 111.0, 109.5, 101.6, 89.3, 57.4, 52.1, 51.5, 51.0, 48.9 , 48.1, 48.0, 41.9, 38.0 ppm; HRMS (ES+) calcd for C 32 H 30 N 8 O 6 35 Cl 2 Na (M+Na) + , 715.1678; Measured value, 715.1651. Calculated C 32 H 30 N 8 O 6 35 Cl 37 ClNa (M+Na) + , 717.1660; calcd., 717.1 663. Calculated C 32 H 30 N 8 O 6 37 Cl 2 Na (M+Na) + , 719.642; measured value, 719.1638 .
282-2:  282-2:
mp = 177.5-178.0。C; 1H NMR (400 Mz, DMSO-i¾) : δ 8.39 (d, J= 2.4 Hz, IH), 8.26 (d, J= 2.4 Hz, IH), 7.85 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, IH), 7.71 (d, J= 1.2 Hz, IH), 7.67 (dd, Ji = 2.4 Hz, J2 = 8.4 Hz, IH), 7.51-7.55 (m, 2H), 7.39 (d, J= 0.8 Hz, IH), 6.55 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, IH), 6.43 (d, J= 3.2 Hz, IH), 6.31 (s, IH), 6.29 (dd, Ji = 2.0 Hz, J2 = 3.2 Hz, IH), 6.12 (d, J = 3.2 Hz, IH), 5.96 (s, IH), 4.80 (d, J = 15.6 Hz, IH), 4.79 (d, J = 15.6 Hz, IH), 4.13 (d, J = 14.8 Hz, IH), 4.01-4.07 (m, IH), 3.82-3.90 (m, 3H), 3.61-3.70 (m, 2H), 3.43-3.56 (m, 2H), 3.20-3.31 (m, IH), 3.05-3.13 (m, 2H) ppm; 13C NMR (100 Mz, OMSO-d6). δ 158.4, 156.9, 150.1, 150.0, 149.9， 149.6， 141.8, 140.1, 139.9, 135.8, 132.0, 131.5, 129.7, 129.1, 127.6, 128.2, 127.7, 126.4, 124.7, 124.6, 104.7, 93.5, 54.8, 52.5, 52.0, 50.9, 49.3, 48.3, 47.3, 42.9, 36.9 ppm; HRMS (ES+) 计算值 C32H31N806 35C12 (M+H)+, 693.1859; 测得值， 693.1860. 计算值 C32H31N806 35C137C1 (M+H)+, 695.1841; 测得值， 695.1847. 计算值 C32H31N806 37C12 (M+H)+, 697.1823; 测得值， 697.1825. 实施例 13 Mp = 177.5-178.0. C; 1H NMR (400 Mz, DMSO-i3⁄4): δ 8.39 (d, J = 2.4 Hz, IH), 8.26 (d, J = 2.4 Hz, IH), 7.85 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, IH), 7.71 (d, J = 1.2 Hz, IH), 7.67 (dd, Ji = 2.4 Hz, J 2 = 8.4 Hz, IH), 7.51-7.55 (m, 2H), 7.39 (d, J = 0.8 Hz, IH), 6.55 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, IH), 6.43 (d, J = 3.2 Hz, IH), 6.31 (s, IH), 6.29 (dd, Ji = 2.0 Hz, J 2 = 3.2 Hz, IH), 6.12 (d, J = 3.2 Hz, IH), 5.96 (s, IH), 4.80 (d, J = 15.6 Hz, IH), 4.79 (d, J = 15.6 Hz, IH), 4.13 (d, J = 14.8 Hz, IH), 4.01-4.07 (m, IH), 3.82-3.90 (m, 3H), 3.61-3.70 (m, 2H), 3.43-3.56 (m, 2H), 3.20-3.31 (m, IH), 3.05-3.13 (m, 2H) ppm; 13 C NMR (100 Mz, OMSO-d 6 ). δ 158.4, 156.9, 150.1, 150.0, 149.9, 149.6, 141.8, 140.1, 139.9, 135.8, 132.0, 131.5, 129.7, 129.1, 127.6, 128.2, 127.7, 126.4, 124.7, 124.6, 104.7, 93.5, 54.8, 52.5, 52.0, 50.9, 49.3, 48.3, 47.3, 42.9, 36.9 ppm; HRMS (ES+) calculated C 32 H 31 N 8 0 6 35 C1 2 (M+H) + , 693.1859; Measured value, 693.1860. Calculated C 32 H 31 N 8 0 6 35 C1 37 C1 (M+H) +, 695.1841; measured The value, calcd 695.1847 C 32 H 31 N 8 0 6 37 C1 2 (M + H) +, 697.1823; Found, 697.1825 Example 13.
表 1-4中其他化合物的制备  Preparation of other compounds in Tables 1-4
重复实施例 1-12的方法，不同点在于:根据表 1-4中所示的化合物结构选用不同的原料， 从而制得化合物 1-286(实施例 1-12中已经制备的化合物不再重复制备；)。 实施例 14  The procedures of Examples 1-12 were repeated except that different starting materials were selected according to the structure of the compounds shown in Tables 1-4, thereby preparing compounds 1-286 (the compounds which have been prepared in Examples 1-12 are not repeated). preparation;). Example 14
本发明化合物的杀虫活性测试  Insecticidal activity test of the compounds of the invention
(1)： 对蚜虫的杀虫活性  (1): Insecticidal activity against aphids
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 ( /^ craccivora)为测试对象， 采用浸渍法测试。  Aphids belong to Homoptera pests and have a sucker, which is a common crop pest. The soybean meal ( /^ craccivora) was used as the test object and tested by the dipping method.
