WO2019214588A1 - 一种苯甲酰胺类化合物及其应用 - Google Patents

一种苯甲酰胺类化合物及其应用 Download PDF

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WO2019214588A1
WO2019214588A1 PCT/CN2019/085737 CN2019085737W WO2019214588A1 WO 2019214588 A1 WO2019214588 A1 WO 2019214588A1 CN 2019085737 W CN2019085737 W CN 2019085737W WO 2019214588 A1 WO2019214588 A1 WO 2019214588A1
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compound
formula
hydrogen
heptafluoroisopropyl
cyanomethyl
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PCT/CN2019/085737
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English (en)
French (fr)
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张立新
张静
张熹晗
高一星
汪杰
康卓
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沈阳化工大学
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Priority to US17/054,259 priority Critical patent/US11407711B2/en
Priority to CA3099870A priority patent/CA3099870C/en
Priority to AU2019264704A priority patent/AU2019264704B2/en
Priority to BR112020022661-0A priority patent/BR112020022661B1/pt
Priority to EP19800087.9A priority patent/EP3792248A4/en
Priority to KR1020207033294A priority patent/KR102573412B1/ko
Priority to JP2021512987A priority patent/JP7138781B2/ja
Priority to CN201980031657.5A priority patent/CN112105599B/zh
Publication of WO2019214588A1 publication Critical patent/WO2019214588A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/29—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups and acylated amino groups bound to the carbon skeleton
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the invention belongs to the field of agricultural insecticides, and in particular relates to a novel benzamide compound and application thereof.
  • Patent JP2007099761A relates to a benzamide compound having insecticidal activity, and specifically discloses the following structures: CK1 (Compound No.: 1-23), CK2 (Compound No.: 1-24), and CK3 (Compound No.: 1- 206).
  • Patent CN102112437A discloses a compound of the following general formula and a specific compound CK4 (compound number: 6-18), CK5 (compound number: 1-128), CK6 (compound number: 1-163), and CK7 (compound number: 1-171).
  • CK8 Compound No.: 7-130
  • CK9 Compound Number: 7-135)
  • CK10 Compound Number: 7-169
  • CK11 Compound Number: 7-174
  • CK12 Compound Number: 8-111)
  • CK13 Compound No.: 8-146)
  • CK14 Compound No.: 8-155
  • Patent CN102119144A discloses the following compound CK15 (Compound No.: 3-14) having a certain insecticidal activity.
  • Patent CN102119143A discloses the following compound CK16 (Compound No.: 7-1574), which has certain insecticidal activity and is being researched and developed as an insecticide, and its general name is broflanilide.
  • R 1 and R 2 are each independently selected from hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 and R 5 are each independently selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or cyanomethyl; and, at least one of R 4 and R 5 is selected from cyanomethyl;
  • X 1 , X 2 , X 3 and X 4 are each independently selected from hydrogen, halogen, cyano or C 1 -C 6 alkoxy; and X 1 , X 2 , X 3 and X 4 are not hydrogen at the same time.
  • More preferred compounds in the present invention are:
  • R 1 and R 2 are each independently selected from hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 and R 5 are each independently selected from hydrogen, methyl, ethyl or cyanomethyl; and at least one of R 4 and R 5 is selected from cyanomethyl;
  • X 1 is selected from fluorine
  • X 2 , X 3 , X 4 are each independently selected from hydrogen, fluorine or cyano.
  • R 1 and R 2 are each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl or difluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 and R 5 are each independently selected from hydrogen, methyl, ethyl or cyanomethyl; and at least one of R 4 and R 5 is selected from cyanomethyl;
  • X 1 is selected from fluorine
  • X 2 , X 3 , X 4 are each independently selected from hydrogen or fluorine.
  • R 1 and R 2 are each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl or difluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from cyanomethyl
  • R 5 is selected from the group consisting of hydrogen, methyl, ethyl or cyanomethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , X 4 are each independently selected from hydrogen or fluorine.
  • R 1 and R 2 are each independently selected from hydrogen, halogen, methyl, ethyl, trifluoromethyl or difluoromethoxy;
  • R 3 is selected from heptafluoroisopropyl or nonafluoro-2-butyl
  • R 4 is selected from the group consisting of hydrogen, methyl or ethyl
  • R 5 is selected from cyanomethyl
  • X 1 is selected from fluorine
  • X 2 , X 3 , X 4 are each independently selected from hydrogen or fluorine.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl straight or branched alkyl such as methyl, ethyl, n-propyl, isopropyl or a different butyl, pentyl or hexyl isomer.
  • Haloalkyl a linear or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl or difluoromethyl.
  • Base trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl Nonafluoro-2-butyl 1,1,2,2,2-pentafluoroethyl and the like.
  • Alkoxy a linear or branched alkyl group bonded to a structure via an oxygen atom such as a methoxy group, an ethoxy group, a t-butoxy group or the like.
  • Haloalkoxy The hydrogen atom on the alkoxy group may be partially or completely substituted by a halogen such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, or Fluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, and the like.
  • a halogen such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, or Fluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, and the like.
  • Alkylthio a linear or branched alkyl group bonded to a structure via a sulfur atom, such as a methylthio group, an ethylthio group or the like.
  • Haloalkylthio The hydrogen atom on the alkylthio group may be partially or completely substituted by a halogen such as a difluoromethylthio group, a trifluoroethylthio group or the like.
  • R 5 cyanomethyl group
  • (R 6 ) n is a different substituent which is identical to Table 1, and corresponds in turn to the substituents described in 1.1-1.321 of Table 1, and represents the compound number of 61.1-61.321.
  • the compound of the formula S can be obtained by reacting a compound of the formula S with a compound of the formula K or a compound of the formula W with a compound of the formula Y in a suitable solvent at a temperature of from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours. It is carried out in the presence of a base.
  • the compound of the formula II can be obtained by reacting a compound of the formula II with a haloacetonitrile in a suitable solvent in the presence of a suitable base at a temperature of from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours, respectively, to obtain the formulae I-1, I-2 and I-3, respectively.
  • the compound of the formula I-3 can be obtained by reacting a compound of the formula I-1 or I-2 with a haloacetonitrile in a suitable solvent in the presence of a suitable base at a temperature from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
  • the compound of the formula I-1 can be obtained by reacting a compound of the formula I-1 with a compound of the formula R 5 - LG in a suitable solvent in the presence of a suitable base at a temperature from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
  • the compound of the formula I-5 can be obtained by reacting a compound of the formula I-2 with a compound of the formula R 4 - LG in a suitable solvent in the presence of a suitable base at a temperature from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
  • the compound of the formula I-4 can be obtained by reacting for 0.5 to 48 hours.
  • the compound of the formula I-5 can be obtained by reacting for 0.5 to 48 hours.
  • the above suitable solvent may be an aromatic hydrocarbon such as benzene, toluene or xylene, a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone, a halogenated hydrocarbon such as chloroform or dichloromethane, or an ester such as methyl acetate or ethyl acetate.
  • aromatic hydrocarbon such as benzene, toluene or xylene
  • a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone
  • a halogenated hydrocarbon such as chloroform or dichloromethane
  • an ester such as methyl acetate or ethyl acetate.
  • Ethers such as tetrahydrofuran, dioxane, diethyl ether, 1,2-dimethoxyethane, water, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide
  • suitable bases may be organic bases such as triethylamine, pyridine, DBU, 4-dimethylaminopyridine, alkali metal hydrides such as sodium hydride and potassium hydride, sodium hydroxide, An alkali metal hydroxide such as potassium hydroxide or an alkaline earth metal hydroxide such as calcium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate; sodium methoxide, sodium ethoxide or ethanol; A metal alkoxide such as potassium, potassium t-butoxide or sodium t-butoxide.
  • the compound of the formula R 4 -LG, the formula R 5 -LG, the compound of the formula K and the compound of the formula CHCH 2 -LG, and the base are usually commercially available or can be produced by a conventional method.
  • the compounds of the formula S, the formula W, the formula Y, the formula II, the formula III and the formula IV can be prepared according to known methods, for example, see WO2011093415, WO20110201687, WO2005021488, WO2005073165, WO2010018857, WO2006137395, JP2007099761, WO2008000438, WO2008074427, Processes are reported in WO2008107091, WO2010013567, WO2010018714, WO2010090282, WO2010127926, WO2010127928, JP2011063549, WO2012020483, WO2012020484, WO2012077221, WO2012164698, WO2013050261, WO2014069665, WO2014
  • the compound of the formula I of the present invention has unexpectedly high insecticidal activity and can be used for controlling pests (the listed objects are only used to illustrate the invention, but in no way limit the invention): Lepidopteran pests such as Plutella xylostella, armyworm, Spodoptera exigua, Spodoptera litura, Nicotiana californica, Spodoptera litura, Chilo suppressalis, Chilo suppressalis, Rice leaf roller, Corn borer, Small heartworm, Helicoverpa armigera, etc.; Homoptera pests such as peas, beans ⁇ , beet ⁇ , cotton aphid, apple ⁇ , peach ⁇ , corn ⁇ , whitefly, leaf ⁇ , ⁇ , rice planthopper, whitefly, etc.; hemipteran pests such as corn long carp, cotton net ⁇ , tomato blind ⁇ , rice green crickets, rice skunks, etc.; pteridophyte pests such as cotton scor
  • the compound of the formula I of the present invention also has an unexpected high insecticidal quick-acting property, has a fast onset of action, can achieve high insecticidal activity after one day of application, and can achieve extremely high insecticidal activity within three days.
