WO2024055801A1 - 一种吡啶酰胺衍生物及其用途 - Google Patents

一种吡啶酰胺衍生物及其用途 Download PDF

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WO2024055801A1
WO2024055801A1 PCT/CN2023/113449 CN2023113449W WO2024055801A1 WO 2024055801 A1 WO2024055801 A1 WO 2024055801A1 CN 2023113449 W CN2023113449 W CN 2023113449W WO 2024055801 A1 WO2024055801 A1 WO 2024055801A1
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compound
isomer
alkyl
pesticide
formula
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English (en)
French (fr)
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王传伟
包如胜
张军
王伟
林健
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顺毅股份有限公司
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • 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
    • A01N43/80—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 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P5/00—Nematocides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/337—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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

Definitions

  • the present invention belongs to the field of pesticides, and specifically relates to a pyridine amide derivative and its use.
  • Pesticides are the most diverse and widely used pesticides and play a vital role in solving human food problems.
  • the first discoveries were natural pesticides and inorganic compounds, which were used in large amounts and had short durations of effect.
  • organic pesticides such as organochlorines, organophosphorus and carbamates, some have high acute toxicity to mammals.
  • many currently commercially available pesticides are becoming increasingly resistant, requiring higher dosages to kill pests, placing a huge burden on the environment. Therefore, there is a continuing need in the field for new compounds that are more effective, more economical, less toxic, safer for the environment, or have different mechanisms of action to replace older generation products.
  • Patent applications CN106103414A, CN105873908A, and CN111050559A all disclose research on polyfluorinated compounds.
  • the above research results are in terms of efficacy and durability. Sex, toxicity and other aspects are still not satisfactory.
  • the object of the present invention is to provide a new class of pyridinamide compounds, which can achieve better pest control effects at lower dosages, especially for Lepidoptera, Hemiptera, Diptera or Homoptera, etc. pests.
  • the invention provides a compound of formula (I) as a pyridine amide derivative, or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or its pesticide-acceptable salt,
  • R 1 , R 2 and R 3 are each independently selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl , C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
  • M is selected from oxygen or sulfur
  • W is selected from C 3 -C 6 cycloalkyl or three- to six-membered heterocycloalkyl, wherein 1 to 3 hydrogens in the C 3 -C 6 cycloalkyl or three- to six-membered heterocycloalkyl
  • the atoms are optionally replaced by halogen, hydroxyl, nitro, amino, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy substitution;
  • Q is a three- to six-membered heterocycloalkyl group or a C 1 -C 3 alkyl group substituted by one or more substituents, each of which is independently selected from halogen, hydroxyl, nitro, amino , cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl, C 1 -C 6 Haloalkoxy, C 3 -C 6 cycloalkyl, three- to six-membered heterocycloalkyl, phenoxy, benzyloxy or -O-(CH 2 ) m -O-(CH 2 ) n -CH 3 ;
  • n is any integer from 1 to 3;
  • n is any integer from 0 to 2.
  • R 1 , R 2 and R 3 are each independently selected from hydrogen, fluorine, chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 fluoroalkyl, C 1 -C 3 alkoxy or C 1 -C 3 fluoroalkoxy group, preferably hydrogen, fluorine, chlorine, bromine, methyl, monofluoromethyl, difluoromethyl, trifluoromethyl, ethyl, fluoroethyl, methoxy, monofluoromethyl Oxygen, difluoromethoxy, trifluoromethoxy or ethoxy;
  • M is selected from oxygen or sulfur
  • W is selected from cyclopropyl, wherein 1 to 3 hydrogen atoms in the cyclopropyl are optionally replaced by halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy substituted, preferably optionally by fluorine, chlorine, bromine, cyano, methyl, monofluoromethyl, difluoromethyl, trifluoromethyl, ethyl, Fluoroethyl, methoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy or ethoxy substitution;
  • Q is a three- to six-membered heterocycloalkyl group or a C 1 -C 3 alkyl group substituted by one or more substituents, each of which is independently selected from cyano, C 1 -C 3 Alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 1 -C 3 alkoxy, C 3 -C 6 cycloalkyl, three- to six-membered heterocycloalkyl, phenoxy , benzyloxy or -O-(CH 2 ) m -O-(CH 2 ) n -CH 3 ;
  • n 1, 2 or 3;
  • n 0, 1 or 2.
  • the heterocycloalkyl group is an oxygen heterocycloalkyl group, an azacycloalkyl group or a thiocycloalkyl group, which contains 1 to 3 oxygen heteroatoms, nitrogen heteroatoms or sulfur heteroatoms, preferably 1 or 2 oxygen heteroatoms. atoms, nitrogen heteroatoms or sulfur heteroatoms.
  • Q is oxanyl, oxanyl, or methyl, ethyl, n-propyl or isopropyl substituted by one or more substituents, each of which is independently selected from cyano Base, methyl, ethyl, ethylene, acetylene, methoxy, ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl, oxanyl, oxetane Butyl, oxanyl, oxanyl, azahexyl, thiahexyl, phenoxy, benzyloxy, -OCH 2 OCH 3 or -OCH 2 CH 2 OCH 3 .
  • the compound of formula (I) particularly has the following structure:
  • pyridine amide derivatives can also cover any isotope-labeled compounds of the compounds of formula (I), or optical isomers thereof, Geometric isomers, tautomers or isomer mixtures, or their pesticide acceptable salts.
  • optical isomer means that when a compound has one or more chiral centers, each chiral center can exist in R configuration or S configuration, and the various isomers formed thereby are optical isomers. conformation. Optical isomers include all diastereoisomers, enantiomers, meso, racemates or mixtures thereof. Optical isomers can be separated, for example, by chiral chromatography columns or by chiral synthesis.
  • geometric isomer means that when a double bond is present in a compound, the compound may exist as cis isomer, trans isomer, E isomer and Z isomer. Geometric isomers include cis isomers, trans isomers, E isomers, Z isomers or mixtures thereof.
  • tautomer refers to an isomer resulting from the rapid movement of an atom between two positions in a molecule. Those skilled in the art can understand that tautomers can transform into each other and may reach an equilibrium state and coexist in a certain state.
  • references herein to "pyridine amide derivatives", “compounds of formula (I)” or “compounds of the present invention” also include isotopically labeled compounds in which any atom in the compound is replaced by its isotope atom.
  • the present invention includes all pharmaceutically acceptable isotopically labeled compounds of the compounds of formula (I) in which one or more atoms are replaced by atoms having the same atomic number but a different atomic mass or mass number than atoms normally found in nature. replace.
  • isotopes suitable for inclusion in the compounds of the invention include isotopes of hydrogen such as 2 H(D) and 3 H(T), isotopes of carbon such as 11 C, 13 C and 14 C, and isotopes of chlorine such as 37 Cl, isotopes of fluorine such as 18 F, isotopes of iodine such as 123 I and 125 I, isotopes of nitrogen such as 13 N and 15 N, isotopes of oxygen such as 15 O, 17 O and 18 O, and of sulfur Isotopes such as 35S .
  • isotopes of hydrogen such as 2 H(D) and 3 H(T)
  • isotopes of carbon such as 11 C, 13 C and 14 C
  • isotopes of chlorine such as 37 Cl
  • isotopes of fluorine such as 18 F
  • isotopes of iodine such as 123 I and 125 I
  • isotopes of nitrogen such as 13 N and
  • Isotopically labeled compounds of formula (I) can generally be prepared by conventional techniques known to those skilled in the art or by using a suitable isotopically labeled reagent in place of a previously used non-labeled reagent, similarly as described in the Examples and preparations attached hereto. method to prepare.
  • the compounds of formula (I) may exist in the form of pesticide-acceptable salts, such as acid addition salts and/or base addition salts of compounds of formula (I).
  • pesticide-acceptable salts such as acid addition salts and/or base addition salts of compounds of formula (I).
  • pesticacetically acceptable salts as used herein include acid addition salts or base addition salts that may occur in compounds of formula (I).
  • Pesticide-acceptable salts of compounds of formula (I) include acid addition salts and base addition salts thereof. Suitable acid addition salts are formed from acids that form nontoxic salts. Examples include, but are not limited to: acetate, adipate, aspartate, benzoate, benzenesulfonate, bicarbonate/carbonate, bisulfate/sulfate, borate , camphor sulfonate, citrate, cyclohexylamine sulfonate, ethylene disulfonate, formate, fumarate, grape heptonate, gluconate, glucuronate, hexanate Fluorophosphate, 2-(4-hydroxybenzyl)benzoate, hydrochloride/chloride, hydrobromide/bromide, hydroiodide/iodide, 2-isethionate, lactate , malate, maleate, malonate, methanesulfonate, methylsulfate, naphthoate
  • Suitable base addition salts are formed from bases that form nontoxic salts. Examples include, but are not limited to: aluminum, arginine, calcium, choline, diethylamine, diethanolamine, glycine, lysine, magnesium, meglumine, ethanolamine, potassium, sodium, tromethamine, and zinc salts. Half-salts of acids and bases may also be formed, such as hemisulfate and hemicalcium salts.
  • suitable salts see Handbook of Pharmaceutical Salts: Properties, Selection and Use by Stahl and Wermuth (Wiley-VCH, 2002). Methods for preparing pesticide-acceptable salts of the compounds described herein are known to those skilled in the art.
  • hydroxy refers to -OH; the term “amino” refers to -NH2 ; the term “nitro” refers to -NO2 ; the term “cyano” refers to -CN; the term “phenoxy” refers to -O -Phe; and the term “benzyloxy” refers to -O- CH2 -Phe.
  • substituted means that one or more (preferably 1 to 5, more preferably 1 to 3) hydrogen atoms in a group are independently replaced by a corresponding number of substituents.
  • each independently means that when there is more than one substituent, the substituents may be the same or different.
  • alkyl refers to saturated aliphatic hydrocarbons, including straight and branched chains. In some embodiments, an alkyl group has 1-8, or 1-6, or 1-3 carbon atoms.
  • C 1-8 alkyl refers to a straight or branched chain radical of atoms having 1 to 8 carbon atoms.
  • C 1-8 alkyl includes in its definition the terms “C 1-6 alkyl", “C 1 -C 3 alkyl” and "C 1 -C 4 alkyl”.