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 500 ug/mL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 500 ug/mL的药液中， 5s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 0.2 mL/L Triton X-100的水溶液。 处理 24小时后， 统计试蚜的死亡虫数， 并计算死亡率 (；％；)。  Operation process: Accurately weigh various samples, add Ν, Ν-dimethylformamide to make 10g/L mother liquor, and dilute it to 500 ug/mL with 0.2mL/L Triton X-100 aqueous solution. concentration. After the wingless mites are stably sucked on the bean sprouts, they are immersed in the medicinal solution with a concentration of 500 ug/mL together with the bean sprouts, and taken out after 5 s. The excess liquid is sucked up with absorbent paper, and transferred to a clean vessel and kept at a constant temperature of 23 °C. . Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.2 mL/L Triton X-100. After 24 hours of treatment, the number of dead insects tested was counted and the mortality (;%;) was calculated.
死亡率(％)= (对照活虫数 -处理活虫数 )/对照活虫数 X 100% (2): 对粘虫的杀虫活性 Mortality (%) = (control live number - number of live insects) / number of live insects X 100% (2): Insecticidal activity against armyworm
采用浸叶饲喂法。 将新鲜的玉米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， 24h后检查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。  Use leaf dip feeding. Fresh corn leaves are immersed in the above solution for 3 seconds, then dried at room temperature for feeding by test insects. After 24 hours, the mortality (%) of the test insects is checked and calculated (the formula is the same as above), and 10 tests are used for each treatment. Insect, set 3 repetitions. Treat with water as a blank control.
表 1. 通式 (I)化合物的杀虫活性  Table 1. Insecticidal activity of compounds of general formula (I)
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000021_0001
Figure imgf000022_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV
Figure imgf000023_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV
Figure imgf000023_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV
Figure imgf000024_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV
Figure imgf000024_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV 88 CH3 C2H5 H H N02 CN C02Et 69 91 Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV 88 CH 3 C 2 H 5 HH N0 2 CN C0 2 Et 69 91
89 C2H5 CH3 H H N02 CN C02Et 67 58 89 C 2 H 5 CH 3 HH N0 2 CN C0 2 Et 67 58
90 C2H5 C2H5 H H N02 CN C02Et 78 77 90 C 2 H 5 C 2 H 5 HH N0 2 CN C0 2 Et 78 77
91 CH3 CH3 CH3 H N02 CN C02Et 64 68 91 CH 3 CH 3 CH 3 H N0 2 CN C0 2 Et 64 68
92 C2H5 CH3 CH3 H N02 CN C02Et 59 100 92 C 2 H 5 CH 3 CH 3 H N0 2 CN C0 2 Et 59 100
93 C2H5 CH3 H CH3 N02 CN C02Et 82 96 93 C 2 H 5 CH 3 H CH 3 N0 2 CN C0 2 Et 82 96
94 CH3 CH3 H CH3 N02 CN C02Et 79 76 94 CH 3 CH 3 H CH 3 N0 2 CN C0 2 Et 79 76
95 H CH3 H
Figure imgf000025_0001
H N02 COCF3 C02Et 72 67 95 H CH 3 H
Figure imgf000025_0001
H N0 2 COCF 3 C0 2 Et 72 67
96 CH3 CH3 H H N02 COCF3 C02Et 69 56 96 CH 3 CH 3 HH N0 2 COCF3 C0 2 Et 69 56
97 CH3 C2H5 H H N02 COCF3 C02Et 65 52 o 97 CH 3 C 2 H 5 HH N0 2 COCF3 C0 2 Et 65 52 o
98 C2H5 CH3 H H N02 COCF3 C02Et 59 67 98 C 2 H 5 CH 3 HH N0 2 COCF3 C0 2 Et 59 67
99 C2H5 CH3 H CI八 ^aBr CH3 N02 CN C02Et 48 89 99 C 2 H 5 CH 3 H CI 八 a Br CH 3 N0 2 CN C0 2 Et 48 89
100 CH3 CH3 CH3 f 100 CH 3 CH 3 CH 3 f
s CH3 N02 CN C02Et 67 100 s CH 3 N0 2 CN C0 2 Et 67 100
101 H CH3 H H N02 COCF3 C02Et 70 43 101 H CH 3 HH N0 2 COCF3 C0 2 Et 70 43
102 CH3 CH3 H H N02 COCF3 C02Et 66 55102 CH 3 CH 3 HH N0 2 COCF3 C0 2 Et 66 55
103 C2H5 CH3 H H N02 COCF3 C02Et 56 56 表 2.通式 (II)化合物的杀虫活性 103 C 2 H 5 CH 3 HH N0 2 COCF3 C0 2 Et 56 56 Table 2. Insecticidal activity of the compound of formula (II)
Figure imgf000025_0002
Figure imgf000026_0001
Figure imgf000025_0002
Figure imgf000026_0001
ZCZZ.0/OlOZN3/X3d 6Ϊ9 ΟΐΟΖ OAV ZCZZ.0/OlOZN3/X3d 6Ϊ9 ΟΐΟΖ OAV
Figure imgf000027_0001
Figure imgf000027_0001
Z£ZZL0/010Z13/I3d 6Ϊ9 ΟΐΟΖ OAV
Figure imgf000028_0001
Z£ZZL0/010Z13/I3d 6Ϊ9 ΟΐΟΖ OAV
