WO2020156512A1 - 具有杀虫活性的芳(杂)环醚类化合物及其制备方法和用途 - Google Patents

具有杀虫活性的芳(杂)环醚类化合物及其制备方法和用途 Download PDF

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WO2020156512A1
WO2020156512A1 PCT/CN2020/074115 CN2020074115W WO2020156512A1 WO 2020156512 A1 WO2020156512 A1 WO 2020156512A1 CN 2020074115 W CN2020074115 W CN 2020074115W WO 2020156512 A1 WO2020156512 A1 WO 2020156512A1
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French (fr)
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李忠
董建生
徐晓勇
郭建法
王正荣
李鹏涛
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华东理工大学
辽宁众辉生物科技有限公司
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    • C07D307/40—Radicals substituted by oxygen atoms
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to the field of pesticides, and more specifically to aromatic heterocyclic ether compounds, their preparation methods and uses.
  • Aromatic ether compounds have been used as insecticides for a long time. The mechanism of action is to disrupt the growth of insects. It is a new type of insecticide that is a juvenile hormone analogue. It has systemic transfer activity, low toxicity, long lasting period, and is safe for crops. It has the characteristics of low toxicity to fish and little impact on the ecological environment. Its unique mode of action and significant control effect are considered to be one of the effective methods of comprehensive pest control, and it has become a hot spot in the research and creation of pesticides.
  • the most widely used chemical pesticides are mainly organophosphorus or carbamates, pyrethroid pesticides, such as thionphos, fenamiphos, thiazophos, aldicarb, carbofuran, cyhalothrin, etc.,
  • pyrethroid pesticides such as thionphos, fenamiphos, thiazophos, aldicarb, carbofuran, cyhalothrin, etc.
  • the safety to humans and other non-target organisms is low, and it can also cause varying degrees of pollution to soil, water sources and agricultural products.
  • Neonicotinoid insecticides and rinidin receptor inhibitors are widely used. Due to the excessive and frequent use of various insecticides, serious resistance has been caused, making the control of pests increasingly difficult.
  • adult insects have the ability to reproduce due to the development of various parts of their bodies. They have the strongest resistance to agricultural pesticides and have the greatest impact on crops. In particular, juvenile hormone analogues are often unsatisfactory as insecticides for adults.
  • the purpose of the present invention is to provide a novel chemical insecticide with high efficiency, low toxicity and good environmental compatibility, especially a new aromatic (hetero)cyclic ether compound with insecticidal activity against adult insects.
  • the present invention provides a compound having a structure represented by the general formula (I) or its optical isomer, cis-trans isomer or agrochemically acceptable salt:
  • Ring ⁇ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-membered or 6-membered heterocyclic group, or a substituted or unsubstituted 8- to 12-membered heteroaromatic bicyclic group;
  • Ring ⁇ is substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted 5-membered or 6-membered heterocyclylene, or substituted or unsubstituted 8- to 12-membered heteroarylene Bicyclic group
  • Ring ⁇ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 5-membered or 6-membered heterocyclic group, or a substituted or unsubstituted 8- to 12-membered heteroaromatic bicyclic group;
  • the substituents of ring ⁇ , ring ⁇ and ring ⁇ are selected from the group consisting of halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C 1-6 alkyl or alkoxy, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, substituted or unsubstituted Phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-membered or 6-membered heterocyclic group, or substituted or unsubstituted 8- to 12-membered heteroaromatic bicyclic group;
  • L 1 and L 3 may be the same or different, and are each independently selected from the following group: -NR'-, -O-, -S-;
  • L 2 is a group selected from the following group: -CR'R"-, R'R" can be the same or different;
  • n is an integer of 1-8; preferably an integer of 1-5; more preferably an integer of 1-3; most preferably 1;
  • G is independent substituents located at any one or more (preferably 1-3) positions of ring ⁇ , and G is selected from the group consisting of halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C 1- 6 Alkoxy, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, or substituted or unsubstituted C 3- 7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, trimethylsilylethynyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5-membered or 6-membered heterocyclic group, substituted or unsubstituted 8- to 12-membered heteroaromatic bicyclic ring system, OR', Si(R')
  • substitution refers to substitution by one or more groups selected from the group consisting of halogen, cyano, nitro, hydroxyl, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkane Group, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 2-6 haloalkynyl, hydroxy, hydroxy C 1-4 alkyl, R', OR', Si(R') 3 , NR'R”, C(O)R', C(O)OR', C(O)NR'R”, SR', S(O) m R', S(O) 2 NR'R”, OC(O)R, OC(O)NR'R”, OS(O) 2 R', OS(O) 2 NR'R”, N(R')C(O)R' , N (R ') C ( O) NR'R ", N (R') S (O) 2 R ' or N (R'
  • the compound has the structure shown in the following formula II:
  • X 1 , X 2 , and X 3 are each C(Ra), N(Ra) or S; X 1 , X 2 , and X 3 are not S at the same time;
  • X 4 , X 5 , and X 6 are C(Ra) and N(Ra) respectively; X 4 , X 5 , and X 6 may be the same or different;
  • L 1 and L 3 may be the same or different, and each is O, NH, S;
  • L 2 is CH 2 ;
  • n 1, 2 or 3;
  • n 0 or 1
  • Ra is selected from the following group: H, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 3 -6 cycloalkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, trimethylsilylethynyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5- or 6-membered heterocyclic group, substituted or unsubstituted 8-membered to 12-membered heteroaromatic bicyclic ring system, OR', Si(R') 3 ,
  • Rb is selected from the following group: H, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 3 -6 cycloalkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, trimethylsilylethynyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5- or 6-membered heterocyclic group, substituted or unsubstituted 8-membered to 12-membered heteroaromatic bicyclic ring system, OR', Si(R') 3 ,
  • the compound has the structure shown in the following formula III:
  • V 1 , V 2 , V 3 , V 4 , and V 5 are each C (Ra), N (Ra) or S; V 2 , V 3 , and V 4 are not S or N at the same time;
  • X 4 , X 5 , and X 6 may be the same or different, and each is C(Ra), N(Ra);
  • L 1 and L 3 may be the same or different, and each is O, NH, S;
  • L 2 is CH 2 ;
  • n 1, 2 or 3;
  • n each is 0 or 1;
  • Ra is selected from the following group: H, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 3 -6 cycloalkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, trimethylsilylethynyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5- or 6-membered heterocyclic group, substituted or unsubstituted 8-membered to 12-membered heteroaromatic bicyclic ring system, OR', Si(R') 3 ,
  • Rb is selected from the following group: H, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C 1-6 alkoxy, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 3 -6 cycloalkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, or substituted or unsubstituted C 3-7 cycloalkyl, substituted or unsubstituted C 5-7 cycloalkenyl, trimethylsilylethynyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 5- or 6-membered heterocyclic group, substituted or unsubstituted 8-membered to 12-membered heteroaromatic bicyclic ring system, OR', Si(R') 3 ,
  • the structural unit Has a structure selected from the following group:
  • the L 1 group is selected from the following structure: O, S; the L 3 group is selected from the following structure: O, NH, S.
  • the selected structure of the L 1 group is O; the selected structure of the L 3 group is O.
  • the structural unit Has a structure selected from the following group:
  • the G group has a structure selected from the group consisting of no, halogen, cyano, CF 3 , methyl, and N-methylformamide.
  • the structural unit Has a structure selected from the following group:
  • the G group has a structure selected from the group consisting of none, halogen, cyano, CF 3 , OCF 3 , alkyl or alkoxy, and N-methylformamide.
  • It has a structure selected from the group consisting of -CH 2 -, -CH 2 CH 2 -.
  • It is -CH 2 -.
  • the compound is selected from the following group:
  • the compound is selected from the following group:
  • the present invention provides an agricultural composition comprising: 0.001-99.99 wt% of the compound described in the first aspect, or an optical isomer, cis-trans isomer, or agrochemical Acceptable salts, or their combination; and agrochemically acceptable carriers and/or excipients.
  • the present invention provides the use of the compound of the first aspect, or the optical isomer, cis-trans isomer, or agrochemically acceptable salt of the compound, or the agricultural composition of the second aspect , which is characterized by being used for killing insects or for preparing insecticide compositions.
  • the composition is used to kill or prevent agricultural and forestry pests, especially Hemiptera pests.
  • the present invention provides a method for preparing the compound described in the first aspect, or an optical isomer, cis-trans isomer, or agrochemically acceptable salt of the compound, characterized in that:
  • LG is a leaving group, and the other groups are defined as described in claim 1.
  • the method further includes the step of optionally resolving the obtained compound into corresponding optical isomers or cis-trans isomers.
  • C 1-6 alkyl refers to a straight or branched chain alkyl group having 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl Group, tert-butyl group, or similar group.
  • C 2-6 alkenyl refers to a straight or branched chain alkenyl group having 2-6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, or similar groups.
  • C 2-6 alkynyl refers to a straight-chain or branched alkynyl group having 2-6 carbon atoms, such as ethynyl, propynyl, or the like.
  • C 3-7 cycloalkyl refers to a cyclic alkyl group having 3-7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or the like.
  • C 5-7 cycloalkenyl refers to a cyclic alkenyl group with 5-7 carbon atoms and one or more double bonds, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, 1 ,3-cyclohexadienyl, 1,4-cyclohexadienyl, or similar groups.
  • C 1-4 alkoxy refers to a straight or branched alkoxy group having 1-4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isobutoxy, sec-butoxy, tert-butoxy, or similar groups.
  • halogen refers to fluorine, chlorine, bromine, or iodine.
  • halogenated refers to a group substituted with the same or different one or more of the aforementioned halogen atoms, such as trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, or similar groups.
  • ring refers to a carbocyclic or heterocyclic ring.
  • heterocyclic ring means that at least one of the atoms forming the heterocyclic ring skeleton is not carbon but is nitrogen, oxygen or sulfur. Generally, the heterocycle contains no more than 4 nitrogens, no more than 2 oxygens, and/or no more than 2 sulfurs. Unless otherwise specified, the heterocyclic ring may be a saturated, partially unsaturated or fully unsaturated ring. In a specific embodiment, the term “ring system” refers to a fused ring in which two or more rings are joined together.
  • 5-membered or 6-membered heterocyclic group refers to a five-membered or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, such as pyridyl, thiazolyl, isothiazolyl, thiophene Group, furanyl, pyrrolyl, pyrazolyl, pyrimidinyl, tetrahydrofuranyl, 4,5-dihydrothiazol-2-yl, 2-cyanoimino-4-oxo-1,3-thiazolidine-3 -Group, 2-cyanoimino-4-oxo-1,3-thiazin-3-yl, oxazolyl, isoxazolyl, 1H-tetrazolyl, 1H-1,2,3- Triazolyl, 4H-1,2,4-triazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazol
  • heterocyclic ring system refers to a ring system in which at least one ring in the ring system is a heterocyclic ring.