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, iso Pentyl, neopentyl, (R)-2-methylbutyl, (S)-2-methylbutyl, 3-methylbutyl, 2,3-dimethylpropyl, 2,3- Dimethylbutyl, hexyl, etc.
  • Alkyl groups may be optionally substituted with one or more (eg, 1 to 5) suitable substituents.
  • haloalkyl refers to an alkyl group having one or more halogen substituents (up to a perhaloalkyl group, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom) .
  • C 1 -C 6 haloalkyl refers to a C 1 -C 6 alkyl group having one or more halogen substituents (up to a perhaloalkyl group, i.e., each hydrogen atom of the alkyl group is replaced by halogen atoms).
  • C 1- C 4 haloalkyl refers to a C 1 - C 4 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen of the alkyl group atoms are all replaced by halogen atoms);
  • C 1- C 3 haloalkyl refers to a C 1- C 3 alkyl group having one or more halogen substituents (up to a perhaloalkyl group, i.e., an alkyl group each hydrogen atom of the group is replaced by a halogen atom);
  • C 1- C 2 haloalkyl refers to a C 1- C 2 alkyl group having one or more halogen substituents (i.e., methyl or ethyl) (up to perhaloalkyl, i.e.
  • C 1 haloalkyl refers to a methyl group having 1, 2 or 3 halogen substituents.
  • haloalkyl groups include: CF3 , C2F5 , CHF2 , CH2F , CH2CF3 , CH2Cl , and the like .
  • n-membered heterocycloalkyl refers to a group having m ring-forming carbon atoms and (nm) Heterocycloalkyl with ring-forming heteroatoms selected from O, S and N.
  • 4-7 membered heterocycloalkyl groups include, but are not limited to, oxetane, thietane, azetidine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, tetrahydropyran, tetrahydrothiopyran , piperidine, morpholine, piperazine, oxepane, thiepane, azepane.
  • heterocycloalkyl groups may be optionally substituted with one or more suitable substituents.
  • the numerical range related to the number of substituents, the number of carbon atoms, and the number of ring atoms represents an enumeration of all integers within the range, and the range is only used as a simplified expression.
  • “1-4 substituents” means 1, 2, 3 or 4 substituents
  • "3-8 ring atoms” means 3, 4, 5, 6, 7 or 8 ring atoms . Therefore, the numerical range related to the number of substituents, the number of carbon atoms, and the number of ring atoms also covers any subrange thereof, and each subrange is also deemed to be disclosed herein.
  • the compounds of the present invention can be prepared in a variety of ways known to those skilled in the art of organic synthesis. Those skilled in the art can refer to the synthesis routes of specific compounds in specific embodiments of the present invention and appropriately adjust the reaction raw materials and reaction conditions to obtain synthesis methods for other compounds.
  • the present invention also lists a number of synthesized exemplary compounds, the specific group selections of which are shown in Table 1 below. It should be understood that the scope of the present invention is not limited to the exemplary compounds listed in the following table, and the selection of each group of the compounds in the following table 1 can be combined in any way without particular limitation.
  • the present invention provides a pesticide composition
  • a pesticide composition comprising a compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer thereof. mixture, or a pesticide-acceptable salt thereof, and a pesticide-acceptable carrier.
  • Pesticide acceptable carriers can be organic or inorganic inert carrier materials, for example, suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oil, polyalkylene glycol, petrolatum, mannitol, Cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, salt water, glycerin, ethanol, etc.
  • suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oil, polyalkylene glycol, petrolatum, mannitol, Cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, salt water, glycerin, ethanol, etc.
  • the pesticide composition may also contain other additives, such as preservatives, stabilizers, emulsifiers, buffers, diluents, binders, wetting agents, lubricants, glidants, and the like.
  • the dosage form of the pesticide composition of the present invention may be a liquid dosage form, a solid dosage form or a semi-solid dosage form, without particular limitation.
  • the dosage form of the pesticide composition is selected from powder, granule, liquid, suspension or spray, preferably wettable powder, wettable liquid, soluble powder, dispersible liquid, water agents, microemulsions, emulsifiable concentrates, aqueous emulsions, sprayable solutions, dispersible oil suspensions, microencapsulated suspensions, water-dispersible granules, water-soluble granules, macrogranules, granules for broadcast and soil application, aerosols Aerosols, ultra-low volume and wax products.
  • the content of the compound of the present invention in its pesticide composition can be adjusted according to actual needs (such as dosage form, application method, application object, etc.), including but not limited to 0.001 mg/L-10 mg/L, such as 0.001 mg/L.
  • L 0.01mg/L, 0.1mg/L, 0.5mg/L, 1mg/L, 2.5mg/L, 5mg/L or 10mg/L.
  • the specific application frequency can be determined by those skilled in the relevant field, for example, once a day, once every 2 days, once every 3 days, once every 4 days, once every 5 days, once every 6 days, twice a day, Three times a day and so on.
  • the present invention provides a compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture thereof, or a pesticide acceptable compound thereof.
  • the compounds of the present invention are suitable for preventing and treating pests or harmful mites, that is, controlling pests or harmful mites, and said pests or harmful mites refer to harmful General susceptibility and resistance of the compounds of the invention to harmful or unwanted insects or mites encountered in particular in the fields of agriculture, forestry, storage and material protection and hygiene
  • the species are all active and effective at all stages of pest or mite development.
  • the present invention also relates to a method for preventing and controlling pests or harmful mites, which method includes applying a control-effective amount of formula (I) to the insect location, insect habitat, pest habitat, area required for protection, or directly to the insect to be controlled. ) compound.
  • the compounds of the present invention may also be used to control other invertebrate pests or organisms.
  • the insect habitat, pest habitat or pest mite habitat refers to the environment where insects, pests or pest mites live or where their eggs exist, including the air around them, food eaten or objects they come into contact with.
  • the active compound for example, by applying the active compound to the seeds of the plant (before planting), to the seedlings, or planted cuttings, leaves, stems, fruits, grains and/or roots, or to the soil or other growing medium (before the crop is planted). before or after), by controlling insects or pest mites that eat, damage or come into contact with edible produce, ornamental plants, turf, pasture plants or other plants of economic value, and by controlling sap-feeding pests such as mealybugs and planthoppers , aphids, etc.
  • insects or harmful mites such as two-spotted spider mites, cinnabar spider mites, etc. to protect these plants against diseases caused by viruses, fungi or bacteria; the plants include plants reproduced by conventional methods, and also include plants modified by modern biotechnology Plants genetically derived for insect or pest mite resistance, herbicide resistance, high yields, and/or other beneficial traits. It is contemplated that these compounds may be useful in protecting fabrics, paper, stored grains, seeds and other foodstuffs, houses, buildings and the like, and/or places by applying the compounds of the present invention to or near these objects.
  • the inventors of the present invention have found that even if the compound of the present invention is applied at a lower dose, it can still show its effect on pests, especially against Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, It has an efficient control effect on pests of the order Isoptera, Diptera, Hymenoptera, Trichophaga, Phytophora, Orthoptera, Blattida, Flea, Acarina, Nematoda and other pests.
  • the pest is selected from the group consisting of Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera, Diptera, Hymenoptera, Trichoptera, Pests of the order Pestida, Phytophthora, Orthoptera, Blattida, Flea, Acari, and Nematoda. More specific pest classifications are as follows:
  • Lepidoptera Heliothis spp., Helicoverpa spp., Spodoptera spp., Mythimna unipuncta, Agrotis ipsilon, Earias spp. .), Trichoplusia ni, Anticarsia gemmatalis, Rachiplusia nu, Plutella xylostella, Chilo spp, Scirpophaga incertulas), Sesamia inferens, Cnaphalocrocismedinalis, Ostrinia nubilalis, Cydia pomonella, Carposina niponensis, Adoxophyes orana , Archipsargyrospilus, Pandemis heparana, Epinotia aporema, Eupoecilia ambiguella, Lobesia botrana, Polychrosisbiteana, Cotton Red Pectinophora gossypiella, Pierisrapae,
  • Coleoptera Diabrotica spp., Leptinotarsa decemlineata, rice mudworm (Oulema oryzae), cotton boll weevil (Anthonomusgrandis), rice water weevil (Lissorhoptrusoryzophilus), wireworm beetle (Agriotes spp.), Melanotus communis, Japanese bean beetle (Popillia japonica), round-headed rhinoceros beetle (Cyclocephala spp. .), Tribolium spp., etc.;
  • Homoptera Aphis spp., Myzus Persicae, Rhopalosiphum spp., Dysaphis plantaginea, Toxoptera spp., Alfalfa aphid (Aphis craccivoraKoch), Euphorbia longum Macrosiphum euphorbiae, Aulacorthum solani, Sitobion avenae, Metopolophium dirhodum, Schizaphisgraminum, Brachycolus noxius), black-tailed leafhopper (Nephotettix spp.), brown planthopper (Nilaparvata lugens), white-backed planthopper (Sogatella furcifera), gray planthopper (Laodelphaxstriatellus), whitefly (Bemisiatabaci), greenhouse whitefly (Trialeurodes vaporariorum), Aleurodes proletella, Aleurothrixus floccosus, Quadraspidiotuspernicio
  • Hemiptera Lygus spp., Eurygaster maura, Nezaraviridula, Piezodorus guildingi, Leptocorisa varicornis, temperate bedbug (Cimexlectularius), tropical bedbug (Cimex hemipterus), etc.;
  • Thysanoptera Frankliniella occidentalis, Thrips spp., Scirtothrips dorsalis, etc.;
  • Isoptera Reticulitermes flavipes, Coptotermesformosanus, Reticulitermes virginicus, Heterotermesaureus, Reticulitermes hesperus, Coptotermes frenchii, Shedorhinotermes spp., Reticulitermes santonensis), Reticulitermes grassei, Reticulitermesbanyulensis, Reticulitermes speratus, Reticulitermes hageni, Reticulitermes tibialis, Zootermopsis spp., Incisitermes spp., Edged termites ( Marginitermes spp.), Macrotermes spp., Microcerotermes spp., Microtermes spp., etc.;
  • Diptera Liriomyza spp., Musca domestica, Aedes spp., Culex spp., Anopheles spp., Fannia spp. ), Stomoxys spp., etc.;
