WO2017008583A1 - 一类含二苯醚结构的吡唑酰胺化合物、其制备方法及应用 - Google Patents

一类含二苯醚结构的吡唑酰胺化合物、其制备方法及应用 Download PDF

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WO2017008583A1
WO2017008583A1 PCT/CN2016/083409 CN2016083409W WO2017008583A1 WO 2017008583 A1 WO2017008583 A1 WO 2017008583A1 CN 2016083409 W CN2016083409 W CN 2016083409W WO 2017008583 A1 WO2017008583 A1 WO 2017008583A1
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group
alkyl
halogen
diphenyl ether
amide compound
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PCT/CN2016/083409
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English (en)
French (fr)
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许天明
胡伟群
孔小林
张蕊蕊
郑志文
朱卫刚
魏优昌
黄红英
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浙江省化工研究院有限公司
中化蓝天集团有限公司
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Priority claimed from CN201510409336.8A external-priority patent/CN106336380B/zh
Application filed by 浙江省化工研究院有限公司, 中化蓝天集团有限公司 filed Critical 浙江省化工研究院有限公司
Priority to MYPI2018700059A priority Critical patent/MY189442A/en
Publication of WO2017008583A1 publication Critical patent/WO2017008583A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals

Definitions

  • the invention belongs to the field of agricultural fungicides and relates to a pyrazole amide compound containing a diphenyl ether structure.
  • Rice and wheat are the world's major food crops, with annual declines due to diseases such as sheath blight. Powdery mildew is also ubiquitous in various crops, which seriously affects the growth of crops.
  • crops are resistant to pesticides that control sheath blight and powdery mildew.
  • it is necessary to increase the amount of pesticides used, which causes serious harm to the environment. Therefore, it is necessary to continuously discover new pesticide varieties with a new mechanism of action.
  • PCT patent application WO9803500 discloses the following pyrazole amide compounds containing a diphenyl ether structure:
  • PCT patent application WO2006027193 discloses the following pyrazole amide compounds containing a diphenyl ether structure:
  • PCT patent application WO2015058444 discloses the following compounds CN-1 and CN-2:
  • PCT Patent Application No. WO2012065947 discloses pyrazole amide compounds containing diphenyl ether structures numbered 160, 161, 165 and 164 which are ineffective at the control of crop sheath blight at 200 ppm.
  • the object of the invention is to provide
  • R1 is selected from the group consisting of hydrogen, halogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxyalkyl, halogen, C1-C10 alkyl, C1-C10 haloalkoxy or C1-C10 haloalkylthio substituted aryl, halogen, a C1-C10 alkyl group, a C1-C10 haloalkoxy group or a C1-C10 haloalkylthio group-substituted heteroaryl group;
  • R2 is selected from halogen or C1-C10 alkyl
  • R3 is selected from C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxyalkyl, halogen, C1-C10 alkyl, C1-C10 haloalkoxy or C1-C10 haloalkyl a thio-substituted aryl group, a heteroaryl group substituted by a halogen, a C1-C10 alkyl group, a C1-C10 haloalkoxy group or a C1-C10 haloalkylthio group;
  • R4 is selected from hydrogen or halogen
  • R7 is selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, difluoromethyl, monofluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy, monofluoromethoxy , nitro, trifluoromethylthio, difluoromethylthio, monofluoromethylthio;
  • R5, R6, R8, R9, R10 are independently selected from the group consisting of hydrogen, halogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 haloalkoxyalkyl, nitrile, nitro, C1-C10 alkoxy a group, a C1-C10 alkylthio group, a C1-C10 alkyl sulfoxide group, a C1-C3 alkylsulfone group;
  • X is selected from nitrogen or carbon
  • Y is selected from nitrogen or -C-R11, and R11 is selected from hydrogen or halogen;
  • M and Q are independently selected from oxygen or sulfur.
  • R7 is selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, difluoromethyl, monofluoromethyl, methoxy, trifluoromethoxy, difluoromethoxy a pyrazole-containing pyrazole amide represented by the above formula F-1 when the group is a monofluoromethyloxy group, a nitro group, a trifluoromethylthio group, a difluoromethylthio group or a monofluoromethylthio group.
  • the compounds have good activity, especially in the sterilization of pesticides.
  • R7 is selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, methoxy, trifluoromethoxy, nitro, trifluoromethylthio.
  • R1 is selected from the group consisting of hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxyalkyl
  • R1 is selected from the group consisting of hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxyalkyl, halogen, C1-C3 alkyl, C1- a C3 haloalkoxy group or a C1-C3 haloalkylthio group-substituted aryl group, a heteroaryl group substituted by a halogen, a C1-C3 alkyl group, a C1-C3 haloalkoxy group or a C1-C3 haloalkylthio group. Still more preferably, R1 is selected from the group consisting of difluoromethyl or trifluoromethyl.
  • R2 is selected from a halogen or a C1-C6 alkyl group. It is further preferred that R2 is selected from halogen or C1-C3 alkyl. Still more preferably, R2 is selected from the group consisting of fluorine.
  • R3 is selected from a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxyalkyl group, a halogen, C1-C6 alkyl, C1-C6 haloalkoxy or C1-C6 haloalkylthio substituted aryl, heteroaryl substituted by halogen, C1-C6 alkyl, C1-C6 haloalkoxy or C1-C6 haloalkylthio base.
  • R3 is selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxyalkyl, halogen, C1-C3 alkyl, C1-C3 haloalkoxy Or a C1-C3 haloalkylthio-substituted aryl group, a heteroaryl group substituted by a halogen, a C1-C3 alkyl group, a C1-C3 haloalkoxy group or a C1-C3 haloalkylthio group. Still more preferably, R3 is selected from methyl or ethyl.
  • R5, R6, R8, R9 and R10 substituents, it is preferred that R5, R6, R8, R9, R10 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1. -C6 haloalkyl, C1-C6 haloalkoxyalkyl, nitrile, nitro, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsulfoxide, C1-C3 alkylsulfone.
  • R5, R6, R8, R9, R10 are independently selected from the group consisting of hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkoxyalkyl, nitrile, nitro, C1-C3 alkoxy group, C1-C3 alkylthio group, C1-C3 alkyl sulfoxide group, C1-C3 alkylsulfone group.
  • R5 is selected from fluorine, chlorine, bromine or iodine
  • R6 is selected from hydrogen, fluorine, chlorine or bromine
  • R5 and R6 are not simultaneously hydrogen
  • R8, R9 and R10 are independently selected from fluorine, chlorine or bromine.
  • the pyrazole amide compound having a diphenyl ether structure represented by the above formula F-1 is the most preferred compound, and the pyrazole amide compound having a diphenyl ether structure is one selected from the group consisting of the compounds represented by the following structural formulas. , two or more combinations:
  • a representative compound of the pyrazole amide compound having a diphenyl ether structure represented by the formula F-1 of the present invention can be used as follows The list illustrates, but these compounds do not limit the invention.
  • R 2 is fluorine or chlorine
  • R 3 is methyl or ethyl
  • R 9 , R 10 , R 6 and R 8 are hydrogen
  • X and Y are carbon
  • the pyrazole amide compound having a diphenyl ether structure is passed.
  • the formula is as follows F-2.
  • R1 R2 R3 R4 R5 R7 1. CF 2 H F CH 3 H Cl CF 3 2. CF 2 H F CH 3 H Br CF 3 3. CF 2 H F CH 3 H I CF 3 4. CF 2 H F CH 3 F Cl CF 3 5. CF 2 H F CH 3 F Br CF 3 6. CF 2 H F CH 3 F I CF 3 7. CF 2 H F CH 3 H Cl Cl 8. CF 2 H F CH 3 H Br Cl 9. CF 2 H F CH 3 H I Cl 10. CF 2 H F CH 3 F Cl Cl 11. CF 2 H F CH 3 F Br Cl 12. CF 2 H F CH 3 F I Cl 13. CF 2 H F CH 3 H Cl OCF 3 14. CF 2 H F CH 3 H Br OCF 3 15.
  • CF 3 F CH 2 CH 3 F Br NO 2 900 CF 3 F CH 2 CH 3 F I NO 2 901. CF 3 F CH 2 CH 3 H Cl CH 3 902. CF 3 F CH 2 CH 3 H Br CH 3 903. CF 3 F CH 2 CH 3 H I CH 3 904. CF 3 F CH 2 CH 3 F Cl CH 3 905. CF 3 F CH 2 CH 3 F Br CH 3 906. CF 3 F CH 2 CH 3 F I CH 3 907. CF 3 F CH 2 CH 3 H Cl OCH 3 908. CF 3 F CH 2 CH 3 H Br OCH 3 909. CF 3 F CH 2 CH 3 H I OCH 3 910. CF 3 F CH 2 CH 3 F Cl OCH 3 911. CF 3 F CH 2 CH 3 F Br OCH 3 912.
  • CH 3 Cl CH 3 F Br OCF 3 1026 CH 3 Cl CH 3 F I OCF 3 1027. CH 3 Cl CH 3 H Cl SCF 3 1028. CH 3 Cl CH 3 H Br SCF 3 1029. CH 3 Cl CH 3 H I SCF 3 1030. CH 3 Cl CH 3 F Cl SCF 3 1031. CH 3 Cl CH 3 F Br SCF 3 1032. CH 3 Cl CH 3 F I SCF 3 1033. CH 3 Cl CH 3 H Cl CN 1034. CH 3 Cl CH 3 H Br CN 1035. CH 3 Cl CH 3 H I CN 1036. CH 3 Cl CH 3 F Cl CN 1037. CH 3 Cl CH 3 F Br CN 1038. CH 3 Cl CH 3 F I CN 1039. CH 3 Cl CH 3 H Cl NO 2 1040.
  • the invention also provides a preparation method of the pyrazole amide compound containing the diphenyl ether structure.
  • the pyrazole amide compound having a diphenyl ether structure is preferably prepared by the following method:
  • R1, R2, R3, R4, R5, R6, R7, R8, X, Y and M are as defined and preferred as previously described, R0 is preferably from methyl or ethyl, and T is preferably selected from fluorine, chlorine, bromine or iodine.
  • the pyrazole amide compound having a diphenyl ether structure is preferably prepared by the following method:
  • R1, R2, R3, R4, R5, R6, R7, R8, X, Y and M are as defined and preferred as previously described, R0 is preferably from methyl or ethyl, and T is preferably selected from fluorine, chlorine, bromine or iodine.
  • an initiator an oxidizing agent, an acid chloride, a catalyst, a base, a solvent, a condensing agent, a condensation reagent, a halogenating agent, a sulfurizing agent and the like which are commonly used in the art can be used in the present invention.
  • the present invention also provides the use of the above pyrazole-containing compound having a diphenyl ether structure.
  • the pyrazole amide compound containing a diphenyl ether structure provided by the present invention is suitable for agricultural sterilization.
  • the pyrazole amide compound containing a diphenyl ether structure is suitable for controlling the genus Rhizoctonia, Puccinia genus, Sphaerotheca genus, Trichoderma genus, Fusarium, nucleus A disease caused by a genus or a basidiomycete fungus.
  • the pyrazole amide compound having a diphenyl ether structure is suitable for controlling sheath blight, blight, powdery mildew or rust.
  • the present invention also provides an agrochemical bactericide comprising 1 to 99% by mass of a pyrazole amide compound having a diphenyl ether structure.
  • the agrochemical bactericide When preparing an agrochemical bactericide, the agrochemical bactericide can be formulated into various liquid preparations, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules. Agent, water-dispersible granules or capsules.
  • the agrochemical bactericide includes the quinoline compound of the present invention and a carrier.
  • the carrier includes at least two types, at least one of which is a surfactant.
  • the carrier can be a solid or a liquid.
  • Suitable solid carriers include natural or synthetic clays and silicates such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminosilicates such as kaolinite, kaolin, montmorillonite and mica; white carbon black Calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine.
  • the liquid carrier includes water and an organic solvent, and when water is used as a solvent or a diluent, the organic solvent can also be used as an adjuvant or an antifreezing additive.
  • Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc.; chlorinated hydrocarbons such as chlorinated Benzene, vinyl chloride, chloroform, dichloromethane, etc.; aliphatic hydrocarbons such as petroleum distillate, cyclohexane, light mineral oil; alcohols such as isopropanol, butanol, ethylene glycol, glycerol and cyclohexane Alcohols and the like; and ethers and esters thereof; and ketones such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.
  • aromatic hydrocarbons such as benzene, xylene, toluene, etc.
  • chlorinated hydrocarbons such as chlorinated Benzene, vinyl chloride, chloroform, dichloromethane, etc.
  • aliphatic hydrocarbons such as petroleum distillate, cyclohexane,
  • the surfactant can be an emulsifier, dispersant or wetting agent; it can be ionic or nonionic.
  • Nonionic emulsifiers such as polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty ammonia, and commercially available emulsifiers: agricultural milk 2201B, agricultural milk 0203B, agricultural milk 100#, agricultural milk 500#, Nong's milk 600#, agricultural milk 600-2#, agricultural milk 1601, agricultural milk 2201, agricultural milk NP-10, agricultural milk NP-15, agricultural milk 507#, agricultural milk OX-635, agricultural milk OX-622, agriculture Milk OX-653, agricultural milk OX-667, Ning milk 36#.
  • the dispersing agent includes sodium lignosulfonate, unrolled powder, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, and the like.