  • heterocyclic ring system refers to a system in which at least one ring in the ring system is an aromatic ring.
  • the term "8- to 12-membered heteroaromatic bicyclic ring system” or “8 to 14-membered heteroaromatic bicyclic or tricyclic ring system” can be selected from the following group: benzofuran, benzo[b] Thiophene, indole, quinoline, isoquinoline, 1H-indazole, 1H-benzo[d]imidazole, benzo[d]thiazole, benzo[d]oxazole, benzo[d]isoxazole, Benzo[d][1,2,3]thiadiazole, 2,3-dihydroimidazo[1,2-a]pyridine, quinazoline, quinoxaline, cinnoline, phthalazine, 1,8 -Naphthyridine, 4,5,6,7-tetrahydrobenzo[b]thiophene, benzo[b]thiophene-1,1-dioxane, 8H-indeno
  • alkyl refers to a group formed by missing one hydrogen atom in an alkane molecule
  • alkylene refers to a group formed by missing two hydrogen atoms in an alkane molecule.
  • alkenylene alkynylene
  • cycloalkylene cycloalkenylene
  • phenylene naphthylene
  • heterocyclylene or cycloalkenylene
  • the groups of the present invention can be substituted by substituents selected from the following group: halogen, cyano, nitro, hydroxy, C 1 -6 alkyl, C 1-6 haloalkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 2-6 haloalkynyl, hydroxyl, hydroxyl C 1- 4 alkyl, OR ', Si (R' ) 3, NR'R ", C (O) R ', C (O) OR', C (O) NR'R", SR ', S (O) mR ', S(O) 2 NR'R”, OC(O)R', OC(O)NR'R”, OS(O) 2 R', OS(O) 2 NR'R”, N(R” )C(O)R', NCH 2 R', N(R”)C(O)NR
  • Inert solvents refer to various solvents that do not react with the raw materials, including various linear, branched or cyclic alcohols, ethers or ketones, alkyl halides, 1,4-dioxane, acetonitrile, tetrahydrofuran, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc.
  • the compounds of the present invention may contain one or more asymmetric centers, and therefore appear as racemates, racemic mixtures, single enantiomers, diastereomeric compounds and single diastereomers.
  • the asymmetric centers that can exist depend on the nature of the various substituents on the molecule. Each such asymmetric center will independently produce two optical isomers, and all possible mixtures of optical isomers and diastereomers and pure or partially pure compounds are included within the scope of the present invention.
  • the present invention includes all isomeric forms of the compounds.
  • compound of the present invention refers to the compound of the present invention, its optical isomers, cis-trans isomers or agrochemically acceptable salts, which It has significantly improved insecticidal activity and expanded insecticidal spectrum.
  • the compound of the present invention is a compound represented by the general formula (I) or its optical isomer, cis-trans isomer or agrochemically acceptable salt:
  • the compound of the present invention has the structure shown in the following formula II:
  • the compound has the structure shown in the following formula III:
  • the structural unit Has a structure selected from the following group:
  • the structural unit Has a structure selected from the following group:
  • the structural unit Has a structure selected from the following group:
  • the compound of the present invention is selected from the following group:
  • the compound of the present invention is represented by the following formula:
  • agrochemically acceptable salt means that the anion of the salt is known and acceptable when it forms a pharmaceutically acceptable salt of an insecticide.
  • the salt is preferably water-soluble.
  • Suitable acid addition salts formed from compounds of formula I include salts formed with inorganic acids, such as hydrochloride, phosphate, sulfate, and nitrate; and include salts formed with organic acids, such as acetate, benzyl Acid salt.
  • aromatic ether compounds are more suitable for eggs or larvae, but may have weaker effects on adults.
  • the inventors discovered that the aromatic ether compound of the present invention is not only suitable for eggs or larvae, but also has excellent insecticidal activity against adults.
  • the active substance of the present invention can be used to control and eliminate a wide range of agricultural and forestry plant pests, stored grain pests, public health pests, and pests that endanger animal health.
  • insecticide is a general term for substances that have the effect of controlling all the above-mentioned pests.
  • the compound of the present invention can be used to control and eliminate a wide range of pests, including Sucking insects, biting insects and other plant parasites, stored cereal pests and sanitary pests that cause health hazards.
  • pests examples include as follows: Coleopteran insects: Sitophilus zeamais, Tribolium castaneum (Herbsts), Potato ladybug (Henosepilach navigintioctomaculata), Agriotes fuscicollis Miwa, Square-headed green beetle, potato leaf A (Monochamusalternatus Hope), Echinocnemussquameus Billberg, Rice Weevil (Echinocnemusbipunctaus), Rice Water Weevil, Brown Powder Stupid.
  • Lepidopteran insects Lymantria dispar, Malacosoma neustriatestacea Motschulsky., Spodoptera litura, Spodoptera exigua, Chilo suppressalis, Corn borer, Pink leaf borer, Cotton roll moth, Chestnut scroll moth, Agrotisfucosa (Agrotisfucosa), wax moth, plutella xylostella, orange lore moth.
  • Hemipteran insects Nephotettixcincticeps, Nilaparvatalugens, Laodelphaxstriatellus, Bemisiatabaci, Mealycoccus kangii, Unaspisyanonensis, Myzuspersicae , Apple aphid, cabbage aphid (Brevicorynebrassicae), radish aphid (Lipaphiserysimipseudobrassicae), pear aphid (Stephanitis nashi Esaki et Takeya), Nazara pests, bed bugs, greenhouse whitefly, and Psylle SPP.
  • Orthoptera insects German cockroach (B.gormanicaLinne), American cockroach (P.Americana Linne), African mole cricket (Gryllotalpa africanaPalisot et Beauvois.), and Asian migratoria (Locus migratoria).
  • Isoptera insects house termite (Coptotermesformosanus).
  • Diptera insects housefly (Musca do mesticalinnacus), Aedes aegypti (Aedes aegypti), species fly, Culex mosquito, Anopheles sinensis (Anopheles sinensis Wiedemann), and Culex trispermum, Tetranychuscinnabarinus ).
  • the compound of the present invention has specific effects on piercing and sucking mouthparts, such as whitefly, scale insect, diamondback moth, beet armyworm, psyllid psyllid, thrips and the like.
  • the compound of the present invention has excellent insecticidal activity against thrips, preferably Thripspalmi and Bemisia tabaci.
  • active compounds can be made into conventional preparations, such as solutions, emulsions, suspensions, powders, granules, foams, pastes, aerosols; especially soluble solid and liquid preparations with good environmental compatibility, such as water Dispersible granules, water solvents and water emulsions, ultra-low-volume preparations, etc., natural and synthetic materials impregnated with active substances, microcapsules in polymers, coating compounds for seeds, and together with combustion devices Preparations used, such as smoking cartridges, smoking cans and smoking trays, as well as ULV cold mist and hot mist preparations.
  • compositions can be produced by known methods, for example, by mixing the active compound with an extender, which is a liquid or liquefied gas or solid diluent or carrier, and optionally surfactants, emulsifiers and/or Dispersant and/or foam former.
  • an extender which is a liquid or liquefied gas or solid diluent or carrier
  • surfactants for example, when water is used as an extender, organic solvents can also be used as additives.
  • organic solvents can also be used as additives.
  • a liquid solvent When a liquid solvent is used as a diluent or carrier, it is basically suitable, such as: aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride Or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffin, such as mineral oil fractions; alcohols, such as ethanol or ethylene glycol and their ethers and lipids; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl Ketone or cyclohexane; or uncommon polar solvents, such as dimethylformamide and dimethylsulfoxide, and water.
  • aromatic hydrocarbons such as xylene, toluene or alkyl naphthalene
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenz
  • the diluent or carrier of liquefied gas refers to a liquid that will become a gas at normal temperature and pressure, such as aerosol propellants, such as halogenated hydrocarbons, butane, propane, nitrogen, and carbon dioxide.
  • the solid carrier can be ground natural minerals, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicate. .
  • the solid carrier for the particles is crushed and classified natural stone, such as calcite, marble, pumice, sepiolite and dolomite, as well as particles synthesized from inorganic and organic coarse powder, and organic materials such as sawdust, coconut shell, Corn on the cob and tobacco stalk particles.
  • Nonionic and anionic emulsifiers can be used as emulsifiers and/or foam formers.
  • polyoxyethylene-fatty acid esters polyoxyethylene-fatty alcohol ethers, such as alkyl aryl polyethylene glycol ethers, alkyl sulfonate esters, alkyl sulfate esters, aryl sulfonate esters and white Protein hydrolysate.
  • Dispersants have been coated, such as lignin sulfite waste liquid and methyl cellulose.
  • Binders such as carboxymethyl cellulose and natural and synthetic polymers in powder, granule or emulsion form, such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulation.
  • Colorants such as inorganic fuels such as iron oxide, cobalt oxide and Prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes; and trace nutrients such as iron, manganese, boron, copper, cobalt, aluminum And zinc salt, etc.
  • compositions usually contain 0.1-95% by weight of active compound, preferably 0.5-90%.
  • the active compounds of the present invention can be prepared as a mixture with other active compounds and exist in their commercial formulations or use dosage forms prepared from these formulations.
  • These other active compounds are insecticides, baits, fungicides, and pesticides.
  • Insecticides are encapsulated, such as phosphate esters, carbamates, pyrethroids, chlorinated hydrocarbons, benzoylureas, sandworm toxins, and substances produced by microorganisms, such as abamectin.
  • these active compounds of the present invention can also be prepared as a mixture with synergists and present in their commercial preparations into use forms prepared from these preparations.
  • the synergist is a compound that enhances the effect of the active compound. Since the active compound is active, it is not necessary to add a synergist.
  • the concentration of the active compound in the dosage form prepared from a commercial preparation can vary within a wide range.
  • the concentration of the active compound in the dosage form can be from 0.0000001 to 100% (by weight of the active compound), preferably between 0.0001 and 1%.
  • the present invention provides chemical insecticides with novel structures with high efficiency, low toxicity and good environmental compatibility
  • the compound of the present invention has particularly killing activity against adults.
  • the compound of the present invention has a good control effect on Hemiptera pests.
  • Example 32 Indoor insecticidal activity test of the compound of the present invention
  • Operation method Weigh 100mg sample, then dissolve it in 9ml N,N-dimethylformamide and 1ml Triton X-100, prepare 104PPM mother liquor and store at 4°C.
  • seedling dip method (young nymphs of brown planthopper and Laodelphax striatellus)
  • the Nanjing 5055 rice seedlings which are about one week after germination, are immersed in a series of chemical solutions (1.25, 2.5, 5, 10, 20, 40, 80 and 160 PPM for each chemical) together with their roots, and taken out Then it was placed in a disposable plastic cup, and the roots of the rice seedlings were wrapped with the moist absorbent paper placed in the cup in advance, and the second instar Nilaparvata lugens nymphs were inserted 5 minutes later, and the treatment without the original medicine was used as a control.