  • Hymenoptera Red ants (Iridomyrmex humilis), fire ants (Solenopsis spp.), Pharaoh ants (Monomorium pharaonis), Atta spp., harvest ants (Pogonomyrmex spp.), Camponotus spp., house ants ( Monomorium spp.), house ants (Tapinoma sessile), pavement ants (Tetramorium spp.), Xylocapa spp., wasps (Vespula spp.), long-legged wasps (Polistes spp.), etc.;
  • Orthoptera black locust (Melanoplus spp.), East Asian migratory locust (Locusta migratoria), desert locust (Schistocerca gregaria), mole cricket (Gryllotalpidae) (mole crickets), etc.;
  • Blattales cockroaches, Blatta orientalis, Blattella germanica, Periplaneta americana, Supellalongipalpa, Periplaneta australasiae, Brown cockroach Periplaneta brunnea, Parcoblatta pennsylvanica, Periplaneta fuliginosa, Pycnoscelus surinamensis, etc.;
  • Fleas (Ctenophalides spp.), human fleas (Pulex irritans), etc.;
  • Tetranychidae Tetranychidae, Eupodidae, Eriophyiade, Phytoseiidae, Acaridae, including but not limited to Tetranychus spp. ), spider mite (Panonychus spp.), cinnabar spider mite (Tetranychuscinnabarinus), Oriental spider mite (Eotetranychus carpini), two-spotted spider mite (Tetranychus urticaeKoch.), citrus rust mite (Phyllocoptruta oleivora), Aculus pelekassi, purple short beard Brevipalpus phoenicis, Boophilus spp., Dermacentorvariabilis, Rhipicephalussanguineus, Amblyommaamericanum, Ixodes spp., Notoedres cati ), scabies mites (Sarcoptesscabiei), dust mites (Dermat
  • Class Nematoda Dirofilaria immitis, Meloidogynespp., Heterodera spp., Hoplolaimus columbus, Belonolaimus spp., root rot Nematodes (Pratylenchus spp.), kidney-shaped nematodes (Rotylenchusreniformis), decorative small ring nematodes (Criconemella ornata), stem nematodes (Ditylenchus spp.), leaf bud nematodes (Aphelenchoides besseyi), rice field hidden root nematodes (Hirschmanniella spp.), etc.
  • the pests may be selected from the group consisting of diamondback moth, brown planthopper, Spodoptera frugiperda, Spodoptera litura, armyworm, leek worm, stink bug, green leafhopper or Lagerstroemia velvet scale.
  • the compound of formula (I) of the present invention can be synthesized by a variety of methods familiar to those skilled in the field of organic synthesis. Some exemplary methods for the synthesis of compounds of formula (I) are given in the following specific examples, and these methods are well known in the field of synthetic chemistry. Obviously, with reference to the exemplary schemes in this patent, those skilled in the art can easily design synthetic routes for other compounds of formula (I) by appropriately adjusting the reactants, reaction conditions and protecting groups.
  • test conditions for hydrogen nuclear magnetic resonance spectroscopy used in the examples are: at room temperature, a Bruker 400MHz or 600MHz nuclear magnetic instrument, with CDCl 3 , d 6 -DMSO, CD 3 OD or d 6 -acetone as the For solvents (reported in ppm), use TMS (0ppm) or chloroform (7.26ppm) as the reference standard.
  • the mass spectrometry analysis methods used in the examples are: using Agilent 1260HPLC; Agilent 6120ESI.
  • Phase A acetonitrile (containing 0.1% formic acid); Phase B: water (containing 0.1% formic acid).
  • MS parameters ESI positive scan, collision induced ionization: 70V.
  • room temperature refers to a temperature between about 0°C and 40°C, or about 20°C and 30°C, or about 23°C and 28°C, or about 25°C.
  • Target compound 2-chloro-N-cyclopropyl-5-(1-(2,6-dichloro-4-(perfluoropropan-2-yl)phenyl)-1H-pyrazol-4-yl) -Synthesis of N-(oxan-2-ylmethyl)nicotinamide (corresponding to compound 26 in Table 1)
  • Step 1 Synthesis of 5-bromo-2-chloro-N-cyclopropyl-N-(oxan-2-ylmethyl)nicotinamide
  • Step 2 2-Chloro-N-cyclopropyl-5-(1-(2,6-dichloro-4-(perfluoropropan-2-yl)phenyl)-1H-pyrazol-4-yl Synthesis of )-N-(oxan-2-ylmethyl)nicotinamide
  • Example 2 Referring to the synthesis method of Example 1, the preparation was carried out in a similar manner using corresponding raw materials and conditions to obtain the target compound of Examples 2-28, whose structure and characterization data are shown in Table 2.
  • Test example biological activity test
  • insecticidal compound IT 2 -2 disclosed as CN106103414A (expressed as KC 1 herein); the insecticidal compound IT 48 -3 disclosed as CN105873908A (expressed as KC 2 herein); and CN111050559A
  • the insecticidal compound 28 (denoted herein as KC 3 ) was used as a positive control.
  • Compound preparation Use an analytical balance (0.0001g) to weigh a certain mass of the original drug, dissolve it in N,N dimethylformamide containing 1 ⁇ Tween-80 emulsifier to prepare a 1% mother solution, and then dilute it with distilled water for later use. .
  • Example 1 The test results show that the compound of the present invention has excellent insecticidal activity against diamondback moth, among which Example 1, Example 2, Example 11, Example 14, Example 16, Example 20, Example 21, Example 24, Compound of Example 28
  • the control effect against diamondback moth was 100% at the dose of 25 mg/L; after further reducing the dose, the compounds of Example 1, Example 11, Example 14, and Example 28 were effective against diamondback moth at the doses of 2.5 mg/L and 1 mg/L.
  • the control effect against diamondback moth is still 100%.
  • the compound of Example 2 has a control effect of more than 80% against diamondback moth at a dose of 2.5 mg/L; after further reducing the dose, the compound of Example 1 still has a control effect against diamondback moth at a dose of 0.25 mg/L. 100%; while the compound of Example 11 has a control effect of more than 80% against diamondback moth at a dose of 0.25 mg/L.
  • the control compound KC 3 was inactive at the test concentration of 0.25 mg/L.
  • the test results show that the compounds of the present invention have certain biological activity against rice brown planthopper.
  • the compounds of Example 1 and Example 11 have a control effect of more than 90% against rice brown planthopper at a dose of 200 mg/L; while the compound of Example 28 has a control effect of more than 90% at a dose of 200 mg/L.
  • the control effect against rice brown planthopper at the dose of 200 mg/L is more than 80%.
  • the control effect of the control compound KC 1 on rice brown planthopper at a dose of 200 mg/L was only 40%;
  • Determination of activity of Spodoptera Frugiperda Use the leaf dipping method. Dip an appropriate amount of corn leaves in the pesticide for 30 seconds, then place them in a plastic petri dish lined with filter paper to dry naturally in the shade. Each dish is connected to 8 2-year-old Spodoptera Frugiperda and placed in the 26°C light (16/8h) observation room. Observe after 48 hours. Touch the insect body lightly with a brush. If there is no reaction, it is considered dead. The test is repeated three times, and a blank control without adding any agent is set up. The test concentration is 1mg/L.
  • the test results show that the compounds of the present invention have good biological activity against Spodoptera Frugiperda.
  • the control effect of the compounds of Example 1 and Example 28 against Spodoptera Frugiperda at a dose of 1 mg/L is 100%; and the implementation The compound in Example 11 has a control effect of more than 95% against Spodoptera Frugiperda at a dose of 1 mg/L.
  • the control efficacy of the control compounds KC 1 and KC 2 against Spodoptera Frugiperda at a test concentration of 1 mg/L was 80%.
  • Example 1 The test results show that the compound of the present invention has excellent biological activity against armyworms, among which Example 1, Example 2, Example 9, Example 11, Example 14, Example 16, Example 20, Example 21, Example
  • the compounds of Example 24 and Example 28 have a control effect of 100% against armyworm at a dose of 100 mg/L; while the compounds of Example 5 and Example 13 have a control effect of more than 90% against armyworm at a dose of 100 mg/L. .
  • the compounds of Example 1, Example 11, Example 14, and Example 28 After further reducing the dosage, have a 100% control effect on armyworm at a dose of 10 mg/L; while the compound of Example 9 has a control effect of 10 mg/L at a dose of 10 mg/L.
  • the control effect against armyworm is over 80%.
  • Table 4 Parallel test results (lethality rate, %) of exemplary compounds against A. chinensis
  • E. lagerstroemia Count the number of second-instar nymphs of E. lagerstroemia on the branches under a microscope and record it as the base number. Carefully immerse the branches with Lagerstroemia velvet scales in the medicinal solution for 10 seconds, take them out, wrap the base of the branches with soaked cotton to moisturize, and place them in a culture box. Place in an incubator with a temperature of 25°C and a humidity of 65%. After 48 hours, count the number of live velvet scales on the branches under a microscope, and use an insect needle to gently stir the velvet scales. If the nymphs crawl or their legs are found swinging, they are considered live insects, otherwise they are dead. Each treatment was replicated 3 times.
  • Determination of armyworm activity The potting method was used, and the armyworms were raised with artificial feed. The 3rd instar larvae were selected as the test insect target. First, spray the wheat with a constant pressure sprayer. Repeat each chemical treatment twice, with one pot of wheat seedlings for each repetition. Each pot is sprayed with 2.5ml of chemical solution. The control treatment is treated with clean water. After the liquid is completely dry, inoculate each pot of wheat seedlings with 10 third-instar armyworm larvae. Place the wheat seedlings into a plastic nursery cup, turn the plastic nursery cup upside down, and use double-sided tape to glue the joints securely.
  • Table 8 Parallel test results of exemplary compounds against wheat armyworm (lethal rate %)
  • Table 9 Parallel test results of exemplary compounds against wheat armyworm (leaf preservation rate %)
  • Determination of Spodoptera litura activity Use the artificial feed film method: first pour the prepared artificial feed into a 12-well plate while it is hot, add 2.5ml of artificial feed to each well, and wait until the feed is fully cooled before use. Make three 12-well plates for each concentration gradient of each agent, and each 12-well plate is repeated for a total of 3 repetitions. Add 50 ⁇ L of the corresponding concentration gradient agent to each well and dry it. One Spodoptera litura larvae was inserted into each hole. Control three 12-well plates, with a total of three replicates, and add 50 ⁇ L of solvent control to each well.
  • the death of the test insects will be investigated 48 hours after the test, and the lethality rate of the test insects will be calculated.
  • the test concentrations are 50mg/L and 10mg/L respectively.
  • the compounds according to the invention surprisingly show improved degradation properties compared to the compounds of the prior art. In addition, the compounds according to the invention also surprisingly show less toxicity to bees (or aquatic animals) than the prior art compounds.
  • any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