  • the humectant is sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate or the like.
  • Agrochemical bactericides can be prepared by a general method.
  • the active substance is mixed with a liquid solvent and/or a solid carrier, and a surfactant such as an emulsifier, a dispersing agent, a stabilizer, a wetting agent, and other auxiliary agents such as a binder, an antifoaming agent, and an oxidizing agent may be added.
  • a surfactant such as an emulsifier, a dispersing agent, a stabilizer, a wetting agent, and other auxiliary agents such as a binder, an antifoaming agent, and an oxidizing agent may be added. Wait.
  • Example 5 30% aqueous suspension
  • compound 2 80% of water to be added and sodium dodecylsulfonate are pulverized together in a ball mill, and then hemicellulose and propylene oxide are dissolved in the remaining 20% of water, and finally, the pulverized material is added by stirring. 30% aqueous suspension.
  • Example 6 30% emulsifiable concentrate
  • the phosphorous acid was dissolved in toluene, and compound 4 and ethoxylated triglyceride were added to obtain a transparent solution, i.e., 30% emulsifiable concentrate.
  • Compound 1 sodium dodecyl naphthalene sulfonate, sodium lignosulfonate and silicon bath soil were mixed together and pulverized in a pulverizer until the granules reached the standard, which was 60% wettable powder.
  • Example 8 Control of rice sheath blight (Rhizoctonia solani) in vivo screening test
  • Grade 1 the incidence of the first sheath
  • Grade 3 incidence of the first leaf and the second leaf sheath
  • Level 7 The whole plant is ill.
  • Example 9 Controlled trial of rice sheath blight control
  • Test method The compounds to be tested were each set at 5 concentrations of 50 ppm, 25 ppm, 12.5 ppm, 6.25 ppm, and 3.15 ppm, and each concentration was set to 3 replicates. Another set of clear water is a blank control.
  • test compound was dissolved in a small amount of N,N-dimethylformamide, and then diluted with water containing 0.1% Tween 80 to the concentration to be tested, and the prepared drug was sprayed on the test with a (double tube) throat sprayer.
  • a true leaf stage growing on the cucumber seedlings, and air-dried, each concentration is a treatment, each treatment is repeated 3 times, and a control agent and a clear water blank control are set up. Washing cucumber leaves The fresh powdery mildew spores were filtered through double-layer gauze to prepare a suspension having a spore concentration of about 100,000/ml, and spray-inoculated.
  • test materials were moved into the artificial climate, the relative humidity was kept between 60-70%, the temperature was maintained at 23 °C, and the incidence of the blank control was investigated on the basis of 10 days, and the control effect was calculated according to the disease index.
  • Level 1 The area of the lesion is less than 5% of the entire leaf area
  • Level 3 The area of the lesions accounts for 6% to 10% of the total leaf area
  • Level 5 The area of the lesions accounts for 11% to 20% of the total leaf area
  • Level 7 The area of the lesions accounts for 21% to 40% of the total leaf area
  • Level 9 The area of the lesions accounts for more than 40% of the entire leaf area
  • Disease index ⁇ (number of diseased leaves at each level ⁇ relative value) ⁇ 100 / (total number of leaves ⁇ 9);
  • Control effect (%) (control disease index - treatment of disease index) ⁇ 100 / control disease index
  • Test method The compounds to be tested were each set at 5 concentrations of 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, and 6.25 ppm, with 3 replicates for each concentration. Another set of clear water is a blank control.

Abstract

本发明公开了一类含二苯醚结构的吡唑酰胺类化合物，结构通式及取代基见说明书。本发明提供的含二苯醚结构的吡唑酰胺类化合物适合用于农用杀菌，尤其适合防治纹枯病、立枯病、白粉病或锈病。

Description

一类含二苯醚结构的吡唑酰胺化合物、其制备方法及应用 技术领域
本发明属于农用杀菌剂领域，涉及一类含二苯醚结构的吡唑酰胺化合物。
背景技术
水稻和小麦是世界上主要的粮食作物，由于纹枯病等病害原因导致每年减产。白粉病也普遍存在于各种农作物中，严重影响作物的生长。现在农业由于农药的长时间的使用，作物上的病害对其产生了抗药性，使现有的农药防治效果明显降低。例如农作物对防治纹枯病和白粉病的农药产生了抗药性。为了提高防治效果，必须提高农药的使用量，这对环境造成了严重的危害，因此需要不断发现新的作用机理的农药新品种。
近年来，随着氟化学技术的提高，越来越多的含氟基团被引入到有机化合物中，有效利用氟原子独特的物理性质和化学性质如伪拟效应、阻断效应、高电负和脂溶性等，使新引入含氟基团的有机化合物具有特独的性能，进而开发新的农药品种。
现有技术对于防治纹枯病和白粉病的新农药品种进行了以下尝试：
PCT专利申请WO9803500公开了以下含二苯醚结构的吡唑酰胺类化合物：
Figure PCTCN2016083409-appb-000001
化合物L-215、L-83、L-12、L-21在浓度50ppm下对作物纹枯病和白粉病的防治无效。
PCT专利申请WO2006027193公开了以下含二苯醚结构的吡唑酰胺类化合物：
Figure PCTCN2016083409-appb-000002
化合物P-1和P-2在浓度50ppm下防治作物纹枯病和白粉病效果甚微。
PCT专利申请WO2015058444公开了以下化合物CN-1和CN-2：
Figure PCTCN2016083409-appb-000003
PCT专利申请WO2012065947公开了含二苯醚结构的吡唑酰胺类化合物，编号为160、161、165和164，该4个编号化合物在200ppm下在对作物纹枯病的防治无效。
因此，仍有希望对防治纹枯病和白粉病的化合物做进一步改进。
发明内容
本发明的目的在于提供
一类含二苯醚结构的吡唑酰胺类化合物，具有如下通式F-1：
Figure PCTCN2016083409-appb-000004
其中：
R1选自氢、卤素、C1-C10烷基、C1-C10卤代烷基、C1-C10烷氧基、C1-C10卤代烷氧烷基、被卤素、C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的芳基、被卤素、 C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的杂芳基；
R2选自卤素或C1-C10烷基；
R3选自C1-C10烷基、C1-C10卤代烷基、C1-C10烷氧基、C1-C10卤代烷氧烷基、被卤素、C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的芳基、被卤素、C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的杂芳基；
R4选自氢或卤素；
R7选自氟、氯、溴、碘、氰基、三氟甲基、二氟甲基、一氟甲基、甲氧基、三氟甲氧基、二氟甲氧基、一氟甲氧基、硝基、三氟甲硫基、二氟甲硫基、一氟甲硫基；
R5、R6、R8、R9、R10独立地选自氢、卤素、C1-C10的烷基、C1-C10的卤代烷基、C1-C10卤代烷氧烷基、腈基、硝基、C1-C10烷氧基、C1-C10烷硫基、C1-C10烷亚砜基、C1-C3烷砜基；
X选自氮或碳；
Y选自氮或-C-R11，且R11选自氢或卤素；
M、Q独立地选自氧或硫。
本申请发明人发现，当R7选自氟、氯、溴、碘、氰基、三氟甲基、二氟甲基、一氟甲基、甲氧基、三氟甲氧基、二氟甲氧基、一氟甲氧基、硝基、三氟甲硫基、二氟甲硫基或一氟甲硫基时，所述通式F-1所示的含二苯醚结构的吡唑酰胺类化合物具有较好的活性，尤其是在农药杀菌上具有很好的活性。优选的是，R7选自氟、氯、溴、碘、氰基、三氟甲基、甲氧基、三氟甲氧基、硝基、三氟甲硫基。
上述通式F-1中，对于R1取代基，优选的是，R1选自氢、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧烷基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的芳基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的杂芳基。进一步优选的是，R1选自氢、卤素、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧烷基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的芳基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的杂芳基。更进一步优选的是，R1选自二氟甲基或三氟甲基。
上述通式F-1中，对于R2取代基，优选的是，R2选自卤素或C1-C6烷基。进一步优选的是，R2选自卤素或C1-C3烷基。更进一步优选的是，R2选自氟。
上述通式F-1中，对于R3取代基，优选的是，R3选自C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧烷基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的芳基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的杂芳基。进 一步优选的是，R3选自C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧烷基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的芳基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的杂芳基。更进一步优选的是，R3选自甲基或乙基。
上述通式F-1中，对于R4取代基，优选的是，R4选自氟、氯或溴。
上述通式F-1中，对于R5、R6、R8、R9和R10取代基，优选的是，R5、R6、R8、R9、R10独立地选自氢、卤素、C1-C6的烷基、C1-C6的卤代烷基、C1-C6卤代烷氧烷基、腈基、硝基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷亚砜基、C1-C3烷砜基。进一步优选的是，R5、R6、R8、R9、R10独立地选自氢、卤素、C1-C3的烷基、C1-C3的卤代烷基、C1-C3卤代烷氧烷基、腈基、硝基、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷亚砜基、C1-C3烷砜基。更进一步优选的是，R5选自氟、氯、溴或碘，R6选自氢、氟、氯或溴，且R5和R6不同时为氢，R8、R9和R10独立地选自氟、氯或溴。