Figure imgf000028_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΐΟΖ OAV
Figure imgf000029_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΐΟΖ OAV
Figure imgf000029_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΐΟΖ OAV 200 H H 0 CN CN CN 100 100 Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΐΟΖ OAV 200 HH 0 CN CN CN 100 100
201 H H 0 N02 CN C02Et 100 100 201 HH 0 N0 2 CN C0 2 Et 100 100
1  1
202 H 02N 。 H 0 N02 CN C02Et 100 100 202 H 0 2 N . H 0 N0 2 CN C0 2 Et 100 100
203 H H 0 N02 CN C02Et 100 100 203 HH 0 N0 2 CN C0 2 Et 100 100
204 H H 0 N02 CN C02Et 100 100 204 HH 0 N0 2 CN C0 2 Et 100 100
205 H H 0 N02 CN C02Et 100 100 205 HH 0 N0 2 CN C0 2 Et 100 100
206 H 02N 。 H 0 N02 COCF3 C02Et 100 100206 H 0 2 N . H 0 N0 2 COCF 3 C0 2 Et 100 100
207 H H 0 N02 COCF3 C02Et 100 100207 HH 0 N0 2 COCF3 C0 2 Et 100 100
208 H 02N S a H 0 N02 COCF3 C02Et 100 100208 H 0 2 N S a H 0 N0 2 COCF3 C0 2 Et 100 100
209 H H 1 N02 CN CN 100 100209 HH 1 N0 2 CN CN 100 100
210 H H 1 N02 CN CN 100 100210 HH 1 N0 2 CN CN 100 100
211 H H 1 N02 CN CN 100 100 表 3.通式 (III)化合物的杀虫活性 211 HH 1 N0 2 CN CN 100 100 Table 3. Insecticidal activity of the compound of formula (III)
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000030_0001
Figure imgf000031_0001
Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV 入 Z£ZZL0/010Z 13/I3d 6Ϊ9 ΟΪΟΖ OAV Enter
242 Η N02 H C2H5 C2H5 100 100 ο2^ 242 Η N0 2 HC 2 H 5 C 2 H 5 100 100 ο 2 ^
入  Enter
243 Η C2H5 100 100 243 Η C 2 H 5 100 100
CI八 s N02 H C2H5 表 4. 通式 (IV)化合物的杀虫活性 CI s N0 2 HC 2 H 5 Table 4. Insecticidal activity of compounds of general formula (IV)
Figure imgf000032_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000033_0001
6Ϊ9 ΟΐΟΖ OAV
Figure imgf000034_0001
实施例 15. 含有本发明化合物的杀虫剂组合物的制备 6Ϊ9 ΟΐΟΖ OAV
Figure imgf000034_0001
Example 15. Preparation of a Pesticide Composition Containing a Compound of the Invention
(a) 油状悬浮液  (a) oily suspension
按比例准备以下组分： 25% (重量百分比， 下同)化合物 1-424 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。  The following components were prepared in proportion: 25% by weight of the compound 1-424; 5% polyoxyethylene sorbitol hexaoleate; 70% higher aliphatic hydrocarbon oil. The components were ground together in a sanding mill until the solid particles fell below about 5 microns. The resulting viscous suspension can be used as it is, but it can also be used after emulsification in water.
(b) 水悬浮液  (b) aqueous suspension
按比例准备以下组分： 25%化合物 1-424 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。  The following components were prepared in proportion: 25% of the compound 1-424; 3% hydrate attapulgit; 10% calcium lignosulfonate; 0.5% sodium dihydrogen phosphate; 61.5% water. The components were ground together in a ball mill until the solid particles fell below about 10 microns. This aqueous suspension can be used directly.
(c) 饵剂  (c) bait
按比例准备以下组分： 0.1-10%化合物 1-424 中任一种化合物； 80%小麦面粉； Prepare the following components in proportion: 0.1-10% of compound 1-424 of any compound; 80% wheat flour;
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。 在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。 19.9-10% molasses. These components are thoroughly mixed and formed into a bait shape as needed. Edible baits can be dispersed in places where health pests are infested, such as in domestic or industrial settings, such as kitchens, hospitals or shops, or outdoor areas to control pests through oral intake. All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entirety as if they are individually incorporated by reference. In addition, it should be understood that various modifications and changes may be made to the present invention, and the equivalents of the scope of the invention.

