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CN108570008B - A class of pyrazole derivatives, their preparation method and application - Google Patents

A class of pyrazole derivatives, their preparation method and application Download PDF

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CN108570008B
CN108570008B CN201710306758.1A CN201710306758A CN108570008B CN 108570008 B CN108570008 B CN 108570008B CN 201710306758 A CN201710306758 A CN 201710306758A CN 108570008 B CN108570008 B CN 108570008B
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haloalkyl
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CN108570008A (en
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许天明
袁静
钟良坤
郁季平
彭伟立
胡冬松
魏优昌
孔小林
郑志文
邢家华
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Corp
Sinochem Lantian Co Ltd
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    • 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
    • C07D231/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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    • 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
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

本发明公开了一类如下通式stru‑1所示的吡唑衍生物，

Figure DDA0001285920270000011
各取代基的定义详见说明书。本发明公开的吡唑衍生物适合用于防治害虫。

Figure 201710306758

The invention discloses a class of pyrazole derivatives represented by the following general formula stru-1,

Figure DDA0001285920270000011
The definition of each substituent is detailed in the specification. The pyrazole derivatives disclosed in the present invention are suitable for controlling pests.

Figure 201710306758

Description

一类吡唑类衍生物、其制备方法及应用A class of pyrazole derivatives, their preparation method and application

技术领域technical field

本发明属于农用杀虫、杀螨领域，具体涉及一类吡唑类衍生物。The invention belongs to the field of agricultural insecticide and acaricide, and in particular relates to a class of pyrazole derivatives.

背景技术Background technique

由于现有农药的长期使用，使得病虫害产生了抗性，从而使得农药使用量显著增加，对环境造成严重的破坏。因此要求不断发现具有新的作用机理的高效新农药，例如对杀虫、杀菌或杀螨具有更高活性的新农药，例如现有的杀螨剂农药品种中，大部分农药只能防治螨卵、若螨、成螨三个阶段中的一阶段，如果能够研究开发出对螨三个阶段都具有防治效果的心的杀螨剂将具有重大意义。Due to the long-term use of existing pesticides, pests and diseases have developed resistance, resulting in a significant increase in the amount of pesticides used, causing serious damage to the environment. Therefore, it is required to continuously discover new and efficient pesticides with new mechanisms of action, such as new pesticides with higher activity against insecticides, bactericidal or acaricidal activities. For example, among the existing acaricides, most of the pesticides can only control the eggs of mites. One of the three stages of mites, nymphs, and adult mites, it will be of great significance to research and develop acaricides that have control effects on all three stages of mites.

PCT专利申请WO01/68589公开了杂环丙烯腈醚类化合物，说明书第71页公开了下述化合物8-1、8-2、8-3和8-4，PCT patent application WO01/68589 discloses heterocycloacrylonitrile ether compounds, and page 71 of the specification discloses the following compounds 8-1, 8-2, 8-3 and 8-4,

Figure BDA0001285920250000011
Figure BDA0001285920250000011

现有技术未公开本申请所述的吡唑类衍生物。The prior art has not disclosed the pyrazole derivatives described in this application.

发明内容SUMMARY OF THE INVENTION

本发明提供一类吡唑衍生物，具有如下通式stru-1：The present invention provides a class of pyrazole derivatives having the following general formula stru-1:

Figure BDA0001285920250000012
Figure BDA0001285920250000012

其中：in:

R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷亚砜基、C1-C20烷砜基、C1-C20烷基磺酸酯基，C1-C20烷基羧酸酯、C1-C20烷基酰基、C1-C20卤代烷基酰基；R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 2 -C 20 alkenyl, C 2 - C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio base, C 1 -C 20 halogenated alkylthio group, C 1 -C 20 alkyl sulfoxide group, C 1 -C 20 alkyl sulfone group, C 1 -C 20 alkyl sulfonate group, C 1 -C 20 alkyl carboxyl group Acid esters, C 1 -C 20 alkyl acyl, C 1 -C 20 haloalkyl acyl;

R6选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基；R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkane oxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 - At least one substituted phenyl group among C 20 haloalkylthio and C 1 -C 20 alkanesulfonyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkane base, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C pyridyl, pyrazolyl, thiophenol, furanyl or thiazolyl substituted by at least one of 1 - C20 haloalkylthio and C1 - C20 alkylsulfone;

R7选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C1-C20烷氧亚甲基；R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 1 -C 20 alkoxymethylene;