上述通式F-1所示含二苯醚结构的吡唑酰胺类化合物，作为最为优选的化合物，所述含二苯醚结构的吡唑酰胺类化合物选自以下结构式所示化合物中的一种、两种或三种以上组合：
Figure PCTCN2016083409-appb-000005
本发明通式F-1所示含二苯醚结构的吡唑酰胺类化合物的部分代表性化合物可以用以下 列表说明，但这些具本化合物并不限定本发明。
作为示例，当R2为氟或氯、R3为甲基或乙基、R9、R10、R6和R8为氢、X和Y为碳时，所述含二苯醚结构的吡唑酰胺类化合物的通式如下F-2。
Figure PCTCN2016083409-appb-000006
当M为氧时，上述通式F-2所示的含二苯醚结构的吡唑酰胺类化合物的典型化合物如下表1。
表1
编号 R1 R2 R3 R4 R5 R7
1. CF2H F CH3 H Cl CF3
2. CF2H F CH3 H Br CF3
3. CF2H F CH3 H I CF3
4. CF2H F CH3 F Cl CF3
5. CF2H F CH3 F Br CF3
6. CF2H F CH3 F I CF3
7. CF2H F CH3 H Cl Cl
8. CF2H F CH3 H Br Cl
9. CF2H F CH3 H I Cl
10. CF2H F CH3 F Cl Cl
11. CF2H F CH3 F Br Cl
12. CF2H F CH3 F I Cl
13. CF2H F CH3 H Cl OCF3
14. CF2H F CH3 H Br OCF3
15. CF2H F CH3 H I OCF3
16. CF2H F CH3 F Cl OCF3
17. CF2H F CH3 F Br OCF3
18. CF2H F CH3 F I OCF3
19. CF2H F CH3 H Cl SCF3
20. CF2H F CH3 H Br SCF3
21. CF2H F CH3 H I SCF3
22. CF2H F CH3 F Cl SCF3
23. CF2H F CH3 F Br SCF3
24. CF2H F CH3 F I SCF3
25. CF2H F CH3 H Cl CN
26. CF2H F CH3 H Br CN
27. CF2H F CH3 H I CN
28. CF2H F CH3 F Cl CN
29. CF2H F CH3 F Br CN
30. CF2H F CH3 F I CN
31. CF2H F CH3 H Cl NO2
32. CF2H F CH3 H Br NO2
33. CF2H F CH3 H I NO2
34. CF2H F CH3 F Cl NO2
35. CF2H F CH3 F Br NO2
36. CF2H F CH3 F I NO2
37. CF2H F CH3 H Cl CH3
38. CF2H F CH3 H Br CH3
39. CF2H F CH3 H I CH3
40. CF2H F CH3 F Cl CH3
41. CF2H F CH3 F Br CH3
42. CF2H F CH3 F I CH3
43. CF2H F CH3 H Cl OCH3
44. CF2H F CH3 H Br OCH3
45. CF2H F CH3 H I OCH3
46. CF2H F CH3 F Cl OCH3
47. CF2H F CH3 F Br OCH3
48. CF2H F CH3 F I OCH3
49. CF2H Cl CH3 H Cl CF3
50. CF2H Cl CH3 H Br CF3
51. CF2H Cl CH3 H I CF3
52. CF2H Cl CH3 F Cl CF3
53. CF2H Cl CH3 F Br CF3
54. CF2H Cl CH3 F I CF3
55. CF2H Cl CH3 H Cl Cl
56. CF2H Cl CH3 H Br Cl
57. CF2H Cl CH3 H I Cl
58. CF2H Cl CH3 F Cl Cl
59. CF2H Cl CH3 F Br Cl
60. CF2H Cl CH3 F I Cl
61. CF2H Cl CH3 H Cl OCF3
62. CF2H Cl CH3 H Br OCF3
63. CF2H Cl CH3 H I OCF3
64. CF2H Cl CH3 F Cl OCF3
65. CF2H Cl CH3 F Br OCF3
66. CF2H Cl CH3 F I OCF3
67. CF2H Cl CH3 H Cl SCF3
68. CF2H Cl CH3 H Br SCF3
69. CF2H Cl CH3 H I SCF3
70. CF2H Cl CH3 F Cl SCF3
71. CF2H Cl CH3 F Br SCF3
72. CF2H Cl CH3 F I SCF3
73. CF2H Cl CH3 H Cl CN
74. CF2H Cl CH3 H Br CN
75. CF2H Cl CH3 H I CN
76. CF2H Cl CH3 F Cl CN
77. CF2H Cl CH3 F Br CN
78. CF2H Cl CH3 F I CN
79. CF2H Cl CH3 H Cl NO2
80. CF2H Cl CH3 H Br NO2
81. CF2H Cl CH3 H I NO2
82. CF2H Cl CH3 F Cl NO2
83. CF2H Cl CH3 F Br NO2
84. CF2H Cl CH3 F I NO2
85. CF2H Cl CH3 H Cl CH3
86. CF2H Cl CH3 H Br CH3
87. CF2H Cl CH3 H I CH3
88. CF2H Cl CH3 F Cl CH3
89. CF2H Cl CH3 F Br CH3
90. CF2H Cl CH3 F I CH3
91. CF2H Cl CH3 H Cl OCH3
92. CF2H Cl CH3 H Br OCH3
93. CF2H Cl CH3 H I OCH3
94. CF2H Cl CH3 F Cl OCH3
95. CF2H Cl CH3 F Br OCH3
96. CF2H Cl CH3 F I OCH3
97. CF2H F CH2CH3 H Cl CF3
98. CF2H F CH2CH3 H Br CF3
99. CF2H F CH2CH3 H I CF3
100. CF2H F CH2CH3 F Cl CF3
101. CF2H F CH2CH3 F Br CF3
102. CF2H F CH2CH3 F I CF3
103. CF2H F CH2CH3 H Cl Cl
104. CF2H F CH2CH3 H Br Cl
105. CF2H F CH2CH3 H I Cl
106. CF2H F CH2CH3 F Cl Cl
107. CF2H F CH2CH3 F Br Cl
108. CF2H F CH2CH3 F I Cl
109. CF2H F CH2CH3 H Cl OCF3
110. CF2H F CH2CH3 H Br OCF3
111. CF2H F CH2CH3 H I OCF3
112. CF2H F CH2CH3 F Cl OCF3
113. CF2H F CH2CH3 F Br OCF3
114. CF2H F CH2CH3 F I OCF3
115. CF2H F CH2CH3 H Cl SCF3
116. CF2H F CH2CH3 H Br SCF3
117. CF2H F CH2CH3 H I SCF3
118. CF2H F CH2CH3 F Cl SCF3
119. CF2H F CH2CH3 F Br SCF3
120. CF2H F CH2CH3 F I SCF3
121. CF2H F CH2CH3 H Cl CN
122. CF2H F CH2CH3 H Br CN
123. CF2H F CH2CH3 H I CN
124. CF2H F CH2CH3 F Cl CN
125. CF2H F CH2CH3 F Br CN
126. CF2H F CH2CH3 F I CN
127. CF2H F CH2CH3 H Cl NO2
128. CF2H F CH2CH3 H Br NO2
129. CF2H F CH2CH3 H I NO2
130. CF2H F CH2CH3 F Cl NO2
131. CF2H F CH2CH3 F Br NO2
132. CF2H F CH2CH3 F I NO2
133. CF2H F CH2CH3 H Cl CH3
134. CF2H F CH2CH3 H Br CH3
135. CF2H F CH2CH3 H I CH3
136. CF2H F CH2CH3 F Cl CH3
137. CF2H F CH2CH3 F Br CH3
138. CF2H F CH2CH3 F I CH3
139. CF2H F CH2CH3 H Cl OCH3
140. CF2H F CH2CH3 H Br OCH3
141. CF2H F CH2CH3 H I OCH3
142. CF2H F CH2CH3 F Cl OCH3
143. CF2H F CH2CH3 F Br OCH3
144. CF2H F CH2CH3 F I OCH3
145. CF2H Cl CH2CH3 H Cl CF3
146. CF2H Cl CH2CH3 H Br CF3
147. CF2H Cl CH2CH3 H I CF3
148. CF2H Cl CH2CH3 F Cl CF3
149. CF2H Cl CH2CH3 F Br CF3
150. CF2H Cl CH2CH3 F I CF3
151. CF2H Cl CH2CH3 H Cl Cl
152. CF2H Cl CH2CH3 H Br Cl
153. CF2H Cl CH2CH3 H I Cl
154. CF2H Cl CH2CH3 F Cl Cl
155. CF2H Cl CH2CH3 F Br Cl
156. CF2H Cl CH2CH3 F I Cl
157. CF2H Cl CH2CH3 H Cl OCF3
158. CF2H Cl CH2CH3 H Br OCF3
159. CF2H Cl CH2CH3 H I OCF3
160. CF2H Cl CH2CH3 F Cl OCF3
161. CF2H Cl CH2CH3 F Br OCF3
162. CF2H Cl CH2CH3 F I OCF3
163. CF2H Cl CH2CH3 H Cl SCF3
164. CF2H Cl CH2CH3 H Br SCF3
165. CF2H Cl CH2CH3 H I SCF3
166. CF2H Cl CH2CH3 F Cl SCF3
167. CF2H Cl CH2CH3 F Br SCF3
168. CF2H Cl CH2CH3 F I SCF3
169. CF2H Cl CH2CH3 H Cl CN
170. CF2H Cl CH2CH3 H Br CN
171. CF2H Cl CH2CH3 H I CN
172. CF2H Cl CH2CH3 F Cl CN
173. CF2H Cl CH2CH3 F Br CN
174. CF2H Cl CH2CH3 F I CN
175. CF2H Cl CH2CH3 H Cl NO2
176. CF2H Cl CH2CH3 H Br NO2
177. CF2H Cl CH2CH3 H I NO2
178. CF2H Cl CH2CH3 F Cl NO2
179. CF2H Cl CH2CH3 F Br NO2
180. CF2H Cl CH2CH3 F I NO2
181. CF2H Cl CH2CH3 H Cl CH3
182. CF2H Cl CH2CH3 H Br CH3
183. CF2H Cl CH2CH3 H I CH3
184. CF2H Cl CH2CH3 F Cl CH3
185. CF2H Cl CH2CH3 F Br CH3
186. CF2H Cl CH2CH3 F I CH3
187. CF2H Cl CH2CH3 H Cl OCH3
188. CF2H Cl CH2CH3 H Br OCH3
189. CF2H Cl CH2CH3 H I OCH3
190. CF2H Cl CH2CH3 F Cl OCH3
191. CF2H Cl CH2CH3 F Br OCH3
192. CF2H Cl CH2CH3 F I OCH3
193. CF3 F CH3 H Cl CF3
194. CF3 F CH3 H Br CF3
195. CF3 F CH3 H I CF3
196. CF3 F CH3 F Cl CF3
197. CF3 F CH3 F Br CF3
198. CF3 F CH3 F I CF3
199. CF3 F CH3 H Cl Cl
200. CF3 F CH3 H Br Cl
201. CF3 F CH3 H I Cl
202. CF3 F CH3 F Cl Cl
203. CF3 F CH3 F Br Cl
204. CF3 F CH3 F I Cl
205. CF3 F CH3 H Cl OCF3
206. CF3 F CH3 H Br OCF3
207. CF3 F CH3 H I OCF3
208. CF3 F CH3 F Cl OCF3
209. CF3 F CH3 F Br OCF3
210. CF3 F CH3 F I OCF3
211. CF3 F CH3 H Cl SCF3
212. CF3 F CH3 H Br SCF3
213. CF3 F CH3 H I SCF3
214. CF3 F CH3 F Cl SCF3
215. CF3 F CH3 F Br SCF3
216. CF3 F CH3 F I SCF3
217. CF3 F CH3 H Cl CN
218. CF3 F CH3 H Br CN
219. CF3 F CH3 H I CN
220. CF3 F CH3 F Cl CN
221. CF3 F CH3 F Br CN
222. CF3 F CH3 F I CN
223. CF3 F CH3 H Cl NO2
224. CF3 F CH3 H Br NO2
225. CF3 F CH3 H I NO2
226. CF3 F CH3 F Cl NO2
227. CF3 F CH3 F Br NO2
228. CF3 F CH3 F I NO2
229. CF3 F CH3 H Cl CH3
230. CF3 F CH3 H Br CH3
231. CF3 F CH3 H I CH3
232. CF3 F CH3 F Cl CH3
233. CF3 F CH3 F Br CH3
234. CF3 F CH3 F I CH3
235. CF3 F CH3 H Cl OCH3
236. CF3 F CH3 H Br OCH3
237. CF3 F CH3 H I OCH3
238. CF3 F CH3 F Cl OCH3
239. CF3 F CH3 F Br OCH3
240. CF3 F CH3 F I OCH3
241. CF3 Cl CH3 H Cl CF3
242. CF3 Cl CH3 H Br CF3
243. CF3 Cl CH3 H I CF3
244. CF3 Cl CH3 F Cl CF3
245. CF3 Cl CH3 F Br CF3
246. CF3 Cl CH3 F I CF3
247. CF3 Cl CH3 H Cl Cl
248. CF3 Cl CH3 H Br Cl
249. CF3 Cl CH3 H I Cl
250. CF3 Cl CH3 F Cl Cl
251. CF3 Cl CH3 F Br Cl