Claims

权 利 要 求  Rights request
-种具有通式 (A)所示结构的化合物、 或所述化合物的光学异构体、 顺反异构体:
Figure imgf000035_0001
a compound having the structure represented by the formula (A), or an optical isomer or a cis-trans isomer of the compound:
Figure imgf000035_0001
通式 (A)  General formula (A)
式中：  In the formula:
Ri为含氮、 氧和 /或硫的五元或六元杂环基， 或卤代的含氮、 氧和 /或硫的五元或六 元杂环基， 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 d— 4 氯代烷氧基； Ri is a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a halogenated five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, a substituted or unsubstituted phenyl group, Wherein the substituent is one or more selected from the group consisting of halogen, d- 4 haloalkyl or d- 4 chloroalkoxy;
R2和 R3 各自独立地为 H， d.6烷基， d.6烷氧基， 烯丙基， 苄基， 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； R 2 and R 3 are each independently H, d 6 alkyl, d 6 alkoxy, allyl, benzyl, d_ 4 alkoxy -d_ 4 alkyl, d- 4 alkoxy. - carbonyl , phenoxycarbonyl, C 2 - 6 alkynyl group - carbonyl group, C 2 - 3 alkenyl - carbonyl group, C 3 - 6 cycloalkyl - carbonyl, benzoyl, or substituted with one or more substituents selected from halogen atoms, d- a benzoyl, furancarbonyl or anthracene, fluorenyl-dimethylcarbonyl group substituted with a substituent of a 4 alkyl group, a d- 4- haloalkyl group, a d- 4 alkoxy group and a- 4 alkyl-carbonyl group;
或者 R2和 R3 共同构成 -CH2-CH2-， -CH2-CH2-CH2-或 -CH2-ZR-CH2-，式中 Z为杂原子， R 为杂原子上的取代基， 选自 H， d_6烷基， d_6烷氧基， 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 d_8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； 为 Η， 饱和或不饱和 d_6烃基， 卤代的饱和或不饱和 d_6烃基， 饱和或不饱和 d_6 烷氧基； Or R 2 and R 3 together form -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - or -CH 2 -ZR-CH 2 - wherein Z is a hetero atom and R is a hetero atom a substituent selected from the group consisting of H, d- 6 alkyl, d- 6 alkoxy, allyl, benzyl, phenyl, d- 4 alkoxy-d- 4 alkyl, d- 4 alkoxy-carbonyl, phenoxycarbonyl group, C 2 - 6 alkynyl group - carbonyl group, C 2 - 3 alkenyl - carbonyl group, C 3 - 6 cycloalkyl - carbonyl, benzoyl, or substituted with one or more substituents selected from halogen atoms, d- 4 haloalkyl, d_ 8 saturated or unsaturated alkyl or alkoxy and d_ 8 - C4 alkyl - substituted carbonyl group substituted benzoyl group, a carbonyl group or a furyl Ν, Ν- dimethyl carbonyl; is [eta], saturated Or an unsaturated d- 6 hydrocarbon group, a halogenated saturated or unsaturated d- 6 hydrocarbon group, a saturated or unsaturated d- 6 alkoxy group;
R5为苯基， 或为含氮、氧和 /或硫的五元或六元杂环基， 或取代的苯基， 取代的含氮、 氧和 /或硫的五元或六元杂环基， 或取代或未取代的 c5_12杂芳基， 其中所述取代基为选自 下组中的一个或多个： 卤素、 硝基、 d_6烷基、 d_6卤代烷基、 羟基 d_6烷基、 羟基、 d_6 烷氧基、 d_6卤代烷氧基、 胺基、 d_6烷基胺基、 未取代或具有 1-3个选自 d_6烷基、 硝基、 氰基、 卤素、 羟基或胺基的取代基的取代的苯基； R 5 is phenyl, or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group, a substituted five- or six-membered heterocyclic ring containing nitrogen, oxygen and/or sulfur a group, or a substituted or unsubstituted c 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, d- 6 halogenated alkyl, hydroxy d_ 6 alkyl, hydroxy, d- 6 alkoxy, d- 6 haloalkoxy, amine, d- 6 alkylamino, unsubstituted or having 1-3 selected from d- 6 alkyl, nitro, cyano, halogen a substituted phenyl group having a substituent of a hydroxyl group or an amino group;