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Abstract

一种吡啶酰胺衍生物及其用途，具体涉及作为吡啶酰胺衍生物的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，以及所述化合物在制备用于害虫防治的杀虫剂中的用途。此类化合物能够以更低的剂量达到更好的害虫防治效果，特别是针对鳞翅目、鞘翅目、同翅目、半翅目、缨翅目、等翅目、双翅目、膜翅目、食毛目、虱目、直翅目、蜚蠊目、蚤目、蜱螨目、线虫纲等害虫。

Description

一种吡啶酰胺衍生物及其用途
相关申请的交叉引用
本申请要求于2022年9月15日提交的申请号为202211122914.6的中国专利申请的优先权，其全部内容通过引用的方式并入本文。
技术领域
本发明属于农药领域，具体地，涉及用于一种吡啶酰胺衍生物及其用途。
背景技术
杀虫剂是农药中品种最多、用量最大的一类药剂，在解决人类粮食问题方面有着至关重要的作用。最开始发现的是天然杀虫剂及无机化合物，其用量大、持效期短；在有机氯、有机磷和氨基甲酸酯等有机杀虫剂中，有些对哺乳动物急性毒性较高。此外，随着农药的使用，当前许多市售杀虫剂的抗药性日益增强，需要加大剂量才能杀灭害虫，给环境带来了极大的负担。因此，本领域持续需要更有效、更经济、毒性更小、对环境更安全或具有不同作用机理的新型化合物来替代老一代产品。
随着研究人员不断的开发和研究，多氟原子取代的化合物逐渐进入研究人员的视野，专利申请CN106103414A、CN105873908A、CN111050559A中均公开了对多氟化合物进行了研究，但上述研究结果在功效、持久性、毒性等方面仍不甚令人满意。
发明内容
本发明的目的在于提供一类新的吡啶酰胺化合物，此类化合物能够以更低的剂量达到更好的害虫防治效果，特别是针对鳞翅目、半翅目、双翅目或同翅目等害虫。
在第一方面，本发明提供了作为吡啶酰胺衍生物的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，
其中，
R1、R2和R3各自独立地选自氢、卤素、羟基、硝基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6烷氧基或C1-C6卤代烷氧基；
M选自氧或硫；
W选自C3-C6环烷基或三元至六元杂环烷基，其中所述C3-C6环烷基或三元至六元杂环烷基中的1至3个氢原子任选地被卤素、羟基、硝基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6烷氧基或C1-C6卤代烷氧基取代；
Q为三元至六元杂环烷基或被一个或多个取代基取代的C1-C3烷基，所述一个或多个取代基各自独立地选自卤素、羟基、硝基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6烷氧基、C1-C6卤代烷基、C1-C6卤代烷氧基、C3-C6环烷基、三元至六元杂环烷基、苯氧基、苯甲氧基或-O-(CH2)m-O-(CH2)n-CH3；
m为1至3中的任一整数；并且
n为0至2中的任一整数。
在本发明的一个实施方式中，
R1、R2和R3各自独立地选自氢、氟、氯、溴、C1-C3烷基、C1-C3氟代烷基、C1-C3烷氧基或C1-C3氟代烷氧基，优选氢、氟、氯、溴、甲基、一氟甲基、二氟甲基、三氟甲基、乙基、氟乙基、甲氧基、一氟甲氧基、二氟甲氧基、三氟甲氧基或乙氧基；
M选自氧或硫；
W选自环丙基，其中所述环丙基中的1至3个氢原子任选地被卤素、氰基、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基或C1-C3卤代烷氧基取代，优选任选地被氟、氯、溴、氰基、甲基、一氟甲基、二氟甲基、三氟甲基、乙基、氟乙基、甲氧基、一氟甲氧基、二氟甲氧基、三氟甲氧基或乙氧基取代；
Q为三元至六元杂环烷基或被一个或多个取代基取代的C1-C3烷基，所述一个或多个取代基各自独立地选自氰基、C1-C3烷基、C2-C3烯基、C2-C3炔基、C1-C3烷氧基、C3-C6环烷基、三元至六元杂环烷基、苯氧基、苯甲氧基或-O-(CH2)m-O-(CH2)n-CH3；
m为1、2或3；并且
n为0、1或2。
在本发明的另一个实施方式中，
所述杂环烷基为氧杂环烷基、氮杂环烷基或硫杂环烷基，其包含1至3个氧杂原子、氮杂原子或硫杂原子，优选1或2个氧杂原子、氮杂原子或硫杂原子。
在本发明的另一个优选实施方式中，
Q为氧杂环戊基、氧杂环己基或被一个或多个取代基取代的甲基、乙基、正丙基或异丙基，所述一个或多个取代基各自独立地选自氰基、甲基、乙基、乙烯、乙炔、甲氧基、乙氧基、丙氧基、异丙氧基、环丙基、环丁基、环戊基、氧杂环丙基、氧杂环丁基、氧杂环戊基、氧杂环己基、氮杂环己基、硫杂环己基、苯氧基、苯甲氧基、-OCH2OCH3或-OCH2CH2OCH3。
在本发明的另一个优选实施方式中，
所述式(I)化合物特别地具有下式结构：
为了简明起见，后文所述“吡啶酰胺衍生物”、“式(I)化合物”或“本发明的化合物”也可以涵盖式(I)化合物的任意同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐。
术语“光学异构体”意指，当化合物具有一个或更多个手性中心时，每个手性中心可以存在R构型或S构型，由此构成的各种异构体为光学异构体。光学异构体包括所有的非对映异构体、对映异构体、内消旋体、外消旋体或其混合物形式。例如，通过手性色谱柱或通过手性合成可以分离光学异构体。
术语“几何异构体”意指，当化合物中存在双键时，该化合物可以存在顺式异构体、反式异构体、E型异构体和Z型异构体。几何异构体包括顺式异构体、反式异构体、E型异构体、Z型异构体或其混合物形式。
术语“互变异构体”指因分子中某一原子在两个位置迅速移动而产生的异构体。本领域技术人员可以理解：互变异构体之间可以互相转变，在某一状态下可能会达到一种平衡状态而共存。
除非另有指明，本文提到“吡啶酰胺衍生物”、“式(I)化合物”或“本发明的化合物”时也涵盖该化合物中任一个原子被其同位素原子代替而得到的同位素标记化合物。本发明包括式(I)化合物的所有药学上可接受的同位素标记化合物，其中，一个或者多个原子被具有与通常在自然界中所发现的原子相同原子序数但是不同原子质量或者质量数的原子所替换。
适用于包含在本发明的化合物中的同位素的实例包括氢的同位素，诸如2H(D)和3H(T)，碳的同位素，诸如11C、13C和14C，氯的同位素，诸如37Cl，氟的同位素，诸如18F，碘的同位素，诸如123I和125I，氮的同位素，诸如13N和15N，氧的同位素，诸如15O、17O和18O，以及硫的同位素，诸如35S。
式(I)的同位素标记化合物一般可以通过本领域技术人员已知的常规技术或者通过使用合适的同位素标记试剂代替先前使用的非标记试剂以类似于在本文所附的实例和制备中所描述的方法，来进行制备。
式(I)化合物可以农药学上可接受的盐的形式存在，比如，式(I)化合物的酸加成盐和/或碱加成盐。除非另有指明，否则本文所用的“农药学上可接受的盐”包括可出现于式(I)化合物内的酸加成盐或碱加成盐。
式(I)化合物的农药学上可接受的盐类包括其酸加成盐和碱加成盐。适当的酸加成盐是由形成无毒性盐的酸所形成的。其实例包括但不限于：乙酸盐、己二酸盐、天冬氨酸盐、苯甲酸盐、苯磺酸盐、碳酸氢盐/碳酸盐、硫酸氢盐/硫酸盐、硼酸盐、樟脑磺酸盐、柠檬酸盐、环己胺磺酸盐、乙二磺酸盐、甲酸盐、反丁烯二酸盐、葡萄庚糖酸盐、葡萄糖酸盐、葡萄糖醛酸盐、六氟磷酸盐、2-(4-羟苄基)苯甲酸盐、氢氯化物/氯化物、氢溴化物/溴化物、氢碘化物/碘化物、2-羟乙磺酸盐、乳酸盐、苹果酸盐、顺丁烯二酸盐、丙二酸盐、甲磺酸盐、甲基硫酸盐、萘酸盐、2-萘磺酸盐、烟碱酸盐、硝酸盐、乳清酸盐、草酸盐、十六酸盐、磷 酸盐/磷酸氢盐/磷酸二氢盐、焦谷氨酸盐、葡萄糖二酸盐、硬脂酸盐、水杨酸盐、单宁酸盐、酒石酸盐、甲苯磺酸盐和三氟乙酸盐。适当的碱加成盐是由形成无毒性盐的碱所形成的。其实例包括但不限于：铝、精氨酸、钙、胆碱、二乙胺、二乙醇胺、甘氨酸、赖氨酸、镁、葡甲胺、乙醇胺、钾、钠、氨丁三醇和锌盐。还可形成酸和碱的半盐，例如半硫酸盐和半钙盐。关于合适的盐的综述，参见Handbook of Pharmaceutical Salts:Properties,Selection and Use by Stahl and Wermuth(Wiley-VCH,2002)。用于制备本文中所述的化合物的农药学上可接受的盐的方法是本领域技术人员已知的。
为了避免歧义，下面对本文中所使用的术语给出定义。除非另有说明，本文所用术语的含义如下。
术语“羟基”是指-OH；术语“氨基”是指-NH2；术语“硝基”是指-NO2；术语“氰基”是指-CN；术语“苯氧基”是指-O-Phe；并且术语“苯甲氧基”是指-O-CH2-Phe。
在本文中使用时，术语“被取代”是指基团中的一个或多个(优选1至5个，更优选1至3个)氢原子独立地被相应数目的取代基所代替。
在本文中使用时，术语“各自独立地”是指当取代基的个数超过一个时，这些取代基可以相同也可以不同。
在本文中使用时，术语“烷基”是指饱和的脂族烃，包括直链及支链。在一些实施方式中，烷基基团具有1-8个、或1-6个、或1-3个碳原子。例如，术语“C1-8烷基”是指具有1-8个碳原子的直链或支链原子团。术语“C1-8烷基”在其定义中包括术语“C1-6烷基”、“C1-C3烷基”和“C1-C4烷基”。烷基的实例包括但不限于甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、2-戊基、3-戊基、异戊基、新戊基、(R)-2-甲基丁基、(S)-2-甲基丁基、3-甲基丁基、2,3-二甲基丙基、2,3-二甲基丁基、己基等。烷基基团可任选地被一或多个(例如，1至5个)适当的取代基所取代。
在本文中使用时，术语“卤代烷基”是指具有一或多个卤素取代基的烷基基团(至多全卤代烷基，即，烷基基团的每个氢原子均被卤素原子所取代)。例如，术语“C1-C6卤代烷基”是指具有一或多个卤素取代基的C1-C6烷基基团(至多全卤代烷基，即，烷基基团的每个氢原子均被卤素原子所取代)。另举一例，术语“C1-C4卤代烷基”是指具有一或多个卤素取代基的C1-C4烷基基团(至多全卤代烷基，即，烷基基团的每个氢原子均被卤素原子所取代)；术语“C1-C3卤代烷基”是指具有一或多个卤素取代基的C1-C3烷基基团(至多全卤代烷基，即，烷基基团的每个氢原子均被卤素原子所取代)；且术语“C1-C2卤代烷基”是指具有一或多个卤素取代基的C1-C2烷基基团(即，甲基或乙基)(至多全卤代烷基，即，烷基基团的每个氢原子均被卤素原子所取代)。再另举一例，术语“C1卤代烷基”是指具有1、2或3个卤素取代基的甲基基团。卤代烷基基团的例子包括：CF3、C2F5、CHF2、CH2F、CH2CF3、CH2Cl等。
在本文中使用时，术语“n元杂环烷基”是指具有m个形成环的碳原子和(n-m)个形 成环的杂原子的杂环烷基，所述杂原子选自O、S及N。例如，4-7元杂环烷基包括但不限于氧杂环丁烷、硫杂环丁烷、氮杂环丁烷、四氢呋喃、四氢噻吩、吡咯烷、四氢吡喃、四氢噻喃、哌啶、吗啉、哌嗪、氧杂环庚烷、硫杂环庚烷、氮杂环庚烷。此外，杂环烷基可任选地被一或多个适当的取代基所取代。
本文中，与取代基个数、碳原子个数、环原子个数相关的数目范围表示该范围内所有整数的逐个列举，而范围仅是作为一种简化的表示法。例如：“1-4个取代基”表示1、2、3或4个取代基；“3-8个环原子”表示3个、4个、5个、6个、7个或8个环原子。因此，与取代基个数、碳原子个数、环原子个数相关的数目范围也涵盖其任意一个子范围，且每一个子范围也视为被本文公开。
本发明化合物可按有机合成领域技术人员已知的多种方式制备。本领域技术人员可以参照本发明具体实施例的具体化合物的合成路线，对反应原料和反应条件进行适当调整而得到其它化合物的合成方法。
此外，本发明还列出了多个已合成的示例性化合物，其具体基团选择如下表1所示。应当理解的是，本发明的范围不限于下表中列出的示例性化合物，并且下表1中化合物的各基团选择可以进行任意组合，而没有特别限制。
表1