252. CF3 Cl CH3 F I Cl
253. CF3 Cl CH3 H Cl OCF3
254. CF3 Cl CH3 H Br OCF3
255. CF3 Cl CH3 H I OCF3
256. CF3 Cl CH3 F Cl OCF3
257. CF3 Cl CH3 F Br OCF3
258. CF3 Cl CH3 F I OCF3
259. CF3 Cl CH3 H Cl SCF3
260. CF3 Cl CH3 H Br SCF3
261. CF3 Cl CH3 H I SCF3
262. CF3 Cl CH3 F Cl SCF3
263. CF3 Cl CH3 F Br SCF3
264. CF3 Cl CH3 F I SCF3
265. CF3 Cl CH3 H Cl CN
266. CF3 Cl CH3 H Br CN
267. CF3 Cl CH3 H I CN
268. CF3 Cl CH3 F Cl CN
269. CF3 Cl CH3 F Br CN
270. CF3 Cl CH3 F I CN
271. CF3 Cl CH3 H Cl NO2
272. CF3 Cl CH3 H Br NO2
273. CF3 Cl CH3 H I NO2
274. CF3 Cl CH3 F Cl NO2
275. CF3 Cl CH3 F Br NO2
276. CF3 Cl CH3 F I NO2
277. CF3 Cl CH3 H Cl CH3
278. CF3 Cl CH3 H Br CH3
279. CF3 Cl CH3 H I CH3
280. CF3 Cl CH3 F Cl CH3
281. CF3 Cl CH3 F Br CH3
282. CF3 Cl CH3 F I CH3
283. CF3 Cl CH3 H Cl OCH3
284. CF3 Cl CH3 H Br OCH3
285. CF3 Cl CH3 H I OCH3
286. CF3 Cl CH3 F Cl OCH3
287. CF3 Cl CH3 F Br OCH3
288. CF3 Cl CH3 F I OCH3
289. CF3 F CH2CH3 H Cl CF3
290. CF3 F CH2CH3 H Br CF3
291. CF3 F CH2CH3 H I CF3
292. CF3 F CH2CH3 F Cl CF3
293. CF3 F CH2CH3 F Br CF3
294. CF3 F CH2CH3 F I CF3
295. CF3 F CH2CH3 H Cl Cl
296. CF3 F CH2CH3 H Br Cl
297. CF3 F CH2CH3 H I Cl
298. CF3 F CH2CH3 F Cl Cl
299. CF3 F CH2CH3 F Br Cl
300. CF3 F CH2CH3 F I Cl
301. CF3 F CH2CH3 H Cl OCF3
302. CF3 F CH2CH3 H Br OCF3
303. CF3 F CH2CH3 H I OCF3
304. CF3 F CH2CH3 F Cl OCF3
305. CF3 F CH2CH3 F Br OCF3
306. CF3 F CH2CH3 F I OCF3
307. CF3 F CH2CH3 H Cl SCF3
308. CF3 F CH2CH3 H Br SCF3
309. CF3 F CH2CH3 H I SCF3
310. CF3 F CH2CH3 F Cl SCF3
311. CF3 F CH2CH3 F Br SCF3
312. CF3 F CH2CH3 F I SCF3
313. CF3 F CH2CH3 H Cl CN
314. CF3 F CH2CH3 H Br CN
315. CF3 F CH2CH3 H I CN
316. CF3 F CH2CH3 F Cl CN
317. CF3 F CH2CH3 F Br CN
318. CF3 F CH2CH3 F I CN
319. CF3 F CH2CH3 H Cl NO2
320. CF3 F CH2CH3 H Br NO2
321. CF3 F CH2CH3 H I NO2
322. CF3 F CH2CH3 F Cl NO2
323. CF3 F CH2CH3 F Br NO2
324. CF3 F CH2CH3 F I NO2
325. CF3 F CH2CH3 H Cl CH3
326. CF3 F CH2CH3 H Br CH3
327. CF3 F CH2CH3 H I CH3
328. CF3 F CH2CH3 F Cl CH3
329. CF3 F CH2CH3 F Br CH3
330. CF3 F CH2CH3 F I CH3
331. CF3 F CH2CH3 H Cl OCH3
332. CF3 F CH2CH3 H Br OCH3
333. CF3 F CH2CH3 H I OCH3
334. CF3 F CH2CH3 F Cl OCH3
335. CF3 F CH2CH3 F Br OCH3
336. CF3 F CH2CH3 F I OCH3
337. CF3 Cl CH2CH3 H Cl CF3
338. CF3 Cl CH2CH3 H Br CF3
339. CF3 Cl CH2CH3 H I CF3
340. CF3 Cl CH2CH3 F Cl CF3
341. CF3 Cl CH2CH3 F Br CF3
342. CF3 Cl CH2CH3 F I CF3
343. CF3 Cl CH2CH3 H Cl Cl
344. CF3 Cl CH2CH3 H Br Cl
345. CF3 Cl CH2CH3 H I Cl
346. CF3 Cl CH2CH3 F Cl Cl
347. CF3 Cl CH2CH3 F Br Cl
348. CF3 Cl CH2CH3 F I Cl
349. CF3 Cl CH2CH3 H Cl OCF3
350. CF3 Cl CH2CH3 H Br OCF3
351. CF3 Cl CH2CH3 H I OCF3
352. CF3 Cl CH2CH3 F Cl OCF3
353. CF3 Cl CH2CH3 F Br OCF3
354. CF3 Cl CH2CH3 F I OCF3
355. CF3 Cl CH2CH3 H Cl SCF3
356. CF3 Cl CH2CH3 H Br SCF3
357. CF3 Cl CH2CH3 H I SCF3
358. CF3 Cl CH2CH3 F Cl SCF3
359. CF3 Cl CH2CH3 F Br SCF3
360. CF3 Cl CH2CH3 F I SCF3
361. CF3 Cl CH2CH3 H Cl CN
362. CF3 Cl CH2CH3 H Br CN
363. CF3 Cl CH2CH3 H I CN
364. CF3 Cl CH2CH3 F Cl CN
365. CF3 Cl CH2CH3 F Br CN
366. CF3 Cl CH2CH3 F I CN
367. CF3 Cl CH2CH3 H Cl NO2
368. CF3 Cl CH2CH3 H Br NO2
369. CF3 Cl CH2CH3 H I NO2
370. CF3 Cl CH2CH3 F Cl NO2
371. CF3 Cl CH2CH3 F Br NO2
372. CF3 Cl CH2CH3 F I NO2
373. CF3 Cl CH2CH3 H Cl CH3
374. CF3 Cl CH2CH3 H Br CH3
375. CF3 Cl CH2CH3 H I CH3
376. CF3 Cl CH2CH3 F Cl CH3
377. CF3 Cl CH2CH3 F Br CH3
378. CF3 Cl CH2CH3 F I CH3
379. CF3 Cl CH2CH3 H Cl OCH3
380. CF3 Cl CH2CH3 H Br OCH3
381. CF3 Cl CH2CH3 H I OCH3
382. CF3 Cl CH2CH3 F Cl OCH3
383. CF3 Cl CH2CH3 F Br OCH3
384. CF3 Cl CH2CH3 F I OCH3
385. CH3 F CH3 H Cl CF3
386. CH3 F CH3 H Br CF3
387. CH3 F CH3 H I CF3
388. CH3 F CH3 F Cl CF3
389. CH3 F CH3 F Br CF3
390. CH3 F CH3 F I CF3
391. CH3 F CH3 H Cl Cl
392. CH3 F CH3 H Br Cl
393. CH3 F CH3 H I Cl
394. CH3 F CH3 F Cl Cl
395. CH3 F CH3 F Br Cl
396. CH3 F CH3 F I Cl
397. CH3 F CH3 H Cl OCF3
398. CH3 F CH3 H Br OCF3
399. CH3 F CH3 H I OCF3
400. CH3 F CH3 F Cl OCF3
401. CH3 F CH3 F Br OCF3
402. CH3 F CH3 F I OCF3
403. CH3 F CH3 H Cl SCF3
404. CH3 F CH3 H Br SCF3
405. CH3 F CH3 H I SCF3
406. CH3 F CH3 F Cl SCF3
407. CH3 F CH3 F Br SCF3
408. CH3 F CH3 F I SCF3
409. CH3 F CH3 H Cl CN
410. CH3 F CH3 H Br CN
411. CH3 F CH3 H I CN
412. CH3 F CH3 F Cl CN
413. CH3 F CH3 F Br CN
414. CH3 F CH3 F I CN
415. CH3 F CH3 H Cl NO2
416. CH3 F CH3 H Br NO2
417. CH3 F CH3 H I NO2
418. CH3 F CH3 F Cl NO2
419. CH3 F CH3 F Br NO2
420. CH3 F CH3 F I NO2
421. CH3 F CH3 H Cl CH3
422. CH3 F CH3 H Br CH3
423. CH3 F CH3 H I CH3
424. CH3 F CH3 F Cl CH3
425. CH3 F CH3 F Br CH3
426. CH3 F CH3 F I CH3
427. CH3 F CH3 H Cl OCH3
428. CH3 F CH3 H Br OCH3
429. CH3 F CH3 H I OCH3
430. CH3 F CH3 F Cl OCH3
431. CH3 F CH3 F Br OCH3
432. CH3 F CH3 F I OCH3
433. CH3 Cl CH3 H Cl CF3
434. CH3 Cl CH3 H Br CF3
435. CH3 Cl CH3 H I CF3
436. CH3 Cl CH3 F Cl CF3
437. CH3 Cl CH3 F Br CF3
438. CH3 Cl CH3 F I CF3
439. CH3 Cl CH3 H Cl Cl
440. CH3 Cl CH3 H Br Cl
441. CH3 Cl CH3 H I Cl
442. CH3 Cl CH3 F Cl Cl
443. CH3 Cl CH3 F Br Cl
444. CH3 Cl CH3 F I Cl
445. CH3 Cl CH3 H Cl OCF3
446. CH3 Cl CH3 H Br OCF3
447. CH3 Cl CH3 H I OCF3
448. CH3 Cl CH3 F Cl OCF3
449. CH3 Cl CH3 F Br OCF3
450. CH3 Cl CH3 F I OCF3
451. CH3 Cl CH3 H Cl SCF3
452. CH3 Cl CH3 H Br SCF3
453. CH3 Cl CH3 H I SCF3
454. CH3 Cl CH3 F Cl SCF3
455. CH3 Cl CH3 F Br SCF3
456. CH3 Cl CH3 F I SCF3
457. CH3 Cl CH3 H Cl CN
458. CH3 Cl CH3 H Br CN
459. CH3 Cl CH3 H I CN
460. CH3 Cl CH3 F Cl CN
461. CH3 Cl CH3 F Br CN
462. CH3 Cl CH3 F I CN
463. CH3 Cl CH3 H Cl NO2
464. CH3 Cl CH3 H Br NO2
465. CH3 Cl CH3 H I NO2
466. CH3 Cl CH3 F Cl NO2
467. CH3 Cl CH3 F Br NO2
468. CH3 Cl CH3 F I NO2
469. CH3 Cl CH3 H Cl CH3
470. CH3 Cl CH3 H Br CH3
471. CH3 Cl CH3 H I CH3
472. CH3 Cl CH3 F Cl CH3
473. CH3 Cl CH3 F Br CH3
474. CH3 Cl CH3 F I CH3
475. CH3 Cl CH3 H Cl OCH3
476. CH3 Cl CH3 H Br OCH3
477. CH3 Cl CH3 H I OCH3
478. CH3 Cl CH3 F Cl OCH3
479. CH3 Cl CH3 F Br OCH3
480. CH3 Cl CH3 F I OCH3
481. CH3 F CH2CH3 H Cl CF3
482. CH3 F CH2CH3 H Br CF3
483. CH3 F CH2CH3 H I CF3
484. CH3 F CH2CH3 F Cl CF3
485. CH3 F CH2CH3 F Br CF3
486. CH3 F CH2CH3 F I CF3
487. CH3 F CH2CH3 H Cl Cl
488. CH3 F CH2CH3 H Br Cl
489. CH3 F CH2CH3 H I Cl
490. CH3 F CH2CH3 F Cl Cl
491. CH3 F CH2CH3 F Br Cl
492. CH3 F CH2CH3 F I Cl
493. CH3 F CH2CH3 H Cl OCF3
494. CH3 F CH2CH3 H Br OCF3
495. CH3 F CH2CH3 H I OCF3
496. CH3 F CH2CH3 F Cl OCF3
497. CH3 F CH2CH3 F Br OCF3
498. CH3 F CH2CH3 F I OCF3
499. CH3 F CH2CH3 H Cl SCF3
500. CH3 F CH2CH3 H Br SCF3
501. CH3 F CH2CH3 H I SCF3
502. CH3 F CH2CH3 F Cl SCF3
503. CH3 F CH2CH3 F Br SCF3
504. CH3 F CH2CH3 F I SCF3
505. CH3 F CH2CH3 H Cl CN
506. CH3 F CH2CH3 H Br CN
507. CH3 F CH2CH3 H I CN
508. CH3 F CH2CH3 F Cl CN
509. CH3 F CH2CH3 F Br CN
510. CH3 F CH2CH3 F I CN
511. CH3 F CH2CH3 H Cl NO2
512. CH3 F CH2CH3 H Br NO2
513. CH3 F CH2CH3 H I NO2
514. CH3 F CH2CH3 F Cl NO2
