WO2024012527A1 - 一种含吡唑结构的化合物和应用以及杀虫剂 - Google Patents

一种含吡唑结构的化合物和应用以及杀虫剂 Download PDF

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WO2024012527A1
WO2024012527A1 PCT/CN2023/107234 CN2023107234W WO2024012527A1 WO 2024012527 A1 WO2024012527 A1 WO 2024012527A1 CN 2023107234 W CN2023107234 W CN 2023107234W WO 2024012527 A1 WO2024012527 A1 WO 2024012527A1
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group
substituted
alkyl
cycloalkyl
halogen
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PCT/CN2023/107234
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English (en)
French (fr)
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杨光富
黄伟
马哲朋
王震宇
王金珍
李建友
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安徽圣丰生化有限公司
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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
    • A01N43/72—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
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • 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
    • 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
    • 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
    • A01P9/00—Molluscicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage

Definitions

  • the invention relates to the field of pesticides and insecticides, specifically to a compound containing a pyrazole structure and its application and insecticides.
  • GABA Gamma-aminobutyric acid
  • GABA As an inhibitory neurotransmitter, GABA is released from the presynaptic membrane of nerve cells, reaches the postsynaptic membrane through the synaptic cleft, and specifically binds to GABA receptors on the postsynaptic membrane, activating the chloride ion channel on the cell membrane. Open, the chloride ions outside the membrane enter the cell, causing hyperpolarization, thereby inhibiting the excitation of nerve cells and exerting physiological effects.
  • Isoxazoline compounds are a new class of pesticides that act on specific sites of ionotropic GABA receptors. This type of compound non-competitively blocks the inflow of chloride ions in nerve cells, interferes with the normal function of the insect's central nervous system, and prevents nerve excitation from being normally suppressed, leading to the death of the insect.
  • Isoxazoline compounds have the characteristics of broad spectrum, high activity and high selectivity. They are effective against Hemiptera, Thysanoptera, Diptera, Lepidoptera and mites. Agricultural pests such as these have good biological activity.
  • isoxazoline compounds are a class of pesticides with great research value and development prospects.
  • the object of the present invention is to provide a new compound containing a pyrazole structure that can achieve good insecticidal, acaricidal, nematicidal and snail-killing effects at low concentrations.
  • the inventor of the present invention unexpectedly discovered during research that the 5-aminopyrazole structure of the prior art isoxazoline compounds was shifted to 4-aminopyrazole, and introduced at positions 1, 3, and 5 or Without introducing characteristic substituents, the new compounds thus obtained have excellent inhibitory activity against pests.
  • the new compound of the present invention has good safety to aquatic organisms such as fish, daphnia, algae, etc. That is to say, the present invention can provide a kind of environmentally friendly and pest-resistant New isoxazoline insecticides with inhibitory activity. In view of this, the inventor provides the solution of the present invention.
  • the first aspect of the present invention provides a compound containing a pyrazole structure or an agrochemically acceptable salt, hydrate and solvate thereof.
  • the compound has a structure represented by formula (I):
  • R 1 is selected from H, halogen, at least one halogen-substituted C 1-6 alkyl group, and at least one halogen-substituted C 1-6 alkoxy group;
  • R 2 is selected from C 1-12 alkyl, C 1-12 alkoxy, halogen, at least one halogen-substituted C 1-6 alkyl, at least one halogen-substituted C 1-6 alkoxy, cyano;
  • R 3 is selected from H, C 1-12 alkyl, C 1-12 alkoxy, C 3-12 cycloalkyl, -CO-R 31 , -CO-CH 2 -R 31 ;
  • R 31 is selected From C 1-12 alkyl, C 3-12 cycloalkyl, C 1-12 alkoxy;
  • R 4 and R 5 are each independently selected from H, C 1-12 alkyl, C 1-12 alkoxy, halogen, at least one halogen-substituted C 1-6 alkyl, at least one halogen-substituted C Alkoxy group of 1-6 ;
  • R 6 is selected from H, an alkyl group of C 1-12 that is unsubstituted or substituted by at least one group in combination A, an alkyl group of C 1-12 that is unsubstituted or substituted by at least one group in combination A.
  • the combination A consists of hydroxyl, halogen, C 1-12 alkyl, C 1-12 alkoxy, and trimethylsilyl.
  • the second aspect of the present invention provides the use of the pyrazole structure-containing compound or its agrochemically acceptable salt, hydrate and solvate described in the first aspect in killing insects, mites, nematodes and snails. Application in at least one of.
  • the third aspect of the present invention provides the use of the aforementioned compounds containing pyrazole structures or their agrochemically acceptable salts, hydrates and solvates as pesticides and insecticides.
  • the fourth aspect of the present invention provides a pesticide containing at least one of the aforementioned compound containing a pyrazole structure or its agrochemically acceptable salt, hydrate and solvate as an active ingredient.
  • the compounds of the present invention or their agrochemically acceptable salts, hydrates and solvates are effective against diamondback moth, Spodoptera frugiperda, Spodoptera litura, Spodoptera exigua, Spodoptera exigua, Asian corn borer, cotton bollworm, Spodoptera exigua, It has excellent control effects on pests such as borers, rice leaf rollers, western flower thrips, and flea beetles, and has good market development prospects.
  • the compounds provided by the invention or their agrochemically acceptable salts, hydrates and solvates can also effectively prevent and control mutant pests that are resistant to existing pesticides, and are important for the development of new pesticides without cross-resistance. significance.
  • Halogen means fluorine, chlorine, bromine, and iodine.
  • C 1-6 alkyl group means a straight-chain alkyl group or a branched-chain alkyl group with a total number of carbon atoms of 1, 2, 3, 4, 5 or 6. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • C 1-8 alkyl group "C 1-10 alkyl group” and “C 1-12 alkyl group” have similar definitions, only the total number of carbon atoms is different.
  • C 1 -C 6 alkoxy group means a linear or branched chain alkoxy group with a total number of carbon atoms of 1, 2, 3, 4, 5 or 6. For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.
  • C 1-8 alkoxy group "C 1-10 alkoxy group” and “C 1-12 alkoxy group” have similar definitions, only the total number of carbon atoms is different.
  • At least one halogen-substituted C 1-6 alkyl group means that at least one H atom in the "C 1-6 alkyl group” is substituted by halogen, and the substituted halogen may be one or more.
  • At least one halogen-substituted C 1-6 alkoxy group has a similar definition, except that the "C 1-6 alkyl group” is replaced by "C 1-6 alkoxy group”.
  • C 3-10 cycloalkyl means a cycloalkyl group with a total number of carbon atoms of 3-10, and the ring atoms are all C atoms.
  • the total number of ring carbon atoms can be 3, 4, 5, 6, or 7 , 8, 9, 10, and any position that can be substituted on the "C 3-10 cycloalkyl group" is directly connected to the mother core.
  • C 3-6 cycloalkyl” and “C 3-12 cycloalkyl” have similar definitions and only differ in the total number of carbon atoms.
  • C 1-12 alkyl group that is unsubstituted or substituted by at least one group in combination A means that the "C 1-12 alkyl group” has no substituent or is substituted by one or more groups in combination A.
  • C 1-10 alkyl group that is unsubstituted or substituted by at least one group in combination A has a similar definition, except that the total number of carbon atoms is different.
  • C 1-12 alkoxy group that is unsubstituted or substituted by at least one group in the combination A means that the "C 1-12 alkoxy group” has no substituent or is substituted by one or more groups in the combination A.
  • a case of group substitution "C 1-10 alkoxy group that is unsubstituted or substituted by at least one group in combination A” has a similar definition, except that the total number of carbon atoms is different.
  • C 3-12 cycloalkyl group that is unsubstituted or substituted by at least one group in the combination A means that the "C 3-12 alkoxy group” has no substituent or is substituted by one or more groups in the combination A. A case of group substitution.