  • a series of chemical solutions (1.25, 2.5, 5, 10, 20, 40, 80 and 160 PPM for each chemical) together with their roots, and taken out Then it was placed in a disposable plastic cup, and the roots of the rice seedlings were wrapped with the moist absorbent paper placed in the cup in advance, and the second instar Nilaparvata lugens nymphs were inserted 5 minutes later, and the treatment without the original medicine was used as a control.
  • the bioassay is carried out in an artificial climate room, temperature: 27 ⁇ 1°C, photoperiod: 14L: 10D.
  • Test agent 10% compound 1 and 15, the control agent is 100 g/L pyriproxyfen EC, 70% imidacloprid dispersible granules WG
  • Spraying equipment MH-D16-3 intelligent electric sprayer is used for spraying, with a nozzle diameter of 0.7mm
  • the first application is the early flowering period of cucumber, the 12-13 leaf stage, and the thrips are the adult and nymph occurrence period. The occurrence is moderately heavy, and the application is repeated 7 days apart.
  • Use capacity 750 liters/ha of water used in the middle of the crop is converted into a corresponding multiple, and sprayed to the surface of the leaf droplets.
  • Aa, Ab, and Aab are the expression methods for whether the difference is significant, and the difference of Aa is greater than that of Aab and that of Ab.
  • Test agent 10% compound 1 and 15, the control agent is 100 g/L pyriproxyfen EC, 70% imidacloprid dispersible granules WG
  • Spraying equipment MH-D16-3 intelligent electric sprayer is used for spraying, with a nozzle diameter of 0.7mm
  • the first application was the early flowering period of cucumber, 15-16 leaf stage, Bemisia tabaci is the adult occurrence stage, and no adults and nymphs were seen on the back of the leaves. The occurrence is moderate to severe, and the second application is 7 days apart.
  • the components were ground together in a sand mill until the solid particles fell below 5 microns.
  • the resulting viscous suspension can be used directly, but it can also be used after emulsification in water.
  • the components were ground together in a ball mill until the solid particles fell below about 10 microns.
  • the aqueous suspension can be used directly.
  • Edible baits can be dispersed to places infested by sanitary pests, such as homes or industrial places, such as kitchens, hospitals, or stores, or outdoor areas, to control pests through oral intake.
  • the plant seeds or plant leaves and/or plant fruits or plants where the plants are growing or are expected to grow are applied by dipping or oral administration in drinking water to control pests.

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Abstract

本发明公开了一种具有杀虫活性的芳(杂)环醚类化合物，或其光学异构体、顺反异构体或农药学上可接受的盐。本发明还公开了包含上述化合物的农用组合物。本发明的化合物结构新颖、具有良好的杀虫杀卵活性，并且具有高效、低毒和环境相容性好等优点。（I）

Description

具有杀虫活性的芳(杂)环醚类化合物及其制备方法和用途 技术领域
本发明涉及农药领域，更具体的涉及芳杂环醚类化合物，其制备方法及用途。
背景技术
芳香醚类化合物很早就用作杀虫剂，作用机理是扰乱昆虫生长，属于保幼激素类似物的新型杀虫剂，具有内吸转移活性，低毒，持效期长，对作物安全，对鱼类低毒，对生态环境影响小等特点。其独特的作用方式及显著的防治效果，被认为是杀虫综合治理的有效手段之一，成为杀虫剂研究创制的热点领域。
农业上对害虫的防治手段有很多，目前以化学防治为主。广泛应用的化学杀虫剂主要部分有机磷或氨基甲酸酯，拟除虫菊酯类农药，如硫线磷、苯线磷、噻唑磷、涕灭威和克百威、氯氟氰菊酯等，对人类与其它非靶标生物的安全性低，对土壤、水源和农产品也会造成不同程度的污染，广泛使用的有新烟碱类杀虫剂，鱼尼丁受体抑制剂等。由于各类杀虫剂被过量、频繁使用，已经引起了严重的抗药性，使得害虫的防治难度日益增加。
此外，昆虫成虫由于身体各部位已发育完成，具有生殖能力，其对农业杀虫剂的抵抗力最强，对农作物的影响也最大。特别是保幼激素类似物作为杀虫剂对于成虫的效果往往不大如意。
因此，寻找高效、低毒和环境相容性好的结构新颖的化学杀虫剂成为本领域迫切需要解决的技术问题。
发明内容
本发明的目的是提供一种高效、低毒和环境相容性好的结构新颖的化学杀虫剂，特别是对昆虫成虫具有杀虫活性的芳(杂)环醚新化合物。
在第一方面，本发明提供一种具有通式(I)所示结构的化合物或其光学异构体、顺反异构体或农药学上可接受的盐：
Figure PCTCN2020074115-appb-000001
式中：
环α为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环基；
环β为取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的5元或6元亚杂环基、或取代或未取代的8元至12元亚杂芳二环基；
环γ为取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8 元至12元杂芳二环基；
所述的环α、环β和环γ的取代基选自下组：卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷基或烷氧基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环基；
L 1、L 3可以相同或不同，且各自独立选自下组：-NR’-、-O-、-S-；
L 2为选自下组的基团：-CR’R”-，R’R”可以相同或不同；
n为1-8的整数；优选1-5的整数；更优选1-3的整数；最优选1；
G为位于环γ任意一个或多个(优选1-3个)位置上各自独立的取代基，且G选自下组：卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O) nR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”；
所述取代是指被选自下组的一个或多个基团所取代：卤素、氰基、硝基、羟基、C 1-6烷基、C 1-6烷氧基、C 1-6卤代烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基、羟基、羟基C 1-4烷基、R’、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O) mR’、S(O) 2NR’R”、OC(O)R、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R’)C(O)R’、N(R’)C(O)NR’R”、N(R’)S(O) 2R’或N(R’)S(O) 2NR’R”，或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、取代或未取代的6-10元芳基、取代或未取代的5元或6元饱和或不饱和杂环基、或取代或未取代的8元至12元杂芳二环环系；其中，环烷基、环烯基、芳基、杂环基、杂芳二环环系上的取代是被选自下组的一个或多个基团所取代：氧基(＝O)、卤素、氰基、硝基、羟基、C 1-6烷基或环烷基、C 1-6卤代烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基、羟基、羟基C 1-4烷基；
其中，R’、R”各自独立地为H、C 1-6烷基、C 3-6环烷基、C 1-6卤代烷基、C 3-6卤代环烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基，或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元饱和或不饱和杂环基、或取代或未取代的8元至12元杂芳二环环系；其中，R’、R”上的取代基是选自下组的一个或多个基团：氧基(＝O)、卤素、氰基、硝基、羟基、C 1-6烷基或环烷基、C 1-6卤代烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基、羟基、羟基C 1-4烷基。
在具体的实施方式中，所述的化合物具有如下式II所示的结构：
Figure PCTCN2020074115-appb-000002
式中：
X 1、X 2、X 3各自为C(Ra)、N(Ra)或S；X 1、X 2、X 3不同时为S；
X 4、X 5、X 6各自为C(Ra)、N(Ra)；X 4、X 5、X 6可以相同或不同；
L 1、L 3可以相同或不同，并且各自为O、NH、S；
L 2为CH 2；
n为1、2或3；
m为0或1；
Ra选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R')S(O) 2NR’R”；
Rb选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”。
在具体的实施方式中，所述的化合物具有如下式Ⅲ所示的结构：
Figure PCTCN2020074115-appb-000003
式中：
V 1、V 2、V 3、V 4、V 5各自为C(Ra)、N(Ra)或S；V 2、V 3、V 4不同时为S或N；
X 4、X 5、X 6可以相同或不同，并且各自为C(Ra)、N(Ra)；
L 1、L 3可以相同或不同，并且各自为O、NH、S；
L 2为CH 2；
n为1、2或3；
m各自为0或1；
Ra选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未 取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”；
Rb选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”。
在具体的实施方式中，所述的结构单元