515. CH3 F CH2CH3 F Br NO2
516. CH3 F CH2CH3 F I NO2
517. CH3 F CH2CH3 H Cl CH3
518. CH3 F CH2CH3 H Br CH3
519. CH3 F CH2CH3 H I CH3
520. CH3 F CH2CH3 F Cl CH3
521. CH3 F CH2CH3 F Br CH3
522. CH3 F CH2CH3 F I CH3
523. CH3 F CH2CH3 H Cl OCH3
524. CH3 F CH2CH3 H Br OCH3
525. CH3 F CH2CH3 H I OCH3
526. CH3 F CH2CH3 F Cl OCH3
527. CH3 F CH2CH3 F Br OCH3
528. CH3 F CH2CH3 F I OCH3
529. CH3 Cl CH2CH3 H Cl CF3
530. CH3 Cl CH2CH3 H Br CF3
531. CH3 Cl CH2CH3 H I CF3
532. CH3 Cl CH2CH3 F Cl CF3
533. CH3 Cl CH2CH3 F Br CF3
534. CH3 Cl CH2CH3 F I CF3
535. CH3 Cl CH2CH3 H Cl Cl
536. CH3 Cl CH2CH3 H Br Cl
537. CH3 Cl CH2CH3 H I Cl
538. CH3 Cl CH2CH3 F Cl Cl
539. CH3 Cl CH2CH3 F Br Cl
540. CH3 Cl CH2CH3 F I Cl
541. CH3 Cl CH2CH3 H Cl OCF3
542. CH3 Cl CH2CH3 H Br OCF3
543. CH3 Cl CH2CH3 H I OCF3
544. CH3 Cl CH2CH3 F Cl OCF3
545. CH3 Cl CH2CH3 F Br OCF3
546. CH3 Cl CH2CH3 F I OCF3
547. CH3 Cl CH2CH3 H Cl SCF3
548. CH3 Cl CH2CH3 H Br SCF3
549. CH3 Cl CH2CH3 H I SCF3
550. CH3 Cl CH2CH3 F Cl SCF3
551. CH3 Cl CH2CH3 F Br SCF3
552. CH3 Cl CH2CH3 F I SCF3
553. CH3 Cl CH2CH3 H Cl CN
554. CH3 Cl CH2CH3 H Br CN
555. CH3 Cl CH2CH3 H I CN
556. CH3 Cl CH2CH3 F Cl CN
557. CH3 Cl CH2CH3 F Br CN
558. CH3 Cl CH2CH3 F I CN
559. CH3 Cl CH2CH3 H Cl NO2
560. CH3 Cl CH2CH3 H Br NO2
561. CH3 Cl CH2CH3 H I NO2
562. CH3 Cl CH2CH3 F Cl NO2
563. CH3 Cl CH2CH3 F Br NO2
564. CH3 Cl CH2CH3 F I NO2
565. CH3 Cl CH2CH3 H Cl CH3
566. CH3 Cl CH2CH3 H Br CH3
567. CH3 Cl CH2CH3 H I CH3
568. CH3 Cl CH2CH3 F Cl CH3
569. CH3 Cl CH2CH3 F Br CH3
570. CH3 Cl CH2CH3 F I CH3
571. CH3 Cl CH2CH3 H Cl OCH3
572. CH3 Cl CH2CH3 H Br OCH3
573. CH3 Cl CH2CH3 H I OCH3
574. CH3 Cl CH2CH3 F Cl OCH3
575. CH3 Cl CH2CH3 F Br OCH3
576. CH3 Cl CH2CH3 F I OCH3
当M为硫时，上述通式F-2所示的含二苯醚结构的吡唑酰胺类化合物的典型化合物如下表2。
表2
编号 R1 R2 R3 R4 R5 R7
577. CF2H F CH3 H Cl CF3
578. CF2H F CH3 H Br CF3
579. CF2H F CH3 H I CF3
580. CF2H F CH3 F Cl CF3
581. CF2H F CH3 F Br CF3
582. CF2H F CH3 F I CF3
583. CF2H F CH3 H Cl Cl
584. CF2H F CH3 H Br Cl
585. CF2H F CH3 H I Cl
586. CF2H F CH3 F Cl Cl
587. CF2H F CH3 F Br Cl
588. CF2H F CH3 F I Cl
589. CF2H F CH3 H Cl OCF3
590. CF2H F CH3 H Br OCF3
591. CF2H F CH3 H I OCF3
592. CF2H F CH3 F Cl OCF3
593. CF2H F CH3 F Br OCF3
594. CF2H F CH3 F I OCF3
595. CF2H F CH3 H Cl SCF3
596. CF2H F CH3 H Br SCF3
597. CF2H F CH3 H I SCF3
598. CF2H F CH3 F Cl SCF3
599. CF2H F CH3 F Br SCF3
600. CF2H F CH3 F I SCF3
601. CF2H F CH3 H Cl CN
602. CF2H F CH3 H Br CN
603. CF2H F CH3 H I CN
604. CF2H F CH3 F Cl CN
605. CF2H F CH3 F Br CN
606. CF2H F CH3 F I CN
607. CF2H F CH3 H Cl NO2
608. CF2H F CH3 H Br NO2
609. CF2H F CH3 H I NO2
610. CF2H F CH3 F Cl NO2
611. CF2H F CH3 F Br NO2
612. CF2H F CH3 F I NO2
613. CF2H F CH3 H Cl CH3
614. CF2H F CH3 H Br CH3
615. CF2H F CH3 H I CH3
616. CF2H F CH3 F Cl CH3
617. CF2H F CH3 F Br CH3
618. CF2H F CH3 F I CH3
619. CF2H F CH3 H Cl OCH3
620. CF2H F CH3 H Br OCH3
621. CF2H F CH3 H I OCH3
622. CF2H F CH3 F Cl OCH3
623. CF2H F CH3 F Br OCH3
624. CF2H F CH3 F I OCH3
625. CF2H Cl CH3 H Cl CF3
626. CF2H Cl CH3 H Br CF3
627. CF2H Cl CH3 H I CF3
628. CF2H Cl CH3 F Cl CF3
629. CF2H Cl CH3 F Br CF3
630. CF2H Cl CH3 F I CF3
631. CF2H Cl CH3 H Cl Cl
632. CF2H Cl CH3 H Br Cl
633. CF2H Cl CH3 H I Cl
634. CF2H Cl CH3 F Cl Cl
635. CF2H Cl CH3 F Br Cl
636. CF2H Cl CH3 F I Cl
637. CF2H Cl CH3 H Cl OCF3
638. CF2H Cl CH3 H Br OCF3
639. CF2H Cl CH3 H I OCF3
640. CF2H Cl CH3 F Cl OCF3
641. CF2H Cl CH3 F Br OCF3
642. CF2H Cl CH3 F I OCF3
643. CF2H Cl CH3 H Cl SCF3
644. CF2H Cl CH3 H Br SCF3
645. CF2H Cl CH3 H I SCF3
646. CF2H Cl CH3 F Cl SCF3
647. CF2H Cl CH3 F Br SCF3
648. CF2H Cl CH3 F I SCF3
649. CF2H Cl CH3 H Cl CN
650. CF2H Cl CH3 H Br CN
651. CF2H Cl CH3 H I CN
652. CF2H Cl CH3 F Cl CN
653. CF2H Cl CH3 F Br CN
654. CF2H Cl CH3 F I CN
655. CF2H Cl CH3 H Cl NO2
656. CF2H Cl CH3 H Br NO2
657. CF2H Cl CH3 H I NO2
658. CF2H Cl CH3 F Cl NO2
659. CF2H Cl CH3 F Br NO2
660. CF2H Cl CH3 F I NO2
661. CF2H Cl CH3 H Cl CH3
662. CF2H Cl CH3 H Br CH3
663. CF2H Cl CH3 H I CH3
664. CF2H Cl CH3 F Cl CH3
665. CF2H Cl CH3 F Br CH3
666. CF2H Cl CH3 F I CH3
667. CF2H Cl CH3 H Cl OCH3
668. CF2H Cl CH3 H Br OCH3
669. CF2H Cl CH3 H I OCH3
670. CF2H Cl CH3 F Cl OCH3
671. CF2H Cl CH3 F Br OCH3
672. CF2H Cl CH3 F I OCH3
673. CF2H F CH2CH3 H Cl CF3
674. CF2H F CH2CH3 H Br CF3
675. CF2H F CH2CH3 H I CF3
676. CF2H F CH2CH3 F Cl CF3
677. CF2H F CH2CH3 F Br CF3
678. CF2H F CH2CH3 F I CF3
679. CF2H F CH2CH3 H Cl Cl
680. CF2H F CH2CH3 H Br Cl
681. CF2H F CH2CH3 H I Cl
682. CF2H F CH2CH3 F Cl Cl
683. CF2H F CH2CH3 F Br Cl
684. CF2H F CH2CH3 F I Cl
685. CF2H F CH2CH3 H Cl OCF3
686. CF2H F CH2CH3 H Br OCF3
687. CF2H F CH2CH3 H I OCF3
688. CF2H F CH2CH3 F Cl OCF3
689. CF2H F CH2CH3 F Br OCF3
690. CF2H F CH2CH3 F I OCF3
691. CF2H F CH2CH3 H Cl SCF3
692. CF2H F CH2CH3 H Br SCF3
693. CF2H F CH2CH3 H I SCF3
694. CF2H F CH2CH3 F Cl SCF3
695. CF2H F CH2CH3 F Br SCF3
696. CF2H F CH2CH3 F I SCF3
697. CF2H F CH2CH3 H Cl CN
698. CF2H F CH2CH3 H Br CN
699. CF2H F CH2CH3 H I CN
700. CF2H F CH2CH3 F Cl CN
701. CF2H F CH2CH3 F Br CN
702. CF2H F CH2CH3 F I CN
703. CF2H F CH2CH3 H Cl NO2
704. CF2H F CH2CH3 H Br NO2
705. CF2H F CH2CH3 H I NO2
706. CF2H F CH2CH3 F Cl NO2
707. CF2H F CH2CH3 F Br NO2
708. CF2H F CH2CH3 F I NO2
709. CF2H F CH2CH3 H Cl CH3
710. CF2H F CH2CH3 H Br CH3
711. CF2H F CH2CH3 H I CH3
712. CF2H F CH2CH3 F Cl CH3
713. CF2H F CH2CH3 F Br CH3
714. CF2H F CH2CH3 F I CH3
715. CF2H F CH2CH3 H Cl OCH3
716. CF2H F CH2CH3 H Br OCH3
717. CF2H F CH2CH3 H I OCH3
718. CF2H F CH2CH3 F Cl OCH3
719. CF2H F CH2CH3 F Br OCH3
720. CF2H F CH2CH3 F I OCH3
721. CF2H Cl CH2CH3 H Cl CF3
722. CF2H Cl CH2CH3 H Br CF3
723. CF2H Cl CH2CH3 H I CF3
724. CF2H Cl CH2CH3 F Cl CF3
725. CF2H Cl CH2CH3 F Br CF3
726. CF2H Cl CH2CH3 F I CF3
727. CF2H Cl CH2CH3 H Cl Cl
728. CF2H Cl CH2CH3 H Br Cl
729. CF2H Cl CH2CH3 H I Cl
730. CF2H Cl CH2CH3 F Cl Cl
731. CF2H Cl CH2CH3 F Br Cl
732. CF2H Cl CH2CH3 F I Cl
733. CF2H Cl CH2CH3 H Cl OCF3
734. CF2H Cl CH2CH3 H Br OCF3
735. CF2H Cl CH2CH3 H I OCF3
736. CF2H Cl CH2CH3 F Cl OCF3
737. CF2H Cl CH2CH3 F Br OCF3
738. CF2H Cl CH2CH3 F I OCF3
739. CF2H Cl CH2CH3 H Cl SCF3
740. CF2H Cl CH2CH3 H Br SCF3
741. CF2H Cl CH2CH3 H I SCF3
742. CF2H Cl CH2CH3 F Cl SCF3
743. CF2H Cl CH2CH3 F Br SCF3
744. CF2H Cl CH2CH3 F I SCF3
745. CF2H Cl CH2CH3 H Cl CN
746. CF2H Cl CH2CH3 H Br CN
747. CF2H Cl CH2CH3 H I CN
748. CF2H Cl CH2CH3 F Cl CN
749. CF2H Cl CH2CH3 F Br CN
750. CF2H Cl CH2CH3 F I CN
751. CF2H Cl CH2CH3 H Cl NO2
752. CF2H Cl CH2CH3 H Br NO2
753. CF2H Cl CH2CH3 H I NO2
754. CF2H Cl CH2CH3 F Cl NO2
755. CF2H Cl CH2CH3 F Br NO2
756. CF2H Cl CH2CH3 F I NO2
757. CF2H Cl CH2CH3 H Cl CH3
758. CF2H Cl CH2CH3 H Br CH3
759. CF2H Cl CH2CH3 H I CH3
760. CF2H Cl CH2CH3 F Cl CH3
761. CF2H Cl CH2CH3 F Br CH3
762. CF2H Cl CH2CH3 F I CH3
763. CF2H Cl CH2CH3 H Cl OCH3
764. CF2H Cl CH2CH3 H Br OCH3