R8选自氢、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基；R8 is selected from hydrogen, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxymethylene group, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl , C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone are substituted with at least one phenyl, is selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halogenated ring At least one of alkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone a substituted pyridyl, pyrazolyl, thiophenol, furanyl or thiazolyl;

R9选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷砜基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基；R9 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkoxy A phenyl group substituted with at least one of thio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C at least one substituted pyridyl, pyrazolyl, thiophenol, furanyl or thiazolyl of 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfonyl;

L选自氧、硫、亚甲基、氮；L is selected from oxygen, sulfur, methylene, nitrogen;

Q选自氧、硫；Q is selected from oxygen and sulfur;

R10选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。R10 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkylcarboxylate, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C phenyl substituted with at least one of 20 alkylthio and C 1 -C 20 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl , C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio and C 1 -C 20 substituted pyridyl, pyrazolyl, thienyl, furyl or thiazolyl at least one of the haloalkylthio groups.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷亚砜基、C1-C20烷砜基、C1-C20烷基磺酸酯基，C1-C20烷基羧酸酯、C1-C20烷基酰基、C1-C20卤代烷基酰基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituents R1, R2, R3, R4 and R5 are independently selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl , C 1 -C 20 haloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 Alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkyl sulfoxide, C 1 -C 20 alkyl sulfone, C 1 -C 20 alkyl sulfonate, C 1 -C 20 alkyl carboxylate, C 1 -C 20 alkyl acyl, C 1 -C 20 haloalkyl acyl.

优选的是，所述取代基R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C10烷基、C1-C10卤代烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10烷亚砜基、C1-C10烷砜基、C1-C10烷基磺酸酯基，C1-C10烷基羧酸酯、C1-C10烷基酰基、C1-C10卤代烷基酰基。Preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 2 - C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy , C 1 -C 10 alkylthio group, C 1 -C 10 halogenated alkylthio group, C 1 -C 10 alkyl sulfoxide group, C 1 -C 10 alkyl sulfone group, C 1 -C 10 alkyl sulfonate group, C 1 -C 10 alkyl carboxylate, C 1 -C 10 alkyl acyl, C 1 -C 10 haloalkyl acyl.

进一步优选的是，所述取代基R1、R2、R3、R4、R5独立地选自氢、卤素、硝基、腈基、C1-C6烷基、C1-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷亚砜基、C1-C6烷砜基、C1-C6烷基磺酸酯基，C1-C6烷基羧酸酯、C1-C6烷基酰基、C1-C6卤代烷基酰基。Further preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, halogen, nitro, nitrile, C1- C6 alkyl, C1 - C6 haloalkyl, C2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy base, C 1 -C 6 alkylthio group, C 1 -C 6 haloalkylthio group, C 1 -C 6 alkyl sulfoxide group, C 1 -C 6 alkyl sulfone group, C 1 -C 6 alkyl sulfonate group , C 1 -C 6 alkyl carboxylate, C 1 -C 6 alkyl acyl, C 1 -C 6 halogenated alkyl acyl.

再进一步优选的是，所述取代基R1、R2、R3、R4、R5独立地选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、叔丁基、三氟甲基、甲氧基、乙氧基、三氟甲氧基、二氟甲氧基、二氟乙氧基、甲硫基、三氟甲硫基、三氟乙硫基、甲砜基、甲磺基酯。Still further preferably, the substituents R1, R2, R3, R4, R5 are independently selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, tert-butyl , trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, difluoroethoxy, methylthio, trifluoromethylthio, trifluoroethylthio, methyl sulfone base, methyl sulfoester.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基R6选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkynyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, selected from hydrogen, halogen, nitro , cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone at least one substituted phenyl group selected from hydrogen, halogen, Nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy , C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfonyl substituted at least one of pyridyl, pyrazolyl, thi Phenol, furyl or thiazolyl.

优选的是，所述取代基R6选自氢、卤素、硝基、腈基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。所示化合物可以为E式、Z式或E式和Z式混合物；Preferably, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 2 -C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy base, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C phenyl substituted with at least one of 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 -C 10 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkane base, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -Pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl substituted by at least one of C 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 -C 10 alkylsulfonyl. The compound shown can be E, Z or a mixture of E and Z;

进一步优选的是，所述取代基R6选自氢、卤素、硝基、腈基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R6 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 - C 6 halocycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkane oxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl , C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 - phenyl substituted with at least one of C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfonyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 Alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C A pyridyl, pyrazolyl, thiophenol, furanyl or thiazolyl group substituted with at least one of 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfonyl.