Figure PCTCN2020074115-appb-000004
具有选自下组的结构：
Figure PCTCN2020074115-appb-000005
在优选的实施方式中，所述的L 1基团选自下组的结构：O，S；所述的L 3基团选自下组的结构：O，NH，S。
在优选的实施方式中，所述的L 1基团所选结构为O；所述的L 3基团所选结构为O。
在具体的实施方式中，所述的结构单元
Figure PCTCN2020074115-appb-000006
具有选自下组的结构：
Figure PCTCN2020074115-appb-000007
在优选的实施方式中，所述的G基团具有选自下组的结构：无、卤素、氰基、CF 3、甲基、N-甲基甲酰胺基。
在具体的实施方式中，所述的结构单元
Figure PCTCN2020074115-appb-000008
具有选自下组的结构：
Figure PCTCN2020074115-appb-000009
在优选的实施方式中，所述的G基团具有选自下组的结构：无、卤素、氰基、CF 3、OCF 3，烷基或烷氧基、N-甲基甲酰胺基。
在优选的实施方式中，
Figure PCTCN2020074115-appb-000010
具有选自下组的结构：-CH 2-、-CH 2CH 2-。
在优选的实施方式中，
Figure PCTCN2020074115-appb-000011
为-CH 2-。
在具体的实施方式中，所述的化合物选自下组：
Figure PCTCN2020074115-appb-000012
Figure PCTCN2020074115-appb-000013
Figure PCTCN2020074115-appb-000014
Figure PCTCN2020074115-appb-000015
Figure PCTCN2020074115-appb-000016
Figure PCTCN2020074115-appb-000017
Figure PCTCN2020074115-appb-000018
Figure PCTCN2020074115-appb-000019
Figure PCTCN2020074115-appb-000020
Figure PCTCN2020074115-appb-000021
Figure PCTCN2020074115-appb-000022
Figure PCTCN2020074115-appb-000023
Figure PCTCN2020074115-appb-000024
Figure PCTCN2020074115-appb-000025
在优选的实施方式中，所述的化合物选自下组：
Figure PCTCN2020074115-appb-000026
在第二方面，本发明提供一种农用组合物，其包含：0.001-99.99wt％的第一方面所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐、或者它们的组合；以及农药学上可接受的载体和/或赋形剂。
在第三方面，本发明提供第一方面所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐或第二方面所述农用组合物的用途，其特征在于，用于杀虫或用于制备杀虫剂组合物。
在优选的实施方式中，所述的组合物用于杀灭或预防农林害虫，特别是半翅目害虫。
在第四方面，本发明提供第一方面所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐的制备方法，其特征在于:
Figure PCTCN2020074115-appb-000027
在惰性溶剂中，用
Figure PCTCN2020074115-appb-000028
反应，得到式II化合物；
在惰性溶剂中，用
Figure PCTCN2020074115-appb-000029
反应，得到式Ⅲ化合物；
其中，LG为离去基团，其它各基团的定义如权利要求1中所述。
在优选的实施方式中，所述方法还包括任选将所得化合物拆分成相应的光学异构体或顺反异构体的步骤。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
具体实施方式
本发明人经过长期而深入的研究，意外地发现并合成了一系列结构新颖、具有显著杀虫活性的芳(杂)环醚化合物。在此基础上，发明人完成了本发明。
基团定义
术语“C 1-6烷基”是指具有1-6个碳原子的直链或支链烷基，例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、或类似基团。
术语“C 2-6烯基”指具有2-6个碳原子的直链或支链的烯基，例如乙烯基、烯丙基、1-丙烯基、异丙烯基、1-丁烯基、2-丁烯基、或类似基团。
术语“C 2-6炔基”是指具有2-6个碳原子的直链或支链的炔基，例如乙炔基、丙炔基、或类似基团。
术语“C 3-7环烷基”指具有3-7个碳原子的环状烷基，例如环丙基、环丁基、环戊基、环己基、环庚基、或类似基团。
术语“C 5-7环烯基”指具有5-7个碳原子的、具有一个或多个双键的环状烯基，例如环戊烯基、环己烯基、环庚烯基、1,3-环己二烯基、1,4-环己二烯基、或类似基团。
如本文所用，术语“C 1-4烷氧基”指具有1-4个碳原子的直链或支链烷氧基，例如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、或类似基团。
术语“卤素”指氟、氯、溴、或碘。术语“卤代的”指被相同或不同的一个或多个上述卤原子取代的基团，例如三氟甲基、五氟乙基、七氟异丙基、或类似基团。
术语“环”或“环系”指碳环或杂环。术语“杂环”指形成所述杂环骨架的原子中至少一个原子不是碳，为氮、氧或硫。通常，杂环包含不超过4个氮、不超过2个氧和/或不超过2个硫。除非另外指明，杂环可以是饱和的、部分不饱和的或完全不饱和的环。在具体的实施方式中，术语“环系”指两个或更多个环并在一起的稠环。
本文所用的术语“5元或6元杂环基”指含一个或多个选自氮、氧或硫的杂原子的五元或六元环，例如吡啶基、噻唑基、异噻唑基、噻吩基、呋喃基、吡咯基、吡唑基、嘧啶基、四氢呋喃基、4,5-二氢噻唑-2-基、2-氰基亚胺基-4-氧-1,3-噻唑烷-3-基、2-氰基亚胺基-4-氧-1,3-噻嗪烷-3-基、噁唑基、异噁唑基、1H-四唑基、1H-1,2,3-三唑基、4H-1,2,4-三唑基、1,2,3-噻二唑基、1,2,4-噻二唑基、1,3,4-噻二唑基、1,2,4-噁二唑基、1,2,5-噁二唑基、1,3,4-噁二唑基或四唑基等。
术语“杂环环系”指环系中的至少一个环是杂环的环系。类似地，术语“杂芳环环系”指环系中的至少一个环为芳族环的体系。
如本文所用，术语“8元至12元杂芳二环环系”或“8元至14元杂芳二环或三环环系”可选自下组：苯并呋喃、苯并[b]噻吩、吲哚、喹啉、异喹啉、1H-吲唑、1H-苯并[d]咪唑、苯并[d]噻唑、苯并[d]噁唑、苯并[d]异噁唑、苯并[d][1,2,3]噻二唑、2,3-二氢咪唑并[1,2-a]吡啶、喹唑啉、喹喔啉、噌啉、酞嗪、1,8-萘啶、4,5,6,7-四氢苯并[b]噻吩、苯并[b]噻吩-1,1-二氧烷、8H-茚并[2,1-b]噻吩、7,8-二氢-6H-环戊[4,5]噻吩并[2,3-d]嘧啶、3,5,6,7-四氢-4H-环戊[4,5]噻吩并[2,3-d]嘧啶-4-酮、螺[吲哚啉-3,2’-[1,3]二氧戊环]-2-酮、螺[吲哚啉-3,2’-[1,3]二氧六环]-2-酮、或吲哚啉-2,3-二酮等。
术语“烷基”是指烷烃分子中少掉一个氢原子而成的基团；术语“亚烷基”是指烷烃分子中少掉两个氢原子而成的基团。类似地，“亚烯基”、“亚炔基”、“亚环烷基”、“亚环烯基”、“亚苯基”、“亚萘基”、“亚杂环基”或“亚杂芳二环或三环环系”的定义类似。
本发明所述的基团除非特别说明是“取代或未取代的”，否则本发明的基团均可被选自下组的取代基所取代：卤素、氰基、硝基、羟基、C 1-6烷基、C 1-6卤代烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基、羟基、羟基C 1-4烷基、OR’、Si(R’) 3、NR’R"、C(O)R’、C(O)OR’、C(O)NR’R"、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”等，其中，所述的R’、R”的定义同前，m为1或2。
惰性溶剂指的是不与原料发生反应的各种溶剂，包括各种直链、支链或环状的醇，醚或酮，卤代烷，1,4-二氧六环，乙腈，四氢呋喃，N,N-二甲基甲酰胺(DMF)，二甲基亚砜(DMSO)等。
本发明的化合物可以含有一个或多个不对称中心，并因此以消旋体、外消旋混合物、单一对映体、非对映异构体化合物和单一非对映体的形式出现。可以存在的不对称中心，取决于分子上各种取代基的性质。每个这种不对称中心将独立地产生两个旋光异构体，并且所 有可能的旋光异构体和非对映体混合物和纯或部分纯的化合物包括在本发明的范围之内。本发明包括化合物的所有异构形式。
本发明的化合物及其杀虫活性
术语“本发明的化合物”、“本发明的活性物质”或“本发明的活性化合物”是指本发明化合物、其光学异构体、顺反异构体或农药学上可接受的盐，其具有显著提高的杀虫活性，以及扩大的杀虫谱。
具体地说，本发明的化合物是通式(I)所示的化合物或其光学异构体、顺反异构体或农药学上可接受的盐：
Figure PCTCN2020074115-appb-000030
在优选的实施方式中，本发明的化合物具有如下式II所示的结构：
Figure PCTCN2020074115-appb-000031
在进一步优选的实施方式中，所述的化合物具有如下式Ⅲ所示的结构：
Figure PCTCN2020074115-appb-000032
其中，结构单元
Figure PCTCN2020074115-appb-000033
具有选自下组的结构：
Figure PCTCN2020074115-appb-000034
所述结构单元
Figure PCTCN2020074115-appb-000035
具有选自下组的结构：
Figure PCTCN2020074115-appb-000036
所述结构单元
Figure PCTCN2020074115-appb-000037
具有选自下组的结构：
Figure PCTCN2020074115-appb-000038
在优选的实施方式中，本发明的化合物选自下组：
Figure PCTCN2020074115-appb-000039
在优选的实施方式中，本发明的化合物如下式所示：
Figure PCTCN2020074115-appb-000040
本文所用的术语“农药学上可接受的盐”意指该盐的阴离子在形成杀虫剂药学上可接受的盐时为已了解的和可接受的。该盐较好的为水溶性的。合适的、由式Ⅰ化合物形成的酸加成盐包括有无机酸形成的盐，例如盐酸盐、磷酸盐、硫酸盐、硝酸盐；及包括有机酸形成的盐，如醋酸盐，苯甲酸盐。
按照本领域的常规理解，芳香醚类化合物更多适用于卵或幼虫，但对于成虫影响可能较弱。然而，本发明人发现本发明的芳香醚类化合物不仅适用于卵或幼虫，对成虫也具备优异的杀虫活性。
本发明的活性物质能用作控制和消灭广泛的农林植物害虫、贮藏谷类的害虫、公共卫生害虫以及危害动物健康的害虫等。在本说明书中，“杀虫剂”是具有防治上述提到的所有害虫的作用的物质的统称。本发明的化合物能用作控制和消灭广泛的害虫，包过吸式虫(Sucking insects)，刺式虫(biting insects)和其它植物寄生虫，贮藏谷类的害虫和引起健康危害的卫生害 虫。
害虫的例子如下：鞘翅目昆虫：玉米象(Sitophilus zeamais)，赤拟谷盗(Triboliumcastaneum(Herbsts))，马铃薯瓢虫(Henosepilachnavigintioctomaculata)，细胸叩头虫(Agriotesfuscicollis Miwa)，方头绿金龟，马铃薯叶甲(Monochamusalternatus Hope)，稻根象(Echinocnemussquameus Billberg)，稻象虫(Echinocnemusbipunctaus)，稻水象甲，褐粉蠢。鳞翅目昆虫：舞毒蛾(Lymantria dispar)，天幕毛虫(Malacosoma neustriatestacea Motschulsky.)，斜纹夜蛾，甘兰夜蛾，二化螟，玉米螟，粉斑螟，棉卷蛾，栗子小卷蛾，小地老虎(Agrotisfucosa)，大蜡螟，菜蛾，桔潜蛾。半翅目昆虫：黑尾叶蝉(Nephotettixcincticeps)，稻褐飞虱(Nilaparvatalugens)，灰飞虱(Laodelphaxstriatellus)，烟粉虱(Bemisiatabaci)，康氏粉蚧，矢尖蚧(Unaspisyanonensis)，桃蚜(Myzuspersicae)，苹蚜，甘蓝蚜虫(Brevicorynebrassicae)，萝卜蚜(Lipaphiserysimipseudobrassicae)，梨班网蝽(Stephanitis nashi Esaki et Takeya)，Nazara属害虫，臭虫，温室白粉虱，和虱属的害虫(Psylle SPP.)。直翅目昆虫：德国小蠊(B.gormanicaLinne)，美国大蠊(P.Americana Linne)，非洲蝼蛄(Gryllotalpa africanaPalisot et Beauvois.)，和亚洲飞蝗(Locus migratoria)。等翅目昆虫：家白蚁(Coptotermesformosanus)。双翅目昆虫：家蝇(Musca do mesticalinnac us)，埃及伊蚊(Aedes aegypti)，种蝇，库蚊，中华按蚊(Anopheles sinensis Wiedemann)，和三带啄库蚊，螨类红蜘蛛(Tetranychuscinnabarinus)。