765. CF2H Cl CH2CH3 H I OCH3
766. CF2H Cl CH2CH3 F Cl OCH3
767. CF2H Cl CH2CH3 F Br OCH3
768. CF2H Cl CH2CH3 F I OCH3
769. CF3 F CH3 H Cl CF3
770. CF3 F CH3 H Br CF3
771. CF3 F CH3 H I CF3
772. CF3 F CH3 F Cl CF3
773. CF3 F CH3 F Br CF3
774. CF3 F CH3 F I CF3
775. CF3 F CH3 H Cl Cl
776. CF3 F CH3 H Br Cl
777. CF3 F CH3 H I Cl
778. CF3 F CH3 F Cl Cl
779. CF3 F CH3 F Br Cl
780. CF3 F CH3 F I Cl
781. CF3 F CH3 H Cl OCF3
782. CF3 F CH3 H Br OCF3
783. CF3 F CH3 H I OCF3
784. CF3 F CH3 F Cl OCF3
785. CF3 F CH3 F Br OCF3
786. CF3 F CH3 F I OCF3
787. CF3 F CH3 H Cl SCF3
788. CF3 F CH3 H Br SCF3
789. CF3 F CH3 H I SCF3
790. CF3 F CH3 F Cl SCF3
791. CF3 F CH3 F Br SCF3
792. CF3 F CH3 F I SCF3
793. CF3 F CH3 H Cl CN
794. CF3 F CH3 H Br CN
795. CF3 F CH3 H I CN
796. CF3 F CH3 F Cl CN
797. CF3 F CH3 F Br CN
798. CF3 F CH3 F I CN
799. CF3 F CH3 H Cl NO2
800. CF3 F CH3 H Br NO2
801. CF3 F CH3 H I NO2
802. CF3 F CH3 F Cl NO2
803. CF3 F CH3 F Br NO2
804. CF3 F CH3 F I NO2
805. CF3 F CH3 H Cl CH3
806. CF3 F CH3 H Br CH3
807. CF3 F CH3 H I CH3
808. CF3 F CH3 F Cl CH3
809. CF3 F CH3 F Br CH3
810. CF3 F CH3 F I CH3
811. CF3 F CH3 H Cl OCH3
812. CF3 F CH3 H Br OCH3
813. CF3 F CH3 H I OCH3
814. CF3 F CH3 F Cl OCH3
815. CF3 F CH3 F Br OCH3
816. CF3 F CH3 F I OCH3
817. CF3 Cl CH3 H Cl CF3
818. CF3 Cl CH3 H Br CF3
819. CF3 Cl CH3 H I CF3
820. CF3 Cl CH3 F Cl CF3
821. CF3 Cl CH3 F Br CF3
822. CF3 Cl CH3 F I CF3
823. CF3 Cl CH3 H Cl Cl
824. CF3 Cl CH3 H Br Cl
825. CF3 Cl CH3 H I Cl
826. CF3 Cl CH3 F Cl Cl
827. CF3 Cl CH3 F Br Cl
828. CF3 Cl CH3 F I Cl
829. CF3 Cl CH3 H Cl OCF3
830. CF3 Cl CH3 H Br OCF3
831. CF3 Cl CH3 H I OCF3
832. CF3 Cl CH3 F Cl OCF3
833. CF3 Cl CH3 F Br OCF3
834. CF3 Cl CH3 F I OCF3
835. CF3 Cl CH3 H Cl SCF3
836. CF3 Cl CH3 H Br SCF3
837. CF3 Cl CH3 H I SCF3
838. CF3 Cl CH3 F Cl SCF3
839. CF3 Cl CH3 F Br SCF3
840. CF3 Cl CH3 F I SCF3
841. CF3 Cl CH3 H Cl CN
842. CF3 Cl CH3 H Br CN
843. CF3 Cl CH3 H I CN
844. CF3 Cl CH3 F Cl CN
845. CF3 Cl CH3 F Br CN
846. CF3 Cl CH3 F I CN
847. CF3 Cl CH3 H Cl NO2
848. CF3 Cl CH3 H Br NO2
849. CF3 Cl CH3 H I NO2
850. CF3 Cl CH3 F Cl NO2
851. CF3 Cl CH3 F Br NO2
852. CF3 Cl CH3 F I NO2
853. CF3 Cl CH3 H Cl CH3
854. CF3 Cl CH3 H Br CH3
855. CF3 Cl CH3 H I CH3
856. CF3 Cl CH3 F Cl CH3
857. CF3 Cl CH3 F Br CH3
858. CF3 Cl CH3 F I CH3
859. CF3 Cl CH3 H Cl OCH3
860. CF3 Cl CH3 H Br OCH3
861. CF3 Cl CH3 H I OCH3
862. CF3 Cl CH3 F Cl OCH3
863. CF3 Cl CH3 F Br OCH3
864. CF3 Cl CH3 F I OCH3
865. CF3 F CH2CH3 H Cl CF3
866. CF3 F CH2CH3 H Br CF3
867. CF3 F CH2CH3 H I CF3
868. CF3 F CH2CH3 F Cl CF3
869. CF3 F CH2CH3 F Br CF3
870. CF3 F CH2CH3 F I CF3
871. CF3 F CH2CH3 H Cl Cl
872. CF3 F CH2CH3 H Br Cl
873. CF3 F CH2CH3 H I Cl
874. CF3 F CH2CH3 F Cl Cl
875. CF3 F CH2CH3 F Br Cl
876. CF3 F CH2CH3 F I Cl
877. CF3 F CH2CH3 H Cl OCF3
878. CF3 F CH2CH3 H Br OCF3
879. CF3 F CH2CH3 H I OCF3
880. CF3 F CH2CH3 F Cl OCF3
881. CF3 F CH2CH3 F Br OCF3
882. CF3 F CH2CH3 F I OCF3
883. CF3 F CH2CH3 H Cl SCF3
884. CF3 F CH2CH3 H Br SCF3
885. CF3 F CH2CH3 H I SCF3
886. CF3 F CH2CH3 F Cl SCF3
887. CF3 F CH2CH3 F Br SCF3
888. CF3 F CH2CH3 F I SCF3
889. CF3 F CH2CH3 H Cl CN
890. CF3 F CH2CH3 H Br CN
891. CF3 F CH2CH3 H I CN
892. CF3 F CH2CH3 F Cl CN
893. CF3 F CH2CH3 F Br CN
894. CF3 F CH2CH3 F I CN
895. CF3 F CH2CH3 H Cl NO2
896. CF3 F CH2CH3 H Br NO2
897. CF3 F CH2CH3 H I NO2
898. CF3 F CH2CH3 F Cl NO2
899. CF3 F CH2CH3 F Br NO2
900. CF3 F CH2CH3 F I NO2
901. CF3 F CH2CH3 H Cl CH3
902. CF3 F CH2CH3 H Br CH3
903. CF3 F CH2CH3 H I CH3
904. CF3 F CH2CH3 F Cl CH3
905. CF3 F CH2CH3 F Br CH3
906. CF3 F CH2CH3 F I CH3
907. CF3 F CH2CH3 H Cl OCH3
908. CF3 F CH2CH3 H Br OCH3
909. CF3 F CH2CH3 H I OCH3
910. CF3 F CH2CH3 F Cl OCH3
911. CF3 F CH2CH3 F Br OCH3
912. CF3 F CH2CH3 F I OCH3
913. CF3 Cl CH2CH3 H Cl CF3
914. CF3 Cl CH2CH3 H Br CF3
915. CF3 Cl CH2CH3 H I CF3
916. CF3 Cl CH2CH3 F Cl CF3
917. CF3 Cl CH2CH3 F Br CF3
918. CF3 Cl CH2CH3 F I CF3
919. CF3 Cl CH2CH3 H Cl Cl
920. CF3 Cl CH2CH3 H Br Cl
921. CF3 Cl CH2CH3 H I Cl
922. CF3 Cl CH2CH3 F Cl Cl
923. CF3 Cl CH2CH3 F Br Cl
924. CF3 Cl CH2CH3 F I Cl
925. CF3 Cl CH2CH3 H Cl OCF3
926. CF3 Cl CH2CH3 H Br OCF3
927. CF3 Cl CH2CH3 H I OCF3
928. CF3 Cl CH2CH3 F Cl OCF3
929. CF3 Cl CH2CH3 F Br OCF3
930. CF3 Cl CH2CH3 F I OCF3
931. CF3 Cl CH2CH3 H Cl SCF3
932. CF3 Cl CH2CH3 H Br SCF3
933. CF3 Cl CH2CH3 H I SCF3
934. CF3 Cl CH2CH3 F Cl SCF3
935. CF3 Cl CH2CH3 F Br SCF3
936. CF3 Cl CH2CH3 F I SCF3
937. CF3 Cl CH2CH3 H Cl CN
938. CF3 Cl CH2CH3 H Br CN
939. CF3 Cl CH2CH3 H I CN
940. CF3 Cl CH2CH3 F Cl CN
941. CF3 Cl CH2CH3 F Br CN
942. CF3 Cl CH2CH3 F I CN
943. CF3 Cl CH2CH3 H Cl NO2
944. CF3 Cl CH2CH3 H Br NO2
945. CF3 Cl CH2CH3 H I NO2
946. CF3 Cl CH2CH3 F Cl NO2
947. CF3 Cl CH2CH3 F Br NO2
948. CF3 Cl CH2CH3 F I NO2
949. CF3 Cl CH2CH3 H Cl CH3
950. CF3 Cl CH2CH3 H Br CH3
951. CF3 Cl CH2CH3 H I CH3
952. CF3 Cl CH2CH3 F Cl CH3
953. CF3 Cl CH2CH3 F Br CH3
954. CF3 Cl CH2CH3 F I CH3
955. CF3 Cl CH2CH3 H Cl OCH3
956. CF3 Cl CH2CH3 H Br OCH3
957. CF3 Cl CH2CH3 H I OCH3
958. CF3 Cl CH2CH3 F Cl OCH3
959. CF3 Cl CH2CH3 F Br OCH3
960. CF3 Cl CH2CH3 F I OCH3
961. CH3 F CH3 H Cl CF3
962. CH3 F CH3 H Br CF3
963. CH3 F CH3 H I CF3
964. CH3 F CH3 F Cl CF3
965. CH3 F CH3 F Br CF3
966. CH3 F CH3 F I CF3
967. CH3 F CH3 H Cl Cl
968. CH3 F CH3 H Br Cl
969. CH3 F CH3 H I Cl
970. CH3 F CH3 F Cl Cl
971. CH3 F CH3 F Br Cl
972. CH3 F CH3 F I Cl
973. CH3 F CH3 H Cl OCF3
974. CH3 F CH3 H Br OCF3
975. CH3 F CH3 H I OCF3
976. CH3 F CH3 F Cl OCF3
977. CH3 F CH3 F Br OCF3
978. CH3 F CH3 F I OCF3
979. CH3 F CH3 H Cl SCF3
980. CH3 F CH3 H Br SCF3
981. CH3 F CH3 H I SCF3
982. CH3 F CH3 F Cl SCF3
983. CH3 F CH3 F Br SCF3
984. CH3 F CH3 F I SCF3
985. CH3 F CH3 H Cl CN
986. CH3 F CH3 H Br CN
987. CH3 F CH3 H I CN
988. CH3 F CH3 F Cl CN
989. CH3 F CH3 F Br CN
990. CH3 F CH3 F I CN
991. CH3 F CH3 H Cl NO2
992. CH3 F CH3 H Br NO2
993. CH3 F CH3 H I NO2
994. CH3 F CH3 F Cl NO2
995. CH3 F CH3 F Br NO2
996. CH3 F CH3 F I NO2
997. CH3 F CH3 H Cl CH3
998. CH3 F CH3 H Br CH3
999. CH3 F CH3 H I CH3
1000. CH3 F CH3 F Cl CH3
1001. CH3 F CH3 F Br CH3
1002. CH3 F CH3 F I CH3
1003. CH3 F CH3 H Cl OCH3
1004. CH3 F CH3 H Br OCH3
1005. CH3 F CH3 H I OCH3
1006. CH3 F CH3 F Cl OCH3
1007. CH3 F CH3 F Br OCH3
1008. CH3 F CH3 F I OCH3
1009. CH3 Cl CH3 H Cl CF3
1010. CH3 Cl CH3 H Br CF3
1011. CH3 Cl CH3 H I CF3
1012. CH3 Cl CH3 F Cl CF3
1013. CH3 Cl CH3 F Br CF3
1014. CH3 Cl CH3 F I CF3
1015. CH3 Cl CH3 H Cl Cl
1016. CH3 Cl CH3 H Br Cl
1017. CH3 Cl CH3 H I Cl
1018. CH3 Cl CH3 F Cl Cl
1019. CH3 Cl CH3 F Br Cl
1020. CH3 Cl CH3 F I Cl
1021. CH3 Cl CH3 H Cl OCF3
1022. CH3 Cl CH3 H Br OCF3
1023. CH3 Cl CH3 H I OCF3
1024. CH3 Cl CH3 F Cl OCF3
1025. CH3 Cl CH3 F Br OCF3
1026. CH3 Cl CH3 F I OCF3
1027. CH3 Cl CH3 H Cl SCF3
1028. CH3 Cl CH3 H Br SCF3
1029. CH3 Cl CH3 H I SCF3
1030. CH3 Cl CH3 F Cl SCF3
1031. CH3 Cl CH3 F Br SCF3