  • the preparation method of the compound of the general formula I of the invention is simple and efficient, easy to be industrialized on a large scale, and has wide application prospects. Accordingly, the technical solution of the present invention also includes the use of the compound of the formula I as a pesticide preparation agent in agriculture or other fields.
  • the above compounds can be advantageously used to protect crops, livestock and stocks important in agriculture and horticulture, as well as the environment in which humans are often exposed to pests.
  • the amount of the compound varies depending on various factors such as the compound used, the pre-protected crop, the type of the pest, the degree of infection, the climatic conditions, the method of administration, the dosage form employed, and the like.
  • a dose of 10 grams to 5 kilograms of compound per hectare provides adequate control.
  • the present invention also encompasses pesticidal compositions having a compound of formula I as an active ingredient.
  • the active ingredient in the pesticidal composition is present in an amount between 0.1 and 99% by weight.
  • Also included in the pesticidal composition are agricultural, forestry, and hygienic acceptable carriers.
  • compositions of the invention may be administered in the form of a formulation.
  • the compound of the formula I is dissolved or dispersed in the carrier as an active ingredient or formulated into a formulation for easier dispersion when used as a pesticidal agent.
  • these chemicals can be formulated into wettable powders, oil suspensions, aqueous suspensions, aqueous emulsions, aqueous solutions or emulsifiable concentrates.
  • at least one liquid or solid carrier is added, and a suitable surfactant may be added as needed.
  • the technical solution of the present invention also includes a method of controlling pests by applying the pesticidal composition of the present invention to the pest or the growth medium thereof.
  • a more suitable effective amount is usually selected from 10 grams to 1000 grams per hectare, preferably from 10 grams to 500 grams per hectare.
  • one or more other fungicides, insecticides, herbicides, herbicides, plant growth regulators or fertilizers may be added to the pesticidal composition of the invention. Produces additional advantages and effects.
  • the compounds of the formula I of the present invention can be separately prepared by using different starting compounds, and further described in detail as follows:
  • test compound was dissolved in a mixed solvent of acetone/methanol (1:1), it was diluted to a desired concentration with water containing 0.1% by weight of Tween 80.
  • the activity of the armyworm, Plutella xylostella, and Chilo suppressalis was measured by Airbrush spray method.
  • Determination method The corn leaves were cut into 2 cm leaf segments, and the pressure of Airbrush spray treatment was 10 psi (about 0.7 kg/cm 2 ), and the spray surface was sprayed on the front and back sides, and the spray amount was 0.5 ml. Ten dry 3rd instar larvae were added to each treatment after drying, and each treatment was repeated 3 times. After the treatment, the cells were cultured at 25 ° C and relative humidity of 60 to 70%, and the number of viable insects was investigated 1, 2, and 3 days after the drug, and the mortality was calculated.
  • the lethal rate of compound 2.7, 2.17, 2.43, 2.321, 3.321, 7.321, 8.321, 9.321, 16.321, 17.321, 21.321, 30.321, 58.321 against armyworm was above 90% after 3 days of drug;
  • the lethal rate of compound 2.7, 2.17, 2.43, 2.321, 9.321, 30.321 against armyworm was above 90% 3 days after the drug.
  • Determination method The cabbage leaves were punched into a disc with a diameter of 2 cm by a puncher, and the pressure of the Airbrush spray treatment was 10 psi (about 0.7 kg/cm 2 ), and the spray was sprayed on the front and back sides of each leaf, and the amount of the spray was 0.5 ml. Ten dry 3rd instar larvae were added to each treatment after drying, and each treatment was repeated 3 times. After the treatment, the cells were cultured at 25 ° C and relative humidity of 60 to 70%, and the number of viable insects was investigated 1, 2, and 3 days after the drug, and the mortality was calculated.
  • CK5, CK8, and CK12 were selected as the control compounds, and the compounds of the present invention 6.321 and 20.321 were selected for the parallel comparison test of the insecticidal activity of Plutella xylostella (3 days after the drug), and the measurement methods were as described above; the results are shown in Table 72:
  • CK7, CK11, CK14 and CK16 were selected as control compounds, and the compounds of the present invention 9.321 and 30.321 were selected for the parallel comparison test of the insecticidal activity of Plutella xylostella (3 days after the drug), and the measurement methods were as described above; the results are shown in Table 74:
  • CK15 was selected as the control compound, and the compounds of the present invention 2.321 and 30.321 were selected for the parallel comparison test of the insecticidal activity of Plutella xylostella to compare the insecticidal quick-acting properties; the results are shown in Table 75:
  • the compound of the present invention has superior insecticidal fastness and higher insecticidal activity at a lower dose than the conventional compound CK15.
  • CK16 was selected as the control compound, and the compound of the present invention 9.321 was selected for the parallel comparison test of the insecticidal activity of Plutella xylostella to compare the insecticidal quick-acting properties; the results are shown in Table 76:
  • the compound of the present invention has superior insecticidal fastness and higher insecticidal activity at a lower dose than the conventional compound CK16.
  • Rice seedling preparation Rice was cultivated in a plastic cup with a diameter of 4.5 cm and a height of 4 cm in a constant temperature room (temperature: 26 to 28 ° C, relative humidity: 60 to 80%, light: 16 hL: 8 hD). At the 4th to 5th leaf stage, strong and consistent rice seedlings were selected for chemical treatment, and each treatment was repeated three times.
  • Test insect preparation Chilo suppressalis, 3rd instar larvae continuously raised indoors.
  • Rice stem spray insecticide method The rice seedlings were sprayed uniformly with the spray method, and 15 ml per treatment was applied. The blank control is processed first, and then the above operation is repeated in descending order of the test concentration.
  • the liquid is dried in a cool place, and the stalks of about 5 cm on the base of the stem are cut and fed to the test insects.
  • the number of live insects was investigated 3 days after the drug.
  • CK15 was selected as the control compound, and the compounds of the present invention 2.321 and 30.321 were selected for the parallel comparison test of the insecticidal activity of the stem borer, and the measurement method was the same as described above; the results are shown in Table 77:
  • the compound of the present invention has an advantage of exerting a better insecticidal effect at a lower dose than the conventional compound CK15.
  • CK16 was selected as the control compound, and the compound of the present invention 9.321 was selected for the parallel comparison test of the insecticidal activity of the stem borer, and the measurement method was as described above; the results are shown in Table 78:
  • the compound of the present invention has an advantage of exerting a better insecticidal effect at a lower dose than the conventional compound CK16.
  • the inventors of the present invention obtained a compound of the general formula I of the present invention by introducing a cyanomethyl group (CNCH 2 -) appropriately on the amide bond N atom thereof based on the molecular skeleton of the existing compound by a large number of tests. From the activity comparison test data of Tables 71 to 78, it can be seen that the introduction of new suitable fragments (pharmacophores) improves the interaction between molecules and receptors and the chance of binding, compared with the existing compounds. Thereby, the compound of the present invention has an unexpected effect relative to the existing compound, that is, the compound of the present invention has higher insecticidal activity and more excellent insecticidal quick-acting property (fast onset, and can be achieved after 1 day of application). Insecticidal activity, can achieve extremely high insecticidal activity within 3 days).
  • the entire molecule may have a large difference in the transport properties or binding to the receptor in organisms such as insects and plants.
  • the difference in activity is also large, and the molecular transport properties and suitability for binding to the receptor are unpredictable and require a large amount of creative labor to be known. Therefore, the present invention has substantial characteristics and significant progress.