在第二方面，本发明提供了一种杀虫剂组合物，其包含式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，以及农药学上可接受的载体。
农药学上可接受的载体可以是有机或无机惰性载体材料，例如，合适的载体包括水、明胶、阿拉伯树胶、硬脂酸镁、滑石、植物油、聚亚烷基二醇、凡士林、甘露醇、纤维素、纤维素衍生物、糖精钠、碳酸镁、盐水、甘油、乙醇等。此外，杀虫剂组合物还可含有其他添加剂，例如防腐剂、稳定剂、乳化剂、缓冲剂、稀释剂、黏合剂、润湿剂、润滑剂、助流剂等。
本发明的杀虫剂组合物的剂型可以是液体剂型、固体剂型或半固体剂型，而没有特别限制。在一些实施方式中，所述杀虫剂组合物的剂型选自粉剂、颗粒剂、液剂、悬浮剂或喷雾剂，优选可湿性粉剂、可湿性液剂、可溶性粉剂、可分散液剂、水剂、微乳剂、乳油、水乳剂、可喷洒溶液、可分散油悬浮剂、微囊悬浮剂、水分散粒剂、水溶性粒剂、大粒剂、用于撒播和土壤施药的颗粒剂、气雾剂、超低容量剂和蜡制品。
本发明的化合物在其杀虫剂组合物中的含量可以根据实际需要(例如剂型、施用方式、施用对象等)进行调整，包括但不限于为0.001mg/L-10mg/L，例如0.001mg/L、0.01mg/L、0.1mg/L、0.5mg/L、1mg/L、2.5mg/L、5mg/L或10mg/L。
具体的施用频率可以由相关领域的技术人员确定，例如为1天1次、2天1次、3天1次、4天1次、5天1次、6天1次、1天2次、1天3次等。
在第三方面，本发明提供了式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐在制备用于害虫防治的杀虫剂中的用途。
本发明化合物适于防治害虫或害螨，也即控制害虫或害螨，所述的害虫或害螨指的有害 的或不想要的昆虫或螨类，尤其是农业、林业、储藏品保护和材料保护以及卫生领域所遇到的有害的或不想要的昆虫或螨类，本发明化合物对于一般敏感性和抗性物种都是有活性的，并且在害虫或害螨发育的所有阶段都有效。
本发明还涉及一种防治害虫或害螨的方法，该方法包括对昆虫所在地、昆虫栖息地、害虫栖息地、要求保护的面积、或直接在要控制的昆虫上施用防治有效量的式(I)化合物。本发明的化合物也可以用来控制其它无脊椎害虫或生物。
具体地，所述昆虫栖息地、害虫栖息地或害螨栖息地是指昆虫、害虫或害螨生活或它们的卵存在的环境，包括其周围的空气、食用的食物或接触的物体。例如，通过将活性化合物施用至植株的种子(在种植前)、至秧苗、或种植的插条、叶子、茎、果实、谷粒和/或根，或至土壤或其它生长介质(在作物种植前或之后)，可以控制食用、毁坏或接触可食用农产品、观赏植物、草皮、牧草植物或其它具有经济价值的植物的昆虫或害螨，也可以通过控制食汁液的害虫如粉虱、飞虱、蚜虫等或害螨如二斑叶螨、朱砂叶螨等而达到保护这些植物抵抗病毒、真菌或细菌导致的疾病；所述植物包括通过常规方法繁殖得到的植物，也包括通过现代生物技术改变基因得到的具有昆虫或害螨抵抗力、除草剂抵抗力、高产量/或其它有益特性的植物。可以预期这些化合物能适用于保护织物、纸、储存的谷物、种子和其它食品、房屋、建筑物等物品和/或场所，通过将本发明的化合物施用到这些物体上或这些物体附近来实现。
本发明的发明人发现，即便以较低的剂量来施用本发明的化合物，其同样能够表现出对害虫，特别是针对鳞翅目、鞘翅目、同翅目、半翅目、缨翅目、等翅目、双翅目、膜翅目、食毛目、虱目、直翅目、蜚蠊目、蚤目、蜱螨目、线虫纲等害虫时具有高效防治效果。因此，在本发明的一个实施方式中，所述害虫选自属于鳞翅目、鞘翅目、同翅目、半翅目、缨翅目、等翅目、双翅目、膜翅目、食毛目、虱目、直翅目、蜚蠊目、蚤目、蜱螨目、线虫纲的害虫。更具体的害虫分类如下所示：
鳞翅目：棉铃虫(Heliothis spp.)、棉铃虫(Helicoverpa spp.)、夜蛾(Spodoptera spp.)、秘夜蛾粘虫(Mythimna unipuncta)、小地老虎(Agrotis ipsilon)、金刚钻(Earias spp.)、粉纹夜蛾(Trichoplusia ni)、黎豆夜蛾(Anticarsia gemmatalis)、薄荷灰叶蛾(Rachiplusia nu)、小菜蛾(Plutella xylostella)、二化螟(Chilo spp)、三化螟(Scirpophaga incertulas)、大螟(Sesamia inferens)、稻纵卷叶螟(Cnaphalocrocismedinalis)、玉米螟(Ostrinia nubilalis)、苹果蠹蛾(Cydia pomonella)、桃小食心虫(Carposina niponensis)、棉褐带卷叶蛾(Adoxophyes orana)、果树黄卷蛾(Archipsargyrospilus)、苹褐卷叶蛾(Pandemis heparana)、夜小卷蛾(Epinotia aporema)、葡萄与苹果卷叶蛾(Eupoecilia ambiguella)、葡萄花翅小卷蛾(Lobesia botrana)、Polychrosisbiteana、棉红铃虫(Pectinophora gossypiella)、菜青虫(Pierisrapae)、Phyllonorycterspp.、旋纹潜蛾(Leucoptera malifoliella)、柑橘潜叶蛾(Phyllocnisitis citrella)、甜菜夜蛾(Podoptera exigua Hübner)等；
鞘翅目：叶甲(Diabrotica spp.)、马铃薯叶甲(Leptinotarsa decemlineata)、稻负泥虫 (Oulema oryzae)、棉铃象甲虫(Anthonomusgrandis)、稻水象甲(Lissorhoptrusoryzophilus)、金针虫叩甲(Agriotes spp.)、Melanotus communis、日本豆金龟子(Popillia japonica)、圆头犀金龟属种(Cyclocephala spp.)、拟谷盗(Tribolium spp.)等；
同翅目：蚜虫(Aphis spp.)、烟蚜(Myzus Persicae)、Rhopalosiphum spp.、车前圆尾蚜(Dysaphis plantaginea)、桔蚜(Toxoptera spp.)、苜蓿蚜虫(Aphis craccivoraKoch)、大戟长管蚜(Macrosiphum euphorbiae)、茄无网蚜(Aulacorthum solani)、麦长管蚜(Sitobion avenae)、麦无网长管蚜(Metopolophium dirhodum)、麦二叉蚜(Schizaphisgraminum)、麦双尾蚜(Brachycolus noxius)、黑尾叶蝉(Nephotettix spp.)、褐飞虱(Nilaparvata lugens)、白背飞虱(Sogatella furcifera)、灰飞虱(Laodelphaxstriatellus)、烟粉虱(Bemisiatabaci)、温室白粉虱(Trialeurodes vaporariorum)、Aleurodes proletella、丝绒粉虱(Aleurothrixus floccosus)、梨园蚧(Quadraspidiotusperniciosus)、矢尖蚧(Unaspis yanonenses)、红蜡蚧(Ceroplastes rubens)、红圆蚧(Aonidiella aurantii)等；
半翅目：盲蝽(Lygus spp.)、Eurygaster maura、稻绿蝽(Nezaraviridula)、Piezodorus guildingi、稻缘椿象(Leptocorisa varicornis)、温带臭虫(Cimexlectularius)、热带臭虫(Cimex hemipterus)等；
缨翅目：西花蓟马(Frankliniella occidentalis)、蓟马(Thrips spp.)、茶黄蓟马(Scirtothrips dorsalis)等；
等翅目：黄肢散白蚁(Reticulitermes flavipes)、家白蚁(Coptotermesformosanus)、南方散白蚁(Reticulitermes virginicus)、Heterotermesaureus、西方散白蚁(Reticulitermes hesperus)、Coptotermes frenchii、Shedorhinotermes spp.、桑特散白蚁(Reticulitermes santonensis)、Reticulitermes grassei、Reticulitermesbanyulensis、黄胸散白蚁(Reticulitermes speratus)、Reticulitermes hageni、美黑胫散白蚁(Reticulitermes tibialis)、湿木白蚁(Zootermopsis spp.)、楹白蚁(Incisitermes spp.)、缘白蚁(Marginitermes spp.)、大白蚁(Macrotermes spp.)、大锯白蚁(Microcerotermes spp.)、蛮白蚁(Microtermes spp.)等；
双翅目：斑潜蝇(Liriomyza spp.)、家蝇(Musca domestica)、斑蚊(Aedes spp.)、家蚊(Culex spp.)、疟蚊(Anopheles spp.)、厕蝇(Fannia spp.)、废蝇(Stomoxys spp.)等；
膜翅目：红蚁(Iridomyrmex humilis)、火蚁(Solenopsis spp.)、法老蚁(Monomorium pharaonis)、Atta spp.、收获蚁(Pogonomyrmex spp.)、弓背蚁(Camponotusspp.)、小家蚁(Monomorium spp.)、臭家蚁(Tapinoma sessile)、铺道蚁(Tetramoriumspp.)、Xylocapa spp.、胡蜂(Vespula spp.)、长足胡蜂(Polistes spp.)等；
食毛目：羽虱(chewing lice)等；
虱目：吸血虱(sucking lice)、耻阴虱(Pthirus pubis)、虱类(Pediculusspp.)等；
直翅目：黑蝗(Melanoplus spp.)、东亚飞蝗(Locusta migratoria)、沙漠蝗(Schistocerca gregaria)、蝼蛄(Gryllotalpidae)(蝼蛄(mole crickets))等；
蜚蠊目：蜚蠊(cockroaches)、东方蠊(Blatta orientalis)、德国小蠊(Blattella germanica)、美洲大蠊(Periplaneta americana)、长须蜚蠊(Supellalongipalpa)、澳洲蜚蠊(Periplaneta australasiae)、褐斑大蠊(Periplaneta brunnea)、宾夕法尼亚木蠊(Parcoblatta pennsylvanica)、黑胸大蠊(Periplaneta fuliginosa)、蔗蠊(Pycnoscelus surinamensis)等；