再进一步优选的是，所述取代基R6选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、环丙基、甲氧基、乙氧基、三氟甲基、二氟甲基、对氯苯基、对氟苯基。Still further preferably, the substituent R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, methoxy, ethoxy, tri Fluoromethyl, difluoromethyl, p-chlorophenyl, p-fluorophenyl.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基R7选自氢、卤素、硝基、腈基、C1-C20烷基、C1-C20卤代烷基、C1-C20烷氧亚甲基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 1 -C 20 alkoxymethylene.

优选的是，所述取代基R7选自氢、卤素、硝基、腈基、C1-C10烷基、C1-C10卤代烷基、C1-C10烷氧亚甲基。Preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, and C 1 -C 10 alkoxymethylene.

进一步优选的是，所述取代基R7选自氢、卤素、硝基、腈基、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧亚甲基。Further preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, and C 1 -C 6 alkoxymethylene.

再进一步优选的是，所述取代基R7选自氢、卤素、硝基、腈基、C1-C5烷基、C1-C5卤代烷基、C1-C5烷氧亚甲基。Still further preferably, the substituent R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 5 alkyl, C 1 -C 5 haloalkyl, and C 1 -C 5 alkoxymethylene.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基R8选自氢、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R8 is selected from hydrogen, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxymethylene, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl , C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 halogenated alkylthio group and at least one substituted phenyl group of C 1 -C 20 alkylsulfone group, selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 Haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, A pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl group substituted with at least one of C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone.

优选的是，所述取代基R8选自氢、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Preferably, the substituent R8 is selected from hydrogen, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxymethylene, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 -C 10 At least one substituted phenyl group in the alkylsulfonyl group, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio and C 1 - At least one substituted pyridyl, pyrazolyl, thiophenol, furanyl or thiazolyl group in the C 10 alkylsulfonyl group.

进一步优选的是，所述取代基R8选自氢、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧亚甲基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R8 is selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxymethylene, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C At least one substituted phenyl group in the 6 alkylsulfonyl group, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl , C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -Pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl substituted with at least one of the C 6 alkylsulfonyl groups.

再进一步优选的是，所述取代基R8选自氢、甲基、乙基、一氟甲基、二氟甲基、三氟甲基、甲氧基亚甲基、乙氧基亚甲基。Still further preferably, the substituent R8 is selected from hydrogen, methyl, ethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, methoxymethylene, and ethoxymethylene.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基R9选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷砜基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基和C1-C20烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R9 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkyne group, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkylsulfone, selected from Hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio and C 1 -C 20 alkylsulfone at least one substituted phenyl group, Selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, and C 1 -C 20 alkylsulfonyl substituted pyridyl , pyrazolyl, thiophenol, furyl or thiazolyl.

优选的是，所述取代基R9选自氢、卤素、硝基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10烷砜基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基和C1-C10烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Preferably, the substituent R9 is selected from hydrogen, halogen, nitro, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halo Cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 1 -C 10 alkylsulfone, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy at least one substituted phenyl group, C 1 -C 10 alkylthio group, C 1 -C 10 haloalkylthio group and C 1 -C 10 alkylsulfone group, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 at least one substituted pyridyl , pyrazolyl , thiophenol , furyl or Thiazolyl.

进一步优选的是，所述取代基R9选自氢、卤素、硝基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷砜基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基和C1-C6烷砜基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R9 is selected from hydrogen, halogen, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halogen Cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfonyl, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkane phenyl substituted with at least one of oxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfone, selected from hydrogen, halogen, nitro, cyano , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C At least one substituted pyridyl, pyrazolyl, thiophenol and furyl group among 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio and C 1 -C 6 alkylsulfone or thiazolyl.

再进一步优选的是，所述取代基R9选自氢、氟、氯、溴、硝基、甲基、乙基、丙基、异丙基、二氟甲基、环丙基、甲硫基亚甲基、苯基、对氯苯基、对氟苯基、苄基。Still further preferably, the substituent R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthioidene Methyl, phenyl, p-chlorophenyl, p-fluorophenyl, benzyl.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基L选自氧、硫、亚甲基、氮。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent L is selected from oxygen, sulfur, methylene, and nitrogen.

优选的是，所述取代基L选自氧、硫、亚甲基。Preferably, the substituent L is selected from oxygen, sulfur and methylene.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基Q选自氧、硫。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent Q is selected from oxygen and sulfur.