  • C 3-10 cycloalkyl group that is unsubstituted or substituted by at least one group in combination A has a similar definition, except that the total number of carbon atoms is different.
  • Phenyl group that is unsubstituted or substituted by at least one group in combination A means that the "phenyl group” has no substituent or is substituted by one or more groups in combination A.
  • C 3-12 cycloalkyl group containing at least one hetero atom as a ring atom means that at least one of the ring atoms of the “C 3-12 cycloalkyl group” is a hetero atom other than carbon, which can be exemplified are oxygen atoms, sulfur atoms and nitrogen atoms.
  • C 3-10 cycloalkyl containing at least one heteroatom as a ring atom has a similar definition, except that the total number of carbon atoms is different.
  • C 2-12 hydrocarbon group containing at least one unsaturated carbon-carbon double bond or unsaturated carbon-carbon triple bond means that the C 2-12 hydrocarbon group contains at least one unsaturated carbon-carbon double bond or unsaturated carbon -Carbon triple bond.
  • C 2-10 hydrocarbon group containing at least one unsaturated carbon-carbon double bond or unsaturated carbon-carbon triple bond has a similar definition, except that the total number of carbon atoms is different.
  • C 2-12 hydrocarbon group that is unsubstituted or substituted by at least one group in combination A and contains at least one unsaturated carbon-carbon double bond or unsaturated carbon-carbon triple bond is expressed in “containing at least one unsaturated carbon- "C 2-12 hydrocarbon group with carbon double bond or unsaturated carbon-carbon triple bond” has no substituents or is composed of One or more groups in A are substituted. "C 2-10 hydrocarbyl group containing at least one unsaturated carbon-carbon double bond or unsaturated carbon-carbon triple bond that is unsubstituted or substituted by at least one group in combination A" has a similar definition, only carbon atoms The total number is just different.
  • the wavy line represents the bond bonded to the parent core structure.
  • the first aspect of the present invention provides a compound containing a pyrazole structure or an agrochemically acceptable salt, hydrate and solvate thereof.
  • the compound has a structure represented by formula (I):
  • R 1 is selected from H, halogen, at least one halogen-substituted C 1-6 alkyl group, and at least one halogen-substituted C 1-6 alkoxy group;
  • R 2 is selected from C 1-12 alkyl, C 1-12 alkoxy, halogen, at least one halogen-substituted C 1-6 alkyl, at least one halogen-substituted C 1-6 alkoxy, cyano;
  • R 3 is selected from H, C 1-12 alkyl, C 1-12 alkoxy, C 3-12 cycloalkyl, -CO-R 31 , -CO-CH 2 -R 31 ;
  • R 31 is selected From C 1-12 alkyl, C 3-12 cycloalkyl, C 1-12 alkoxy;
  • R 4 and R 5 are each independently selected from H, C 1-12 alkyl, C 1-12 alkoxy, halogen, at least one halogen-substituted C 1-6 alkyl, at least one halogen-substituted C Alkoxy group of 1-6 ;
  • R 6 is selected from H, an alkyl group of C 1-12 that is unsubstituted or substituted by at least one group in combination A, an alkyl group of C 1-12 that is unsubstituted or substituted by at least one group in combination A.
  • the combination A consists of hydroxyl, halogen, C 1-12 alkyl, C 1-12 alkoxy, and trimethylsilyl.
  • R 1 is selected from H, halogen, at least one halogen-substituted C 1-6 alkyl group, at least one halogen-substituted C 1-6 alkoxy group; more preferably, R 1 is selected from H, F, chlorine, and bromine.
  • R 2 is selected from C 1-8 alkyl, C 1-8 alkoxy, halogen, at least one halogen-substituted C 1-6 alkyl, at least one halogen-substituted C 1-6 alkoxy group, cyano group; more preferably, R 2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyano group.
  • R 3 is selected from H, C 1-8 alkyl group, C 1-8 alkoxy group, C 3-10 cycloalkyl group, -CO-R 31 , -CO -CH 2 -R 31 ;
  • R 31 is selected from C 1-8 alkyl, C 3-10 cycloalkyl, C 1-8 alkoxy; more preferably, R 3 is selected from H, methyl, Ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, cyclopropyl , cyclobutyl, cyclopentyl, cyclohexyl, -CO-R 31 , -CO-CH 2 -R 31 ;
  • R 31 is selected from C 1-6 alkyl, C 3-6 cycloalkyl, C 1 -6 alkoxy group.
  • R 4 and R 5 are each independently selected from H, C 1-8 alkyl, C 1-8 alkoxy, halogen, at least one halogen substitution C 1-6 alkyl, at least one halogen-substituted C 1-6 alkoxy; more preferably, R 4 and R 5 are each independently selected from H, methyl, ethyl, n-propyl, iso Propyl, n-butyl, tert-butyl.
  • R 6 is selected from H, an alkyl group of C 1-10 that is unsubstituted or substituted by at least one group in combination A, unsubstituted or by at least one group in combination A.
  • C 1-10 alkoxy group substituted by the group C 3-10 cycloalkyl group unsubstituted or substituted by at least one group in the combination A, unsubstituted or by at least one group in the combination A.
  • Substituted phenyl, C 3-10 cycloalkyl containing at least one heteroatom as a ring atom, unsubstituted or substituted by at least one group in combination A containing at least one unsaturated carbon-carbon double bond or not C 2-10 hydrocarbon group with saturated carbon-carbon triple bond, -(CH 2 ) n -R 61 , -CO-R 62 , -COO-R 62 , -CO-N(R 63 R 64 ), -S( O) 2
  • R 1 is selected from H, halogen, at least one halogen-substituted C 1-6 alkyl group, and at least one halogen-substituted C 1-6 alkoxy group;
  • R 2 is selected from C 1-8 alkyl, C 1-8 alkoxy, halogen, at least one halogen-substituted C 1-6 alkyl, at least one halogen-substituted C 1-6 alkoxy, cyano;
  • R 3 is selected from H, C 1-8 alkyl group, C 1-8 alkoxy group, C 3-10 cycloalkyl group, -CO-R 31 , -CO-CH 2 -R 31 ;
  • R 31 is selected From C 1-8 alkyl, C 3-10 cycloalkyl, C 1-8 alkoxy;
  • R 4 and R 5 are each independently selected from H, C 1-8 alkyl, C 1-8 alkoxy, halogen, at least one halogen-substituted C 1-6 alkyl, at least one halogen-substituted C Alkoxy group of 1-6 ;
  • R 6 is selected from H, an alkyl group of C 1-10 that is unsubstituted or substituted by at least one group in combination A, an alkyl group of C 1-10 that is unsubstituted or substituted by at least one group in combination A.
  • the combination A consists of hydroxyl, halogen, C 1-8 alkyl, C 1-8 alkoxy, and trimethylsilyl.
  • R 1 is selected from H, F, chlorine, bromine
  • R 2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and cyano;
  • R 3 is selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , tert-butoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, -CO-R 31 , -CO-CH 2 -R 31 ;
  • R 31 is selected from C 1-6 alkyl, C 3 -6 cycloalkyl, C 1-6 alkoxy;
  • R 4 and R 5 are each independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl;
  • R 6 is selected from H, an alkyl group of C 1-10 that is unsubstituted or substituted by at least one group in combination A, an alkyl group of C 1-10 that is unsubstituted or substituted by at least one group in combination A.
  • the combination A consists of hydroxyl, halogen, C 1-8 alkyl, C 1-8 alkoxy, and trimethylsilyl.
  • the compound is selected from any one of the following:
  • the present invention has no special requirements on the method for preparing the compound described in the first aspect. Those skilled in the art can determine a suitable synthetic route based on the structural formula provided by the present invention and the known knowledge in the field of organic synthesis to obtain the first aspect of the present invention. Compounds described in aspects.
  • the second aspect of the present invention provides the use of the pyrazole structure-containing compound described in the first aspect or its agrochemically acceptable salts, hydrates and solvates in killing insects, mites, nematodes, and snails. application in at least one of the insects.