本发明涉及的化合物尤其对刺吸式、刮吸式口器害虫，如烟粉虱、介壳虫、小菜蛾、甜菜夜蛾、梨黄木虱、蓟马等有特效。
在优选的实施方式中，本发明人化合物对蓟马，优选棕榈蓟马(Thripspalmi)和烟粉虱等具备优异的杀虫活性。
这些活性化合物可做成常规的制剂，例如溶液剂，乳剂，混悬剂，粉剂，颗粒剂，泡沫剂，糊剂，气雾剂；特别是环境相容性好的可溶性固体和液体制剂，如水分散粒剂，水溶剂和水乳剂，超低容量制剂等，用活性物质浸渍的天然的和合成的材料，在多聚物中的微胶囊，用于种子的包衣复方，和与燃烧装置一块使用的制剂，例如烟熏药筒，烟熏罐和烟熏盘，以及ULV冷雾和热雾制剂。这些制剂可用已知的方法生产，例如，将活性化合物与扩充剂混合，这些扩充剂就是液体的或液化气的或固体的稀释剂或载体，并可任意选用表面活性剂即乳化剂和/或分散剂和/或泡沫形成剂。例如在用水作扩充剂时，有机溶剂也可用作助剂。
用液体溶剂作稀释剂或载体时，基本上是合适的，如：芳香烃类，例如二甲苯，甲苯或烷基萘；氯化的芳香或氯化的脂肪烃类，例如氯苯，氯乙烯或二氯甲烷；脂肪烃类，例如环己烷或石蜡，例如矿物油馏分；醇类，例如乙醇或乙二醇以及它们的醚和脂类；酮类，例如丙酮，甲乙酮，甲基异丁基酮或环己烷；或不常用的极性溶剂，例如二甲基甲酰胺和二甲基亚砜，以及水。
就液化气的稀释剂或载体说，指的是在常温常压下将成为气体的液体，例如气溶胶推进剂，如卤化的烃类以及丁烷，丙烷，氮气和二氧化碳。
固体载体可用地面天然的矿物质，例如高岭土，粘土，滑石，石英，活性白土，蒙脱土，或硅藻土，和地面合成的矿物质，例如高度分散的硅酸，氧化铝和硅酸盐。供颗粒用的 固体载体是碾碎的和分级的天然告石，例如方解石，大理石，浮石，海泡石和白云石，以及无机和有机粗粉合成的颗粒，和有机材料例如锯木屑，椰子壳，玉米棒子和烟草梗的颗粒等。
非离子的和阴离子的乳化剂可用作乳化剂和/或泡沫形成剂。例如聚氧乙烯-脂肪酸酯类，聚氧乙烯-脂肪醇醚类，例如烷芳基聚乙二醇醚类，烷基磺酸酯类，烷基硫酸酯类，芳基磺酸酯类以及白蛋白水解产物。分散剂包过，例如木质素亚硫酸盐废液和甲基纤维素。
在制剂中可以用粘合剂，例如羧甲基纤维素和以粉末，颗粒或乳液形式的天然和合成的多聚物，例如阿拉伯胶，聚乙烯基醇和聚乙烯醋酸酯。
可以用着色剂例如无机燃料，如氧化铁，氧化钴和普鲁士蓝；有机染料，如偶氮染料或金属钛菁染料；和用痕量营养剂，如铁，猛，硼，铜，钴，铝和锌的盐等。
这些制剂通常含0.1-95％按重量计的活性化合物，最好是含0.5-90％。
本发明的这些活性化合物可与其他活性化合物制成一种混合物存在于它们的商品制剂中或从这些制剂制备的使用剂型中，这些其他的活性化合物为杀虫剂，饵剂，杀菌剂，杀螨剂，杀线虫剂，杀真菌剂，生长控制剂等。杀虫剂包过，例如磷酸酯类，氨基甲酸酯类，除虫菊酯类，氯化烃类，苯甲酰脲类，沙蚕毒素类以及由微生物产生的物质，如阿维菌素。
此外，本发明的这些活性化合物也可与增效剂制成一种混合物存在于它们的商品制剂中成从这些制剂制备的使用剂型中。增效剂时提高活性化合物作用的化合物，由于活性化合物本身有活性，也可不必加增效剂。从商品制剂制成使用剂型中的活性化合物的浓度可在广阔的范围内变动。使用剂型中的活性化合物的浓度可从0.0000001到100％(按活性化合物重量计)，最好在0.0001与1％之间。
本发明的主要优点包括：
1.本发明提供高效、低毒和环境相容性好的结构新颖的化学杀虫剂；
2.本发明化合物相对于二苯醚类保幼激素类似物对于成虫尤其具备杀灭活性；和
3.本发明化合物对于半翅目害虫防治效果好。
以下结合具体实施案例对本发明的技术方案进一步描述，但以下实施案例不构成对本发明的限制，所有依据本发明的原理和技术手段采用的各种施用方法，均属于本发明范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。
实施例1
2-氯-6-((4-苯氧基苯氧基)甲基)吡啶的合成(化合物1)
Figure PCTCN2020074115-appb-000041
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加 热回流带水，待水分带干净后，加入8.75g(0.054mol)2-氯-6-氯甲基吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体15.9g，纯度97％，收率95％。
GC-MS(m/s)M +311；
1H NMR(400MHz,DMSO)8.52(d,J＝4Hz,1H),7.95(d,J＝8Hz,1H),7.55(d,J＝8Hz,1H),7.36-7.32(m,2H),7.09-7.04(m,3H),7.02-6.99(m,2H),6.93-6.91(m,2H),5.14(s,2H)；
13C NMR(100MHz,DMSO)157.7,154.2,149.9,149.7,149.1,139.3,132.3,129.9,124.2,122.7,120.6,117.4,116.1,66.5
实施例2
4-(4-((6-氯吡啶-2-基)甲氧基)苯氧基)-2-氟苯腈的合成(化合物2)
Figure PCTCN2020074115-appb-000042
将10g(0.043mol)2-氟-4-(4-羟基苯氧基)苯腈加入到50mL环己烷中，加入3.1g(0.056mol)氢氧化钾，加热回流带水，待水分带干净后，加入6.96g(0.043mol)2-氯-6-氯甲基吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体12.9g，纯度97％，收率85％。
GC-MS(m/s)M +354；
1H NMR(400MHz,DMSO)8.25-7.95(m,2H),7.58-7.55(m,2H),7.47(s,1H),7.36-7.32(m,2H),6.95-6.92(m,3H),5.53(s,2H)；
13C NMR(100MHz,DMSO)162.9,160.3,156.3,152.1,151.0,149.3,137.8,133.5,122.9,121.3,119.8,117.6,114.0,113.8,106.3,105.5,77.3；
实施例3
2-氯-6-((4-(2,4-二氯苯氧基)苯氧基)甲基)吡啶的合成(化合物4)
Figure PCTCN2020074115-appb-000043
将10g(0.039mol)4-(2，4-二氯苯氧基)苯酚加入到50mL环己烷中，加入2.8g(0.056mol)氢氧化钾，加热回流带水，待水分带干净后，加入6.32g(0.043mol)2-氯-6-氯甲基吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体11.8g，纯度97％，收率80％。
GC-MS(m/s)M +378.9；
1H NMR(400MHz,DMSO)8.25(t,J＝8.0Hz,1H),7.95(d,J＝6.8Hz,1H),7.65(s,1H),7.56(d,J＝6.8Hz,1H),7.34-7.32(m,3H),7.02-6.95(m,3H),5.50(s,2H)；
13C NMR(100MHz,DMSO)156.3,152.1,151.0,150.0,137.8,130.1128.8,127.8,122.9,120.3,119.8,114.0,77.3；
实施例4
2-氯-6-((4-(3,4-二氟苯氧基)苯氧基)甲基)吡啶的合成(化合物6)
Figure PCTCN2020074115-appb-000044
将10g(0.045mol)4-(3，4-二氟苯氧基)苯酚加入到50mL环己烷中，加入2.8g(0.056mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.29g(0.045mol)2-氯-6-氯甲基吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体13.4g，纯度97％，收率86％。
GC-MS(m/s)M +347.0；
1H NMR(400MHz,DMSO)8.30-8.05(m,2H),7.60-7.57(m,2H),7.50(s,1H),7.39-7.35(m,2H),6.96-6.93(m,3H),5.58(s,2H)；
13C NMR(100MHz,DMSO)156.3,154.2,152.1,151.0,149.3,149.1,142.6,137.8,122.9,119.8,117.6,116.8,115.8,114.0,107.2,77.5；
实施例5
2-氯-6-((4-(4-氯苯氧基)苯氧基)甲基)吡啶的合成(化合物7)
Figure PCTCN2020074115-appb-000045
将10g(0.045mol)4-(4-氯苯氧基)苯酚加入到50mL环己烷中，加入2.8g(0.056mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.29g(0.045mol)2-氯-6-氯甲基吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体13.7g，纯度97％，收率88％。
GC-MS(m/s)M +345.0；
1H NMR(400MHz,DMSO)8.26(t,J＝8.0Hz,1H),7.95(d,J＝6.8Hz,1H),7.58-7.55(m,3H),7.46-7.44(m,2H),7.35-7.32(m,2H),6.95-6.93(m,2H),5.61(s,2H)；
13C NMR(100MHz,DMSO)156.3,155.1,152.1,151.0,149.3,137.8,129.6,127.4,122.9,119.8,118.9,117.6,114.0,77.5；
实施例6
2-氯-6-((4-(4-甲苯氧基)苯氧基)甲基)吡啶的合成(化合物8)
Figure PCTCN2020074115-appb-000046
将10g(0.05mol)4-(4-甲苯氧基)苯酚加入到50mL环己烷中，加入3.64g(0.065mol)氢氧化钾，加热回流带水，待水分带干净后，加入8.1g(0.045mol)2-氯-6-氯甲基吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体14.6g，纯度97％，收率90％。
GC-MS(m/s)M +325.1；
1H NMR(400MHz,DMSO)8.25(t,J＝8.0Hz,1H),7.94(d,J＝6.8Hz,1H),7.58-7.55(m,1H),7.35-7.32(m,2H),7.22-7.18(m,2H),6.95-6.86(m,4H),5.53(s,2H),2.34(s,3H)；
13C NMR(100MHz,DMSO)156.3,154.0,152.1,151.0,149.3,137.8,131.5,128.7,122.9,119.8,117.6,117.1,114.0,77.3,21.3；
实施例7
2-氯-6-((4-(4-硝基苯氧基)苯氧基)甲基)吡啶的合成(化合物11)
Figure PCTCN2020074115-appb-000047
将10g(0.043mol)4-(4-甲苯氧基)苯酚加入到50mL环己烷中，加入3.15g(0.065mol)氢氧化钾，加热回流带水，待水分带干净后，加入6.9g(0.045mol)2-氯-6-氯甲基吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体14.1g，纯度97％，收率92％。
GC-MS(m/s)M +356.1；
1H NMR(400MHz,DMSO)8.35(t,J＝8.0Hz,1H),7.98(d,J＝6.8Hz,1H),7.56-7.54(m,1H),7.37-7.34(m,2H),7.23-7.18(m,2H),6.96-6.88(m,4H),5.60(s,2H)； 13C NMR(100MHz,DMSO)157.3,155.0,153.2,152.3,149.6,138.8,131.6,128.8,123.2,119.6,117.5,117.3,114.2,77.6；
实施例8
2-氯-5-((4-苯氧基苯氧基)甲基)噻唑的合成(化合物15)
Figure PCTCN2020074115-appb-000048
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入9.07g(0.054mol)2-氯-5-氯甲基噻唑，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体16.5g，纯度97％，收率96％。
GC-MS(m/s)317,185,132,77；
1H NMR(400MHz,DMSO)7.8(s,1H),7.37-7.33(m,2H),7.10-7.04(m,3H),7.02-7.0(m,2H),6.95-6.93(m,2H),5.32(s,2H)；
13C NMR(100MHz,DMSO)157.7,153.7,150.9,150.2,140.9,137.1,129.9,122.7,120.5,117.5,116.3,62.2.