1032. CH3 Cl CH3 F I SCF3
1033. CH3 Cl CH3 H Cl CN
1034. CH3 Cl CH3 H Br CN
1035. CH3 Cl CH3 H I CN
1036. CH3 Cl CH3 F Cl CN
1037. CH3 Cl CH3 F Br CN
1038. CH3 Cl CH3 F I CN
1039. CH3 Cl CH3 H Cl NO2
1040. CH3 Cl CH3 H Br NO2
1041. CH3 Cl CH3 H I NO2
1042. CH3 Cl CH3 F Cl NO2
1043. CH3 Cl CH3 F Br NO2
1044. CH3 Cl CH3 F I NO2
1045. CH3 Cl CH3 H Cl CH3
1046. CH3 Cl CH3 H Br CH3
1047. CH3 Cl CH3 H I CH3
1048. CH3 Cl CH3 F Cl CH3
1049. CH3 Cl CH3 F Br CH3
1050. CH3 Cl CH3 F I CH3
1051. CH3 Cl CH3 H Cl OCH3
1052. CH3 Cl CH3 H Br OCH3
1053. CH3 Cl CH3 H I OCH3
1054. CH3 Cl CH3 F Cl OCH3
1055. CH3 Cl CH3 F Br OCH3
1056. CH3 Cl CH3 F I OCH3
1057. CH3 F CH2CH3 H Cl CF3
1058. CH3 F CH2CH3 H Br CF3
1059. CH3 F CH2CH3 H I CF3
1060. CH3 F CH2CH3 F Cl CF3
1061. CH3 F CH2CH3 F Br CF3
1062. CH3 F CH2CH3 F I CF3
1063. CH3 F CH2CH3 H Cl Cl
1064. CH3 F CH2CH3 H Br Cl
1065. CH3 F CH2CH3 H I Cl
1066. CH3 F CH2CH3 F Cl Cl
1067. CH3 F CH2CH3 F Br Cl
1068. CH3 F CH2CH3 F I Cl
1069. CH3 F CH2CH3 H Cl OCF3
1070. CH3 F CH2CH3 H Br OCF3
1071. CH3 F CH2CH3 H I OCF3
1072. CH3 F CH2CH3 F Cl OCF3
1073. CH3 F CH2CH3 F Br OCF3
1074. CH3 F CH2CH3 F I OCF3
1075. CH3 F CH2CH3 H Cl SCF3
1076. CH3 F CH2CH3 H Br SCF3
1077. CH3 F CH2CH3 H I SCF3
1078. CH3 F CH2CH3 F Cl SCF3
1079. CH3 F CH2CH3 F Br SCF3
1080. CH3 F CH2CH3 F I SCF3
1081. CH3 F CH2CH3 H Cl CN
1082. CH3 F CH2CH3 H Br CN
1083. CH3 F CH2CH3 H I CN
1084. CH3 F CH2CH3 F Cl CN
1085. CH3 F CH2CH3 F Br CN
1086. CH3 F CH2CH3 F I CN
1087. CH3 F CH2CH3 H Cl NO2
1088. CH3 F CH2CH3 H Br NO2
1089. CH3 F CH2CH3 H I NO2
1090. CH3 F CH2CH3 F Cl NO2
1091. CH3 F CH2CH3 F Br NO2
1092. CH3 F CH2CH3 F I NO2
1093. CH3 F CH2CH3 H Cl CH3
1094. CH3 F CH2CH3 H Br CH3
1095. CH3 F CH2CH3 H I CH3
1096. CH3 F CH2CH3 F Cl CH3
1097. CH3 F CH2CH3 F Br CH3
1098. CH3 F CH2CH3 F I CH3
1099. CH3 F CH2CH3 H Cl OCH3
1100. CH3 F CH2CH3 H Br OCH3
1101. CH3 F CH2CH3 H I OCH3
1102. CH3 F CH2CH3 F Cl OCH3
1103. CH3 F CH2CH3 F Br OCH3
1104. CH3 F CH2CH3 F I OCH3
1105. CH3 Cl CH2CH3 H Cl CF3
1106. CH3 Cl CH2CH3 H Br CF3
1107. CH3 Cl CH2CH3 H I CF3
1108. CH3 Cl CH2CH3 F Cl CF3
1109. CH3 Cl CH2CH3 F Br CF3
1110. CH3 Cl CH2CH3 F I CF3
1111. CH3 Cl CH2CH3 H Cl Cl
1112. CH3 Cl CH2CH3 H Br Cl
1113. CH3 Cl CH2CH3 H I Cl
1114. CH3 Cl CH2CH3 F Cl Cl
1115. CH3 Cl CH2CH3 F Br Cl
1116. CH3 Cl CH2CH3 F I Cl
1117. CH3 Cl CH2CH3 H Cl OCF3
1118. CH3 Cl CH2CH3 H Br OCF3
1119. CH3 Cl CH2CH3 H I OCF3
1120. CH3 Cl CH2CH3 F Cl OCF3
1121. CH3 Cl CH2CH3 F Br OCF3
1122. CH3 Cl CH2CH3 F I OCF3
1123. CH3 Cl CH2CH3 H Cl SCF3
1124. CH3 Cl CH2CH3 H Br SCF3
1125. CH3 Cl CH2CH3 H I SCF3
1126. CH3 Cl CH2CH3 F Cl SCF3
1127. CH3 Cl CH2CH3 F Br SCF3
1128. CH3 Cl CH2CH3 F I SCF3
1129. CH3 Cl CH2CH3 H Cl CN
1130. CH3 Cl CH2CH3 H Br CN
1131. CH3 Cl CH2CH3 H I CN
1132. CH3 Cl CH2CH3 F Cl CN
1133. CH3 Cl CH2CH3 F Br CN
1134. CH3 Cl CH2CH3 F I CN
1135. CH3 Cl CH2CH3 H Cl NO2
1136. CH3 Cl CH2CH3 H Br NO2
1137. CH3 Cl CH2CH3 H I NO2
1138. CH3 Cl CH2CH3 F Cl NO2
1139. CH3 Cl CH2CH3 F Br NO2
1140. CH3 Cl CH2CH3 F I NO2
1141. CH3 Cl CH2CH3 H Cl CH3
1142. CH3 Cl CH2CH3 H Br CH3
1143. CH3 Cl CH2CH3 H I CH3
1144. CH3 Cl CH2CH3 F Cl CH3
1145. CH3 Cl CH2CH3 F Br CH3
1146. CH3 Cl CH2CH3 F I CH3
1147. CH3 Cl CH2CH3 H Cl OCH3
1148. CH3 Cl CH2CH3 H Br OCH3
1149. CH3 Cl CH2CH3 H I OCH3
1150. CH3 Cl CH2CH3 F Cl OCH3
1151. CH3 Cl CH2CH3 F Br OCH3
1152. CH3 Cl CH2CH3 F I OCH3
本发明还提供了所述含二苯醚结构的吡唑酰胺化合物的制备方法。
当R2选自氯或溴时，所述含二苯醚结构的吡唑酰胺化合物优选按照以下方法制备：
Figure PCTCN2016083409-appb-000007
其中：R1、R2、R3、R4、R5、R6、R7、R8、X、Y和M的定义及优选如前所述，R0优选自甲基或乙基，T优选自氟、氯、溴或碘。
当R2为氟时，所述含二苯醚结构的吡唑酰胺化合物优选按照以下方法制备：
Figure PCTCN2016083409-appb-000008
其中：R1、R2、R3、R4、R5、R6、R7、R8、X、Y和M的定义及优选如前所述，R0优选自甲基或乙基，T优选自氟、氯、溴或碘。
在上述制备方法中，本领域常用的引发剂、氧化剂、酰氯化、催化剂、碱、溶剂、缩合剂、缩合试剂、卤化剂、硫化试剂等均能用于本发明。
本发明还提供了上述含二苯醚结构的吡唑酰胺化合物的应用。本发明提供的含二苯醚结构的吡唑酰胺类化合物适合用于农用杀菌。优选的是，所述含二苯醚结构的吡唑酰胺类化合物适合用于防治由丝核菌属、柄锈菌属、黑粉菌属、腥黑粉菌属、伏革菌属、核腔菌属或担子菌纲真菌引起的病害。进一步优选的是，所述含二苯醚结构的吡唑酰胺类化合物适合用于防治纹枯病、立枯病、白粉病或锈病。
本发明还提供了一种农用化学杀菌剂，所述农用化学杀菌剂含有1～99％质量百分含量的含二苯醚结构的吡唑酰胺类化合物。
当配制农用化学杀菌剂时，所述农用化学杀菌剂可以被配制成各种液剂、乳油、悬浮剂、水悬剂、微乳剂、乳剂、水乳剂、粉剂、可湿性粉剂、可溶性粉剂、颗粒剂、水分散型颗粒剂或胶囊剂。所述农用化学杀菌剂包括本发明所述喹啉类化合物和载体。载体至少包括两种，其中至少一种是表面活性剂。载体可以是固体或液体。合适的固体载体包括天然的或合成的粘土和硅酸盐，例如天然硅石和硅藻土；硅酸镁例如滑石；硅酸铝镁例如高岭石、高岭土、蒙脱土和云母；白碳黑、碳酸钙、轻质碳酸钙；硫酸钙；石灰石；硫酸钠；胺盐如硫酸铵、六甲撑二胺。液体载体包括水和有机溶剂，当用水做溶剂或稀释剂时，有机溶剂也能用做辅助剂或防冻添加剂。合适的有机溶剂包括芳烃例如苯、二甲苯、甲苯等；氯代烃，例如氯代 苯、氯乙烯、三氯甲烷、二氯甲烷等；脂肪烃，例如石油馏分、环己烷、轻质矿物油；醇类，例如异丙醇、丁醇、乙二醇、丙三醇和环己醇等；以及它们的醚和酯；还有酮类，例如丙酮、环己酮以及二甲基甲酰胺和N-甲基-吡咯烷酮。
表面活性剂可以是乳化剂、分散剂或湿润剂；可以是离子型的或非离子型的。非离子型乳化剂例如聚氧乙烯脂肪酸脂、聚氧乙烯脂肪醇醚、聚氧乙烯脂肪氨，以及市售的乳化剂：农乳2201B、农乳0203B、农乳100#、农乳500#、农乳600#、农乳600-2#、农乳1601、农乳2201、农乳NP-10、农乳NP-15、农乳507#、农乳OX-635、农乳OX-622、农乳OX-653、农乳OX-667、宁乳36#。分散剂包括木质素磺酸钠、拉开粉、木质素磺酸钙、甲基萘磺酸甲醛缩合物等。湿润剂为：月桂醇硫酸钠、十二烷基苯磺酸钠、烷基萘磺酸钠等。
农用化学杀菌剂可由通用的方法制备。例如，将活性物质与液体溶剂和/或固体载体混合，同时加入表面活性剂如乳化剂、分散剂、稳定剂、湿润剂，还可以加入其它助剂如：粘合剂、消泡剂、氧化剂等。
具体实施方式
下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。
(一)化合物制备
实施例1：化合物1合成
Figure PCTCN2016083409-appb-000009
步骤(1)：1-甲基-3-二氟甲基-5-羟基-1H-吡唑合成
在500ml的三口瓶中，加入42克二氟乙酰乙酯乙酯的300ml甲苯溶液，加入10克乙酸，冷却，在搅拌下加入1.1倍摩尔量的40％甲基肼水溶液，大约1h滴加完毕，反应体系升到室温，反应过夜，第二天向体系加入100ml水，分出甲苯层，有机层用无水硫酸镁干燥，减压蒸出甲苯得浅红色固体32克。浅红色固体即为1-甲基-3-二氟甲基-5-羟基-1H-吡唑，熔点为130～132℃，不用提纯用于下一步反应。
步骤(2)：1-甲基-3-二氟甲基-5-氯-4-甲醛-1H-吡唑合成
将无水34ml的N,N-二甲基甲酰胺加入到250ml三口瓶中，将体系冷却至0℃，然后搅拌下滴加143克三氯氧磷，大约2h加完，继续搅拌30分钟，慢慢加入30克步骤(1)得到的1-甲基-3-二氟甲基-5-羟基-1H-吡唑，缓慢升温到室温搅拌2h，然后体系升温到90℃反应3h，冷却到室温，加入到1000ml的冰水中，用乙酯乙酯萃取，乙酸乙酯用无水硫酸镁干燥，蒸出乙酸乙酯得棕色固体36克。得到的棕色固体即为1-甲基-3-二氟甲基-5-氯-4-甲醛-1H-吡唑，不用提纯直接用于下一步反应。
步骤(3)：1-甲基-3-二氟甲基-5-氟-4-甲醛-1H-吡唑合成
将步骤(2)得到的30克1-甲基-3-二氟甲基-5-氯-4-甲醛-1H-吡唑加入到250ml单口瓶中，加入100mlN,N-二甲基甲酰胺，加入2倍摩尔量的无水氟化钾，体系搅拌加热回流5h,HPLC跟踪反应完全，减压蒸出溶剂，将残留加入到100ml水中，用乙酸乙酯萃取，乙酸乙酯用无水硫酸镁干燥，蒸出乙酸乙酯得棕色固体21克。棕色固体即为1-甲基-3-二氟甲基-5-氟-4-甲醛-1H-吡唑，熔点为66.5-67.2℃，1HNMR(600MHZ,CDCl3/TMS)：δ＝9.81(1H，s),6.87(1H,t),3.71(3H,s)ppm。
步骤(4)：1-甲基-3-二氟甲基-5-氟-4-甲酰氯-1H-吡唑合成
将步骤(3)得到的15克1-甲基-3-二氟甲基-5-氟-4-甲醛-1H-吡唑加入到150ml的单口瓶中，加入二氯乙烷60ml，加入偶氮二异丁腈0.5克，加入等摩尔量的磺酰氯，体系加热回流1h，蒸出二氯乙烷，得油状物18克。得到的油状物即为1-甲基-3-二氟甲基-5-氟-4-甲酰氯-1H-吡唑，1HNMR(600MHZ,CDCl3/TMS)：δ＝6.87(1H,t),3.71(3H,s)ppm。
步骤(5)：2-氯-1-(2-硝基-苯氧基)-4-三氟甲基苯合成
将14.1克(0.1mol)2-氟硝基苯加入到150ml单口瓶中，加入70mllN,N-二甲基甲酰胺，加入1.5倍摩尔量的碳酸钾，加入19.6克(0.1mol)2-氯-4-三氟甲基苯酚，然后体系加热回流反应5h，蒸出溶剂，将残留倒到100ml水中，用乙酸乙酯萃取，用无水硫酸镁干燥，蒸出溶剂，柱层析提纯得产物20克。产物即为2-氯-1-(2-硝基-苯氧基)-4-三氟甲基苯。
步骤(6)：2-氯-1-(2-氨基-苯氧基)-4-三氟甲基苯合成
将步骤(5)制备的15克2-氯-1-(2-硝基-苯氧基)-4-三氟甲基苯加入到加氢还原釜 中，加入100ml乙醇，加入1克10％钯碳，在室温通氢还原，直到体系不再吸氢，过滤去催化剂，蒸溶剂得白色固体14.2克。白色固体即为2-氯-1-(2-氨基-苯氧基)-4-三氟甲基苯。
步骤(7)：目标化合物1的合成
将步骤(4)制备的0.3克1-甲基-3-二氟甲基-5-氟-4-甲酰氯-1H-吡唑溶于20ml的四氢呋喃中，加入等摩尔量的步骤(6)制备的2-氯-1-(2-氨基-苯氧基)-4-三氟甲基苯，然后加入1.5倍量的缚酸剂三乙胺，体系室温反应2h，TLC跟踪反应完成，过滤去固体，滤液蒸出溶剂，用柱层析提纯得0.5克产物。产物即为结构式1所示化合物，其核磁数据如下：
1HNMR(600MHZ,CDCl3/TMS)：δ＝8.55～8.56(1H，d),8.31(1H,s),
7.77(1H,s),7.46～7.48(1H,d)，7.23～7.25(1H，t)，7.11～7.10(1H，t)，
7.00～7.01(1H,d),7.01～6.89(1H，t),6.89～6.90(1H,d),3.82(3H,s)ppm。
实施例2：化合物2合成
Figure PCTCN2016083409-appb-000010
步骤(1)：2-溴-4-三氟甲基-苯酚合成