  • the third aspect of the present invention provides the use of the aforementioned compounds containing pyrazole structures or their agrochemically acceptable salts, hydrates and solvates as pesticides and insecticides.
  • the fourth aspect of the present invention provides a pesticide, which contains at least one of the aforementioned compounds containing a pyrazole structure or an agrochemically acceptable salt, hydrate and solvate thereof as an active ingredient. .
  • the content of the active ingredient in the pesticide is 1-99.9% by weight.
  • the content of the active ingredient in the pesticide is 1-99.9% by weight, for example, it can be 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, etc.
  • the content of said active ingredient in the insecticide is 5-95% by weight.
  • the dosage form of the pesticide is selected from at least one of emulsifiable concentrate, suspension, wettable powder, dust, granule, aqueous formulation, poison bait, mother liquor and mother powder.
  • room temperature or normal temperature mentioned below means 25 ⁇ 3°C.
  • the numbering of the compounds provided in the following example part of the present invention is different from the numbering of the compounds in the foregoing, that is, there is a situation in the present invention where a structural formula has two numbers, which does not affect the clear presentation of the present invention. For the same structure, any number is clear.
  • Table 1 lists the characterization data of some compounds of the present invention.
  • step i Take the compound shown in formula 1-1 (21.50g), palladium acetate (0.23g), and potassium carbonate (27.64g) in order and place them in a Schlenk tube, and pump and fill with nitrogen three times. Then add n-butyl vinyl ether (30.00g) and 100 mL of n-butanol, and reflux for 6 hours at 120°C. After the reaction is completed, evaporate the solvent to dryness under reduced pressure, add 1N HCl solution to acidify to pH 2, filter and dry to obtain the product. Intermediate 1-2, yield 92%.
  • step ii Take intermediate 1-2 (10.00g), 3,5-dichloro-2,2,2-trifluoroacetophenone (16.38g), and triethylamine in sequence (11.37g) and 100mL of toluene were placed in a three-necked flask and reacted at 50°C for 16 hours. After the raw materials were completed, the mixture was cooled to room temperature, filtered, and the solid was dried to obtain intermediate 1-3 with a yield of 98%.
  • step iii) Take 100 mL of compound 1-3 (26.52g), 4-dimethylaminopyridine (6.20g), and toluene in a three-necked flask, and add acetic anhydride (10.36g). React at 60°C for 12 hours. After the reaction is completed, add 1N HCl solution to acidify to pH 2, filter and dry to obtain intermediate 1-4, with a yield of 95%.
  • step iv Take intermediate 1-4 (16.70g), tetrabutylammonium bromide (4.01g), and 300mL of toluene in a three-necked flask, and add 5.47g of 50% hydroxylamine Aqueous solution, react at room temperature for 7 hours. After the reaction is completed, add 1N HCl solution to acidify to pH 2, filter and dry to obtain intermediate 1-5, the yield is 95%.
  • step v Take intermediate 1-5 (0.50g), CDI (0.39g), DIPEA (0.56g), and 10 mL of dichloromethane in a three-necked flask, and add 4-aminopyrazole ( 0.16g), react at room temperature for 4 hours. After the reaction is completed, wash 3 times with saturated NaHCO 3 solution, extract the aqueous layer 3 times with 20 mL of dichloromethane, combine the organic layers after the extraction is completed, and then use anhydrous Na 2 SO 4 to dissolve the organic layer. After drying, the organic layer was purified by column chromatography to obtain compound 1 with a yield of 83%.
  • step vi Take 20 mL of intermediate 1-6 (1.00g), potassium carbonate (1.47g), methyl iodide (1.50g), and N,N-dimethylaminoformamide in order. In a three-necked flask, react at room temperature for 3 hours. After the reaction is completed, add 100 mL of ethyl acetate, wash with saturated brine three times, and then add The organic layer was dried over anhydrous Na 2 SO 4 and purified by column chromatography to obtain intermediate 1-7 with a yield of 93%.
  • step vii) Take intermediate 1-7 (0.50g), ammonium chloride (0.95g), 5mL of water, and 15mL of ethanol in sequence, heat to boiling, and then add reduced iron powder (1.54 g), reflux for 30 min. After the reaction is completed, add 50 mL of ethyl acetate, wash with saturated brine three times, then dry the organic layer with anhydrous Na 2 SO 4 , and purify by column chromatography to obtain intermediate 1-8, the yield is 78%.
  • step viii Take intermediate 1-5 (0.50g), CDI (0.39g), DIPEA (0.56g), and 10 mL of dichloromethane in a three-necked flask, and add intermediate 1-8 ( 0.18g), react at room temperature for 4 hours. After the reaction is completed, wash 3 times with saturated NaHCO 3 solution, extract the aqueous layer 3 times with 20 mL of dichloromethane, combine the organic layers after the extraction is complete, and then use anhydrous Na 2 SO 4 to dissolve the organic layer. After drying and purification by column chromatography, compound 2 was obtained with a yield of 82%.
  • Compound 58 was prepared according to a method similar to Preparation Example 2, except that equal moles of acetyl chloride, triethylamine, and dichloromethane were used to replace methyl iodide, potassium carbonate, and N,N-dimethylamino in step VI.
  • Formamide specifically, the preparation steps of intermediate 1-7 include: sequentially taking intermediate 1-6, triethylamine, and methylene chloride into a three-necked flask, adding acetyl chloride dropwise at 0°C, and reacting at room temperature for 3 hours. The reaction is completed. , add 100 mL of ethyl acetate, wash with saturated brine three times, then dry the organic layer with anhydrous Na 2 SO 4 and purify by column chromatography to obtain intermediate 1-7 with a yield of 68%.
  • Compound 95 was prepared according to a method similar to Preparation Example 1, except that the 4-aminopyrazole in step v was replaced with an equal molar amount of 3,5-dimethyl-1H-pyrazole-4-amine, specifically Ground, in the preparation of compound 95: Take intermediate 1-5 (0.50g), CDI (0.39g), DIPEA (0.56g), and 10 mL of dichloromethane in a three-necked flask, and add 3,5-dimethyl Base-1H-pyrazole-4-amine, react at room temperature for 4 hours.
  • Compound 96 was prepared according to a method similar to Preparation Example 2, except that intermediate 1-6 in step VI was replaced with equimolar 3,5-dimethyl-4-nitropyrazole, specifically, Preparation of intermediate 1-7: Take 20 mL of 3,5-dimethyl-4-nitropyrazole, potassium carbonate (1.47g), methyl iodide (1.50g), and N,N-dimethylaminoformamide in sequence. In a three-necked flask, react at room temperature for 3 hours. After the reaction is completed, add 100 mL of ethyl acetate and wash with saturated brine three times. The organic layer is then dried with anhydrous Na 2 SO 4 and purified by column chromatography to obtain intermediate 1-7, which is collected. The rate is 94%.
  • Compound 97 was prepared according to a method similar to Preparation Example 96, except that the methyl iodide in step VI was replaced by equimolar ethyl iodide. Specifically, the preparation steps of intermediate 1-7 included:
  • Compound 105 was prepared according to a method similar to the preparation of compound 58, except that intermediate 1-6 in step VI was replaced with equimolar 3,5-dimethyl-4-nitropyrazole, specifically, Preparation of intermediate 1-7: Place 3,5-dimethyl-4-nitropyrazole, triethylamine, and dichloromethane in a three-necked flask in sequence, add acetyl chloride (0.83g) dropwise at 0°C, and keep at room temperature After 3 hours of reaction, the reaction was completed. 100 mL of ethyl acetate was added, washed three times with saturated brine, and then the organic layer was dried with anhydrous Na 2 SO 4 and purified by column chromatography to obtain intermediate 1-7 with a yield of 63%.