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Abstract

式（I）所示的苯甲酰胺类化合物、包含所述化合物的杀虫组合物以及所述化合物在农业、林业、卫生领域中作为杀虫剂的应用。

Description

一种苯甲酰胺类化合物及其应用 技术领域
本发明属农用杀虫剂领域，具体涉及一种新型的苯甲酰胺类化合物及其应用。
背景技术
专利JP2007099761A涉及一种具有杀虫活性的苯甲酰胺类化合物，并具体公开了如下结构：CK1(化合物编号:1-23)、CK2(化合物编号:1-24)及CK3(化合物编号:1-206)。
Figure PCTCN2019085737-appb-000001
专利CN102112437A公开了如下通式化合物及具体化合物CK4(化合物编号:6-18)、CK5(化合物编号:1-128)、CK6(化合物编号:1-163)、CK7(化合物编号:1-171)、CK8(化合物编号:7-130)、CK9(化合物编号:7-135)、CK10(化合物编号:7-169)、CK11(化合物编号:7-174)、CK12(化合物编号:8-111)、CK13(化合物编号:8-146)、CK14(化合物编号:8-155)，具有一定的杀虫活性：
Figure PCTCN2019085737-appb-000002
专利CN102119144A公开了如下化合物CK15(化合物编号:3-14)，具有一定的杀虫活性。
Figure PCTCN2019085737-appb-000003
专利CN102119143A公开了如下化合物CK16(化合物编号:7-1574)，该化合物具有一定的杀虫活性，作为杀虫剂正在进行研究开发，其通用名为broflanilide。
Figure PCTCN2019085737-appb-000004
现有技术中如本发明通式I所示的化合物及其杀虫活性未见报道。并且，同现有技术相比，本发明化合物具有更高的杀虫活性以及更优良的杀虫速效性。
发明内容
本发明的目的在于提供一种苯甲酰胺类化合物。它可用于制备农业和其它领域中防治害虫的药物。
本发明的技术方案如下：
一种苯甲酰胺类化合物，如通式I所示：
Figure PCTCN2019085737-appb-000005
式中：
R 1、R 2各自独立地选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基；
R 3选自七氟异丙基或九氟-2-丁基；
R 4、R 5各自独立地选自氢、C 1-C 6烷基、C 1-C 6卤代烷基或氰甲基；并且，R 4、R 5至少有一个选自氰甲基；
R 6选自氢、卤素、氰基、硝基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 1-C 6烷硫基或C 1-C 6卤代烷硫基；n＝1、2、3、4或5；当n大于1时，R 6可相同或不同；
X 1、X 2、X 3、X 4各自独立地选自氢、卤素、氰基或C 1-C 6烷氧基；且，X 1、X 2、X 3、X 4不同时为氢。
本发明中较优选的化合物为：通式I中
R 1、R 2各自独立地选自氢、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基或C 1-C 4卤代烷氧基；
R 3选自七氟异丙基或九氟-2-丁基；
R 4、R 5各自独立地选自氢、甲基、乙基或氰甲基；并且，R 4、R 5至少有一个选自氰甲基；
R 6选自氢、卤素、氰基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；n＝1、2、3或4；
X 1选自氟；
X 2、X 3、X 4各自独立地选自氢、氟或氰基。
本发明中进一步优选的化合物为：通式I中
R 1、R 2各自独立地选自氢、卤素、甲基、乙基、三氟甲基或二氟甲氧基；
R 3选自七氟异丙基或九氟-2-丁基；
R 4、R 5各自独立地选自氢、甲基、乙基或氰甲基；并且，R 4、R 5至少有一个选自氰甲基；
R 6选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、丙基、叔丁基、三氟甲基、七氟异丙基、甲氧基或三氟甲氧基；n＝1、2或3；
X 1选自氟；
X 2、X 3、X 4各自独立地选自氢或氟。
本发明中更进一步优选的化合物为：通式I中
R 1、R 2各自独立地选自氢、卤素、甲基、乙基、三氟甲基或二氟甲氧基；
R 3选自七氟异丙基或九氟-2-丁基；
R 4选自氰甲基；
R 5选自氢、甲基、乙基或氰甲基；
R 6选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、丙基、叔丁基、三氟甲基、七氟异丙基、甲氧基或三氟甲氧基；n＝1、2或3；
X 1选自氟；
X 2、X 3、X 4各自独立地选自氢或氟。
或者，本发明中更进一步优选的化合物为：通式I中
R 1、R 2各自独立地选自氢、卤素、甲基、乙基、三氟甲基或二氟甲氧基；
R 3选自七氟异丙基或九氟-2-丁基；
R 4选自氢、甲基或乙基；
R 5选自氰甲基；
R 6选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、丙基、叔丁基、三氟甲基、七氟异丙基、甲氧基或三氟甲氧基；n＝1、2或3；
X 1选自氟；
X 2、X 3、X 4各自独立地选自氢或氟。
上面给出的通式化合物的定义中，汇集所用术语一般代表如下取代基：
卤素：指氟、氯、溴或碘。
烷基：直链或支链烷基，例如甲基、乙基、正丙基、异丙基或不同的丁基、戊基或己基异构体。
卤代烷基：直链或支链烷基，在这些烷基上的氢原子可部分或全部被卤素所取代，例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、七氟异丙基
Figure PCTCN2019085737-appb-000006
九氟-2-丁基
Figure PCTCN2019085737-appb-000007
1,1,2,2,2-五氟乙基等。
烷氧基：直链或支链烷基，经氧原子键连接到结构上，例如甲氧基、乙氧基、叔丁氧基等。
卤代烷氧基：烷氧基上的氢原子可部分或全部被卤素所取代，例如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、三氟乙氧基等。
烷硫基：直链或支链烷基，经硫原子键连接到结构上，例如甲硫基、乙硫基等。
卤代烷硫基：烷硫基上的氢原子可部分或全部被卤素所取代，例如二氟甲硫基、三氟乙硫基等。
氰甲基：CNCH 2-。
本发明部分通式I化合物如表1～表70所示，但本发明绝非仅限于这些化合物。
Figure PCTCN2019085737-appb-000008
通式I中，当R 1＝R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基见表1，代表化合物编号为1.1-1.321。
表1
编号 (R 6) n 编号 (R 6) n 编号 (R 6) n
1.1 2-F 1.2 2-Cl 1.3 2-Br
1.4 3-F 1.5 3-Cl 1.6 3-Br
1.7 4-F 1.8 4-Cl 1.9 4-Br
1.10 2-I 1.11 2-CN 1.12 2-NO 2
1.13 3-I 1.14 3-CN 1.15 3-NO 2
1.16 4-I 1.17 4-CN 1.18 4-NO 2
1.19 2-CH 3 1.20 2-C 2H 5 1.21 2-CH 2CH 2CH 3
1.22 3-CH 3 1.23 3-C 2H 5 1.24 3-CH 2CH 2CH 3
1.25 4-CH 3 1.26 4-C 2H 5 1.27 4-CH 2CH 2CH 3
1.28 2-CH(CH 3) 2 1.29 2-CH 2CH 2CH 2CH 3 1.30 2-C(CH 3) 3
1.31 3-CH(CH 3) 2 1.32 3-CH 2CH 2CH 2CH 3 1.33 3-C(CH 3) 3
1.34 4-CH(CH 3) 2 1.35 4-CH 2CH 2CH 2CH 3 1.36 4-C(CH 3) 3
1.37 2-CF 3 1.38 2-CF(CF 3) 2 1.39 2-OCH 3
1.40 3-CF 3 1.41 3-CF(CF 3) 2 1.42 3-OCH 3
1.43 4-CF 3 1.44 4-CF(CF 3) 2 1.45 4-OCH 3
1.46 2-OC 2H 5 1.47 2-OCF 3 1.48 2-OCHF 2
1.49 3-OC 2H 5 1.50 3-OCF 3 1.51 3-OCHF 2
1.52 4-OC 2H 5 1.53 4-OCF 3 1.54 4-OCHF 2
1.55 2-OCH 2CF 3 1.56 2-SCH 3 1.57 2-SCF 3
1.58 3-OCH 2CF 3 1.59 3-SCH 3 1.60 3-SCF 3
1.61 4-OCH 2CF 3 1.62 4-SCH 3 1.63 4-SCF 3
1.64 2,3-2F 1.65 2,3-2Cl 1.66 2,3-2Br
1.67 2,4-2F 1.68 2,4-2Cl 1.69 2,4-2Br
1.70 2,5-2F 1.71 2,5-2Cl 1.72 2,5-2Br
1.73 2,6-2F 1.74 2,6-2Cl 1.75 2,6-2Br
1.76 3,4-2F 1.77 3,4-2Cl 1.78 3,4-2Br
1.79 3,5-2F 1.80 3,5-2Cl 1.81 3,5-2Br
1.82 2,3-2CN 1.83 2,3-2NO 2 1.84 2,3-2CH 3
1.85 2,4-2CN 1.86 2,4-2NO 2 1.87 2,4-2CH 3
1.88 2,5-2CN 1.89 2,5-2NO 2 1.90 2,5-2CH 3
1.91 2,6-2CN 1.92 2,6-2NO 2 1.93 2,6-2CH 3
1.94 3,4-2CN 1.95 3,4-2NO 2 1.96 3,4-2CH 3
1.97 3,5-2CN 1.98 3,5-2NO 2 1.99 3,5-2CH 3
1.100 2,3-2C 2H 5 1.101 2,3-2(CH 2) 2CH 3 1.102 2,3-2CH(CH 3) 2
1.103 2,4-2C 2H 5 1.104 2,4-2(CH 2) 2CH 3 1.105 2,4-2CH(CH 3) 2
1.106 2,5-2C 2H 5 1.107 2,5-2(CH 2) 2CH 3 1.108 2,5-2CH(CH 3) 2
1.109 2,6-2C 2H 5 1.110 2,6-2(CH 2) 2CH 3 1.111 2,6-2CH(CH 3) 2
1.112 3,4-2C 2H 5 1.113 3,4-2(CH 2) 2CH 3 1.114 3,4-2CH(CH 3) 2
1.115 3,5-2C 2H 5 1.116 3,5-2(CH 2) 2CH 3 1.117 3,5-2CH(CH 3) 2
1.118 2,3-2C(CH 3) 3 1.119 2,3-2CF 3 1.120 2,3-2OCH 3
1.121 2,4-2C(CH 3) 3 1.122 2,4-2CF 3 1.123 2,4-2OCH 3
1.124 2,5-2C(CH 3) 3 1.125 2,5-2CF 3 1.126 2,5-2OCH 3
1.127 2,6-2C(CH 3) 3 1.128 2,6-2CF 3 1.129 2,6-2OCH 3
1.130 3,4-2C(CH 3) 3 1.131 3,4-2CF 3 1.132 3,4-2OCH 3
1.133 3,5-2C(CH 3) 3 1.134 3,5-2CF 3 1.135 3,5-2OCH 3
1.136 2,3-2OCF 3 1.137 2,3-2SCH 3 1.138 2,3-2SCF 3
1.139 2,4-2OCF 3 1.140 2,4-2SCH 3 1.141 2,4-2SCF 3
1.142 2,5-2OCF 3 1.143 2,5-2SCH 3 1.144 2,5-2SCF 3
1.145 2,6-2OCF 3 1.146 2,6-2SCH 3 1.147 2,6-2SCF 3
1.148 3,4-2OCF 3 1.149 3,4-2SCH 3 1.150 3,4-2SCF 3