本发明提供的通式stru-1所示的吡唑衍生物中，取代基R10选自氢、卤素、硝基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C2-C20烯基、C2-C20卤代烯基、C2-C20炔基、C2-C20卤代炔基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基、C1-C20卤代烷硫基、C1-C20烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C20烷基、C1-C20卤代烷基、C3-C20环烷基、C3-C20卤代环烷基、C1-C20烷氧基、C1-C20卤代烷氧基、C1-C20烷硫基和C1-C20卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, the substituent R10 is selected from hydrogen, halogen, nitro, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 2 -C 20 alkenyl, C 2 -C 20 haloalkenyl, C 2 -C 20 alkynyl, C 2 -C 20 haloalkyne base, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio, C 1 -C 20 haloalkylthio, C 1 -C 20 alkyl carboxylate, Selected from hydrogen, halogen, nitro, cyano, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 3 -C 20 cycloalkyl, C 3 -C 20 halocycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio and C 1 -C 20 haloalkylthio at least one substituted phenyl group selected from hydrogen, halogen, nitro group, cyano group, C 1 -C 20 alkyl group, C 1 -C 20 halogenated alkyl group, C 3 -C 20 cycloalkyl group, C 3 -C 20 halogenated cycloalkyl group, C 1 -C 20 alkoxy group, A pyridyl, pyrazolyl, thiophenol, furanyl or thiazolyl group substituted with at least one of C 1 -C 20 haloalkoxy, C 1 -C 20 alkylthio and C 1 -C 20 haloalkylthio.

优选的是，所述取代基R10选自氢、卤素、硝基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C2-C10烯基、C2-C10卤代烯基、C2-C10炔基、C2-C10卤代炔基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基、C1-C10卤代烷硫基、C1-C10烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基和C1-C10卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C10烷基、C1-C10卤代烷基、C3-C10环烷基、C3-C10卤代环烷基、C1-C10烷氧基、C1-C10卤代烷氧基、C1-C10烷硫基和C1-C10卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Preferably, the substituent R10 is selected from hydrogen, halogen, nitro, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halo Cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 10 haloalkenyl, C 2 -C 10 alkynyl, C 2 -C 10 haloalkynyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 1 -C 10 alkylcarboxylate, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 phenyl substituted with at least one of haloalkoxy, C 1 -C 10 alkylthio and C 1 -C 10 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 10 alkyl , C 1 -C 10 haloalkyl, C 3 -C 10 cycloalkyl, C 3 -C 10 halocycloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 - A pyridyl, pyrazolyl, thiophenol, furanyl or thiazolyl group substituted with at least one of C 10 alkylthio and C 1 -C 10 haloalkylthio.

进一步优选的是，所述取代基R10选自氢、卤素、硝基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸酯、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基和C1-C6卤代烷硫基中的至少一个取代的苯基、被选自氢、卤素、硝基、氰基、C1-C6烷基、C1-C6卤代烷基、C3-C6环烷基、C3-C6卤代环烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基和C1-C6卤代烷硫基中的至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Further preferably, the substituent R10 is selected from hydrogen, halogen, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halogen Cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylcarboxylate, selected from hydrogen, halogen, nitro, cyano , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C phenyl substituted with at least one of 6 haloalkoxy, C 1 -C 6 alkylthio and C 1 -C 6 haloalkylthio, selected from hydrogen, halogen, nitro, cyano, C 1 -C 6 alkane base, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -Pyridyl, pyrazolyl, thiophenol, furyl or thiazolyl substituted with at least one of C 6 alkylthio and C 1 -C 6 haloalkylthio.

再进一步优选的是，所述取代基R10选自氢、氟、氯、硝基、C1-C6烷基、C3-C6环烷基、C3-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸甲酯、C1-C6烷基羧酸乙酯、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的苯基、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。Still further preferably, the substituent R10 is selected from hydrogen, fluorine, chlorine, nitro, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 haloalkyl, C 2 - C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy , C 1 -C 6 alkylthio group, C 1 -C 6 haloalkylthio group, C 1 -C 6 alkyl carboxylate methyl ester, C 1 -C 6 alkyl carboxylate ethyl ester, selected from hydrogen, fluorine, Phenyl substituted with at least one of chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy and methylthio, selected from hydrogen , fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy and methylthio at least one substituted pyridyl, pyridyl azolyl, thiophenol, furyl or thiazolyl.