蚤目：跳蚤(Ctenophalides spp.)、人蚤(Pulex irritans)等；
蜱螨目：叶螨科(Tetranychidae)、真足螨科(Eupodidae)、瘿螨科(Eriophyiade)、植绥螨科(Phytoseiidae)、粉螨科(Acaridae)，具体包括但不限于叶螨(Tetranychus spp.)、蜘蛛螨(Panonychus spp.)、朱砂叶螨(Tetranychuscinnabarinus)、东方叶螨(Eotetranychus carpini)、二斑叶螨(Tetranychus urticaeKoch.)、柑桔锈螨(Phyllocoptruta oleivora)、Aculus pelekassi、紫红短须螨(Brevipalpus phoenicis)、牛蜱(Boophilus spp.)、变异革蜱(Dermacentorvariabilis)、血红扇头蜱(Rhipicephalussanguineus)、美洲花蜱(Amblyommaamericanum)、真蜱(Ixodes spp.)、猫背肛螨(Notoedres cati)、疥螨(Sarcoptesscabiei)、尘螨(Dermatophagoides spp.)等；
线虫纲(Nematoda)：犬恶丝虫(Dirofilaria immitis)、根结线虫(Meloidogynespp.)、包囊线虫(Heterodera spp.)、冠线虫(Hoplolaimus columbus)、针刺线虫(Belonolaimus spp.)、根腐线虫(Pratylenchus spp.)、肾形线虫(Rotylenchusreniformis)、装饰小环线虫(Criconemella ornata)、茎线虫(Ditylenchus spp.)、叶芽线虫(Aphelenchoides besseyi)、稻田潜根线虫(Hirschmanniella spp.)等。
在本发明的另一个优选实施方式中，所述害虫可以选自小菜蛾、褐飞虱、草地贪夜蛾、斜纹夜蛾、粘虫、韭菜迟眼蕈蚊、点蜂缘蝽、茶小绿叶蝉或紫薇绒蚧。
本领域技术人员能够理解，在本发明的一个方面中描述的定义和优选项同样适用于其他方面。本领域技术人员能够明了本发明各个方面的实施方式可以以各种方式组合，而不偏离本发明的主题和思想，这些组合也包括在本发明的范围内。
具体实施方式
本发明式(I)化合物可以用有机合成领域的技术人员所熟悉的多种方法合成。以下具体实施例中给出了一些示例性的式(I)化合物的合成方法，这些方法是合成化学领域所公知的。显然，参照本专利中的示例性方案，本领域技术人员可以适当调整反应物、反应条件和保护基团而容易地设计其他式(I)化合物的合成路线。
下面进一步结合实施例来阐述本发明；但这些实施例并不限制本发明的范围。除非另有声明，各实施例中所用的所有反应物均从商业途径获得；合成实验和产物分析检测中所用仪器设备等均为有机合成中通常使用的常规仪器和设备。
具体地，实施例中使用的核磁共振氢谱的测试条件是：室温条件下，布鲁克(Bruker)400MHz或600MHz的核磁仪，以CDCl3，d6-DMSO，CD3OD或d6-丙酮为溶剂(报导以ppm为单位)，用TMS(0ppm)或氯仿(7.26ppm)作为参照标准。当出现多重峰的时候，将 使用下面的缩写：s(singlet，单峰)，d(doublet，双峰)，t(triplet，三重峰)，q(quartet，四重峰)，m(multiplet，多重峰)，br(broadened，宽峰)，dd(doublet of doublets，双二重峰)，dt(doublet of triplets，双三重峰)。偶合常数J，单位用赫兹(Hz)表示。
实施例中所用质谱分析方法为：使用Agilent 1260HPLC；Agilent 6120ESI。
A相：乙腈(含0.1％甲酸)；B相：水(含0.1％甲酸)。
梯度洗脱：0-2min，80-5％B；2-6min，5％B。
流速：0.6ml/min。
检测波长：254nm。
MS参数：ESI正扫描，碰撞诱导电离：70V。
干燥氮气：12L/min，雾化气压力：40psi，气体温度：350℃。
取适量样品，溶于0.5mL甲醇，进样，在正ESI模式下进行一级MS全扫描得到准分子离子峰[M+1]+读数。
“RT”、“室温”是指温度在大约0℃-40℃或大约20℃-30℃或大约23℃-28℃或大约25℃。
实施例
在以下实施例中，发明人以本发明的部分化合物为例，详细描述了本发明化合物的制备过程。
实施例1：
中间体NA03：1-(2,6-二氯-4-(全氟丙烷-2-基)苯基)-4-碘代-1H-吡唑的合成
步骤1：2,6-二氯-4-(全氟丙烷-2-基)苯胺的合成
将2,6-二氯苯胺(64.8g,0.4mol)和500ml乙酸乙酯+500ml水置于2L的反应瓶中，搅拌中依次加入四丁基硫酸氢铵(13.6g,40mmol)、连二亚硫酸钠(69.6g,0.4mol)，然后经过60min缓慢滴加七氟异丙基碘(130.24g,0.44mol)和100ml乙酸乙酯的混合液，期间通过滴加40％K2CO3溶液使pH保持在6～7之间，完毕后，RT下搅拌反应。6h后，反应完毕，静置分层，乙酸乙酯萃取水层，合并有机相，有机相用饱和NaCl溶液和2.5％HCl溶液洗涤，硫酸钠干燥，抽滤旋蒸得产物。得红色液体63.2g，收率：48％。LC-MS:(M+1)m/z＝330.2。
步骤2：1-(2,6-二氯-4-(全氟丙烷-2-基)苯基)-1H-吡唑的合成
将2,6-二氯-4-(全氟丙烷-2-基)苯胺(22.4g，68mmol)和150ml冰乙酸、75ml质量分数50％的硫酸，置于1000ml的四口瓶中，在0～5℃下，30min内缓慢加入亚硝酸钠(5.4g，78.2mmol)于10ml水中的溶液。添加完成后，将反应混合物在该温度下搅拌15min，然后一次性加入抗坏血酸(14.0g，78.2mmol)。将反应混合物在2h内升至室温，然后加热至65℃，并在此温度下加入1,1,3,3-四甲氧基丙烷(11.3g，68mmol)。将反应在此温度下再搅拌5h。反应完毕后，冷却至室温，加水250ml稀释，混合物用200ml乙酸乙酯萃取2次，合并的有机相用150ml,10％质量分数的NaOH水溶液洗涤，有机相用NaSO4干燥，抽滤，减压旋蒸除去溶剂，得红色油状物21.5g，收率：83％。LC-MS:(M+1)m/z＝381.1。
步骤3：1-(2,6-二氯-4-(全氟丙烷-2-基)苯基)-4-碘代-1H-吡唑的合成
将1-(2,6-二氯-4-(全氟丙烷-2-基)苯基)-1H-吡唑(38.1g，0.1mol)和200ml乙腈置于500ml的反应瓶中，搅拌中分批加入NIS(24.8g，0.11mol)，在RT下搅拌反应30min，然后升温至90℃回流搅拌反应6h。反应完毕后，冷却至室温，加水淬灭，乙酸乙酯萃取200ml*3次，合并有机相，依次用水洗，饱和食盐水洗涤，硫酸钠干燥，抽滤旋蒸得产物。反复多次通过铺有硅胶的砂芯漏斗用正己烷进行洗涤，纯化。得到红色液体45.0g，收率：89％。LC-MS:(M+1)m/z＝507.2。
中间体NB01：5-溴-2-氯-N-环丙基烟酰胺的合成
将5-溴-2-氯烟酸(118g，0.5mol)和300ml甲苯置于1000ml的反应瓶中，搅拌中缓慢加入氯化亚砜(59.5g,5mol)，然后加入2ml DMF催化。完毕后升温至80℃下回流反应2h。反应完毕后，冷却至室温，减压旋蒸除去溶剂及未反应物，得酰氯备用。
将环丙胺(34.2g，0.6mol)和800ml二氯甲烷置于2000ml的反应瓶中，冰浴条件下，搅拌中加入三乙胺(60.6g，0.6mol)，然后缓慢滴加上述步骤得到的酰氯，完毕后，RT下搅拌反应过夜。12h后，结束反应，加水500ml搅拌，静置分层，乙酸乙酯萃取水层，合并有机相，旋蒸除去溶剂得到白色固体128g，收率：93％。LC-MS:(M+1)m/z＝275.1。
目标化合物：2-氯-N-环丙基-5-(1-(2,6-二氯-4-(全氟丙烷-2-基)苯基)-1H-吡唑-4-基)-N-(氧杂环丙-2-基甲基)烟酰胺的合成(对应于表1中的化合物26)
第一步：5-溴-2-氯-N-环丙基-N-(氧杂环丙-2-基甲基)烟酰胺的合成
将5-溴-2-氯-N-环丙基烟酰胺(1.10g，4mmol)和30ml THF置于100ml的单口瓶中，冰 浴条件下，分批加入60％NaH(0.24g，6mmol)，30min后再将溴甲基环氧丙烷(0.82g，6mmol)缓慢加入反应体系中，室温下搅拌反应过夜。12h后反应完毕，加水淬灭(30ml)，水相用乙酸乙酯萃取(20ml x 3次)，合并有机相，有机相用无水硫酸钠干燥，过滤，减压浓缩滤液，残留物经硅胶柱层析分离[石油醚/乙酸乙酯(v/v)＝10/1]，得到标题化合物(白色固体，0.96g，收率：73％)。LC-MS:(M+1)m/z＝331.1。
第二步：2-氯-N-环丙基-5-(1-(2,6-二氯-4-(全氟丙烷-2-基)苯基)-1H-吡唑-4-基)-N-(氧杂环丙-2-基甲基)烟酰胺的合成
将5-溴-2-氯-N-环丙基-N-(氧杂环丙-2-基甲基)烟酰胺(0.66g，2mmol)和20ml二甲基亚砜加入100ml单口瓶中，然后加入乙酸钾(0.78g，8mmol)、[1,1'-双(二苯基膦基)二茂铁]二氯化钯(0.08g，0.12mmol)、双(频哪醇合)二硼(1.02g，4mmol)，氮气置换3次，完毕后，80℃下反应6h。反应完毕后，冷却至室温，得到目标物，不经进一步处理直接进行下步反应。
向上述步骤得到的硼酯反应液中，依次加入10ml水和1-(2,6-二氯-4-(全氟丙烷-2-基)苯基)-4-碘代-1H-吡唑(1.12g，2mmol)、碳酸钾(0.83g，6mmol)、四(三苯基膦)钯(0.23g，0.2mmol)，氮气置换3次，完毕后100℃下回流反应24h。反应完毕后，冷却至室温，加水淬灭(15ml)，水相用二氯甲烷萃取(10ml x 3)，合并有机相，有机相用无水硫酸钠干燥，过滤，减压浓缩滤液，残留物经硅胶柱层析分离[石油醚/乙酸乙酯(v/v)＝3/1]，得到标题化合物(白色固体，0.65g，收率：52％)。
1H NMR(400MHz,氯仿-d)δ8.65(d,J＝2.6Hz,1H),8.29(d,J＝2.5Hz,1H),8.16(s,1H),7.95(s,1H),7.75(s,2H),2.96(tt,J＝7.1,3.6Hz,2H),1.33-1.31(m，1H)，1.28(s,1H),1.02–0.90(m,2H),0.91–0.81(m,2H),0.78–0.63(m,2H).
19F NMR(377MHz,CDCl3)δ-75.19,-181.64.LC-MS:(M+1)m/z＝631.1。
参考实施例1的合成方法，以类似的方式采用相应的原料及条件进行制备，得到实施例2-28的目标化合物，其结构和表征数据如表2中所示。
表2示例性化合物的结构及表征数据