  • Compound 123 was prepared according to a method similar to Preparation Example 1, except that the 3,5-dichloro-2,2,2-trifluoroacetophenone in step ii was replaced with an equal molar amount of 3,5-dichloroacetophenone.
  • Chloro-4-fluoro-2,2,2-trifluoroacetophenone specifically, the preparation of intermediate 1-3 includes: taking intermediate 1-2 (10.00g), 3,5-dichloro-4 in sequence -Fluoro-2,2,2-trifluoroacetophenone, triethylamine (11.37g), and 100mL of toluene were placed in a three-necked flask, and reacted at 50°C for 16 hours. After the raw materials were completed, they were cooled to room temperature, filtered, and the solids were dried. Intermediate 1-3 was obtained with a yield of 93%.
  • Compound 124 was prepared according to a method similar to Preparation Example 2, except that the 3,5-dichloro-2,2,2-trifluoroacetophenone in step ii was replaced with an equal molar amount of 3,5-dichloroacetophenone.
  • Chloro-4-fluoro-2,2,2-trifluoroacetophenone specifically, the preparation of intermediate 1-3 includes: taking intermediate 1-2 and 3,5-dichloro-4-fluoro-2 in sequence , 100mL of 2,2-trifluoroacetophenone, triethylamine, and toluene were placed in a three-necked flask, and reacted at 50°C for 16 hours. After the raw materials were completed, they were cooled to room temperature, filtered, and the solids were dried to obtain intermediate 1-3. The rate is 93%.
  • Compound 140 was prepared according to a method similar to the preparation of compound 58, except that the 3,5-dichloro-2,2,2-trifluoroacetophenone in step ii was replaced with an equal molar amount of 3,5-dichloroacetophenone.
  • Chloro-4-fluoro-2,2,2-trifluoroacetophenone specifically, the preparation of intermediate 1-3 includes: taking intermediate 1-2 and 3,5-dichloro-4-fluoro-2 in sequence , 100mL of 2,2-trifluoroacetophenone, triethylamine, and toluene were placed in a three-necked flask, and reacted at 50°C for 16 hours. After the raw materials were completed, they were cooled to room temperature, filtered, and the solids were dried to obtain intermediate 1-3. The rate is 93%.
  • Compound 158 was prepared according to a method similar to the preparation of compound 123, except that 4-aminopyrazole in step v was replaced with 3,5-dimethyl-1H-pyrazole-4-amine, specifically, in sequence Take 10 mL of intermediate 1-5 (0.50g), CDI (0.39g), DIPEA (0.56g), and methylene chloride in a three-necked flask, and add 3,5-dimethyl-1H-pyrazole-4-amine. , react at room temperature for 4 hours.
  • Compound 159 was prepared according to a method similar to the preparation of compound 124, except that intermediate 1-6 in step VI was replaced with equimolar 3,5-dimethyl-4-nitropyrazole, specifically, Preparation of intermediate 1-7: Take 20 mL of 3,5-dimethyl-4-nitropyrazole, potassium carbonate (1.47g), methyl iodide (1.50g), and N,N-dimethylaminoformamide in sequence. In a three-necked flask, react at room temperature for 3 hours. After the reaction is completed, add 100 mL of ethyl acetate and wash with saturated brine three times. The organic layer is then dried with anhydrous Na 2 SO 4 and purified by column chromatography to obtain intermediate 1-7, which is collected. The rate is 94%.
  • Compound 168 was prepared according to a method similar to the preparation of compound 140, except that intermediate 1-6 in step VI was replaced with equimolar 3,5-dimethyl-4-nitropyrazole, specifically,
  • the preparation steps of intermediate 1-7 include: sequentially placing 3,5-dimethyl-4-nitropyrazole, triethylamine, and dichloromethane in a three-necked flask, adding acetyl chloride dropwise at 0°C, and reacting at room temperature for 3 hours. , after the reaction is completed, add 100 mL of ethyl acetate, wash with saturated brine three times, then dry the organic layer with anhydrous Na 2 SO 4 , and purify by column chromatography to obtain intermediate 1-7 with a yield of 68%.
  • the leaf dipping method was used to determine the toxic activity of some compounds against the second instar larvae of Diamondback moth.
  • the mortality rate is calculated according to the following formula 1, and then the corrected mortality rate is calculated according to the formula 2. Finally, the corrected mortality value is combined with the rating standards shown in Table 2 for classification. The specific results are shown in Table 3 and Table 4.
  • Mortality rate % (number of dead insects/total number of insects) ⁇ 100%;
  • the leaf dipping method was used to determine the toxic activity of some compounds against the fourth instar larvae of rice leaf roller.
  • Mortality rate % (number of dead insects/total number of insects) ⁇ 100%;