将32克对三氟甲基苯酚溶于200ml二氯甲烷中，在冷却下滴加等摩尔液溴，大约2h滴加完毕，然后室温搅拌反应12h，体系用饱和碳酸氢钠洗到中性，干燥，蒸出溶剂得到稠状液体40g。得到的稠状液体即为2-溴-4-三氟甲基-苯酚，其核磁数据为：1HNMR(600MHZ,CDCl3/TMS)
δ＝7.75(1H,s),7.47～7.49(1H,d),7.08～7.10(1H,d),6.21(1H,s)ppm，不用提纯用于下一步反应。
步骤(2)：2-溴-1-(2-硝基-苯氧基)-4-三氟甲基苯合成
将14.1克(0.1mol)2-氟硝基苯加入到150ml单口瓶中，加入70mllN,N-二甲基甲酰胺，加入1.5倍摩尔量的碳酸钾，加入步骤(1)制得的24.1克(0.1mol)2-溴-4-三氟甲基苯酚，然后体系加热回流反应5h，蒸出溶剂，将残留倒到100ml水中，用乙酸乙酯萃取，用无水硫酸镁干燥，蒸出溶剂，柱层析提纯得产物25克。产物即为2-溴-1-(2-硝基-苯氧基)-4-三 氟甲基苯。
步骤(3)：2-溴-1-(2-氨基-苯氧基)-4-三氟甲基苯合成
将步骤(2)制得的20克2-溴-1-(2-硝基-苯氧基)-4-三氟甲基苯加入到加氢还原釜中，加入100ml乙醇，加入2克10％钯碳，在室温通氢还原，直到体系不再吸氢，过滤去催化剂，蒸溶剂得白色固体18.2克。白色固体即为2-溴-1-(2-氨基-苯氧基)-4-三氟甲基苯。
步骤(4)：目标化合物2的合成
将0.3克1-甲基-3-二氟甲基-5-氟-4-甲酰氯-1H-吡唑溶于20ml的四氢呋喃中，加入等摩尔量的步骤(3)制得的2-溴-1-(2-氨基-苯氧基)-4-三氟甲基苯，然后加入1.5倍量的缚酸剂三乙胺，体系室温反应2h，TLC跟踪反应完成，过滤去固体，滤液蒸出溶剂，用柱层析提纯得0.6克产物。产物即为结构式2所示化合物，其核磁数据如下：
1HNMR(600MHZ,CDCl3/TMS)：δ＝8.54～8.56(1H，d),8.29(1H,s),
7.93(1H,s),7.64～7.65(1H,d)，7.23～7.25(1H，t)，7.11～7.12(1H，t)，
6.96～6.97(1H,d),6.90～7.08(1H，t),6.88～6.90(1H,d),3.82(3H,s)ppm。
实施例3：化合物4合成
Figure PCTCN2016083409-appb-000011
步骤(1)：2-氯-1-(2-硝基-5-氟-苯氧基)-4-三氟甲基苯合成
将15.9克(0.1mol)2，4-二氟硝基苯加入到150ml单口瓶中，加入150mllN,N-二甲基甲酰胺，加入1.5倍摩尔量的碳酸钾，将体系冷却到10℃，然后慢慢加入19.6克(0.1mol)2-氯-4-三氟甲基苯酚大约1h加完，保持温度反应2h，，然后体系倒入500水中用乙酸乙酯萃取，用无水硫酸镁干燥，蒸出溶剂，柱层析提纯得产物10克。产物即为2-氯-1-(2-硝基-5-氟-苯氧基)-4-三氟甲基苯，熔点为118～120℃，核磁数据如下：
1HNMR(600MHZ,CDCl3/TMS)：δ＝8.13～8.16(1H,q),7.80(1H,s),
7.56～7.58(1H,d),7.14～7.15(1H,d)，6.99～7.02(1H,m)，6.62～6.64(1H,q)ppm。
步骤(2)：2-氯-1-(2-氨基-5-氟-苯氧基)-4-三氟甲基苯合成
将步骤(1)制得的10克2-氯-1-(2-硝基-5-氟-苯氧基)-4-三氟甲基苯加入到加氢还原釜中，加入100ml乙醇，加入2克10％钯碳，在室温通氢还原，直到体系不再吸氢，过滤去催化剂，蒸溶剂得白色固体9.5克。白色固体即为2-氯-1-(2-氨基-5-氟-苯氧基)-4-三氟甲基苯。
步骤(3)：目标化合物4的合成
将0.3克1-甲基-3-二氟甲基-5-氟-4-甲酰氯-1H-吡唑溶于20ml的四氢呋喃中，加入等摩尔量的步骤(2)制得的2-氯-1-(2-氨基-5-氟-苯氧基)-4-三氟甲基苯，然后加入1.5倍量的缚酸剂三乙胺，体系室温反应2h，TLC跟踪反应完成，过滤去固体，滤液蒸出溶剂，用柱层析提纯得0.45克产物。产物即为结构式4所示化合物。
(二)制剂配制
以下实施例中按照质量配比配制。
实施例4、30％悬浮剂
Figure PCTCN2016083409-appb-000012
将化合物1及其它组分充分混合，由此得到的30％悬浮剂。用水稀释所得悬浮剂可得到任何所需浓度的稀释液。
实施例5、30％水悬浮液
Figure PCTCN2016083409-appb-000013
Figure PCTCN2016083409-appb-000014
先将化合物2、应加水量的80％和十二烷基磺酸钠在球磨机中一起粉碎，再将半纤维素和环氧丙烷溶解在剩余20％的水中，最后搅拌加入粉碎后的物质得到30％水悬浮液。
实施例6、30％乳油
Figure PCTCN2016083409-appb-000015
将亚磷酸溶解在甲苯中，加入化合物4和乙氧基化甘油三酸酯，得到透明的溶液，即为30％乳油。
实施例7、60％可湿粉剂
Figure PCTCN2016083409-appb-000016
将化合物1、十二烷基萘磺酸钠、木质素磺酸钠及硅澡土混合在一起，在粉碎机中粉碎，直到颗粒达到标准后即为60％可湿粉剂。
(三)生物活性测试
实施例8：防治水稻纹枯病(Rhizoctonia solani)活体筛选测试
1、选择两叶一心、长势一致的盆栽稻苗，待测化合物用少量N,N-二甲基甲酰胺溶解，然后用含0.1％吐温80的水稀释成所要测试的浓度，将配制好的药剂用(双管)喉头喷雾器喷施在供试水稻苗，药剂喷雾处理后自然晾干，24h左右进行接种，在已喷过药的每盆稻苗基部中央夹接一块纹枯病菌丝块，菌块不要与盆土及水层接触。接种后的试材移至保湿箱中培养，温度26℃，湿度80－90％，每天观察稻苗生长状况，5天后空白对照充分发病时调查防治效果。分级标准采用《创制农药生物活性评价SOP》，以病情指数计算防治效果。
2、数据调查与统计分析
调查方法和分级标准
0级：不发病；
1级：第一叶鞘发病；
3级：第一叶片及第二叶鞘发病；
5级：第二叶片及第三叶鞘发病；
7级：整株发病。
Figure PCTCN2016083409-appb-000017
Figure PCTCN2016083409-appb-000018
通过测试，化合物1、2、3、4、5、6、7、8、9、10、11、12、193、194、195、196、197、198、199、200、201、202、、203、204、577和578在200ppm下对水稻纹枯病防治效果大于90％，其中化合物1和2的防治效果100％。
实施例9、防治水稻纹枯病对照试验
测试方法：将要测试的化合物均设5个浓度50ppm、25ppm、12.5ppm、6.25ppm和3.15ppm，每个浓度设3个重复。另设清水为空白对照。
防治水稻纹枯病测试结果表
Figure PCTCN2016083409-appb-000019
Figure PCTCN2016083409-appb-000020
根据对照试验发现化合物1和化合物2防治水稻纹病的活性明显优于对照化合物。
实施例10、黄瓜白粉病预防试验
待测化合物用少量N,N-二甲基甲酰胺溶解，然后用含0.1％吐温80的水稀释成所要测试的浓度，将配制好的药剂用(双管)喉头喷雾器喷施在供试一张真叶期、长势一致黄瓜苗上，并风干，每浓度为一处理，每处理3次重复，另设对照药剂和清水空白对照。洗取黄瓜叶片 上的新鲜白粉病菌孢子，用双层纱布过滤，制成孢子浓度为10万个/ml左右的悬浮液，喷雾接种。接种后的试材移入人工气候内，相对湿度保持在60-70％之间，温度保持23℃，10d左右视空白对照发病情况进行分级调查，按病指计算防效％。
黄瓜白粉病调查方法分级标准：
0级：无病；
1级：病斑面积占整片叶面积的5％以下；
3级：病斑面积占整片叶面积的6％～10％；
5级：病斑面积占整片叶面积的11％～20％；
7级：病斑面积占整片叶面积的21％～40％；
9级：病斑面积占整片叶面积的40％以上
病情指数＝∑(各级病叶数×相对级数值)×100/(总叶数×9)；
防治效果(％)＝(对照病情指数-处理病情指数)×100/对照病情指数
通过测试，化合物1、2、3、4、5、6、7、8、9、10、11、12、193、194、195、196、197、198、199、200、201、202、、203、204、577和578在150ppm下对黄瓜白粉病的防治效果100％。
实施例11、防治黄瓜白粉病对照试验
测试方法：将要测试的化合物均设5个浓度100ppm、50ppm、25ppm、12.5ppm和6.25ppm，每个浓度设3个重复。另设清水为空白对照。
Figure PCTCN2016083409-appb-000021
Figure PCTCN2016083409-appb-000022
根据对照试验发现化合物1和化合物2防治黄瓜白粉的活性明显优于对照化合物。

Claims (11)

  1. 一类含二苯醚结构的吡唑酰胺类化合物，具有如下通式F-1：
    Figure PCTCN2016083409-appb-100001
    其中：
    R1选自氢、卤素、C1-C10烷基、C1-C10卤代烷基、C1-C10烷氧基、C1-C10卤代烷氧烷基、被卤素、C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的芳基、被卤素、C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的杂芳基；
    R2选自卤素或C1-C10烷基；
    R3选自C1-C10烷基、C1-C10卤代烷基、C1-C10烷氧基、C1-C10卤代烷氧烷基、被卤素、C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的芳基、被卤素、C1-C10烷基、C1-C10卤代烷氧基或C1-C10卤代烷硫基取代的杂芳基；
    R4选自氢或卤素；
    R7选自氟、氯、溴、碘、氰基、三氟甲基、二氟甲基、一氟甲基、甲氧基、三氟甲氧基、二氟甲氧基、一氟甲氧基、硝基、三氟甲硫基、二氟甲硫基、一氟甲硫基；
    R5、R6、R8、R9、R10独立地选自氢、卤素、C1-C10的烷基、C1-C10的卤代烷基、C1-C10卤代烷氧烷基、腈基、硝基、C1-C10烷氧基、C1-C10烷硫基、C1-C10烷亚砜基、C1-C3烷砜基；
    X选自氮或碳；
    Y选自氮或-C-R11，且R11选自氢或卤素；
    M、Q独立地选自氧或硫。
  2. 按照权利要求1所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于所述：
    R1选自氢、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧烷基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的芳基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的杂芳基；
    R2选自卤素或C1-C6烷基；
    R3选自C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧烷基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的芳基、被卤素、C1-C6烷基、C1-C6卤代烷氧基或C1-C6卤代烷硫基取代的杂芳基；
    R7选自氟、氯、溴、碘、氰基、三氟甲基、甲氧基、三氟甲氧基、硝基、三氟甲硫基；
    R5、R6、R8、R9、R10独立地选自氢、卤素、C1-C6的烷基、C1-C6的卤代烷基、C1-C6卤代烷氧烷基、腈基、硝基、C1-C6烷氧基、C1-C6烷硫基、C1-C6烷亚砜基、C1-C3烷砜基。
  3. 按照权利要求2所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于所述：
    R1选自氢、卤素、C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧烷基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的芳基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的杂芳基；
    R2选自卤素或C1-C3烷基；
    R3选自C1-C3烷基、C1-C3卤代烷基、C1-C3烷氧基、C1-C3卤代烷氧烷基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的芳基、被卤素、C1-C3烷基、C1-C3卤代烷氧基或C1-C3卤代烷硫基取代的杂芳基；
    R5、R6、R8、R9、R10独立地选自氢、卤素、C1-C3的烷基、C1-C3的卤代烷基、C1-C3卤代烷氧烷基、腈基、硝基、C1-C3烷氧基、C1-C3烷硫基、C1-C3烷亚砜基、C1-C3烷砜基。
  4. 按照权利要求3所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于所述：
    R1选自二氟甲基或三氟甲基；
    R2选自氟；
    R3选自甲基或乙基；
    R4选自氟、氯或溴；
    R5选自氟、氯、溴或碘；
    R6选自氢、氟、氯或溴；
    且R5和R6不同时为氢；
    R8、R9和R10独立地选自氟、氯或溴。
  5. 按照权利要求4所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于所述含二苯醚结构的吡唑酰胺类化合物选自以下结构式所示化合物中的一种、两种或三种以上组合：
    Figure PCTCN2016083409-appb-100002
  6. 按照权利要求1所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于当R2选自氯或溴时，所述含二苯醚结构的吡唑酰胺类化合物按照以下方法制备：
    Figure PCTCN2016083409-appb-100003
    其中：R0选自甲基或乙基，T选自氟、氯、溴或碘。
  7. 按照权利要求1所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于当R2选自氟时，所述含二苯醚结构的吡唑酰胺类化合物按照以下方法制备：
    Figure PCTCN2016083409-appb-100004
    其中：R0选自甲基或乙基，T选自氟、氯、溴或碘。
  8. 按照权利要求1至5之一所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于所述含二苯醚结构的吡唑酰胺类化合物用于农用杀菌。
  9. 按照权利要求8所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于所述含二苯醚结构的吡唑酰胺类化合物用于防治由丝核菌属、柄锈菌属、黑粉菌属、腥黑粉菌属、伏革菌属、核腔菌属或担子菌纲真菌引起的病害。
  10. 按照权利要求9所述的一类含二苯醚结构的吡唑酰胺类化合物，其特征在于所述含二苯醚结构的吡唑酰胺类化合物用于防治纹枯病、立枯病、白粉病或锈病。
  11. 一种农用化学杀菌剂，其特征在于所述农用化学杀菌剂含有1～99％质量百分含量的含二苯醚结构的吡唑酰胺类化合物。
PCT/CN2016/083409 2015-07-13 2016-05-26 一类含二苯醚结构的吡唑酰胺化合物、其制备方法及应用 WO2017008583A1 (zh)

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