1.151 3,5-2OCF 3 1.152 3,5-2SCH 3 1.153 3,5-2SCF 3
1.154 2-F-4-Cl 1.155 2-F-4-Br 1.156 2-F-4-I
1.157 2-F-3-Cl 1.158 2-F-5-Cl 1.159 2-F-6-Cl
1.160 3-F-2-Cl 1.161 3-F-4-Cl 1.162 3-F-5-Cl
1.163 3-F-6-Cl 1.164 4-F-2-Cl 1.165 4-F-3-Cl
1.166 2-Cl-4-Br 1.167 2-Cl-4-I 1.168 3-Cl-4-I
1.169 4-Cl-2-Br 1.170 2-CN-3-F 1.171 2-CN-3-Cl
1.172 2-CN-4-Cl 1.173 2-CN-4-Br 1.174 2-CN-4-NO 2
1.175 4-CN-2-Cl 1.176 4-CN-2-CF 3 1.177 4-CN-2-NO 2
1.178 2-NO 2-4-F 1.179 2-NO 2-4-Cl 1.180 2-NO 2-4-Br
1.181 2-NO 2-4-OCH 3 1.182 2-NO 2-4-OC 2H 5 1.183 2-NO 2-5-Cl
1.184 3-NO 2-4-F 1.185 3-NO 2-4-Cl 1.186 3-NO 2-4-Br
1.187 4-NO 2-2-Cl 1.188 4-NO 2-2-OCH 3 1.189 5-NO 2-2-F
1.190 5-NO 2-2-Cl 1.191 5-NO 2-2-Br 1.192 5-NO 2-2-OCH 3
1.193 2-CH 3-4-F 1.194 2-CH 3-4-Cl 1.195 2-CH 3-4-Br
1.196 2-CH 3-4-I 1.197 2-CH 3-4-NO 2 1.198 2-CH 3-4-OCH 3
1.199 2-CH 3-3-F 1.200 2-CH 3-3-Cl 1.201 2-CH 3-3-NO 2
1.202 2-CH 3-5-F 1.203 2-CH 3-5-Cl 1.204 2-CH 3-5-Br
1.205 2-CH 3-5-NO 2 1.206 2-CH 3-6-Cl 1.207 2-CH 3-6-C 2H 5
1.208 2-CH 3-6-NO 2 1.209 3-CH 3-2-Cl 1.210 3-CH 3-2-Br
1.211 3-CH 3-4-Cl 1.212 3-CH 3-4-Br 1.213 3-CH 3-4-I
1.214 4-CH 3-2-Cl 1.215 4-CH 3-3-Cl 1.216 4-CH 3-2-Br
1.217 4-CH 3-3-Br 1.218 4-CH 3-3-F 1.219 4-CH 3-2-NO 2
1.220 4-CH 3-3-NO 2 1.221 5-CH 3-2-F 1.222 5-CH 3-2-CN
1.223 5-CH 3-2-OCH 3 1.224 4-C(CH 3) 3-2-Cl 1.225 2-CF 3-4-Cl
1.226 2-CF 3-4-Br 1.227 2-CF 3-4-NO 2 1.228 3-CF 3-4-F
1.229 3-CF 3-4-Cl 1.230 3-CF 3-4-NO 2 1.231 4-CF 3-2-Cl
1.232 4-CF 3-2-Br 1.233 4-CF 3-2-NO 2 1.234 5-CF 3-2-Cl
1.235 5-CF 3-2-Br 1.236 5-CF 3-2-OCH 3 1.237 2-OCH 3-5-Cl
1.238 4-OCH 3-3-F 1.239 4-OCH 3-3-Cl 1.240 2-OCF 3-4-Cl
1.241 2-OCF 3-4-Br 1.242 2-OCF 3-4-CN 1.243 4-OCF 3-2-Cl
1.244 4-OCF 3-2-Br 1.245 4-OCF 3-2-NO 2 1.246 2-SCH 3-5-Cl
1.247 2,3,4-3F 1.248 2,3,4-3Cl 1.249 2,3,4-3Br
1.250 2,3,5-3F 1.251 2,3,5-3Cl 1.252 2,3,5-3Br
1.253 2,3,6-3F 1.254 2,3,6-3Cl 1.255 2,3,6-3Br
1.256 2,4,5-3F 1.257 2,4,5-3Cl 1.258 2,4,5-3Br
1.259 2,4,6-3F 1.260 2,4,6-3Cl 1.261 2,4,6-3Br
1.262 3,4,5-3F 1.263 3,4,5-3Cl 1.264 3,4,5-3Br
1.265 2,4,6-3CH 3 1.266 2,4,6-3C 2H 5 1.267 2,4,6-3CH(CH 3) 2
1.268 2,4,6-3C(CH 3) 3 1.269 2,4,6-3CF 3 1.270 2,4,6-3NO 2
1.271 2,4,6-3OCH 3 1.272 3,4,5-3OCH 3 1.273 2,4,6-3OCF 3
1.274 2,4,6-3SCH 3 1.275 2,4,6-3SCF 3 1.276 2-F-4,6-2Br
1.277 2-F-4-Cl-6-Br 1.278 4-F-2,6-2Br 1.279 2,4-2F-6-Cl
1.280 2,3-2Cl-4-Br 1.281 2-CH 3-4,6-2Br 1.282 3-CH 3-2,6-2Cl
1.283 4-CH 3-2,6-2Br 1.284 2,3-2CH 3-6-NO 2 1.285 4,5-2CH 3-2-NO 2
1.286 2,6-2CH 3-4-C(CH 3) 3 1.287 2-CH 3-4-NO 2-6-Cl 1.288 2-CH 3-4-NO 2-6-Br
1.289 2-CH 3-6-NO 2-4-Cl 1.290 2-CH 3-6-NO 2-4-Br 1.291 5-CH 3-4-F-6-Cl
1.292 5-CH 3-2-OCH 3-4-Cl 1.293 2-CF 3-4,6-2Cl 1.294 2-CF 3-4,6-2Br
1.295 4-CF 3-2,6-2Cl 1.296 4-CF 3-2,6-2Br 1.297 4-CF 3-2-NO 2-5-Cl
1.298 4-CF 3-2-NO 2-6-Cl 1.299 4-CF 3-2-NO 2-6-Br 1.300 4-CF 3-2-Cl-6-Br
1.301 2-NO 2-4,6-2Br 1.302 2-NO 2-4-F-5-Cl 1.303 4-NO 2-2,6-2Cl
1.304 4-NO 2-2,6-2Br 1.305 4-NO 2-2,5-2Cl 1.306 2,4-2NO 2-6-Cl
1.307 2,4-2NO 2-6-Br 1.308 2-CN-4,6-2Cl 1.309 2-CN-4,6-2Br
1.310 4-CN-2,6-2Cl 1.311 2-CN-4-NO 2-6-Cl 1.312 2-CN-4-NO 2-6-Br
1.313 2,5-2OCH 3-4-NO 2 1.314 2,4-2OCH 3-5-Cl 1.315 2,3,5,6-4F
1.316 4-F-3-Cl-2,6-2Br 1.317 6-NO 2-2,3,4-3F 1.318 2,3,4,5,6-5F
1.319 2,3,4,5,6-5Cl 1.320 2,3,5,6-4F-4-CF 3 1.321 H
表2：通式I中，当R 1＝R 2＝Br,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为2.1-2.321。
表3：通式I中，当R 1＝R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为3.1-3.321。
表4：通式I中，当R 1＝R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为4.1-4.321。
表5：通式I中，当R 1＝CH 3,R 2＝CH 2CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为5.1-5.321。
表6：通式I中，当R 1＝Br,R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为6.1-6.321。
表7：通式I中，当R 1＝Br,R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为7.1-7.321。
表8：通式I中，当R 1＝Br,R 2＝I,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为8.1-8.321。
表9：通式I中，当R 1＝Br,R 2＝CF 3R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为9.1-9.321。
表10：通式I中，当R 1＝Cl,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为10.1-10.321。
表11：通式I中，当R 1＝I,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为11.1-11.321。
表12：通式I中，当R 1＝Br,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为12.1-12.321。
表13：通式I中，当R 1＝Cl,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321 记载的取代基，代表化合物编号为13.1-13.321。
表14：通式I中，当R 1＝I,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝H时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为14.1-14.321。
表15：通式I中，当R 1＝R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为15.1-15.321。
表16：通式I中，当R 1＝R 2＝Br,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为16.1-16.321。
表17：通式I中，当R 1＝R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为17.1-17.321。
表18：通式I中，当R 1＝R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为18.1-18.321。
表19：通式I中，当R 1＝CH 3,R 2＝CH 2CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为19.1-19.321。
表20：通式I中，当R 1＝Br,R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为20.1-20.321。
表21：通式I中，当R 1＝Br,R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为21.1-21.321。
表22：通式I中，当R 1＝Br,R 2＝I,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为22.1-22.321。
表23：通式I中，当R 1＝Br,R 2＝CF 3R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为23.1-23.321。
表24：通式I中，当R 1＝Cl,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为24.1-24.321。