为苯基， 或为含氮、氧和 /或硫的五元或六元杂环基， 或取代的苯基，取代的含氮、 氧和 /或硫的五元或六元杂环基， 或取代或未取代的 c5_12杂芳基， 其中所述取代基为选自 下组中的一个或多个： 卤素、 硝基、 d_6烷基、 d_6卤代烷基、 羟基 d_6烷基、 羟基、 d_6 烷氧基、 d_6卤代烷氧基、 胺基、 d_6烷基胺基、 未取代或具有 1-3个选自 d_6烷基、 硝基、 氰基、 卤素、 羟基或胺基的取代基的取代的苯基； a phenyl group, or a five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, or a substituted phenyl group, a substituted five- or six-membered heterocyclic group containing nitrogen, oxygen and/or sulfur, Or a substituted or unsubstituted c 5 -12 heteroaryl group, wherein the substituent is one or more selected from the group consisting of halogen, nitro, d- 6 alkyl, d- 6 halogenated alkyl, hydroxy d- 6 alkyl Alkyl, hydroxy, d- 6 alkoxy, d- 6 alkoxy, amino, d- 6 alkylamino, unsubstituted or having 1-3 selected from d- 6 alkyl, nitro, cyano, halogen, hydroxy Or a substituted phenyl group of an amine substituent;
R7和 各自独立地为 H或 d_6烷基， d_6烷氧基， 或者被 F， Cl， Br取代的 d_6烷基或 C1-6焼氧基； R 7 and each independently H or d 6 alkyl, d 6 alkoxy, or d 6 alkyl or C 1-6 alkoxy substituted by F, Cl, Br;
X为氰基， 硝基， 三氟甲基， 三氟乙酰基或三氟甲磺酰基；  X is cyano, nitro, trifluoromethyl, trifluoroacetyl or trifluoromethanesulfonyl;
Υ Υ2各自独立地为氢、 硝基， 氰基， 酯基， 三氟乙酰基， 乙酰基， 三氟甲磺酰基， 酰胺基、 三氟甲基或 R9， 其中 R9为 R3， 其中 Ri , R2， R3， R4如上所定义。 Υ Υ 2 are each independently hydrogen, nitro, cyano, ester, trifluoroacetyl, acetyl, trifluoromethanesulfonyl, amide, trifluoromethyl or R 9 , wherein R 9 is R 3 , wherein Ri, R 2 , R 3 and R 4 are as defined above.
2. 如权利要求 1所述的化合物、 或所述化合物的光学异构体、 顺反异构体， 其特征 在于， 所述化合物具有选自以下通式的结构：  2. The compound according to claim 1, or an optical isomer or cis-trans isomer of the compound, wherein the compound has a structure selected from the group consisting of:
Figure imgf000036_0001
Figure imgf000036_0001
通式 (I) 通式 (II) 通式 (III) 通式 (IV)  General formula (I) general formula (II) general formula (III) general formula (IV)
式中：  In the formula:
Ri R2、 R3、 、 R5、 Re、 R7、 R9和 X如权利要求 1中所定义， Ri R 2 , R 3 , , R 5 , Re, R 7 , R 9 and X are as defined in claim 1,
为硝基， 氰基， 酯基， 三氟乙酰基， 乙酰基， 三氟甲磺酰基， 酰胺基、 或三氟甲 基；  Is nitro, cyano, ester, trifluoroacetyl, acetyl, trifluoromethanesulfonyl, amide, or trifluoromethyl;
Y3为硝基， 氰基或酯基； Y 3 is a nitro group, a cyano group or an ester group;
η为 0或 1。  η is 0 or 1.
3. 如权利要求 1所述的化合物、 或所述化合物的光学异构体、 顺反异构体其特征在 于， 其中 选自： 吡啶基、 噻唑基、 嘧啶基、 四氢呋喃基、 噁唑基， 或其卤代物。  3. The compound according to claim 1, or an optical isomer, cis-trans isomer of the compound, wherein: selected from the group consisting of: pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, oxazolyl, Or its halogenated substance.
4. 如权利要求 1所述的化合物、 或所述化合物的光学异构体、 顺反异构体， 其特征 在于， R2和 R3独立地为氢或 d_6烷基， 为 H或 d_6烷基， R7为氢或 d_6烷基。 4. The compound according to claim 1, or an optical isomer, cis-trans isomer of the compound, wherein R 2 and R 3 are independently hydrogen or d 6 alkyl, H or d_ 6 alkyl, R 7 is hydrogen or d 6 alkyl.
5. 如权利要求 1所述的化合物、 或所述化合物的光学异构体、 顺反异构体， 其特征 在于， 其中 R5选自： 取代或未取代的苯基， 呋喃基， 噻吩基， 吡咯基， 咪唑基， 噻唑基， 或噁唑基。 The compound according to claim 1, or the optical isomer or cis-trans isomer of the compound, wherein R 5 is selected from the group consisting of: substituted or unsubstituted phenyl, furyl, thienyl , pyrrolyl, imidazolyl, thiazolyl, or oxazolyl.
6. 一种农用组合物， 其包含：  6. An agricultural composition comprising:
Ca)0.00001-99.99重量％的权利要求 1-5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、 或它们的组合； 以及  Ca) 0.00001-99.99% by weight of a compound according to any one of claims 1 to 5, an optical isomer, a cis-trans isomer or a pesticide-acceptable salt thereof, or a combination thereof;
(b)农药学上可接受的载体和 /或赋形剂。  (b) Agrochemically acceptable carriers and/or excipients.
7. 如权利要求 6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。  7. Use of the agricultural composition according to claim 6, characterized in that it is used for killing or preventing agricultural pests, sanitary pests and pests harmful to animal health; or for killing or preventing agricultural pests, sanitary pests and A pesticide composition that is harmful to animal health.
8. —种杀虫和 /或防虫方法， 其特征在于， 所述方法包括步骤： 将如权利要求 1-5 中 任一项所述的化合物、 其光学异构体、 顺反异构体、 盐或权利要求 7所述的杀虫剂组合物 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。  8. An insecticidal and/or pest control method, characterized in that the method comprises the steps of: a compound according to any one of claims 1 to 5, an optical isomer thereof, a cis-trans isomer, The salt or the pesticide composition of claim 7 is applied to a plant body that is or may be subject to pests, soil surrounding it, or the environment.
9. 如权利要求 1-5中任一项所述的化合物、 其光学异构体、 顺反异构体的制备方法， 所述方法包括步骤：  The method for producing a compound according to any one of claims 1 to 5, an optical isomer thereof, and a cis-trans isomer, the method comprising the steps of:
在惰性溶剂中，使式 (a)的化合物与式 (b)的化合物发生加成反应从而制得具有通式 (I) 或 (II)的化合物； 或者使式 (a)自身发生加成反应从而制得具有通式 (III)或 (IV)的化合物 RC 、The compound of the formula (a) is subjected to an addition reaction with the compound of the formula (b) in an inert solvent to obtain a compound having the formula (I) or (II); or the addition reaction of the formula (a) itself is carried out. Thus producing a compound of the formula (III) or (IV) RC,
Figure imgf000037_0001
式 (b)，
Figure imgf000037_0001
Formula (b),
式中， R2、 R3、 、 R5、 Re、 R7、 X、 n、 Yi 和 Y3如权利要求 1和 2中所定义, Wherein R 2 , R 3 , R 5 , Re, R 7 , X, n, Yi and Y 3 are as defined in claims 1 and 2,
10. 如权利要求 9所述的制备方法， 其特征在于， 所述化合物具有通式 (I), (II), (111)， 或 (IV)所示的 The method according to claim 9, wherein the compound has the formula (I), (II), (111), or (IV)
在二氯甲 )的化合物：  Compounds in dichloromethane:
通式 (I) General formula (I)
在二氯甲烷中， 进行如下反应， 从而获得通式 (II)的化合物：  In dichloromethane, the following reaction is carried out to obtain a compound of the formula (II):
Figure imgf000037_0002
通式 (II)
Figure imgf000037_0002
General formula (II)
在二氯甲烷中， 进行如下反应， 从而获得通式 (III)的化合物:  In dichloromethane, the following reaction is carried out to obtain a compound of the formula (III):
Figure imgf000037_0003
Figure imgf000037_0003
在二氯甲烷中 进行如下反应， 从而获得通式 (IV)的化合物:  The following reaction is carried out in dichloromethane to obtain a compound of the formula (IV):
Figure imgf000037_0004
Figure imgf000037_0004
通式 (IV)。  General formula (IV).
PCT/CN2010/072232 2009-04-28 2010-04-27 1,2,3-3h pyridine heterocyclic compounds, their agricultural compositions, their use and their preparation methods WO2010124619A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200910050137.7 2009-04-28
CN200910050137.7A CN101875653B (en) 2009-04-28 2009-04-28 Preparation and application of 1,2,3-3H pyridine-heterocyclic compound