测试例：生物活性测试
在以下测试例中，以CN106103414A公开的杀虫化合物I-T2-2(在本文中以KC1表示)；CN105873908A公开的杀虫化合物I-T48-3(在本文中以KC2表示)；以及CN111050559A公开的杀虫化合物28(在本文中以KC3表示)作为阳性对照物。
化合物配制：用分析天平(0.0001g)称取一定质量的原药，用含1‰吐温-80乳化剂的N,N二甲基甲酰胺溶解配制成1％的母液，然后用蒸馏水稀释备用。
试验方法：
1)小菜蛾活性测定：采用浸叶法，取适量萝卜叶浸药30s后，置于垫有滤纸的塑料培养皿中自然阴干，每皿接2龄小菜蛾8头，置于22℃光照(16/8h)观察室内。48h后观察，以毛笔轻触虫体，无反应视为死虫。每处理重复3次，并设溶剂对照。试验浓度分别为25mg/L、2.5mg/L、1mg/L、0.25mg/L。
试验结果发现，本发明化合物对小菜蛾有优秀的杀虫活性，其中实施例1、实施例2、实施例11、实施例14、实施例16、实施例20、实施例21、实施例24、实施例28的化合物 在25mg/L剂量下对小菜蛾的防效为100％；进一步降低剂量后，实施例1、实施例11、实施例14、实施例28的化合物在2.5mg/L、1mg/L剂量下对小菜蛾的防效仍为100％。而实施例2的化合物在2.5mg/L剂量下对小菜蛾的防效为80％以上；再进一步降低剂量后，实施例1的化合物在0.25mg/L剂量下对小菜蛾的防效仍为100％；而实施例11的化合物在0.25mg/L剂量下对小菜蛾的防效为80％以上。相比之下，对照化合物KC3在0.25mg/L的测试浓度下无活性。
2)褐飞虱活性测定：采用喷雾法，选取两叶一心的水稻苗，置于6cm的培养皿中，再在培养皿中铺上石英沙，接3龄初褐飞虱若虫，每皿接15头若虫，用Potter喷雾塔喷雾处理，喷液量为2.5ml，处理后置于26～28℃观察室内培养，48h后调查结果，以镊子触动虫体，无反应视为死虫。每处理重复3次，并设溶剂对照。试验浓度为200mg/L。
试验结果发现，本发明化合物对水稻褐飞虱有一定的生物活性，其中实施例1、实施例11的化合物在200mg/L剂量下对水稻褐飞虱的防效为90％以上；而实施例28的化合物在200mg/L剂量下对水稻褐飞虱的防效为80％以上。相比之下，对照化合物KC1在200mg/L剂量下对水稻褐飞虱的防效仅为40％；
3)草地贪夜蛾活性测定：采用浸叶法，取适量玉米叶浸药30s后，置于垫有滤纸的塑料培养皿中自然阴干，每皿接2龄草地贪夜蛾8头，置于26℃光照(16/8h)观察室内。48h后观察，以毛笔轻触虫体，无反应视为死虫，试验重复3次，另设不加药剂的空白对照。试验浓度为1mg/L。
试验结果发现，本发明化合物对草地贪夜蛾具有较好的生物活性，其中，实施例1、实施例28的化合物在1mg/L剂量下对草地贪夜蛾的防效为100％；而实施例11的化合物在1mg/L剂量下对草地贪夜蛾的防效为95％以上。相比之下，对照化合物KC1、KC2在1mg/L测试浓度下对草地贪夜蛾的防效为80％。
4)粘虫活性测定：采用浸叶法，将适量玉米叶片在配好的药液中充分浸润后自然阴干，放入垫有滤纸的培养皿中，接粘虫3龄中期幼虫10头/皿，置于24～27℃观察室内培养，96h后调查结果。以毛笔触动虫体，无反应视为死虫。试验浓度分别为100mg/L、10mg/L。
试验结果发现，本发明化合物对粘虫有优异的生物活性，其中实施例1、实施例2、实施例9、实施例11、实施例14、实施例16、实施例20、实施例21、实施例24、实施例28的化合物在100mg/L剂量下对粘虫的防效为100％；而实施例5、实施例13的化合物在100mg/L剂量下对粘虫的防效为90％以上。进一步降低剂量后，实施例1、实施例11、实施例14、实施例28的化合物在10mg/L剂量下对粘虫的防效为100％；而实施例9的化合物在10mg/L剂量下对粘虫的防效为80％以上。
另外，本发明化合物在进一步降低剂量后，仍对粘虫具有较好的防效(致死率)，具体试验结果如表3所示：
表3：示例性化合物对粘虫较低剂量下的平行测试结果(致死率，％)
5)韭菜迟眼蕈蚊活性测定：采用胃毒触杀联合法。将干净滤纸平铺在直径为8cm，底下铺有琼脂的培养皿内，在滤纸上滴加1mL配好的药液，将韭菜假茎部分用剪成约2cm的小段，分别放于不同浓度剂量药液中浸泡30s，取出后用吸水纸吸去多余药液，放于滴加相同浓度药液的滤纸上，每培养皿5段。随后用毛笔挑大小一致的3龄韭菜迟眼蕈蚊幼虫放于培养皿内，每皿30头，3次重复，同时设空白对照。48小时后调查结果，以毛笔轻触虫体，无反应视为死亡，结果如下表4所示。
表4：示例性化合物对韭菜迟眼蕈蚊的平行测试结果(致死率，％)
6)点蜂缘蝽活性测定：采用浸渍法。点蜂缘蝽成虫置于下铺滤纸的透明塑料盒(顶部开小孔)中，将四季豆切成2cm小段，置于不同浓度的药液中30s后取出，待四季豆表面药液晾干后放入透明塑料盒中，每个盒中4段，置于25±1℃培养箱内。每个处理10头，重复3次，同时设溶剂对照。96小时后调查结果，以镊子触动虫体，无反应视为死虫，结果如下表5所示。
表5：示例性化合物对点蜂缘蝽的平行测试结果(致死率，％)
7)茶小绿叶蝉活性测定：采用浸叶法，选择新鲜的桃树叶，用湿棉花包住叶柄，浸液后置于垫有滤纸的一次性塑料杯中阴干，每杯接茶小绿叶蝉3龄若虫15-20头，于26～28℃、光照(16/8h)观察室内。药后48h调查结果。每处理重复3次，并设溶剂对照。
表6：示例性化合物对茶小绿叶蝉的平行测试结果(致死率，％)
8)紫薇绒蚧活性测定：在显微镜下数枝干上的紫薇绒蚧2龄若虫数量，记录为基数。小心地将有紫薇绒蚧的枝条浸入药液中10秒，取出，用浸湿的棉花包住枝条基部以保湿，置于培养盒中。放入温度为25℃，湿度为65％的培养箱内。48小时后在显微镜下数枝条上的活的紫薇绒蚧数量，用昆虫针轻轻拨动紫薇绒蚧，若虫体爬动，或者发现足摆动，视为活虫，否则为死虫。每个处理3个重复。
表7：示例性化合物对紫薇绒蚧的平行测试结果(致死率，％)
9)粘虫活性测定：采用盆栽法，粘虫用人工饲料饲养，试验选取3龄幼虫作为试验昆虫靶标。先进行小麦的喷雾处理，用恒压喷雾机进行喷雾处理，每个药剂处理重复2次，每重复1盆小麦苗，每盆喷雾2.5ml药液，对照采用清水对照处理。待药液干透后每盆小麦苗接种10头3龄期粘虫幼虫，将小麦苗放入塑料育苗杯中，上方倒扣塑料育苗杯，用双面胶将接缝位置粘牢，上方塑料育苗杯用尖头镊子扎10个左右透气孔，将施药接虫后的小麦苗放入24±2℃养虫室饲养，光照周期D:L＝16h:8h，室内相对湿度50％-70％。统计各组的致死率和保叶率。试验浓度分别为50mg/L、5mg/L。
表8：示例性化合物对小麦粘虫的平行测试结果(致死率％)