表25：通式I中，当R 1＝I,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H, R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为25.1-25.321。
表26：通式I中，当R 1＝Br,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为26.1-26.321。
表27：通式I中，当R 1＝Cl,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为27.1-27.321。
表28：通式I中，当R 1＝I,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝H,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为28.1-28.321。
表29：通式I中，当R 1＝R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为29.1-29.321。
表30：通式I中，当R 1＝R 2＝Br,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为30.1-30.321。
表31：通式I中，当R 1＝R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为31.1-31.321。
表32：通式I中，当R 1＝R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为32.1-32.321。
表33：通式I中，当R 1＝CH 3,R 2＝CH 2CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为33.1-33.321。
表34：通式I中，当R 1＝Br,R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为34.1-34.321。
表35：通式I中，当R 1＝Br,R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为35.1-35.321。
表36：通式I中，当R 1＝Br,R 2＝I,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为36.1-36.321。
表37：通式I中，当R 1＝Br,R 2＝CF 3R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为37.1-37.321。
表38：通式I中，当R 1＝Cl,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为38.1-38.321。
表39：通式I中，当R 1＝I,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为39.1-39.321。
表40：通式I中，当R 1＝Br,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为40.1-40.321。
表41：通式I中，当R 1＝Cl,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为41.1-41.321。
表42：通式I中，当R 1＝I,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝CH 3,R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为42.1-42.321。
表43：通式I中，当R 1＝R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为43.1-43.321。
表44：通式I中，当R 1＝R 2＝Br,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为44.1-44.321。
表45：通式I中，当R 1＝R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为45.1-45.321。
表46：通式I中，当R 1＝R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为46.1-46.321。
表47：通式I中，当R 1＝CH 3,R 2＝CH 2CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为47.1-47.321。
表48：通式I中，当R 1＝Br,R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321 记载的取代基，代表化合物编号为48.1-48.321。
表49：通式I中，当R 1＝Br,R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为49.1-49.321。
表50：通式I中，当R 1＝Br,R 2＝I,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为50.1-50.321。
表51：通式I中，当R 1＝Br,R 2＝CF 3R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为51.1-51.321。
表52：通式I中，当R 1＝Cl,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为52.1-52.321。
表53：通式I中，当R 1＝I,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为53.1-53.321。
表54：通式I中，当R 1＝Br,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为54.1-54.321。
表55：通式I中，当R 1＝Cl,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为55.1-55.321。
表56：通式I中，当R 1＝I,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝氰甲基,R 5＝CH 3时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为56.1-56.321。
表57：通式I中，当R 1＝R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为57.1-57.321。
表58：通式I中，当R 1＝R 2＝Br,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为58.1-58.321。
表59：通式I中，当R 1＝R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为59.1-59.321。
表60：通式I中，当R 1＝R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝ 氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为60.1-60.321。
表61：通式I中，当R 1＝CH 3,R 2＝CH 2CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为61.1-61.321。
表62：通式I中，当R 1＝Br,R 2＝CH 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为62.1-62.321。
表63：通式I中，当R 1＝Br,R 2＝Cl,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为63.1-63.321。
表64：通式I中，当R 1＝Br,R 2＝I,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为64.1-64.321。
表65：通式I中，当R 1＝Br,R 2＝CF 3R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为65.1-65.321。
表66：通式I中，当R 1＝Cl,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为66.1-66.321。
表67：通式I中，当R 1＝I,R 2＝CF 3,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为67.1-67.321。
表68：通式I中，当R 1＝Br,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为68.1-68.321。
表69：通式I中，当R 1＝Cl,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为69.1-69.321。
表70：通式I中，当R 1＝I,R 2＝OCHF 2,R 3＝七氟异丙基,X 1＝F,X 2＝X 3＝X 4＝H,R 4＝R 5＝氰甲基时，(R 6) n为不同的取代基与表1一致，依次对应表1中1.1-1.321记载的取代基，代表化合物编号为70.1-70.321。
本发明的通式I化合物可按照以下方法制备(式中各基团除另有说明外定义同前；式中LG＝Cl或Br)：
Figure PCTCN2019085737-appb-000009
通式S化合物与通式K化合物或通式W化合物与通式Y化合物在适宜的溶剂中，在温度从-10℃到溶剂沸点下反应0.5-48小时可制得通式II化合物，反应可在碱存在下进行。
通式II化合物与卤乙腈在适宜的溶剂、适宜的碱存在下，在温度从-10℃到溶剂沸点下反应0.5-48小时可分别制得通式I-1、I-2及I-3化合物。通式I-1或I-2化合物与卤乙腈在适宜的溶剂、适宜的碱存在下，在温度从-10℃到溶剂沸点下反应0.5-48小时均可制得通式I-3化合物。通式I-1化合物与通式R 5-LG化合物在适宜的溶剂、适宜的碱存在下，在温度从-10℃到溶剂沸点下反应0.5-48小时可制得通式I-4化合物。通式I-2化合物与通式R 4-LG化合物在适宜的溶剂、适宜的碱存在下，在温度从-10℃到溶剂沸点下反应0.5-48小时可制得通式I-5化合物。通式III化合物(其中R 5仅为C 1-C 6烷基或C 1-C 6卤代烷基)与卤乙腈在适宜的溶剂、适宜的碱存在下，在温度从-10℃到溶剂沸点下反应0.5-48小时可制得通式I-4化合物。通式IV化合物(其中R 4仅为C 1-C 6烷基或C 1-C 6卤代烷基)与卤乙腈在适宜的溶剂、适宜的碱存在下，在温度从-10℃到溶剂沸点下反应0.5-48小时可制得通式I-5化合物。
上述适宜的溶剂可为苯、甲苯、二甲苯等芳烃类，丙酮、甲乙酮、甲基异丁基酮等酮类，氯仿、二氯甲烷等卤代烃类，乙酸甲酯、乙酸乙酯等酯类，四氢呋喃、二噁烷、二***、1,2-二甲氧基乙烷等醚类，水、乙腈、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲基亚砜等极性溶剂类或上述溶剂的混合溶剂；适宜的碱可 为三乙胺、吡啶、DBU、4-二甲氨基吡啶等有机碱，氢化钠、氢化钾等碱金属氢化物，氢氧化钠、氢氧化钾等碱金属氢氧化物，氢氧化钙等碱土类金属氢氧化物，碳酸钠、碳酸钾等碱金属碳酸盐，碳酸氢钠等碱金属碳酸氢盐，甲醇钠、乙醇钠、乙醇钾、叔丁醇钾、叔丁醇钠等金属醇盐。