  • the compound containing a pyrazole structure provided by the invention can achieve good insecticidal, acaricidal, nematicidal and snail-killing effects at low concentrations.
  • the compounds containing pyrazole structures provided by the invention are effective against diamondback moth, Asian corn borer, cotton bollworm, stem borer, rice leaf roller, Spodoptera frugiperda, exigua exigua, Spodoptera litura, and whitefly.
  • rice planthoppers, aphids, thrips, flea beetles and other agricultural insects have excellent insecticidal activity.
  • the compound 127 containing a pyrazole structure provided by the present invention can have a lethality rate of 100% on diamondback moth at a concentration of 0.25 ppm, while the effects of the control compounds K1 and K2 are both less than 50%. Moreover, compound 127 has a lethality rate of 100% against rice leaf roller at a concentration of 5 ppm, which is much better than the control compounds K1 and K2.

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Abstract

本发明涉及农药杀虫剂领域，公开了一种含吡唑结构的化合物和应用以及杀虫剂。该含吡唑结构的化合物具有式(I)所示的结构。本发明提供的化合物能够在低浓度下实现良好的杀昆虫、杀螨虫、杀线虫以及杀螺虫的效果。

Description

一种含吡唑结构的化合物和应用以及杀虫剂
相关申请的交叉引用
本申请要求2022年07月13日提交的中国专利申请202210826763.6的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及农药杀虫剂领域，具体涉及一种含吡唑结构的化合物和应用以及杀虫剂。
背景技术
γ-氨基丁酸(GABA)是动物体内一类重要的神经递质，主要存在于中枢神经系统中，由谷氨酸经体内酶代谢转化而来。
作为一种抑制性神经递质，GABA由神经细胞突触前膜释放，经突触间隙到达突触后膜，并与后膜上的GABA受体发生特异性结合，促使细胞膜上的氯离子通道开放，膜外的氯离子进入细胞内，产生超极化现象，从而抑制神经细胞兴奋，发挥生理作用。
异噁唑啉类化合物是一类作用于离子型GABA受体特异性位点的新型杀虫剂。该类化合物非竞争性地阻滞神经细胞氯离子的内流，干扰昆虫中枢神经系统的正常功能，使神经兴奋不能够正常的抑制，从而导致昆虫死亡。
异噁唑啉类化合物具有广谱性、高活性、高选择性等特点，对半翅目(Hemiptera)、缨翅目(Thysanoptera)、双翅目(Diptera)以及鳞翅目(Lepidoptera)和螨类等农业害虫都具有较好的生物活性。
因此，异噁唑啉类化合物是一类非常具有研究价值和发展前景的杀虫剂。
2005年，日产化学株式会社在WO2005085216A1公开报道了异噁唑啉类化合物具有杀虫特性。其中代表性物质为化合物K1和化合物K2，且结构如下，该类物质主要用于防治农作物中的鳞翅目害虫。
随后，WO2007026965、W02008108448、WO2011104089、WO2019243262、WO2012007426等现有技术在此基础上公开了一系列具有杀虫活性的含异噁唑啉结构的化合物。但上述化合物杀虫或杀螨活性在实际应用中仍存在不足，除粉虱外对其它靶标生物的活性不甚让人满意。
发明内容
本发明的目的是提供一种新的含吡唑结构的化合物能够在低浓度下实现良好的杀昆虫、杀螨虫、杀线虫以及杀螺虫的效果。
本发明的发明人在研究中意外地发现，将现有技术的异噁唑啉类化合物的5-氨基吡唑结构移位为4-氨基吡唑，并在1、3、5号位引入或者不引入特征取代基，由此获得的新化合物对害虫具有优异的抑制活性。同时，本发明的新化合物对鱼、溞、藻等水生生物具有良好的安全性。也即，本发明能够提供一类兼具环境友好和害虫高 抑制活性的新型异噁唑啉类杀虫剂。有鉴于此，发明人提供了本发明的方案。
为了实现上述目的，本发明的第一方面提供一种含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物，该化合物具有式(I)所示的结构：
其中，在式(I)中，
R1选自H、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
R2选自C1-12的烷基、C1-12的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基、氰基；
R3选自H、C1-12的烷基、C1-12的烷氧基、C3-12的环烷基、-CO-R31、-CO-CH2-R31；R31选自C1-12的烷基、C3-12的环烷基、C1-12的烷氧基；
R4、R5各自独立地选自H、C1-12的烷基、C1-12的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
R6选自H、未取代或由组合A中的至少一种基团取代的C1-12的烷基、未取代或由组合A中的至少一种基团取代的C1-12的烷氧基、未取代或由组合A中的至少一种基团取代的C3-12的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-12的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-12的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-12的环烷基、含有至少一个杂原子作为成环原子的C3-12的环烷基、苯基；R62选自C1-12的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-12的环烷基、含有至少一个杂原子作为成环原子的C3-12的环烷基；R63、R64各自独立地选自C1-12的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；
所述组合A由羟基、卤素、C1-12的烷基、C1-12的烷氧基、三甲基硅基组成。
本发明第二方面提供第一方面所述的含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物在杀灭昆虫、杀灭螨虫、杀灭线虫、杀灭螺虫中的至少一种中的应用。
本发明的第三方面提供前述含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物作为农药杀虫剂的应用。
本发明的第四方面提供一种杀虫剂，该杀虫剂中含有前述含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物中的至少一种作为活性成分。
本发明的化合物或其农业化学上可接受的盐、水合物和溶剂化物对小菜蛾、草地贪夜蛾，斜纹夜蛾、烟蚜夜蛾、甜菜夜蛾、亚洲玉米螟、棉铃虫、二化螟、稻纵卷叶螟、和西花蓟马、跳甲等害虫具有优异的防治效果，具有很好的市场开发前景。
本发明提供的化合物或其农业化学上可接受的盐、水合物和溶剂化物还能够有效防治对现有杀虫剂产生抗性的突变害虫，对开发新型无交互抗性的杀虫剂具有重要意义。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以下针对本发明的部分基团提供一些示例性的解释，在没有特别说明的情况下，未列举的部分参照如下示例性的解释进行解释。
“卤素”表示氟、氯、溴、碘。
“C1-6的烷基”表示碳原子总数为1、2、3、4、5或6的直链烷基或者支链烷基。例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等。“C1-8的烷基”、“C1-10的烷基”、“C1-12的烷基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“C1-C6的烷氧基”表示碳原子总数为1、2、3、4、5或6的直链烷氧基或者支链烷氧基。例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、叔丁氧基等。“C1-8的烷氧基”、“C1-10的烷氧基”和“C1-12的烷氧基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“至少一个卤素取代的C1-6的烷基”表示“C1-6的烷基”中的至少一个H原子由卤素取代，且取代的卤素可以为一种或者多种。“至少一个卤素取代的C1-6的烷氧基”具有与其相似的定义，仅仅是将其中的“C1-6的烷基”换成“C1-6的烷氧基”。
“C3-10的环烷基”表示碳原子总数为3-10的环烷基，且成环原子均为C原子，例如可以为成环碳原子总数为3、4、5、6、7、8、9、10，且所述“C3-10的环烷基”上任意能够被取代的位置直接与母核连接。“C3-6的环烷基”和“C3-12的环烷基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“未取代或由组合A中的至少一种基团取代的C1-12的烷基”表示“C1-12的烷基”中没有取代基或者由组合A中的一种或多种基团取代的情况。“未取代或由组合A中的至少一种基团取代的C1-10的烷基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“未取代或由组合A中的至少一种基团取代的C1-12的烷氧基”表示“C1-12的烷氧基”中没有取代基或者由组合A中的一种或多种基团取代的情况。“未取代或由组合A中的至少一种基团取代的C1-10的烷氧基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“未取代或由组合A中的至少一种基团取代的C3-12的环烷基”表示“C3-12的烷氧基”中没有取代基或者由组合A中的一种或多种基团取代的情况。“未取代或由组合A中的至少一种基团取代的C3-10的环烷基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“未取代或由组合A中的至少一种基团取代的苯基”表示“苯基”中没有取代基或者由组合A中的一种或多种基团取代的情况。