Publications (1)

Publication Number Publication Date
WO2010124619A1 true WO2010124619A1 (en) 2010-11-04

Family

ID=43018346

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2010/072232 WO2010124619A1 (en) 2009-04-28 2010-04-27 1,2,3-3h pyridine heterocyclic compounds, their agricultural compositions, their use and their preparation methods

Country Status (2)

Country Link
CN (1) CN101875653B (en)
WO (1) WO2010124619A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015117563A1 (en) * 2014-02-07 2015-08-13 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105461724B (en) * 2014-08-11 2019-11-05 华东理工大学 Nitrogenous endocyclic compound and its preparation and use with insecticidal activity
CN106397419B (en) * 2016-09-09 2019-06-25 华东理工大学 A kind of diarylethene can photochromic Pesticidal compound and its preparation method and application
CN113004263B (en) * 2021-03-11 2024-01-26 陕西大美化工科技有限公司 4-thiophene ring substituted pyridine derivative and application thereof in pesticides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1295228C (en) * 2004-11-23 2007-01-17 华东理工大学 Nitryl methylene derivatives and uses thereof
WO2007101369A1 (en) * 2006-03-09 2007-09-13 East China University Of Science And Technology Preparation method and use of compounds having high biocidal activities
CN101045728B (en) * 2006-03-28 2012-03-21 华东理工大学 Preparation method and use of compound with high insecticidal activity