通式R 4-LG、通式R 5-LG、通式K化合物及通式CNCH 2-LG化合物、碱通常有市售，也可按常规方法自制。通式S、通式W、通式Y、通式II、通式III及通式IV化合物可以按公知方法制备，例如参照WO2011093415、WO20110201687、WO2005021488、WO2005073165、WO2010018857、WO2006137395、JP2007099761、WO2008000438、WO2008074427、WO2008107091、WO2010013567、WO2010018714、WO2010090282、WO2010127926、WO2010127928、JP2011063549、WO2012020483、WO2012020484、WO2012077221、WO2012164698、WO2013050261、WO2014069665、WO2014067838、WO2014161848、WO2014161850、WO2015097091或WO2015097094等报道的方法制得。
本发明通式I化合物具有意想不到的高杀虫活性，可用于防治如下害虫(所列对象仅用来说明本发明，但绝不限定本发明)：鳞翅目害虫如小菜蛾、粘虫、甜菜夜蛾、斜纹夜蛾、烟夜蛾、粉纹夜蛾、二化螟、三化螟、稻纵卷叶螟、玉米螟、小食心虫、棉铃虫等；同翅目害虫如豌蚜、豆蚜、甜菜蚜、棉蚜、苹果蚜、桃蚜、玉米蚜、粉虱、叶蝉、飞虱、稻飞虱、粉蚧等；半翅目害虫如玉米长蝽、棉网蝽、番茄盲蝽、稻绿蝽、稻臭椿等；缨翅目害虫如棉蓟马、苜蓿蓟马、黄豆蓟马等；鞘翅目害虫如马铃薯甲虫、叩甲、恶性叶甲、潜叶甲、灰象甲等；双翅目害虫如蝇、蚊等；膜翅目害虫如蜂、蚁等。本发明通式I化合物还具有意想不到的高杀虫速效性，起效快，在施用1天后就可以达到较高的杀虫活性，在3天内就可以达到极高的杀虫活性。本发明通式I化合物制备方法简单高效、易于大规模工业化生产，应用前景广泛。因此，本发明的技术方案还包括通式I化合物在农业或其它领域中用作制备杀虫剂药物的用途。
由于其积极的特性，上述化合物可有利地用于保护农业和园艺业重要的作物、家畜和种畜，以及人类常去的环境免于害虫的伤害。
为获得理想效果，化合物的用量因各种因素而改变，例如所用化合物、预保护的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型等。
每公顷10克-5公斤的化合物剂量能提供充分的防治。
本发明还包括以通式I化合物作为活性组分的杀虫组合物。该杀虫组合物中活性组分的重量百分含量在0.1-99％之间。该杀虫组合物中还包括农业、林业、卫生上可接受的载体。
本发明的组合物可以制剂的形式施用。通式I化合物作为活性组分溶解或分 散于载体中或配制成制剂以便作为杀虫使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂、油悬剂、水悬剂、水乳剂、水剂或乳油等。在这些组合物中，至少加入一种液体或固体载体，并且当需要时可以加入适当的表面活性剂。
本发明的技术方案还包括防治害虫的方法：将本发明的杀虫组合物施于所述的害虫或其生长介质上。通常选择的较为适宜有效量为每公顷10克到1000克，优选有效量为每公顷10克到500克。
对于某些应用，例如在农业上可在本发明的杀虫组合物中加入一种或多种其它的杀菌剂、杀虫杀螨剂、除草剂、植物生长调节剂或肥料等，由此可产生附加的优点和效果。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
具体实施方式
以下具体实施例用来进一步说明本发明，但本发明绝非限于这些例子。(除另有注明外，所用原料均有市售)
合成实施例
按照上述记载的合成路线，采用不同的原料化合物，即可分别制备获得本发明通式I所示化合物，进一步具体描述如下：
实施例1：化合物2.321的制备
Figure PCTCN2019085737-appb-000010
(1)3-苯甲酰胺基-N-(2,6-二溴-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-1)的制备
向30ml甲苯中加入1.00克(1.80mmol)N-(2,6-二溴-4-七氟异丙基苯基)-2-氟-3-氨基苯甲酰胺(中间体S-1，参照WO2010013567、WO2010018714、WO20110201687或WO2011093415等报道的方法制得)及0.27克(1.93mmol)苯甲酰氯，加热回流。TLC监测反应完毕后，减压脱溶，残余物柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:6～1:2)纯化，得白色固体1.09克，即中间体II-1。
(2)化合物2.321的制备
Figure PCTCN2019085737-appb-000011
向10ml四氢呋喃中加入0.30克(7.5mmol)60％氢化钠，在室温下滴入溶解于 10ml四氢呋喃中的0.50克(0.75mmol)3-苯甲酰胺基-N-(2,6-二溴-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-1)，室温下搅拌10分钟；加入0.45克(3.78mmol)溴乙腈，室温下继续搅拌1小时。TLC监测反应完毕后，用冰水淬灭反应，加入乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:6～1:2)纯化，得白色固体0.38克。
化合物2.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.10(t,1H),7.98(d,1H),7.86(s,2H),7.54–7.48(m,1H),7.41–7.29(m,4H),7.28–7.21(m,2H),4.80(d,2H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.62(d,1H),8.04(d,2H),7.66(d,2H),7.44–7.27(m,6H),4.93(s,2H).
LC-MS(m/z):722.0(m+Na+H)。
同样地，按照实施例1所描述的方法制备化合物2.7、2.17、2.43。
Figure PCTCN2019085737-appb-000012
化合物2.7的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.13(t,1H),7.95(d,1H),7.87(s,2H),7.54–7.49(m,1H),7.44–7.39(m,2H),7.35(t,1H),6.95(t,2H),4.79(d,2H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.62(s,1H),8.04(s,2H),7.73–7.65(m,2H),7.48–7.42(m,2H),7.38(t,1H),7.15(t,2H),4.94(s,2H).
LC-MS(m/z):718.1(m+H)。
化合物2.17的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.16(t,1H),7.88(s,2H),7.57(d,2H),7.53–7.48(m,3H),7.37(t,1H),7.34(s,1H),4.99(s,1H),4.67(s,1H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.59(s,1H),8.04(s,2H),7.80(d,2H),7.77–7.67(m,2H),7.55(d,2H),7.38(t,1H),4.99(s,2H).
LC-MS(m/z):725.2(m+H)。
化合物2.43的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):7.90–7.80(m,4H),7.55(d,2H),7.23(s,1H),7.11(s,1H),6.85(s,1H),4.39–4.31(m,1H),4.08(d,2H).LC-MS(m/z):767.9(m+H)。
实施例2：化合物3.321的制备
Figure PCTCN2019085737-appb-000013
由3-苯甲酰胺基-N-(2,6-二氯-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-2，参照WO2010018857报道的方法制得)制备化合物3.321的方法同实施例1。
化合物3.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.10(t,1H),7.95(d,1H),7.67(s,2H),7.49(t,1H),7.41–7.34(m,3H),7.31(t,1H),7.29–7.22(m,2H),4.80(d,2H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.61(s,1H),7.92(s,2H),7.70–7.58(m,2H),7.42–7.27(m,6H),4.93(s,2H).
LC-MS(m/z):610.0(m+H)。
实施例3：化合物6.321的制备
Figure PCTCN2019085737-appb-000014
由3-苯甲酰胺基-N-(2-溴-6-甲基-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-3，参照WO2010018857报道的方法制得)制备化合物6.321的方法同实施例1。
化合物6.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.12-8.06(m,1H),7.90(d,1H),7.72(s,1H),7.51(t,1H),7.51(t,1H),7.48(s,1H),7.42–7.30(m,4H),7.28–7.22(m,1H),4.81(d,2H),2.38(s,3H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.29(s,1H),7.80(d,1H),7.70–7.64(m,2H),7.59(t,1H),7.38(d,3H),7.35–7.27(m,3H),4.93(s,2H),2.35(s,3H).
LC-MS(m/z):634.0(m+H)。
实施例4：化合物7.321的制备
Figure PCTCN2019085737-appb-000015
由3-苯甲酰胺基-N-(2-溴-6-氯-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-4，参照WO2014161849报道的方法制得)制备化合物7.321的方法同实施例1。
化合物7.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.10(t,1H),7.96(d,1H),7.88–7.80(m,1H),7.71(d,1H),7.54–7.46(m,1H),7.42–7.29(m,4H),7.28–7.21(m,2H),4.80(d,2H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.61(s,1H),8.05–7.99(m,1H),7.95(s,1H),7.71–7.58(m,2H),7.42–7.27(m,6H),4.93(s,2H).
LC-MS(m/z):654.0(m+H)。
实施例5：化合物8.321的制备
Figure PCTCN2019085737-appb-000016
由3-苯甲酰胺基-N-(2-溴-6-碘-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-5，参照WO2010018857报道的方法制得)制备化合物8.321的方法同实施例1。
化合物8.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.12(t,1H),8.06(d,1H),7.96(d,1H),7.89(d,1H),7.54(t,1H),7.42–7.31(m,4H),7.28–7.21(m,2H),4.81(d,2H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.61(s,1H),8.14(s,1H),8.02(s,1H),7.70(t,1H),7.66–7.60(m,1H),7.41–7.28(m,6H),4.93(s,2H).