“含有至少一个杂原子作为成环原子的C3-12的环烷基”表示“C3-12的环烷基”的成环原子中至少有一个是除碳以外的杂原子，可以示例性的为氧原子、硫原子和氮原子。“含有至少一个杂原子作为成环原子的C3-10的环烷基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“含有至少一个不饱和碳-碳双键或者不饱和碳-碳三键的C2-12的烃基”表示在C2-12的烃基中至少含有一个不饱和碳-碳双键或者不饱和碳-碳三键。“含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基”具有与其相似的定义，仅仅是碳原子总数不同而已。
“未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-12的烃基”表示在“含有至少一个不饱和碳-碳双键或者不饱和碳-碳三键的C2-12的烃基”中没有取代基或者由组合 A中的一种或多种基团取代的情况。“未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基”具有与其相似的定义，仅仅是碳原子总数不同而已。
在本发明提供的化合物的结构式中，波浪线表示与母核结构结合的键。
如前所述，本发明的第一方面提供了一种含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物，该化合物具有式(I)所示的结构：
其中，在式(I)中，
R1选自H、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
R2选自C1-12的烷基、C1-12的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基、氰基；
R3选自H、C1-12的烷基、C1-12的烷氧基、C3-12的环烷基、-CO-R31、-CO-CH2-R31；R31选自C1-12的烷基、C3-12的环烷基、C1-12的烷氧基；
R4、R5各自独立地选自H、C1-12的烷基、C1-12的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
R6选自H、未取代或由组合A中的至少一种基团取代的C1-12的烷基、未取代或由组合A中的至少一种基团取代的C1-12的烷氧基、未取代或由组合A中的至少一种基团取代的C3-12的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-12的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-12的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-12的环烷基、含有至少一个杂原子作为成环原子的C3-12的环烷基、苯基；R62选自C1-12的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-12的环烷基、含有至少一个杂原子作为成环原子的C3-12的环烷基；R63、R64各自独立地选自C1-12的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；
所述组合A由羟基、卤素、C1-12的烷基、C1-12的烷氧基、三甲基硅基组成。
优选地，在式(I)中，R1选自H、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；更优选地，R1选自H、F、氯、溴。
优选地，在式(I)中，R2选自C1-8的烷基、C1-8的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基、氰基；更优选地，R2选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、氰基。
优选地，在式(I)中，R3选自H、C1-8的烷基、C1-8的烷氧基、C3-10的环烷基、-CO-R31、-CO-CH2-R31；R31选自C1-8的烷基、C3-10的环烷基、C1-8的烷氧基；更优选地，R3选自H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基、环丙基、环丁基、环戊基、环己基、-CO-R31、-CO-CH2-R31；R31选自C1-6的烷基、C3-6的环烷基、C1-6的烷氧基。
优选地，在式(I)中，R4、R5各自独立地选自H、C1-8的烷基、C1-8的烷氧基、卤素、至少一个卤素取代 的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；更优选地，R4、R5各自独立地选自H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基。
优选地，在式(I)中，R6选自H、未取代或由组合A中的至少一种基团取代的C1-10的烷基、未取代或由组合A中的至少一种基团取代的C1-10的烷氧基、未取代或由组合A中的至少一种基团取代的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基、苯基；R62选自C1-10的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基；R63、R64各自独立地选自C1-10的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；所述组合A由羟基、卤素、C1-8的烷基、C1-8的烷氧基、三甲基硅基组成；更优选地，R6选自H、未取代或由组合A中的至少一种基团取代的C1-10的烷基、未取代或由组合A中的至少一种基团取代的C1-10的烷氧基、未取代或由组合A中的至少一种基团取代的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基、苯基；R62选自C1-10的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基；R63、R64各自独立地选自C1-10的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；所述组合A由羟基、卤素、C1-8的烷基、C1-8的烷氧基、三甲基硅基组成。
优选地，在式(I)中，
R1选自H、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
R2选自C1-8的烷基、C1-8的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基、氰基；
R3选自H、C1-8的烷基、C1-8的烷氧基、C3-10的环烷基、-CO-R31、-CO-CH2-R31；R31选自C1-8的烷基、C3-10的环烷基、C1-8的烷氧基；
R4、R5各自独立地选自H、C1-8的烷基、C1-8的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
R6选自H、未取代或由组合A中的至少一种基团取代的C1-10的烷基、未取代或由组合A中的至少一种基团取代的C1-10的烷氧基、未取代或由组合A中的至少一种基团取代的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基、苯基；R62选自C1-10的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基；R63、R64各自独立地选自C1-10的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；
所述组合A由羟基、卤素、C1-8的烷基、C1-8的烷氧基、三甲基硅基组成。
更优选地，在式(I)中，
R1选自H、F、氯、溴；
R2选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、氰基；
R3选自H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基、环丙基、环丁基、环戊基、环己基、-CO-R31、-CO-CH2-R31；R31选自C1-6的烷基、C3-6的环烷基、C1-6的烷氧基；
R4、R5各自独立地选自H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基；
R6选自H、未取代或由组合A中的至少一种基团取代的C1-10的烷基、未取代或由组合A中的至少一种基团取代的C1-10的烷氧基、未取代或由组合A中的至少一种基团取代的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基、苯基；R62选自C1-10的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基；R63、R64各自独立地选自C1-10的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；
所述组合A由羟基、卤素、C1-8的烷基、C1-8的烷氧基、三甲基硅基组成。
根据一种特别优选的具体实施方式，该化合物选自以下中的任意一种：











本发明对制备第一方面中所述的化合物的方法没有特别的要求，本领域技术人员可以根据本发明提供的结构式结合有机合成领域内的已知知识确定合适的合成路线以获得本发明第一方面中所述的化合物。
本发明第二方面提供了第一方面所述的含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物在杀灭昆虫、杀灭螨虫、杀灭线虫、杀灭螺虫中的至少一种中的应用。
本发明的第三方面提供了前述含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物作为农药杀虫剂的应用。
本发明的第四方面提供了一种杀虫剂，该杀虫剂中含有前述含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物中的至少一种作为活性成分。
优选地，该杀虫剂中的所述活性成分的含量为1-99.9重量％。
更优选地，该杀虫剂中的所述活性成分的含量为1-99.9重量％，例如可以为5wt％、10wt％、15wt％、20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％、85wt％、90wt％、95wt％等。