实施例9
4-(4-((2-氯噻唑-5-基)甲氧基)苯氧基)-3-氟苯腈的合成(化合物17)
Figure PCTCN2020074115-appb-000049
将10g(0.043mol)3-氟-4-(4-羟基苯氧基)苯腈加入到50mL环己烷中，加入2.68g(0.048mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.22g(0.043mol)2-氯-5-氯甲基噻唑，继续回流反应2小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体14.5g，纯度98％，收率96％。
GC-MS(m/s)360；
1H NMR(400MHz,DMSO)7.61(d,J＝6.8Hz,1H),7.32-7.30(m,3H),7.18(s,1H),6.97-6.95(m,3H),5.2(s,2H)；
13C NMR(100MHz,DMSO)156.0,153.1,152.1,149.3,147.4,138.1,137.6,127.5,119.8,118.9,118.6,114.0,107.3,62.9.
实施例10
1-(乙氧基甲基)-2-((4-苯氧基苯氧基)甲基)5-三氟甲基-1H吡咯的合成(化合物29)
Figure PCTCN2020074115-appb-000050
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入13g(0.054mol)2-氯甲基-1乙氧基甲基-5-三氟甲基-1H-吡咯，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体20.1g，纯度98％，收率95％。
GC-MS(m/s)391.1；
1H NMR(400MHz,DMSO)7.41-7.33(m,4H),7.17-7.14(m,3H),6.96-6.94(m,2H),5.93(s,2H),5.60(d,J＝6.8Hz,1H),5.54(d,J＝6.8Hz,1H),5.24(s,2H),3.5(m,2H),1.1(t,J＝6.4Hz,3H)；
13C NMR(100MHz,DMSO)157.0,152.1,149.3,131.6,128.4,122.2,121.8,119.8,118.9,116.4,114.0,107.5,107.1,73.1,70.3,65.5,14.9；
实施例11
5-氰基-N，3-二甲基-2-((4-苯氧基苯氧基)甲基)苯酰胺的合成(化合物43)
Figure PCTCN2020074115-appb-000051
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入12g(0.054mol)2-氯甲基-5-氰基-N,3-二甲基苯酰胺，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体12.1g，纯度98％，收率60％。
GC-MS(m/s)372.1；
1H NMR(400MHz,DMSO)8.22(s,1H),8.13(s,1H),7.61(s,1H),7.41-7.32(m,4H),7.17-7.15(m,3H),6.96-6.93(m,2H),5.16(s,2H),2.85(s,3H),2.34(s,3H)；
13C NMR(100MHz,DMSO)167.8,157.0,154.8,149.3,141.3,136.8,135.7,134.1,128.4,127.9,121.8,119.8,118.9,118.6,114.0,65.1,26.7,18.2；
实施例12
2-(3-溴-5-((4-苯氧基苯氧基)甲基)-1H-吡唑基-1-基)-3-氯吡啶的合成(化合物57)
Figure PCTCN2020074115-appb-000052
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入16.5g(0.054mol)2-(3-溴-5-(氯甲基)-1H-吡唑基-1-基)-3-氯吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体19.6g，纯度98％，收率80％。
GC-MS(m/s)455.0；
1H NMR(400MHz,DMSO)8.50(d,J＝6.8Hz,1H),7.86(d,J＝6.8Hz,1H),7.59(t,J＝6.8Hz,1H),7.41-7.32(m,4H),7.17-7.14(m,3H),6.96-6.93(m,2H),6.37(s,1H),5.20(s,2H)；
13C NMR(100MHz,DMSO)160.7,157.0,152.1,149.3,146.6,142.0,135.3,128.4,123.1,122.1,121.8,119.8,118.9,114.0,106.7,68.5；
实施例13
3-氯-2-(5-((4-苯氧基苯氧基)甲基)3-三氟甲基)-1H-吡唑-1-基)吡啶的合成(化合物70)
Figure PCTCN2020074115-appb-000053
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入15.9g(0.054mol)3-氯-2-(5-(氯甲基)-3-三氟甲基-1H-吡唑基-1-基)吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体19.9g，纯度98％，收率83％。
GC-MS(m/s)445.1；
1H NMR(400MHz,DMSO)8.53(d,J＝6.8Hz,1H),7.88(d,J＝6.8Hz,1H),7.63(t,J＝6.8Hz,1H),7.41-7.32(m,4H),7.17-7.15(m,3H),6.96-6.92(m,2H),6.43(s,1H),5.26(s,2H)；
13C NMR(100MHz,DMSO)160.7,157.0,152.1,149.3,146.6,142.0,135.3,128.4,123.1,122.1,121.8,121.5,119.8,118.9,114.0,106.7,68.5；
实施例14
4-氯-3-乙基-1-甲基-5-((4-苯氧基苯氧基)甲基)-1H-吡唑的合成(化合物84)
Figure PCTCN2020074115-appb-000054
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入10.4g(0.054mol)4-氯-(5-(氯甲基)-3-乙基-1-甲基-1H-吡唑，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体15.7g，纯度98％，收率85％。
GC-MS(m/s)342.1；
1H NMR(400MHz,DMSO)7.41-7.32(m,4H),7.17-7.14(m,3H),6.96-6.92(m,2H),5.20(s,2H),3.63(s,3H),3.07(q,J 1＝6.4Hz,J 2＝3.8Hz,2H),1.25(t,J＝6.8Hz,3H)；
13C NMR(100MHz,DMSO)157.0,152.1,150.6,149.3,142.5,128.4,121.8,119.8,118.9,114.0,105.7,64.5,37.8,18.8,12.2；
实施例15
5-((4-苯氧基苯氧基)甲基)嘧啶的合成(化合物98)
Figure PCTCN2020074115-appb-000055
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入6.9g(0.054mol)5-(氯甲基)嘧啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体12.9g，纯度98％，收率86％。
GC-MS(m/s)278.1；
1H NMR(400MHz,DMSO)9.04(s,1H),8.57(s,2H),7.41-7.31(m,4H),7.17-7.15(m,3H),6.95(d,J＝6.4Hz,2H),5.16(s,2H)；
13C NMR(100MHz,DMSO)157.0,156.8,155.9,154.8,149.3,130.4,128.4,121.8,119.8,118.9,114.0,70.8；
实施例16
2-氯-5-((4-苯氧基苯氧基)甲基)噻吩的合成(化合物112)
Figure PCTCN2020074115-appb-000056
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入9.1g(0.054mol)2-氯-5-(氯甲基)噻吩，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体15.3g，纯度98％，收率90％。
GC-MS(m/s)316.0；
1H NMR(400MHz,DMSO)7.41-7.32(m,4H),7.17-7.14(m,3H),6.94(d,J＝6.4Hz,2H),6.61(d,J＝6.8Hz,1H),6.47(d,J＝6.8Hz,1H),5.3(s,2H)；
13C NMR(100MHz,DMSO)157.1,152.1,149.3,139.4,128.5,128.3,126.5,124.5,121.8,119.8,118.9,114.0,63.4；
实施例17
3-((4-苯氧基苯氧基)甲基)呋喃的合成(化合物114)
Figure PCTCN2020074115-appb-000057
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入6.3g(0.054mol)3-(氯甲基)呋喃，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体12.6g，纯度98％，收率88％。
GC-MS(m/s)266.1；
1H NMR(400MHz,DMSO)7.41-7.32(m,4H),7.17-7.10(m,5H),6.95(d,J＝6.4Hz,2H),6.13(d,J＝6.8Hz,1H),5.16(s,2H)；
13C NMR(100MHz,DMSO)157.0,154.8,149.3,142.8,139.3,128.4,121.8,119.8,118.9,118.5,114.0,110.7,60.5；
实施例18
2-甲基-4-((4-苯氧基苯氧基)甲基)噁唑的合成(化合物115)
Figure PCTCN2020074115-appb-000058
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.1g(0.054mol)4-(氯甲基)-2-甲基噁唑，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体13.8g，纯度 98％，收率92％。
GC-MS(m/s)281.1；
1H NMR(400MHz,DMSO)7.69(s,1H),7.41-7.32(m,4H),7.17-7.14(m,3H),6.95(d,J＝6.4Hz,2H),5.20(s,2H),2.62(s,3H)；
13C NMR(100MHz,DMSO)165.0,157.0,152.1,149.0,137.7,128.4,125.4,121.8,119.8,118.9,114.0,72.3,14.2；
实施例19
1-((4-苯氧基苯氧基)甲基)-1H-咪唑的合成(化合物117)
Figure PCTCN2020074115-appb-000059
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入6.2g(0.054mol)1-(氯甲基)-1H-咪唑，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体10.9g，纯度98％，收率76％。
GC-MS(m/s)266.1；
1H NMR(400MHz,DMSO)7.83(s,1H),7.41-7.32(m,4H),7.17-7.13(m,4H),6.96(d,J＝6.4Hz,2H),6.96(d,J＝6.8Hz,1H),6.38(s,2H)；
13C NMR(100MHz,DMSO)157.0,153.7,149.1,137.0,128.8,128.4,121.8,119.8,118.9,114.0,84.5；
实施例20
3,4-二氯-5-((4-苯氧基苯氧基)甲基)异噻唑的合成(化合物119)
Figure PCTCN2020074115-appb-000060
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入10.9g(0.054mol)3,4-二氯-5-氯甲基异噻唑，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体15.2g，纯度98％，收率80％。
GC-MS(m/s)350.9；
1H NMR(400MHz,DMSO)7.41-7.32(m,4H),7.17-7.13(m,3H),6.95(d,J＝6.4Hz,2H),5.2(s,2H)；
13C NMR(100MHz,DMSO)157.3,157.0,152.1,149.3,147.8,128.4,123.4,121.8,119.8,118.9,114.0,57.8；
实施例21
2-甲基-5-((4-苯氧基苯氧基)甲基)吡嗪的合成(化合物122)
Figure PCTCN2020074115-appb-000061
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加 热回流带水，待水分带干净后，加入7.7g(0.054mol)2-氯甲基-5-甲基吡嗪，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体12.9g，纯度98％，收率82％。
GC-MS(m/s)292.1；