本发明提供的通式stru-1所示的吡唑衍生物，作为一种比较优选的方式，所述通式stru-1中：The pyrazole derivatives represented by the general formula stru-1 provided by the present invention, as a more preferred way, in the general formula stru-1:

R1、R2、R3、R4、R5独立地选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、叔丁基、三氟甲基、甲氧基、乙氧基、三氟甲氧基、二氟甲氧基、二氟乙氧基、甲硫基、三氟甲硫基、三氟乙硫基、甲砜基、甲磺基酯；R1, R2, R3, R4, R5 are independently selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, tert-butyl, trifluoromethyl, methoxy, Ethoxy, trifluoromethoxy, difluoromethoxy, difluoroethoxy, methylthio, trifluoromethylthio, trifluoroethylthio, methylsulfonyl, methylsulfoester;

R6选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、环丙基、三氟甲基、二氟甲基、甲氧基、乙氧基、对氯苯基、对氟苯基；R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, p- Chlorophenyl, p-fluorophenyl;

R7选自氢、卤素、硝基、腈基、C1-C5烷基、C1-C5卤代烷基、C1-C5烷氧亚甲基；R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 5 alkyl, C 1 -C 5 haloalkyl, C 1 -C 5 alkoxymethylene;

R8选自甲基、乙基；R8 is selected from methyl, ethyl;

R9选自氢、氟、氯、溴、硝基、甲基、乙基、丙基、异丙基、二氟甲基、环丙基、甲硫基亚甲基、苯基、对氯苯基、对氟苯基、苄基；R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthiomethylene, phenyl, p-chlorophenyl , p-fluorophenyl, benzyl;

L选自氧、硫、亚甲基；L is selected from oxygen, sulfur, methylene;

Q选自氧、硫；Q is selected from oxygen and sulfur;

R10选自氢、氟、氯、硝基、C1-C6烷基、C3-C6环烷基、C3-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸甲酯、C1-C6烷基羧酸乙酯、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的苯基、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、三氟甲基、甲氧基、乙氧基、三氟乙氧基和甲硫基中至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。R10 is selected from hydrogen, fluorine, chlorine, nitro, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio group, C 1 -C 6 alkyl carboxylate methyl ester, C 1 -C 6 alkyl carboxylate ethyl ester, are selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, phenyl substituted with at least one of methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy and methylthio selected from hydrogen, fluorine, chlorine, bromine, nitro, pyridyl, pyrazolyl, thiophenol, furyl or substituted at least one of cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy and methylthio Thiazolyl.

本发明提供的通式stru-1所示的吡唑衍生物，作为另一种比较优选的方式，所述通式stru-1中：The pyrazole derivatives represented by the general formula stru-1 provided by the present invention, as another preferred way, in the general formula stru-1:

R1、R2、R4、R5选自氢；R1, R2, R4, R5 are selected from hydrogen;

R3选自叔丁基；R3 is selected from tert-butyl;

R6选自氢、氟、氯、溴、硝基、腈基、甲基、乙基、异丙基、环丙基、三氟甲基、二氟甲基、甲氧基、乙氧基、对氯苯基、对氟苯基；R6 is selected from hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, p- Chlorophenyl, p-fluorophenyl;

R7选自氢、卤素、硝基、腈基、C1-C5烷基、C1-C5卤代烷基、C1-C5烷氧亚甲基；R7 is selected from hydrogen, halogen, nitro, nitrile, C 1 -C 5 alkyl, C 1 -C 5 haloalkyl, C 1 -C 5 alkoxymethylene;

R8选自甲基、乙基；R8 is selected from methyl, ethyl;

R9选自氢、氟、氯、溴、硝基、甲基、乙基、丙基、异丙基、二氟甲基、环丙基、甲硫基亚甲基、苯基、对氯苯基、对氟苯基、苄基；R9 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, propyl, isopropyl, difluoromethyl, cyclopropyl, methylthiomethylene, phenyl, p-chlorophenyl , p-fluorophenyl, benzyl;

L选自氧、硫、亚甲基；L is selected from oxygen, sulfur, methylene;

Q选自氧、硫；Q is selected from oxygen and sulfur;

R10选自氢、氟、氯、硝基、C1-C6烷基、C3-C6环烷基、C3-C6卤代烷基、C2-C6烯基、C2-C6卤代烯基、C2-C6炔基、C2-C6卤代炔基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6卤代烷硫基、C1-C6烷基羧酸甲酯、C1-C6烷基羧酸乙酯、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、甲氧基、乙氧基、三氟甲基、三氟乙氧基和甲硫基中至少一个取代的苯基、被选自氢、氟、氯、溴、硝基、氰基、甲基、乙基、甲氧基、乙氧基、三氟甲基、三氟乙氧基和甲硫基中至少一个取代的吡啶基、吡唑基、噻酚基、呋喃基或噻唑基。R10 is selected from hydrogen, fluorine, chlorine, nitro, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio group, C 1 -C 6 alkyl carboxylate methyl ester, C 1 -C 6 alkyl carboxylate ethyl ester, are selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, phenyl substituted with at least one of methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoroethoxy and methylthio, selected from hydrogen, fluorine, chlorine, bromine, nitro, pyridyl, pyrazolyl, thiophenol, furyl or substituted at least one of cyano, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoroethoxy and methylthio Thiazolyl.