特别优选地，该杀虫剂中的所述活性成分的含量为5-95重量％。
优选情况下，该杀虫剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、毒饵、母液和母粉中的至少一种。
在未具体列举的情况下，以下实例中所应用的均为外消旋体。
以下将通过实例对本发明进行详细描述。以下实例中，在没有特别说明的情况下，使用的各种原料均为市售品。
在没有特别说明的情况下，以下所述的室温或常温均表示25±3℃。
本发明的以下实例部分提供的化合物的编号与前文中的化合物的编号不同，也即，本发明中存在一个结构式具有两个编号的情形，这并不影响本发明的清楚表述方式。针对同一个结构，任意一个编号表示时，均是清楚的。
首先，表1中列举了本发明部分化合物的表征数据。
表1















制备例1
本制备例用来说明化合物1的合成：
中间体1-2的制备(步骤ⅰ)：依次取式1-1所示化合物(21.50g)、醋酸钯(0.23g)、碳酸钾(27.64g)置于Schlenk管中，抽充氮气三次，随后加入正丁基乙烯基醚(30.00g)、正丁醇100mL，在120℃回流反应6h，反应完毕将溶剂减压蒸干，加入1N的HCl溶液酸化至pH为2，抽滤干燥即得中间体1-2，产率92％。
中间体1-3的制备(步骤ⅱ)：依次取中间体1-2(10.00g)、3,5-二氯-2,2,2-三氟苯乙酮(16.38g)、三乙胺(11.37g)、甲苯100mL置于三口瓶中，50℃反应16h，待原料完毕后冷却至室温，抽滤，固体烘干得中间体1-3，产率98％。
中间体1-4的制备(步骤ⅲ)：依次取化合物1-3(26.52g)、4-二甲氨基吡啶(6.20g)、甲苯100mL置于三口瓶中，加入醋酸酐(10.36g)，60℃反应12h，反应完毕后加入1N的HCl溶液酸化至pH为2，抽滤干燥即得中间体1-4，产率95％。
中间体1-5的制备(步骤ⅳ)：依次取中间体1-4(16.70g)、四丁基溴化铵(4.01g)、甲苯300mL置于三口瓶中，加入5.47g的50％羟胺水溶液，室温反应7h，反应完毕后加入1N的HCl溶液酸化至pH为2，抽滤干燥即中间体1-5，产率95％。
化合物1的制备(步骤ⅴ)：依次取中间体1-5(0.50g)、CDI(0.39g)、DIPEA(0.56g)、二氯甲烷10mL置于三口瓶中，加入4-氨基吡唑(0.16g)，常温反应4h，反应完毕，用饱和NaHCO3溶液洗涤3次，用20mL的二氯甲烷萃取水层3次，萃取完毕后有机层合并，随后将有机层用无水Na2SO4干燥，有机层柱层析纯化得到化合物1，收率为83％。
制备例2
本制备例用来说明化合物2的合成：
中间体1-7的制备(步骤ⅵ)：依次取中间体1-6(1.00g)、碳酸钾(1.47g)、碘甲烷(1.50g)、N,N-二甲氨基甲酰胺20mL置于三口瓶中，常温反应3h，反应完毕，加入100mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有 机层用无水Na2SO4干燥，柱层析纯化得到中间体1-7，收率为93％。
中间体1-8的制备(步骤ⅶ)：依次取中间体1-7(0.50g)、氯化铵(0.95g)、水5mL、乙醇15mL，加热至沸腾后分批加入还原铁粉(1.54g)，回流反应30min，反应完毕，加入50mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有机层用无水Na2SO4干燥，柱层析纯化得到中间体1-8，收率为78％。
化合物2的制备(步骤ⅷ)：依次取中间体1-5(0.50g)、CDI(0.39g)、DIPEA(0.56g)、二氯甲烷10mL置于三口瓶中，加入中间体1-8(0.18g)，常温反应4h，反应完毕，用饱和NaHCO3溶液洗涤3次，用20mL的二氯甲烷萃取水层3次，萃取完毕后有机层合并，随后将有机层用无水Na2SO4干燥，柱层析纯化得到化合物2，收率为82％。
制备化合物3-化合物57、化合物76-94：
按照与制备例2相似的方法制备化合物3-化合物57、化合物76-94。
制备化合物58：
按照与制备例2相似的方法制备化合物58，不同之处在于，使用等摩尔的乙酰氯、三乙胺、二氯甲烷分别替换步骤ⅵ中的碘甲烷、碳酸钾、N,N-二甲氨基甲酰胺，具体地，中间体1-7的制备步骤包括：依次取中间体1-6、三乙胺、二氯甲烷置于三口瓶中，0℃滴加乙酰氯，常温反应3h，反应完毕，加入100mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有机层用无水Na2SO4干燥，柱层析纯化得到中间体1-7，收率为68％。
制备化合物59-化合物75：
按照与制备化合物58相似的方法制备化合物59-化合物75。
制备化合物95：
按照与制备例1相似的方法制备化合物95，不同之处在于，将步骤ⅴ中的4-氨基吡唑替换为等摩尔的3,5-二甲基-1H-吡唑-4-胺，具体地，在化合物95的制备中：依次取中间体1-5(0.50g)、CDI(0.39g)、DIPEA(0.56g)、二氯甲烷10mL置于三口瓶中，加入3,5-二甲基-1H-吡唑-4-胺，常温反应4h，反应完毕，用饱和NaHCO3溶液洗涤3次，用20mL的二氯甲烷萃取水层3次，萃取完毕后有机层合并，随后将有机层用无水Na2SO4干燥，柱层析纯化得到化合物95，收率为89％。
制备化合物96：
按照与制备例2相似的方法制备化合物96，不同之处在于，将步骤ⅵ中的中间体1-6替换为等摩尔的3,5-二甲基-4-硝基吡唑，具体地，中间体1-7的制备：依次取3,5-二甲基-4-硝基吡唑、碳酸钾(1.47g)、碘甲烷(1.50g)、N,N-二甲氨基甲酰胺20mL置于三口瓶中，常温反应3h，反应完毕，加入100mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有机层用无水Na2SO4干燥，柱层析纯化得到中间体1-7，收率为94％。
制备化合物97：
按照与制备例96相似的方法制备化合物97，不同之处在于，将步骤ⅵ中的碘甲烷替换为等摩尔的碘乙烷，具体地，中间体1-7的制备步骤包括：
依次取3,5-二甲基-4-硝基吡唑、碳酸钾、碘乙烷、N,N-二甲氨基甲酰胺20mL置于三口瓶中，常温反应3h，反应完毕，加入100mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有机层用无水Na2SO4干燥，柱层析纯化得 到中间体1-7，收率为96％。
制备化合物98-化合物104：
按照与制备化合物96相似的方法制备化合物98-化合物104。
制备化合物105：
按照与制备化合物58相似的方法制备化合物105，不同之处在于，将步骤ⅵ中的中间体1-6替换为等摩尔的3,5-二甲基-4-硝基吡唑，具体地，中间体1-7的制备：依次取3,5-二甲基-4-硝基吡唑、三乙胺、二氯甲烷置于三口瓶中，0℃滴加乙酰氯(0.83g)，常温反应3h，反应完毕，加入100mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有机层用无水Na2SO4干燥，柱层析纯化得到中间体1-7，收率为63％。
制备化合物106-化合物122：
按照与制备化合物105相似的方法制备化合物106-化合物122。
制备化合物123：
按照与制备例1相似的方法制备化合物123，不同之处在于，将步骤ⅱ中的3,5-二氯-2,2,2-三氟苯乙酮替换为等摩尔的3,5-二氯-4-氟-2,2,2-三氟苯乙酮，具体地，中间体1-3的制备包括：依次取中间体1-2(10.00g)、3,5-二氯-4-氟-2,2,2-三氟苯乙酮、三乙胺(11.37g)、甲苯100mL置于三口瓶中，50℃反应16h，待原料完毕后冷却至室温，抽滤，固体烘干得中间体1-3，产率93％。
制备化合物124：
按照与制备例2相似的方法制备化合物124，不同之处在于，将步骤ⅱ中的3,5-二氯-2,2,2-三氟苯乙酮替换为等摩尔的3,5-二氯-4-氟-2,2,2-三氟苯乙酮，具体地，中间体1-3的制备包括：依次取中间体1-2、3,5-二氯-4-氟-2,2,2-三氟苯乙酮、三乙胺、甲苯100mL置于三口瓶中，50℃反应16h，待原料完毕后冷却至室温，抽滤，固体烘干得中间体1-3，产率93％。
制备化合物125-化合物139：
按照与制备化合物124相似的方法制备化合物125-化合物139。
制备化合物140：
按照与制备化合物58相似的方法制备化合物140，不同之处在于，将步骤ⅱ中的3,5-二氯-2,2,2-三氟苯乙酮替换为等摩尔的3,5-二氯-4-氟-2,2,2-三氟苯乙酮，具体地，中间体1-3的制备包括：依次取中间体1-2、3,5-二氯-4-氟-2,2,2-三氟苯乙酮、三乙胺、甲苯100mL置于三口瓶中，50℃反应16h，待原料完毕后冷却至室温，抽滤，固体烘干得中间体1-3，产率93％。
制备化合物141-化合物157：
按照与制备化合物140相似的方法制备化合物141-化合物157。
制备化合物158：
按照与制备化合物123相似的方法制备化合物158，不同之处在于，将步骤ⅴ中的4-氨基吡唑替换为3,5-二甲基-1H-吡唑-4-胺，具体地，依次取中间体1-5(0.50g)、CDI(0.39g)、DIPEA(0.56g)、二氯甲烷10mL置于三口瓶中，加入3,5-二甲基-1H-吡唑-4-胺，常温反应4h，反应完毕，用饱和NaHCO3溶液洗涤3次，用20mL的二氯甲烷萃取水层3次，萃取完毕后有机层合并，随后将有机层用无水Na2SO4干燥，有机层柱层析纯化得到化合物158，收率为88％。
制备化合物159：
按照与制备化合物124相似的方法制备化合物159，不同之处在于，将步骤ⅵ中的中间体1-6替换为等摩尔的3,5-二甲基-4-硝基吡唑，具体地，中间体1-7的制备：依次取3,5-二甲基-4-硝基吡唑、碳酸钾(1.47g)、碘甲烷(1.50g)、N,N-二甲氨基甲酰胺20mL置于三口瓶中，常温反应3h，反应完毕，加入100mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有机层用无水Na2SO4干燥，柱层析纯化得到中间体1-7，收率为94％。
制备化合物160-化合物167：
按照与制备化合物159相似的方法制备化合物160-化合物167。
制备化合物168：
按照与制备化合物140相似的方法制备化合物168，不同之处在于，将步骤ⅵ中的中间体1-6替换为等摩尔的3,5-二甲基-4-硝基吡唑，具体地，中间体1-7的制备步骤包括：依次取3,5-二甲基-4-硝基吡唑、三乙胺、二氯甲烷置于三口瓶中，0℃滴加乙酰氯，常温反应3h，反应完毕，加入100mL的乙酸乙酯，饱和食盐水洗涤三次，随后将有机层用无水Na2SO4干燥，柱层析纯化得到中间体1-7，收率为68％。
制备化合物169-化合物185：
按照与制备化合物168相似的方法制备化合物169-化合物185。
测试例1：
采用叶片浸渍法测定部分化合物对小菜蛾二龄幼虫的毒力活性。