1H NMR(400MHz,DMSO)8.42(s,1H),8.39(s,1H),7.41-7.32(m,4H),7.17-7.14(m,3H),6.96(d,J＝6.4Hz,2H),5.25(s,2H),2.33(s,3H)；
13C NMR(100MHz,DMSO)157.0,152.1,150.7,150.3,149.3,144.4,144.0,128.4,121.8,119.8,118.9,114.0,77.8,20.9；
实施例22
6-((4-苯氧基苯氧基)甲基)喹啉的合成(化合物123)
Figure PCTCN2020074115-appb-000062
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入9.5g(0.054mol)6-(氯甲基)喹啉，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体15.1g，纯度98％，收率86％。
GC-MS(m/s)327.1；
1H NMR(400MHz,DMSO)8.79(d,J＝6.8Hz,1H),8.35(d,J＝6.4Hz,1H),7.92(d,J＝6.8Hz,1H),7.75(d,J＝6.8Hz,1H),7.66(s,1H),7.57(t,J＝6.8Hz,1H),7.41-7.32(m,4H),7.17-7.14(m,3H),6.95(d,J＝6.4Hz,2H),5.16(s,2H)；
13C NMR(100MHz,DMSO)157.0,154.8,149.3,148.8,146.5,135.8,135.5,131.4,129.1,128.6,128.4,126.6,121.8,121.3,119.8,118.9,114.0,71.2；
实施例23
6-((4-苯氧基苯氧基)甲基)喹唑啉的合成(化合物137)
Figure PCTCN2020074115-appb-000063
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入9.6g(0.054mol)6-(氯甲基)喹唑啉，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体15.0g，纯度98％，收率85％。
GC-MS(m/s)328.1；
1H NMR(400MHz,DMSO)9.74(s,1H),9.36(s,1H),8.0(s,1H),7.83-7.80(m,2H),7.41-7.32(m,4H),7.17-7.14(m,3H),6.96(d,J＝6.4Hz,2H),5.18(s,2H)；
13C NMR(100MHz,DMSO)159.4,157.0,155.1,154.7,149.3,147.3,137.3,137.0,131.7,128.4,127.7,125.1,121.8,119.8,118.9,114.0,70.8；
实施例24
6-((4-苯氧基苯氧基)甲基)二氮杂萘的合成(化合物138)
Figure PCTCN2020074115-appb-000064
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入9.6g(0.054mol)6-(氯甲基)二氮杂萘，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体14.1g，纯度98％，收率80％。
GC-MS(m/s)328.1；
1H NMR(400MHz,DMSO)9.44(s,1H),9.40(s,1H),7.86-7.80(m,3H),7.41-7.32(m,4H),7.17-7.14(m,3H),6.93(d,J＝6.4Hz,2H),5.13(s,2H)；
13C NMR(100MHz,DMSO)157.0,154.8,151.5,151.0,149.3,142.4,135.1,128.4,126.8,125.8,125.3,124.5,121.8,119.8,118.9,114.0,70.8；
实施例25
5-氯-3-((4-苯氧基苯氧基)甲基)苯并噻吩的合成(化合物140)
Figure PCTCN2020074115-appb-000065
将10g(0.054mol)对苯氧基苯酚加入到50mL环己烷中，加入4g(0.071mol)氢氧化钾，加热回流带水，待水分带干净后，加入11.7g(0.054mol)5-氯-3-(氯甲基)苯并噻吩，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体17.8g，纯度98％，收率90％。
GC-MS(m/s)366.1；
1H NMR(400MHz,DMSO)8.24(s,1H),7.92(d,J＝6.4Hz,1H),7.70(s,1H),7.48-7.32(m,5H),7.17-7.14(m,3H),6.96(d,J＝6.4Hz,2H),5.18(s,2H)；
13C NMR(100MHz,DMSO)157.0,154.8,149.3,140.7,138.7,138.5,131.0,128.4,127.6,124.2,121.8,121.4,119.8,118.9,114.0,64.3；
实施例26
2-氯-6-((4-苯硫基苯氧基)甲基)吡啶的合成(化合物141)
Figure PCTCN2020074115-appb-000066
将10g(0.049mol)对苯硫基苯酚加入到50mL环己烷中，加入3.3g(0.059mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.9g(0.049mol)2-氯-6-(氯甲基)吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体14.7g，纯度98％，收率92％。
GC-MS(m/s)327.1；
1H NMR(400MHz,DMSO)8.54(t,J＝4Hz,1H),7.97(d,J＝8Hz,1H),7.53(d,J＝8Hz,1H),7.36-7.33(m,2H),7.09-7.05(m,3H),7.02-6.96(m,2H),6.94-6.91(m,2H),5.15(s,2H)；
13C NMR(100MHz,DMSO)157.8,154.6,149.7,149.5,149.1,139.3,132.3,129.9,124.2,122.7,120.6,117.4,116.5,66.3；
实施例27
2-氯-6-(((4-苯氧基苯基)硫基)甲基)吡啶的合成(化合物142)
Figure PCTCN2020074115-appb-000067
将10g(0.049mol)对苯氧基苯硫酚加入到50mL环己烷中，加入3.3g(0.059mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.9g(0.049mol)2-氯-6-(氯甲基)吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体14.1g，纯度98％，收率88％。
GC-MS(m/s)327.1；
1H NMR(400MHz,DMSO)8.55(t,J＝4Hz,1H),7.95(d,J＝8Hz,1H),7.55(d,J＝8Hz,1H),7.36-7.33(m,2H),7.09-7.05(m,3H),7.02-6.96(m,2H),6.94-6.91(m,2H),5.25(s,2H)；
13C NMR(100MHz,DMSO)157.6,154.3,149.5,149.5,149.1,139.3,132.3,129.9,124.2,122.7,120.6,117.5,116.7,66.8；
实施例28
N-((6-氯吡啶-2-基)甲基)4-苯氧基苯胺的合成(化合物143)
Figure PCTCN2020074115-appb-000068
将10g(0.054mol)对苯氧基苯胺加入到50mL环己烷中，加入3.3g(0.059mol)氢氧化钾，加热回流带水，待水分带干净后，加入8.7g(0.054mol)2-氯-6-(氯甲基)吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体13.3g，纯度98％，收率80％。
GC-MS(m/s)310.1；
1H NMR(400MHz,DMSO)8.02(t,J＝4Hz,1H),7.60(d,J＝8Hz,1H),7.45(d,J＝8Hz,1H),7.36-7.33(m,2H),7.09-7.05(m,3H),7.02-6.96(m,2H),6.94-6.91(m,2H),4.72(s,2H),4.0(s,1H)；
13C NMR(100MHz,DMSO)157.0,156.7,151.5,142.5,142.1,139.3,132.3,129.9,124.2,122.7,120.6,117.5,116.7,47.3；
实施例29
5-氯-2-(4-((6-氯吡啶-2-基)甲氧基)苯氧基)-3-氟吡啶的合成(化合物12)
Figure PCTCN2020074115-appb-000069
将10g(0.042mol)4-((5-氯-3-氟吡啶-2-基)氧基)苯酚加入到50mL环己烷中，加入2.6g(0.046mol)氢氧化钾，加热回流带水，待水分带干净后，加入6.8g(0.042mol)2-氯-6-(氯甲基)吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体12.6g，纯度98％，收率83％。
GC-MS(m/s)364.0；
1H NMR(400MHz,DMSO)8.02(t,J＝4Hz,1H),7.93(s,1H),7.70(s,1H),7.62(d,J＝8Hz, 1H),7.46(d,J＝8Hz,1H),6.71-6.60(m,4H),5.75(s,2H)；
13C NMR(100MHz,DMSO)156.3,154.2,151.2,150.8,148.3,147.5,145.1,137.8,129.8,126.1,123.6,122.9,117.6,115.3,77.5；
实施例30
2-(4-氯苯氧基)-5-((6-氯吡啶-2-基)甲氧基)吡啶的合成(化合物13)
Figure PCTCN2020074115-appb-000070
将10g(0.045mol)6-(4-氯苯氧基)吡啶-3-醇加入到50mL环己烷中，加入2.8g(0.049mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.29g(0.045mol)2-氯-6-(氯甲基)吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体13.2g，纯度98％，收率85％。
GC-MS(m/s)346.0；
1H NMR(400MHz,DMSO)8.25(t,J＝4Hz,1H),7.95(d,J＝8Hz,1H),7.56(d,J＝8Hz,1H),7.38-7.29(m,6H),6.69(d,J＝6.8Hz,1H),5.55(s,2H)；
13C NMR(100MHz,DMSO)156.5,155.2,153.2,151.0,150.0,137.8,130.9,130.2,127.5,123.6,122.9,122.7,117.6,105.9,77.3；
实施例31
4-((6-氯吡啶-2基)甲氧基)-6-(4-甲氧基苯氧基)嘧啶的合成(化合物14)
Figure PCTCN2020074115-appb-000071
将10g(0.045mol)6-(4-氯苯氧基)吡啶-3-醇加入到50mL环己烷中，加入2.8g(0.049mol)氢氧化钾，加热回流带水，待水分带干净后，加入7.29g(0.045mol)2-氯-6-(氯甲基)吡啶，继续回流反应3小时，冷却，加水分层，有机相脱溶后残余物加入乙醇重结晶，得到白色固体12.5g，纯度98％，收率80％。
GC-MS(m/s)343.1；
1H NMR(400MHz,DMSO)8.96(s,1H),8.26(t,J＝4Hz,1H),7.96(d,J＝8Hz,1H),7.58(d,J＝8Hz,1H),7.13-7.10(m,2H),6.82-6.80(m,2H),6.20(s,2H),5.53(s,2H),3.83(s,3H)；
13C NMR(100MHz,DMSO)172.4,172.1,161.9,156.5,156.1,151.0,147.5,137.8,123.6,122.9,117.6,115.3,77.5,77.3,55.8；
实施例32：本发明化合物的室内杀虫活性测试
操作方法：称取100mg样品，然后溶于9ml N,N-二甲基甲酰胺和1ml曲拉通X-100，配制成104PPM母液4℃保存。采用浸苗法：(褐飞虱和灰飞虱低龄若虫)
生测时，将出芽后一周左右的南粳5055稻苗连根一起在系列浓度的药液中浸10s(每个药剂配制1.25、2.5、5、10、20、40、80和160PPM)，取出后置于一次性塑料杯中，用杯中事先放置的湿润的吸水纸包住稻苗根部，5min后接入2龄褐飞虱若虫，以不加原药的处理作为对照。每个实验设8个浓度，每个浓度设3个重复，各接入10头3龄若虫，于药后120h检查试虫存活情况(中间每天注意稻苗根部保湿，昆虫生长调节剂和新烟碱类一般药后120h检查)，用镊子轻触试虫，不动者视为死亡。生测在人工气候室中进行，温度：27±1℃，光周期:14L：10D。
表1：式Ⅰ化合物的杀虫活性
Figure PCTCN2020074115-appb-000072
Figure PCTCN2020074115-appb-000073
Figure PCTCN2020074115-appb-000074
Figure PCTCN2020074115-appb-000075
Figure PCTCN2020074115-appb-000076
Figure PCTCN2020074115-appb-000077
Figure PCTCN2020074115-appb-000078
Figure PCTCN2020074115-appb-000079
Figure PCTCN2020074115-appb-000080
Figure PCTCN2020074115-appb-000081