本发明提供的通式stru-1所示的吡唑衍生物，作为最为优选的方式，所述吡唑衍生物选自以下结构式所示化合物中的至少一种：The pyrazole derivative represented by the general formula stru-1 provided by the present invention, as the most preferred mode, the pyrazole derivative is selected from at least one of the compounds represented by the following structural formula:

Figure BDA0001285920250000091
Figure BDA0001285920250000091

Figure BDA0001285920250000101
Figure BDA0001285920250000101

Figure BDA0001285920250000111
Figure BDA0001285920250000111

Figure BDA0001285920250000121
Figure BDA0001285920250000121

Figure BDA0001285920250000131
Figure BDA0001285920250000131

Figure BDA0001285920250000141
Figure BDA0001285920250000141

Figure BDA0001285920250000151
Figure BDA0001285920250000151

Figure BDA0001285920250000161
Figure BDA0001285920250000161

Figure BDA0001285920250000171
Figure BDA0001285920250000171

Figure BDA0001285920250000181
Figure BDA0001285920250000181

Figure BDA0001285920250000191
Figure BDA0001285920250000191

Figure BDA0001285920250000201
Figure BDA0001285920250000201

Figure BDA0001285920250000211
Figure BDA0001285920250000211

Figure BDA0001285920250000221
Figure BDA0001285920250000221

Figure BDA0001285920250000231
Figure BDA0001285920250000231

Figure BDA0001285920250000241
Figure BDA0001285920250000241

Figure BDA0001285920250000251
Figure BDA0001285920250000251

Figure BDA0001285920250000261
Figure BDA0001285920250000261

Figure BDA0001285920250000271
Figure BDA0001285920250000271

Figure BDA0001285920250000281
Figure BDA0001285920250000281

Figure BDA0001285920250000291
Figure BDA0001285920250000291

Figure BDA0001285920250000301
Figure BDA0001285920250000301

Figure BDA0001285920250000311
Figure BDA0001285920250000311

Figure BDA0001285920250000321
Figure BDA0001285920250000321

以上编号表示的吡唑衍生物，优选的是，所述化合物为E式吡唑衍生物，即E式异构体。For the pyrazole derivatives represented by the above numbers, preferably, the compounds are E-form pyrazole derivatives, that is, E-form isomers.

本发明提供的通式stru-1所示的吡唑衍生物，所述吡唑衍生物包括选自E式吡唑衍生物和Z式吡唑衍生物中的至少一种。当所述吡唑衍生物包括E式吡唑衍生物和Z式吡唑衍生物时，所述E式吡唑衍生物和Z式吡唑衍生物之间可以以任何比例存在。The pyrazole derivatives represented by the general formula stru-1 provided by the present invention include at least one selected from the group consisting of E-form pyrazole derivatives and Z-form pyrazole derivatives. When the pyrazole derivatives include E-form pyrazole derivatives and Z-form pyrazole derivatives, the E-form pyrazole derivatives and Z-form pyrazole derivatives may exist in any ratio.

本发明提供的通式stru-1所示的吡唑衍生物，当取代基R1、R2、R4、R5为氢和Q为氧时，作为示例，当所述通式stru-1所示的吡唑衍生物为E式化合物时，所述通式stru-1所示的吡唑衍生物可以是表1所示化合物。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, when the substituents R1, R2, R4, R5 are hydrogen and Q is oxygen, as an example, when the pyrazole derivatives represented by the general formula stru-1 are When the azole derivative is the compound of formula E, the pyrazole derivative represented by the general formula stru-1 may be the compound shown in Table 1.