用电子分析天平准确称取表2中对应化合物的供试药剂，将原药先以二甲基亚砜为溶剂进行溶解为10000ppm的溶液，再以0.1％的曲拉通水溶液稀释为1ppm和0.25ppm的药液。取未接触药液的包菜，将其叶片裁剪为6cm直径圆形叶片。将叶片浸泡在配置好的药液中15秒后取出晾干，放入6cm培养皿中，每个培养皿放1片包菜叶片。放标准一致的二龄幼虫入培养皿中，每个培养皿10头，每个浓度重复4次，共40头。接虫后将培养皿放入25±1℃，光照周期为16(D):(8L)h的恒温培养室中，48h、72h后调查死、活幼虫数量。另设空白对照和化合物K1以及化合物K2的对比组。
根据以下公式1计算死亡率，再根据公式2计算校正死亡率，最后根据校正死亡率数值结合表2所示评级标准进行分级，具体结果见表3、表4。
公式1：死亡率％＝(死亡虫数/总虫数)×100％；
公式2：校正死亡率％＝[(处理组死亡率-对照组死亡率)/(1-对照组死亡率)]×100％。
测试例2：
采用叶片浸渍法测定部分化合物对稻纵卷叶螟四龄幼虫的毒力活性。
用电子分析天平准确称取表2中对应化合物的供试药剂，将原药先以二甲基亚砜完全溶解为10000ppm的溶液，再以0.1％的曲拉通水溶液稀释为5ppm的药液。选取实验室内种植、未接触药液的水稻植株，将其叶片剪到8cm左右。将叶片浸泡在配置好的药液中15秒后取出晾干，将根部用脱脂棉包住放入9cm培养皿中，每个培养皿放3-5片水稻叶片。轻轻剥开用作幼虫食物的茭白段，从茭白段中标准一致的四龄幼虫，放入培养皿中，每个培养皿10头，每个浓度重复4次，共40头。接虫后培养皿放入26±1℃，光照周期为16(D):8(L)h的恒温培养室中，48h后调查死、活幼虫数量。另设空白对照和化合物K1以及化合物K2的对比组。
根据以下公式1计算死亡率，再根据公式2计算校正死亡率，最后根据校正死亡率数值结合表2所示评级标准进行分级，具体结果见表5。
公式1：死亡率％＝(死亡虫数/总虫数)×100％；
公式2：校正死亡率％＝[(处理组死亡率-对照组死亡率)/(1-对照组死亡率)]×100％。
表2
表3


注：“/”表示未进行测试记录。
表4
表5
本发明提供的含吡唑结构的化合物能够在低浓度下实现良好的杀昆虫、杀螨虫、杀线虫以及杀螺虫的效果。
特别的，本发明提供的含吡唑结构的化合物对小菜蛾、亚洲玉米螟、棉铃虫、二化螟、稻纵卷叶螟、草地贪夜蛾，甜菜夜蛾，斜纹夜蛾、烟粉虱、稻飞虱、蚜虫和蓟马、跳甲等农业昆虫具有优异的杀虫活性。
具体地，本发明提供的含吡唑结构的化合物127在0.25ppm的浓度下对小菜蛾的致死率能达到100％，而对照化合物K1和K2的效果均小于50％。并且化合物127在5ppm的浓度下对稻纵卷叶螟的致死率为100％，远优于对照化合物K1和K2。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。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，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物，其特征在于，该化合物具有式(I)所示的结构：
    其中，在式(I)中，
    R1选自H、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
    R2选自C1-12的烷基、C1-12的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基、氰基；
    R3选自H、C1-12的烷基、C1-12的烷氧基、C3-12的环烷基、-CO-R31、-CO-CH2-R31；R31选自C1-12的烷基、C3-12的环烷基、C1-12的烷氧基；
    R4、R5各自独立地选自H、C1-12的烷基、C1-12的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
    R6选自H、未取代或由组合A中的至少一种基团取代的C1-12的烷基、未取代或由组合A中的至少一种基团取代的C1-12的烷氧基、未取代或由组合A中的至少一种基团取代的C3-12的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-12的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-12的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-12的环烷基、含有至少一个杂原子作为成环原子的C3-12的环烷基、苯基；R62选自C1-12的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-12的环烷基、含有至少一个杂原子作为成环原子的C3-12的环烷基；R63、R64各自独立地选自C1-12的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；
    所述组合A由羟基、卤素、C1-12的烷基、C1-12的烷氧基、三甲基硅基组成。
  2. 根据权利要求1所述的化合物，其中，在式(I)中，
    R1选自H、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
    R2选自C1-8的烷基、C1-8的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基、氰基；
    R3选自H、C1-8的烷基、C1-8的烷氧基、C3-10的环烷基、-CO-R31、-CO-CH2-R31；R31选自C1-8的烷基、C3-10的环烷基、C1-8的烷氧基；
    R4、R5各自独立地选自H、C1-8的烷基、C1-8的烷氧基、卤素、至少一个卤素取代的C1-6的烷基、至少一个卤素取代的C1-6的烷氧基；
    R6选自H、未取代或由组合A中的至少一种基团取代的C1-10的烷基、未取代或由组合A中的至少一种基团取代的C1-10的烷氧基、未取代或由组合A中的至少一种基团取代的C3-10的环烷基、未取代或由组合A中的至 少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基、苯基；R62选自C1-10的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基；R63、R64各自独立地选自C1-10的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；
    所述组合A由羟基、卤素、C1-8的烷基、C1-8的烷氧基、三甲基硅基组成。
  3. 根据权利要求2所述的化合物，其中，在式(I)中，
    R1选自H、F、氯、溴；
    R2选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、氰基；
    R3选自H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基、环丙基、环丁基、环戊基、环己基、-CO-R31、-CO-CH2-R31；R31选自C1-6的烷基、C3-6的环烷基、C1-6的烷氧基；
    R4、R5各自独立地选自H、甲基、乙基、正丙基、异丙基、正丁基、叔丁基；
    R6选自H、未取代或由组合A中的至少一种基团取代的C1-10的烷基、未取代或由组合A中的至少一种基团取代的C1-10的烷氧基、未取代或由组合A中的至少一种基团取代的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的苯基、含有至少一个杂原子作为成环原子的C3-10的环烷基、未取代或由组合A中的至少一种基团取代的含有至少一个不饱和碳碳双键或者不饱和碳碳三键的C2-10的烃基、-(CH2)n-R61、-CO-R62、-COO-R62、-CO-N(R63R64)、-S(＝O)2-R62、-(CH2)n-CO-R62；R61选自C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基、苯基；R62选自C1-10的烷基、未取代或由组合A中的至少一种基团取代的苯基、C3-10的环烷基、含有至少一个杂原子作为成环原子的C3-10的环烷基；R63、R64各自独立地选自C1-10的烷基；所述杂原子各自独立地选自N、O、S中的至少一种；所述n各自独立地为1或2；
    所述组合A由羟基、卤素、C1-8的烷基、C1-8的烷氧基、三甲基硅基组成。
  4. 根据权利要求3所述的化合物，其中，该化合物选自以下中的任意一种：












  5. 权利要求1-4中任意一项所述的含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物在杀灭昆虫、杀灭螨虫、杀灭线虫、杀灭螺虫中的至少一种中的应用。
  6. 权利要求1-4中任意一项所述的含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物作为农药杀虫剂的应用。
  7. 一种杀虫剂，其特征在于，该杀虫剂中含有杀虫有效量的权利要求1-4中任意一项所述的含吡唑结构的化合物或其农业化学上可接受的盐、水合物和溶剂化物中的至少一种作为活性成分。
  8. 根据权利要求7所述的杀虫剂，其中，该杀虫剂中的所述活性成分的含量为1-99.9重量％。
  9. 根据权利要求8所述的杀虫剂，其中，该杀虫剂中的所述活性成分的含量为5-95重量％。
  10. 根据权利要求7-9中任意一项所述的杀虫剂，其中，该杀虫剂的剂型选自乳油、悬浮剂、可湿性粉剂、粉剂、粒剂、水剂、毒饵、母液和母粉中的至少一种。
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1930136A (zh) * 2004-03-05 2007-03-14 日产化学工业株式会社 异噁唑啉取代苯甲酰胺化合物及有害生物防除剂
WO2021127188A1 (en) * 2019-12-18 2021-06-24 Elanco Tiergesundheit Ag Isoxazoline derivatives as pesticides

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1930136A (zh) * 2004-03-05 2007-03-14 日产化学工业株式会社 异噁唑啉取代苯甲酰胺化合物及有害生物防除剂
WO2021127188A1 (en) * 2019-12-18 2021-06-24 Elanco Tiergesundheit Ag Isoxazoline derivatives as pesticides

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