Figure PCTCN2020074115-appb-000082
实施例33.黄瓜蓟马田间试验
试验对象：蓟马，棕榈蓟马(Thripspalmi),作物：黄瓜，品种“申青一号”)
试验药剂：10％化合物1和15，对照药剂为100克/升吡丙醚乳油EC，70％吡虫啉可分散粒剂WG
使用方法：喷雾法，正反面均匀喷雾
喷雾器械：采用MH-D16-3智能电动喷雾器喷雾，喷孔直径0.7mm
施药时间和次数：第一次施药为黄瓜开花初期，12-13叶期，蓟马为成虫、若虫发生期，发生量中等偏重，间隔7天再次施药。
使用容量：以作物中期用量水750升/公顷折算成相应的倍数，喷雾至叶面微滴水为度。
表2.供试药剂试验设计
Figure PCTCN2020074115-appb-000083
表3.10％化合物1、10％化合物15防治黄瓜蓟马试验结果
Figure PCTCN2020074115-appb-000084
其中，Aa、Ab、Aab是差异是否显著的表达方法，Aa的差异显著性大于Aab大于Ab。
结论：从数据可以看出化合物1和15使用40、60、80ml/亩剂量，各处理防治黄瓜蓟马的防效均良好，各处理与化合物1使用40ml/亩的剂量防效差异显著，其它剂量防效相当，与二种对照药剂相比，除化合物1使用40ml/亩的处理与对照相当外，其余处理好于对照，差异显著。
实施例34.黄瓜烟粉虱田间试验
试验对象：
烟粉虱(Bemisia argentifolii)，作物：黄瓜，品种“申青一号”)
试验药剂：10％化合物1和15，对照药剂为100克/升吡丙醚乳油EC，70％吡虫啉可分散粒剂WG
使用方法：喷雾法，正反面均匀喷雾
喷雾器械：采用MH-D16-3智能电动喷雾器喷雾，喷孔直径0.7mm
施药时间和次数：第一次施药为黄瓜开花初期，15-16叶期，烟粉虱为成虫发生期，叶 背未见成虫和若虫。发生量中等偏重，间隔7天第二次施药。
使用容量：
以作物中期用量水750升/公顷折算成相应的倍数，喷雾至叶面微滴水为度。
表4供试药剂试验设计
Figure PCTCN2020074115-appb-000085
表5 10％化合物1、10％化合物15防治黄瓜烟粉虱试验结果
Figure PCTCN2020074115-appb-000086
结论：
从数据可以看出化合物1和15使用40、60、80ml/亩剂量，除了40ml/亩剂量防治黄瓜烟粉虱的防效稍差外，其它剂量防效相当，与二种对照药剂相比，速效与对照相当，持效性明显好于对照，差异显著。
组合物实施例1
(a)油状悬浮液
表2中化合物中任一种化合物                 25重量％
聚氧乙烯山梨醇六油酸酯                    5重量％
高级脂肪族烃油                            70重量％
将各组分在砂磨机中一起研磨，直到固体颗粒降至5微米以下为止。所得的粘稠悬浮液可直接使用，但也在水中乳化后使用。
(b)水悬浮液
Figure PCTCN2020074115-appb-000087
将各组分在球磨机中一起研磨，直到固体颗粒降至约10微米以下为止。该水悬浮液可直接使用。
(c)饵剂
按以下组成制备可食用的饵：
表2中化合物中任一种化合物                     0.1-10重量％
小麦面粉                                      80重量％
糖蜜                                          19.9-10重量％
将这些组分完全混合，按需要形成饵形状。可食用饵可以分散到卫生害虫所侵染的场所，例如家居或工业场所，诸如厨房、医院或商店或户外区域，以通过口服摄入来防治害虫。
(d)可润湿性粉剂
按以下组成制备可润湿性粉剂：
Figure PCTCN2020074115-appb-000088
将这些组分混合，并在锤磨机中研磨成粒径小于50微米的粉末。通过浸渍或在饮用水中口服给药的方式施用需要施用的植物种子或植物叶子和/或植物果实或植物正在生长或预期要生长的地方，以防治害虫。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种具有通式(I)所示结构的化合物或其光学异构体、顺反异构体或农药学上可接受的盐：
    Figure PCTCN2020074115-appb-100001
    式中：
    环α为取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环基；
    环β为取代或未取代的亚苯基、取代或未取代的亚萘基、取代或未取代的5元或6元亚杂环基、或取代或未取代的8元至12元亚杂芳二环基；
    环γ为取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环基；
    所述的环α、环β和环γ的取代基选自下组：卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷基或烷氧基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、或取代或未取代的8元至12元杂芳二环基；
    L 1、L 3可以相同或不同，且各自独立选自下组：-NR’-、-O-、-S-；
    L 2为选自下组的基团：-CR’R”-，R’R”可以相同或不同；
    n为1-8的整数；优选1-5的整数；更优选1-3的整数；最优选1；
    G为位于环γ任意一个或多个(优选1-3个)位置上各自独立的取代基，且G选自下组：卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O) nR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”；
    所述取代是指选自下组的一个或多个基团所取代：卤素、氰基、硝基、C 1-6烷基、C 1-6烷氧基、C 1-6卤代烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基、羟基、羟基C 1-4烷基、R’、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O) mR’、S(O) 2NR’R”、OC(O)R、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R’)C(O)R’、N(R’)C(O)NR’R”、N(R’)S(O) 2R’或N(R’)S(O) 2NR’R”，或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、取代或未取代的6-10元芳基、取代或未取代的5元或6元饱和或不饱和杂环基、或取代或未取代的8元至12元杂芳二环环系；其中，环烷基、环烯基、芳基、杂环基、杂芳 二环环系上的取代是被选自下组的一个或多个基团所取代：氧基(＝O)、卤素、氰基、硝基、羟基、C 1-6烷基或环烷基、C 1-6卤代烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基、羟基、羟基C 1-4烷基；
    其中，R’、R”各自独立地为H、C 1-6烷基、C 3-6环烷基、C 1-6卤代烷基、C 3-6卤代环烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基，或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元饱和或不饱和杂环基、或取代或未取代的8元至12元杂芳二环环系；其中，R’、R”上的取代基是选自下组的一个或多个基团：氧基(＝O)、卤素、氰基、硝基、羟基、C 1-6烷基或环烷基、C 1-6卤代烷基、C 2-6烯基、C 2-6卤代烯基、C 2-6炔基、C 2-6卤代炔基、羟基、羟基C 1-4烷基。
  2. 如权利要求1所述的化合物，其特征在于，所述的化合物具有如下式II所示的结构：
    Figure PCTCN2020074115-appb-100002
    式中：
    X 1、X 2、X 3各自为C(Ra)、N(Ra)或S；X 1、X 2、X 3不同时为S；
    X 4、X 5、X 6各自为C(Ra)、N(Ra)；X 4、X 5、X 6可以相同或不同；
    L 1、L 3可以相同或不同，并且各自为O、NH、S；
    L 2为CH 2；
    n为1、2或3；
    m为0或1；
    Ra选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R')S(O) 2NR’R”；
    Rb选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”。
  3. 如权利要求1所述的化合物，其特征在于，所述的化合物具有如下式Ⅲ所示的结构：
    Figure PCTCN2020074115-appb-100003
    式中：
    V 1、V 2、V 3、V 4、V 5各自为C(Ra)、N(Ra)或S；V 2、V 3、V 4不同时为S或N；
    X 4、X 5、X 6可以相同或不同，并且各自为C(Ra)、N(Ra)；
    L 1、L 3可以相同或不同，并且各自为O、NH、S；
    L 2为CH 2；
    n为1、2或3；
    m各自为0或1；
    Ra选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”；
    Rb选自下组：H、卤素、氰基、硝基、羟基、取代或未取代的C 1-6烷氧基、取代或未取代的C 1-6烷基、取代或未取代的C 3-6环烷基、取代或未取代的C 2-6烯基、取代或未取代的C 2-6炔基、或取代或未取代的C 3-7环烷基、取代或未取代的C 5-7环烯基、三甲基硅烷基乙炔基、取代或未取代的苯基、取代或未取代的萘基、取代或未取代的5元或6元杂环基、取代或未取代的8元至12元杂芳二环环系、OR’、Si(R’) 3、NR’R”、C(O)R’、C(O)OR’、C(O)NR’R”、SR’、S(O)mR’、S(O) 2NR’R”、OC(O)R’、OC(O)NR’R”、OS(O) 2R’、OS(O) 2NR’R”、N(R”)C(O)R’、NCH 2R’、N(R”)C(O)NR’R”、N(R”)S(O) 2R’或N(R’)S(O) 2NR’R”。
  4. 如权利要求1所述的化合物，其特征在于，所述的结构单元
    Figure PCTCN2020074115-appb-100004
    具有选自下组的结构：
    Figure PCTCN2020074115-appb-100005
  5. 如权利要求1所述的化合物或其光学异构体、顺反异构体或农药学上可接受的盐， 其特征在于，所述的结构单元
    Figure PCTCN2020074115-appb-100006
    具有选自下组的结构：
    Figure PCTCN2020074115-appb-100007
  6. 如权利要求1所述的化合物，或其光学异构体、顺反异构体或农药学上可接受的盐，其特征在于，所述的结构单元
    Figure PCTCN2020074115-appb-100008
    具有选自下组的结构：
    Figure PCTCN2020074115-appb-100009
  7. 如权利要求1所述的化合物，其特征在于，所述的化合物选自下组：
    Figure PCTCN2020074115-appb-100010
    Figure PCTCN2020074115-appb-100011
    Figure PCTCN2020074115-appb-100012
    Figure PCTCN2020074115-appb-100013
    Figure PCTCN2020074115-appb-100014
    Figure PCTCN2020074115-appb-100015
    Figure PCTCN2020074115-appb-100016
    Figure PCTCN2020074115-appb-100017
    Figure PCTCN2020074115-appb-100018
    Figure PCTCN2020074115-appb-100019
    Figure PCTCN2020074115-appb-100020
    Figure PCTCN2020074115-appb-100021
    Figure PCTCN2020074115-appb-100022
  8. 一种农用组合物，其特征在于，其包含：0.001-99.99wt％的权利要求1-7中任一项所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐、或者它们的组合；以及农药学上可接受的载体和/或赋形剂。
  9. 如权利要求1-7中任一项所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐或如权利要求8所述农用组合物的用途，其特征在于，用于杀虫或用于制备杀虫剂组合物。
  10. 一种如权利要求1-7中任一项所述的化合物、或所述化合物的光学异构体、顺反异构体或农药学上可接受的盐的制备方法，其特征在于:
    Figure PCTCN2020074115-appb-100023
    在惰性溶剂中，用
    Figure PCTCN2020074115-appb-100024
    与
    Figure PCTCN2020074115-appb-100025
    反应，得到式II化合物；
    在惰性溶剂中，用
    Figure PCTCN2020074115-appb-100026
    与
    Figure PCTCN2020074115-appb-100027
    反应，得到式Ⅲ化合物；
    其中，LG为离去基团，其它各基团的定义如权利要求1中所述。
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