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DEWEN DONG ET AL.: "[5C + IN] Annulation: a novel synthetic strategy for functionalized 2,3-dihydro-4-pyridones.", CHEMICAL COMMUNICATIONS, vol. 28, 2005, pages 3580 - 3582 *
KELLER, P. A. ET AL., ALK-1-ENE-1,1-DIAMINES WITH RETENTION OF THE FUNCTIONAL GROUP SCIENCE OF SYNTHESIS., vol. 24, 2006, pages 707 - 746 *
XUSHENG SHAO ET AL., SYNTHESIS, CRYSTAL STRUCTURE, AND INSECTICIDAL ACTIVITIES OF HIGHLY CONGESTED HEXAHYDROIMIDAZO[1,2-A]PYRIDINE DERIVATIVES: EFFECT OF CONFORMATION ON ACTIVITIES., vol. 58, no. 5, December 2009 (2009-12-01), pages 2690 - 2695 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015117563A1 (en) * 2014-02-07 2015-08-13 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives
US9586969B2 (en) 2014-02-07 2017-03-07 Syngenta Participations Ag Microbiocidal heterobicyclic derivatives

Also Published As

Publication number Publication date
CN101875653B (en) 2014-12-24
CN101875653A (en) 2010-11-03

Similar Documents

Publication Publication Date Title
EP2377845B1 (en) Heterocyclic nitrogenous or oxygenous compounds with insecticidal activity formed from dialdehydes and their preparation and uses thereof
AU2013226812B2 (en) Pest control composition including novel iminopyridine derivative
KR101504575B1 (en) Divalent and oxabridged heterocyclic neonicotinoid compounds and preparation methods thereof
CN108003162B (en) Condensed heterocyclic compouds and its application
KR20150013692A (en) Macrocyclic picolinamides as fungicides
WO2006056108A1 (en) Nitromethylene derivatives and their use
JP2012180339A (en) Isoxazoline compound and harmful organism-controlling agent
US8232407B2 (en) Nitrogenous heterocyclic compounds with insecticidal activity, and the preparation and use thereof
CN108129481A (en) Condensed heterocyclic compouds and its application of the one kind containing pyrazole ring
KR20180128004A (en) Herbicide
CN102070607A (en) Pyridine-n-oxide anabasine compound with insecticidal activity, and application thereof
WO2010124619A1 (en) 1,2,3-3h pyridine heterocyclic compounds, their agricultural compositions, their use and their preparation methods
WO2012065568A1 (en) Azo heterocyclic compound having insecticidal activity, and preparation and applications thereof
KR20180128427A (en) Herbicide
WO2021169699A1 (en) Use of eight-membered oxygen-bridge heterocyclic compound as insecticide synergist having selectivity to bee
CN102863446B (en) Preparation of pyrrole and pyrrolin fused ring compound with insecticidal activity and use thereof
JP2022536757A (en) Fused heterocyclic compounds and their use as pest control agents
CN110452167B (en) Quinoline derivatives, preparation method and application thereof
CN103242323B (en) Nitrogen (sulfur) containing bridge ring compound with insecticidal activity, preparation method and application
CN110452238B (en) Pyrimidinium compounds and uses thereof
WO2019086009A1 (en) Nitrogen-containing fused tricyclic compound and use thereof as agroforestry insecticide
CN103570729B (en) Bicyclic neonicotine compounds constructed by cycloalkenone, and preparation method and application thereof
CN103518745B (en) Dialdehyde-built nitrogen-containing or oxygen-containing heterocyclic compound with insecticidal activity and preparation method thereof
CN104557963A (en) Dialdehyde-constructed nitrogenous or heterocyclic oxygen compound with insecticidal activity and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10769308

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10769308

Country of ref document: EP

Kind code of ref document: A1