表1Table 1

Figure BDA0001285920250000331
Figure BDA0001285920250000331

Figure BDA0001285920250000341
Figure BDA0001285920250000341

Figure BDA0001285920250000351
Figure BDA0001285920250000351

Figure BDA0001285920250000361
Figure BDA0001285920250000361

Figure BDA0001285920250000371
Figure BDA0001285920250000371

Figure BDA0001285920250000381
Figure BDA0001285920250000381

Figure BDA0001285920250000391
Figure BDA0001285920250000391

Figure BDA0001285920250000401
Figure BDA0001285920250000401

Figure BDA0001285920250000411
Figure BDA0001285920250000411

Figure BDA0001285920250000421
Figure BDA0001285920250000421

Figure BDA0001285920250000431
Figure BDA0001285920250000431

Figure BDA0001285920250000441
Figure BDA0001285920250000441

Figure BDA0001285920250000451
Figure BDA0001285920250000451

Figure BDA0001285920250000461
Figure BDA0001285920250000461

Figure BDA0001285920250000471
Figure BDA0001285920250000471

Figure BDA0001285920250000481
Figure BDA0001285920250000481

Figure BDA0001285920250000491
Figure BDA0001285920250000491

Figure BDA0001285920250000501
Figure BDA0001285920250000501

Figure BDA0001285920250000511
Figure BDA0001285920250000511

Figure BDA0001285920250000521
Figure BDA0001285920250000521

Figure BDA0001285920250000531
Figure BDA0001285920250000531

Figure BDA0001285920250000541
Figure BDA0001285920250000541

Figure BDA0001285920250000551
Figure BDA0001285920250000551

Figure BDA0001285920250000561
Figure BDA0001285920250000561

Figure BDA0001285920250000571
Figure BDA0001285920250000571

Figure BDA0001285920250000581
Figure BDA0001285920250000581

Figure BDA0001285920250000591
Figure BDA0001285920250000591

Figure BDA0001285920250000601
Figure BDA0001285920250000601

Figure BDA0001285920250000611
Figure BDA0001285920250000611

Figure BDA0001285920250000621
Figure BDA0001285920250000621

Figure BDA0001285920250000631
Figure BDA0001285920250000631

Figure BDA0001285920250000641
Figure BDA0001285920250000641

Figure BDA0001285920250000651
Figure BDA0001285920250000651

本发明提供的通式stru-1所示的吡唑衍生物，当取代基R1、R2、R4、R5为氢和Q为氧时，作为示例，当所述通式stru-1所示的吡唑衍生物为Z式化合物时，所述通式stru-1所示的吡唑衍生物可以是表2所示化合物。In the pyrazole derivatives represented by the general formula stru-1 provided by the present invention, when the substituents R1, R2, R4, R5 are hydrogen and Q is oxygen, as an example, when the pyrazole derivatives represented by the general formula stru-1 are When the azole derivative is the Z-form compound, the pyrazole derivative represented by the general formula stru-1 may be the compound shown in Table 2.

表2Table 2

Figure BDA0001285920250000661
Figure BDA0001285920250000661

Figure BDA0001285920250000671
Figure BDA0001285920250000671

Figure BDA0001285920250000681
Figure BDA0001285920250000681

Figure BDA0001285920250000691
Figure BDA0001285920250000691

Figure BDA0001285920250000701
Figure BDA0001285920250000701

Figure BDA0001285920250000711
Figure BDA0001285920250000711

Figure BDA0001285920250000721
Figure BDA0001285920250000721

Figure BDA0001285920250000731
Figure BDA0001285920250000731

Figure BDA0001285920250000741
Figure BDA0001285920250000741

Figure BDA0001285920250000751
Figure BDA0001285920250000751

Figure BDA0001285920250000761
Figure BDA0001285920250000761

Figure BDA0001285920250000771
Figure BDA0001285920250000771

Figure BDA0001285920250000781
Figure BDA0001285920250000781

Figure BDA0001285920250000791
Figure BDA0001285920250000791

Figure BDA0001285920250000801
Figure BDA0001285920250000801

Figure BDA0001285920250000811
Figure BDA0001285920250000811

Figure BDA0001285920250000821
Figure BDA0001285920250000821

Figure BDA0001285920250000831
Figure BDA0001285920250000831

Figure BDA0001285920250000841
Figure BDA0001285920250000841

Figure BDA0001285920250000851
Figure BDA0001285920250000851

Figure BDA0001285920250000861
Figure BDA0001285920250000861

Figure BDA0001285920250000871
Figure BDA0001285920250000871

Figure BDA0001285920250000881
Figure BDA0001285920250000881

Figure BDA0001285920250000891
Figure BDA0001285920250000891

Figure BDA0001285920250000901
Figure BDA0001285920250000901

Figure BDA0001285920250000911
Figure BDA0001285920250000911

Figure BDA0001285920250000921
Figure BDA0001285920250000921

Figure BDA0001285920250000931
Figure BDA0001285920250000931

Figure BDA0001285920250000941
Figure BDA0001285920250000941

Figure BDA0001285920250000951
Figure BDA0001285920250000951

Figure BDA0001285920250000961
Figure BDA0001285920250000961

Figure BDA0001285920250000971
Figure BDA0001285920250000971

本发明提供的部分化合物的物性数据如下表3。The physical property data of some compounds provided by the present invention are shown in Table 3 below.