表9：示例性化合物对小麦粘虫的平行测试结果(保叶率％)
10)斜纹夜蛾活性测定：采用人工饲料药膜法：先将配制好的人工饲料趁热倒入12孔板中，每孔加2.5ml人工饲料，待饲料充分凉透后备用。每种药剂每个浓度梯度做3个12孔板，每个12孔板为1个重复，共3个重复，每孔加入50μL对应浓度梯度药剂，晾干。每孔接入1头斜纹夜蛾幼虫。对照3个12孔板，共3个重复，每孔加入50μL溶剂对照。放入温度26±2℃、光照为16h:8h(L:D)，湿度50＝70％的养虫室中饲养，于试验后的48h调查试虫死亡情况，统计试虫的致死率。试验浓度分别为50mg/L、10mg/L。
表10：示例性化合物对斜纹夜蛾的平行测试结果(致死率％)
除了害虫防治特性外，与现有技术的化合物相比，根据本发明的化合物还出人意料地显示具有改进的降解特性。另外，与现有技术化合物相比，根据本发明的化合物还出人意料地显示出对蜜蜂(或水生动物)的毒性更低。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。

Claims (10)

  1. 作为吡啶酰胺衍生物的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，
    其中，
    R1、R2和R3各自独立地选自氢、卤素、羟基、硝基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6烷氧基或C1-C6卤代烷氧基；
    M选自氧或硫；
    W选自C3-C6环烷基或三元至六元杂环烷基，其中所述C3-C6环烷基或三元至六元杂环烷基中的1至3个氢原子任选地被卤素、羟基、硝基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6卤代烷基、C1-C6烷氧基或C1-C6卤代烷氧基取代；
    Q为三元至六元杂环烷基或被一个或多个取代基取代的C1-C3烷基，所述一个或多个取代基各自独立地选自卤素、羟基、硝基、氨基、氰基、C1-C6烷基、C2-C6烯基、C2-C6炔基、C1-C6烷氧基、C1-C6卤代烷基、C1-C6卤代烷氧基、C3-C6环烷基、三元至六元杂环烷基、苯氧基、苯甲氧基或-O-(CH2)m-O-(CH2)n-CH3；
    m为1至3中的任一整数；并且
    n为0至2中的任一整数。
  2. 根据权利要求1所述的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，其中，
    R1、R2和R3各自独立地选自氢、氟、氯、溴、C1-C3烷基、C1-C3氟代烷基、C1-C3烷氧基或C1-C3氟代烷氧基，优选氢、氟、氯、溴、甲基、一氟甲基、二氟甲基、三氟甲基、乙基、氟乙基、甲氧基、一氟甲氧基、二氟甲氧基、三氟甲氧基或乙氧基；
    M选自氧或硫；
    W选自环丙基，其中所述环丙基中的1至3个氢原子任选地被卤素、氰基、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基或C1-C3卤代烷氧基取代，优选任选地被氟、氯、溴、氰基、甲基、一氟甲基、二氟甲基、三氟甲基、乙基、氟乙基、甲氧基、一氟甲氧基、二氟甲氧基、三氟甲氧基或乙氧基取代；
    Q为三元至六元杂环烷基或被一个或多个取代基取代的C1-C3烷基，所述一个或多个取代基各自独立地选自氰基、C1-C3烷基、C2-C3烯基、C2-C3炔基、C1-C3烷氧基、C3-C6环烷基、三元至六元杂环烷基、苯氧基、苯甲氧基或-O-(CH2)m-O-(CH2)n-CH3；
    m为1、2或3；并且
    n为0、1或2。
  3. 根据权利要求1所述的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，其中，
    所述杂环烷基为氧杂环烷基、氮杂环烷基或硫杂环烷基，其包含1至3个氧杂原子、氮杂原子或硫杂原子，优选1或2个氧杂原子、氮杂原子或硫杂原子。
  4. 根据权利要求1所述的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，其中，
    Q为氧杂环戊基、氧杂环己基或被一个或多个取代基取代的甲基、乙基、正丙基或异丙基，所述一个或多个取代基各自独立地选自氰基、甲基、乙基、乙烯、乙炔、甲氧基、乙氧基、丙氧基、异丙氧基、环丙基、环丁基、环戊基、氧杂环丙基、氧杂环丁基、氧杂环戊基、氧杂环己基、氮杂环己基、硫杂环己基、苯氧基、苯甲氧基、-OCH2OCH3或-OCH2CH2OCH3。
  5. 根据权利要求1所述的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，其具有下式结构：

  6. 一种杀虫剂组合物，其包含根据权利要求1-5中任一项所述的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐，以及农药学上可接受的载体。
  7. 根据权利要求6所述的杀虫剂组合物，其剂型选自粉剂、颗粒剂、液剂、悬浮剂或喷雾剂，优选可湿性粉剂、可湿性液剂、可溶性粉剂、可分散液剂、水剂、微乳剂、乳油、水乳剂、可喷洒溶液、可分散油悬浮剂、微囊悬浮剂、水分散粒剂、水溶性粒剂、大粒剂、用于撒播和土壤施药的颗粒剂、气雾剂、超低容量剂和蜡制品。
  8. 根据权利要求1-5中任一项所述的式(I)化合物或其同位素标记化合物、或其光学异构体、几何异构体、互变异构体或异构体混合物、或其农药学上可接受的盐在制备用于害虫防治的杀虫剂中的用途。
  9. 根据权利要求8所述的用途，其中所述害虫选自属于鳞翅目、鞘翅目、同翅目、半翅目、缨翅目、等翅目、双翅目、膜翅目、食毛目、虱目、直翅目、蜚蠊目、蚤目、蜱螨目、线虫纲的害虫。
  10. 根据权利要求9所述的用途，其中所述害虫选自小菜蛾、褐飞虱、草地贪夜蛾、斜纹夜蛾、粘虫、韭菜迟眼蕈蚊、点蜂缘蝽、茶小绿叶蝉或紫薇绒蚧。
PCT/CN2023/113449 2022-09-15 2023-08-17 一种吡啶酰胺衍生物及其用途 WO2024055801A1 (zh)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105873908A (zh) * 2013-11-05 2016-08-17 拜耳作物科学股份公司 用于防治节肢动物的新的化合物
CN105873906A (zh) * 2013-11-05 2016-08-17 拜耳作物科学股份公司 用于防治节肢动物的新化合物
WO2016174052A1 (en) * 2015-04-30 2016-11-03 Bayer Animal Health Gmbh Antiparasitic combinations
CN110049975A (zh) * 2016-12-08 2019-07-23 拜耳作物科学股份公司 制备5-(1-苯基-1h-吡唑-4-基)烟酰胺衍生物及类似化合物而不分离或纯化苯肼中间体的方法
CN111050559A (zh) * 2017-08-11 2020-04-21 先正达参股股份有限公司 杀有害生物活性吡唑衍生物
CN112334457A (zh) * 2018-06-22 2021-02-05 拜耳公司 制备三环化合物的方法
CN115894442A (zh) * 2022-11-04 2023-04-04 海利尔药业集团股份有限公司 一种取代的苯酰胺类衍生物或其作为农药可接受的盐、组合物及其用途

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105873908A (zh) * 2013-11-05 2016-08-17 拜耳作物科学股份公司 用于防治节肢动物的新的化合物
CN105873906A (zh) * 2013-11-05 2016-08-17 拜耳作物科学股份公司 用于防治节肢动物的新化合物
CN106103414A (zh) * 2013-11-05 2016-11-09 拜耳作物科学股份公司 用于节肢动物处理的取代的苯酰胺类
WO2016174052A1 (en) * 2015-04-30 2016-11-03 Bayer Animal Health Gmbh Antiparasitic combinations
CN110049975A (zh) * 2016-12-08 2019-07-23 拜耳作物科学股份公司 制备5-(1-苯基-1h-吡唑-4-基)烟酰胺衍生物及类似化合物而不分离或纯化苯肼中间体的方法
CN111050559A (zh) * 2017-08-11 2020-04-21 先正达参股股份有限公司 杀有害生物活性吡唑衍生物
CN112334457A (zh) * 2018-06-22 2021-02-05 拜耳公司 制备三环化合物的方法
CN115894442A (zh) * 2022-11-04 2023-04-04 海利尔药业集团股份有限公司 一种取代的苯酰胺类衍生物或其作为农药可接受的盐、组合物及其用途

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