LC-MS(m/z):745.9(m+H)。
实施例6：化合物9.321的制备
Figure PCTCN2019085737-appb-000017
由3-苯甲酰胺基-N-(2-溴-6-三氟甲基-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-6，参照WO2010013567、WO2010018714、WO20110201687或WO2011093415等报道的方法制得)制备化合物9.321的方法同实施例1。
化合物9.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.13(s,1H),8.08(t,1H),8.03(d,1H),7.91(s,1H),7.53(t,1H),7.40–7.30(m,4H),7.28–7.22(m,2H),4.80(d,2H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):10.66(s,1H),8.40(d,1H),7.94(d,1H),7.62(q,2H),7.39–7.31(m,4H),7.28(t,2H),4.91(s,2H).
LC-MS(m/z):687.9(m+H)。
实施例7：化合物16.321的制备
Figure PCTCN2019085737-appb-000018
将0.5克(0.75mmol)3-苯甲酰胺基-N-(2,6-二溴-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-1)、0.18克(1.51mmol)溴乙腈、0.17克(1.52mmol)叔丁醇钾加入到20ml四氢呋喃中，室温下搅拌5小时。TLC监测反应完毕后，加入水和乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:6～1:2)纯化，得白色固体0.29克。
化合物16.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.52(td,1H),8.08(s,1H),7.88–7.83(m,2H),7.79(s,2H),7.62–7.57(m,1H),7.54–7.50(m,2H),6.98–6.93(m,1H),6.92–6.88(m,1H),4.72(s,2H).LC-MS(m/z):699.9(m+H)。
同样地，按照实施例7所描述的方法制备化合物17.321、20.321、21.321。
Figure PCTCN2019085737-appb-000019
化合物17.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.54–8.48(m,1H),8.04(d,1H),7.87–7.82(m,2H),7.60–7.57(m,3H),7.54–7.50(m,2H),6.97(t,1H),6.92–6.87(m,1H),4.74(s,2H).LC-MS(m/z):610.0(m+H)。
化合物20.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.51–8.45(m,1H),8.00(d,1H),7.87–7.82(m,2H),7.71(s,1H),7.62–7.58(m,1H),7.54–7.50(m,2H),7.37(s,1H),6.97(t,1H),6.93–6.89(m,1H),5.14(d,1H),4.35(d,1H),2.43(s,3H).LC-MS(m/z):634.0(m+H)。
化合物21.321的核磁及质谱数据如下： 1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):8.56–8.50(m,1H),8.05(s,1H),7.88–7.83(m,2H),7.76(d,1H),7.64–7.58(m,2H),7.56–7.50(m,2H),6.97(t,1H),6.93–6.87(m,1H),4.79(d,1H),4.68(d,1H).LC-MS(m/z):654.0(m+H)。
实施例8：化合物30.321的制备
Figure PCTCN2019085737-appb-000020
将0.5克(0.74mmol)N-(2,6-二溴-4-七氟异丙基苯基)-2-氟-3-(N-甲基苯甲酰基)苯甲酰胺(中间体IV-1，参照WO2010013567、WO2010018714、WO20110201687或WO2011093415等报道的方法制得)、0.18克(1.51mmol)溴乙腈、0.17克(1.52mmol)叔丁醇钾加入到20ml DMF中，室温下搅拌10小时。TLC监测反应完毕后，加入水和乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:6～1:2)纯化，得白色固体0.34克。
化合物30.321的核磁及质谱数据如下：
1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):7.76(s,2H),7.49–7.37(m,1H),7.28–7.21(m,2H),7.18–7.10(m,3H),7.00–6.94(m,1H),6.80–6.74(m,1H),4.69(s,2H),3.27(s,3H).
1H NMR(600MHz，内标TMS，溶剂DMSO)δ(ppm):7.99(s,2H),7.31–7.25(m,2H),7.24–7.16(m,4H),7.07–7.01(m,1H),6.94–6.88(m,1H),4.88(s,2H),3.18(s,3H).
LC-MS(m/z):713.9(m+H)。
实施例9：化合物58.321的制备
Figure PCTCN2019085737-appb-000021
将0.5克(0.75mmol)3-苯甲酰胺基-N-(2,6-二溴-4-七氟异丙基苯基)-2-氟苯甲酰胺(中间体II-1)、0.45克(3.78mmol)溴乙腈、0.42克(3.75mmol)叔丁醇钾加入到20ml四氢呋喃中，室温下搅拌5小时。TLC监测反应完毕后，加入水和乙酸乙酯萃取、无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析(洗脱剂为乙酸乙酯与石油醚，体积比为1:6～1:2)纯化，得白色固体0.26克。
化合物58.321的核磁及质谱数据如下： 1H NMR(600MHz，内标TMS，溶剂CDCl 3)δ(ppm):7.77(s,2H),7.33–7.28(m,3H),7.18(t,2H),7.16–7.12(m,1H),7.09(t,1H),6.82(t,1H),5.05(s,1H),4.69(d,2H),4.20(s,1H).LC-MS(m/z):760.9(m+H)。
参照以上实施例可以制备本发明通式I中其它化合物。
生物活性测定
实施例10：杀虫活性测定
用本发明化合物对几种昆虫进行了杀虫活性测定实验。测定方法如下：
待测化合物用丙酮/甲醇(1:1)的混合溶剂溶解后，用含有0.1％(wt)吐温80的水稀释至所需的浓度。
以粘虫、小菜蛾、二化螟为靶标，采用Airbrush喷雾法进行活性测定。
(1)杀粘虫的活性测定
测定方法：将玉米叶片剪成长2cm的叶段，Airbrush喷雾处理的压力为10psi(约合0.7kg/cm 2)，每叶段正反面喷雾，喷液量为0.5ml。阴干后每处理接入10头3龄幼虫，每处理3次重复。处理后放入25℃、相对湿度60～70％观察室内培养，药后1、2、3天后调查存活虫数，计算死亡率。
对粘虫的部分测试结果如下：
在0.5mg/L剂量下，药后3天，化合物2.7、2.17、2.43、2.321、3.321、6.321、7.321、8.321、9.321、16.321、17.321、20.321、21.321、30.321、58.321对粘虫的致死率在90％以上；
在0.1mg/L剂量下，药后3天，化合物2.7、2.17、2.43、2.321、3.321、7.321、8.321、9.321、16.321、17.321、21.321、30.321、58.321对粘虫的致死率在90％以上；
在0.05mg/L剂量下，药后3天，化合物2.7、2.17、2.43、2.321、9.321、30.321对粘虫的致死率在90％以上。
(2)杀小菜蛾的活性测定
测定方法：将甘蓝叶片用打孔器打成直径2cm的叶碟，Airbrush喷雾处理的压力为10psi(约合0.7kg/cm 2)，每叶碟正反面喷雾，喷液量为0.5ml。阴干后每处理接入10头3龄幼虫，每处理3次重复。处理后放入25℃、相对湿度60～70％观察室内培养，药后1、2、3天后调查存活虫数，计算死亡率。
对小菜蛾的部分测试结果如下：
在1mg/L剂量下，药后3天，化合物2.7、2.17、2.43、2.321、3.321、6.321、7.321、8.321、9.321、16.321、17.321、20.321、21.321、30.321、58.321对小菜蛾的致死率在90％以上；
在0.5mg/L剂量下，药后3天，化合物2.7、2.17、2.43、2.321、9.321、16.321、30.321、58.321对小菜蛾的致死率在90％以上。
在0.05mg/L剂量下，药后3天，化合物9.321、30.321对小菜蛾的致死率在90％以上。
选取CK1、CK2、CK3、CK4作为对照化合物，选取本发明化合物2.7、2.17、2.43、2.321、3.321、6.321、7.321、8.321、9.321、16.321、17.321、20.321、21.321、30.321、58.321进行小菜蛾杀虫活性平行比较试验(药后3天)，测定方法同前所述；结果如表71所示：
表71本发明部分化合物与CK1～CK4对小菜蛾杀虫活性平行比较试验
Figure PCTCN2019085737-appb-000022
Figure PCTCN2019085737-appb-000023
选取CK5、CK8、CK12作为对照化合物，选取本发明化合物6.321、20.321进行小菜蛾杀虫活性平行比较试验(药后3天)，测定方法同前所述；结果如表72所示：
表72本发明化合物6.321、20.321与CK5、CK8、CK12对小菜蛾杀虫活性平行比较试验
Figure PCTCN2019085737-appb-000024
选取CK6、CK9、CK10、CK13、CK15作为对照化合物，选取本发明化合物2.7、2.17、2.43、2.321、16.321、30.321、58.321进行小菜蛾杀虫活性平行比较试验(药后3天)，测定方法同前所述；结果如表73所示：
表73本发明部分化合物与CK6、CK9、CK10、CK13、CK15对小菜蛾杀虫活性平行比较试验
Figure PCTCN2019085737-appb-000025
Figure PCTCN2019085737-appb-000026
选取CK7、CK11、CK14、CK16作为对照化合物，选取本发明化合物9.321、30.321进行小菜蛾杀虫活性平行比较试验(药后3天)，测定方法同前所述；结果如表74所示：
表74本发明化合物9.321、30.321与CK7、CK11、CK14、CK16对小菜蛾杀虫活性平行比较试验
Figure PCTCN2019085737-appb-000027
选取CK15作为对照化合物，选取本发明化合物2.321、30.321进行小菜蛾杀虫活性平行比较试验，以比较杀虫速效性；结果如表75所示：
表75本发明化合物2.321、30.321与CK15对小菜蛾杀虫活性速效性比较试验
Figure PCTCN2019085737-appb-000028
由表75可以得知，本发明的化合物与现有化合物CK15相比，在较低剂量下，具有更优良的杀虫速效性以及更高的杀虫活性。
选取CK16作为对照化合物，选取本发明化合物9.321进行小菜蛾杀虫活性平行比较试验，以比较杀虫速效性；结果如表76所示：
表76本发明化合物9.321与CK16对小菜蛾杀虫活性速效性比较试验
Figure PCTCN2019085737-appb-000029
由表76可以得知，本发明的化合物与现有化合物CK16相比，在较低剂量下，具有更优良的杀虫速效性以及更高的杀虫活性。
(3)杀二化螟的活性测定
测定方法：1)稻苗准备：在恒温室(温度26～28℃、相对湿度60～80％左右，光照16hL:8hD)内用直径为4.5cm、高4cm塑料小杯培养水稻，待水稻长至4～5叶期时，选择健壮的、长势一致的水稻幼苗进行药剂处理，每处理设3次重复。2)试虫准备：室内连续饲养的二化螟，3龄幼虫。3)稻茎喷雾接虫法。采用喷雾法，对稻苗进行全株均匀喷雾处理，每处理用药15ml。先处理空白对照，然后按试验浓度由低到高的顺序重复上述操作。稻苗喷雾处理后，放置阴凉处将药液晾干，剪取茎基部上5厘米左右茎秆饲喂试虫。准备直径9mm的玻璃培养皿，皿底垫滤纸，加水保湿，每皿放入约20根稻茎，接幼虫10头，用无纺布密闭培养皿，置于恒温房间培养。药后3天调查残留活虫数。
对二化螟的部分测试结果如下：
在40mg/L剂量下，化合物2.7、2.17、2.43、2.321、3.321、6.321、7.321、8.321、9.321、16.321、17.321、20.321、21.321、30.321、58.321对二化螟的致死率在90％以上；
在4mg/L剂量下，化合物2.7、2.17、2.43、2.321、3.321、7.321、8.321、9.321、16.321、17.321、21.321、30.321、58.321对二化螟的致死率在90％以上；
在1mg/L剂量下，化合物2.7、2.17、2.43、2.321、9.321、30.321对二化螟的致死率在90％以上。
选取CK15作为对照化合物，选取本发明化合物2.321、30.321进行二化螟杀虫活性平行比较试验，测定方法同前所述；结果如表77所示：
表77本发明化合物2.321、30.321与CK15对二化螟杀虫活性的比较
Figure PCTCN2019085737-appb-000030
由表77可以得知，本发明的化合物与现有化合物CK15相比，具有在更低剂量下发挥更好杀虫效果的优势。
选取CK16作为对照化合物，选取本发明化合物9.321进行二化螟杀虫活性平行比较试验，测定方法同前所述；结果如表78所示：
表78本发明化合物9.321与CK16对二化螟杀虫活性的比较
化合物编号 致死率(％，药后3天)
2.5mg/L 1.25mg/L 0.625mg/L
9.321 100 100 98
CK16 85.5 60.3 10
由表78可以得知，本发明的化合物与现有化合物CK16相比，具有在更低剂量下发挥更好杀虫效果的优势。
本发明的发明人通过大量试验，在现有化合物分子骨架的基础上，在其酰胺键N原子上适当地引入了氰甲基(CNCH 2-)，从而获得了本发明通式I化合物。由表71～表78活性对比试验数据可以看出：与现有化合物相比，由于引入了新的适当的片段(药效基团)，提高了分子与受体相互作用力和结合的机会，从而使得本发明化合物相对于现有化合物具有意想不到的效果，即本发明化合物具有更高的杀虫活性以及更优良的杀虫速效性(起效快，在施用1天后就可以达到较高的杀虫活性，在3天内就可以达到极高的杀虫活性)。
在有机分子中，由于取代基的电负性、体积大小或空间构型的不同，整个分子在昆虫和植物等生物体内的输导性能或与受体结合差异性会很大，表现出的生物活性差异也会很大，而分子的输导性能和与受体结合的合适性是不可预测的，需要大量的创造性劳动才能获知，因此，本发明具有实质性的特点和显著的进步。

Claims (8)

  1. 一种苯甲酰胺类化合物，如通式I所示：
    Figure PCTCN2019085737-appb-100001
    式中：
    R 1、R 2各自独立地选自氢、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基或C 1-C 6卤代烷氧基；
    R 3选自七氟异丙基或九氟-2-丁基；
    R 4、R 5各自独立地选自氢、C 1-C 6烷基、C 1-C 6卤代烷基或氰甲基；并且，R 4、R 5至少有一个选自氰甲基；
    R 6选自氢、卤素、氰基、硝基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基、C 1-C 6烷硫基或C 1-C 6卤代烷硫基；n＝1、2、3、4或5；
    X 1、X 2、X 3、X 4各自独立地选自氢、卤素、氰基或C 1-C 6烷氧基；且，X 1、X 2、X 3、X 4不同时为氢。
  2. 根据权利要求1所述的化合物，其特征在于：通式I中
    R 1、R 2各自独立地选自氢、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基或C 1-C 4卤代烷氧基；
    R 3选自七氟异丙基或九氟-2-丁基；
    R 4、R 5各自独立地选自氢、甲基、乙基或氰甲基；并且，R 4、R 5至少有一个选自氰甲基；
    R 6选自氢、卤素、氰基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；n＝1、2、3或4；
    X 1选自氟；
    X 2、X 3、X 4各自独立地选自氢、氟或氰基。
  3. 根据权利要求2所述的化合物，其特征在于：通式I中
    R 1、R 2各自独立地选自氢、卤素、甲基、乙基、三氟甲基或二氟甲氧基；
    R 3选自七氟异丙基或九氟-2-丁基；
    R 4、R 5各自独立地选自氢、甲基、乙基或氰甲基；并且，R 4、R 5至少有一个选自氰甲基；
    R 6选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、丙基、叔丁基、三氟 甲基、七氟异丙基、甲氧基或三氟甲氧基；n＝1、2或3；
    X 1选自氟；
    X 2、X 3、X 4各自独立地选自氢或氟。
  4. 根据权利要求1、2或3所述的化合物，其特征在于：通式I中
    R 1、R 2各自独立地选自氢、卤素、甲基、乙基、三氟甲基或二氟甲氧基；
    R 3选自七氟异丙基或九氟-2-丁基；
    R 4选自氰甲基；
    R 5选自氢、甲基、乙基或氰甲基；
    R 6选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、丙基、叔丁基、三氟甲基、七氟异丙基、甲氧基或三氟甲氧基；n＝1、2或3；
    X 1选自氟；
    X 2、X 3、X 4各自独立地选自氢或氟。
  5. 根据权利要求1、2或3所述的化合物，其特征在于：通式I中
    R 1、R 2各自独立地选自氢、卤素、甲基、乙基、三氟甲基或二氟甲氧基；
    R 3选自七氟异丙基或九氟-2-丁基；
    R 4选自氢、甲基或乙基；
    R 5选自氰甲基；
    R 6选自氢、氟、氯、溴、氰基、硝基、甲基、乙基、丙基、叔丁基、三氟甲基、七氟异丙基、甲氧基或三氟甲氧基；n＝1、2或3；
    X 1选自氟；
    X 2、X 3、X 4各自独立地选自氢或氟。
  6. 一种根据权利要求1所述的通式I化合物在农业、林业及卫生领域中用作制备杀虫剂药物的用途。
  7. 一种杀虫组合物，其特征在于：组合物中含有如权利要求1所述的通式I化合物作为活性组分，组合物中活性组分的重量百分含量为0.1-99％。
  8. 一种控制农业或林业害虫的方法，其特征在于：将有效量的权利要求7所述的组合物施于需要控制的害虫或其生长介质上。
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