表3table 3

Figure BDA0001285920250000972
Figure BDA0001285920250000972

Figure BDA0001285920250000981
Figure BDA0001285920250000981

Figure BDA0001285920250000991
Figure BDA0001285920250000991

Figure BDA0001285920250001001
Figure BDA0001285920250001001

Figure BDA0001285920250001011
Figure BDA0001285920250001011

Figure BDA0001285920250001021
Figure BDA0001285920250001021

Figure BDA0001285920250001031
Figure BDA0001285920250001031

本发明还提供了通式stru-1所示的吡唑衍生物的制备方法，所述方法包括：The present invention also provides a method for preparing a pyrazole derivative represented by the general formula stru-1, the method comprising:

Figure BDA0001285920250001032
Figure BDA0001285920250001032

所述X选自卤素。The X is selected from halogen.

本发明提供的制备方法，所述碱：优选的是，选自有机碱和无机碱中的至少一种；进一步优选的是，选自碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾、氢化钠、醇钠和醇钾中的至少一种。In the preparation method provided by the present invention, the base: preferably, at least one selected from organic bases and inorganic bases; more preferably, selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, hydrogen At least one of sodium oxide, potassium hydroxide, sodium hydride, sodium alkoxide and potassium alkoxide.

本发明提供的制备方法，所述酸：优选的是，选自有机酸和无机酸中的至少一种；进一步优选的是，选自盐酸、硫酸和乙酸中的至少一种。In the preparation method provided by the present invention, the acid: preferably, at least one selected from organic acids and inorganic acids; more preferably, at least one selected from hydrochloric acid, sulfuric acid and acetic acid.

本发明提供的制备方法，所述溶剂：优选的是，独立地选自质子性溶剂和非质子性溶剂中的至少一种；进一步优选的是，独立地选自丙酮、甲基乙基酮、四氢呋喃、乙腈、N、N-二甲基甲酰胺、甲苯和氯苯中的至少一种。In the preparation method provided by the present invention, the solvent: preferably, independently selected from at least one of protic solvents and aprotic solvents; further preferably, independently selected from acetone, methyl ethyl ketone, At least one of tetrahydrofuran, acetonitrile, N,N-dimethylformamide, toluene and chlorobenzene.

本发明提供的制备方法，所述X选自卤素，优选的是，所述X选自氯、溴或碘。In the preparation method provided by the present invention, the X is selected from halogen, preferably, the X is selected from chlorine, bromine or iodine.

本发明提供的制备方法，所述催化剂选自碘化钾、碘化钠和相转移催化剂中的至少一种。In the preparation method provided by the present invention, the catalyst is selected from at least one of potassium iodide, sodium iodide and phase transfer catalyst.

本发明还提供一种农用杀虫、杀螨剂，所述杀虫、杀螨剂含有0.1～99％质量百分含量的通式stru-1所示吡唑衍生物。所述杀虫、杀螨剂中，除通式stru-1所示吡唑衍生物外，还可以进一步包括本行业常用的载体和助剂。The present invention also provides an agricultural insecticide and acaricide, wherein the insecticide and acaricide contain 0.1-99% by mass of a pyrazole derivative represented by the general formula stru-1. In the insecticide and acaricide, in addition to the pyrazole derivative represented by the general formula stru-1, the carrier and auxiliary agents commonly used in the industry may be further included.

本发明提供的通式stru-1所示的吡唑衍生物，适合用于防治害虫，特别适合用于防治作物上的成螨、若螨、螨卵、蚜虫和飞虱中的至少一种。所述吡唑衍生物很适合用于防治藤蔓植物、水果、园艺、农业、动物康、森林、贮藏产品和材料和卫生领域中的动物害虫。The pyrazole derivatives represented by the general formula stru-1 provided by the present invention are suitable for controlling pests, especially suitable for controlling at least one of adult mites, nymphs, mite eggs, aphids and planthoppers on crops. The pyrazole derivatives are very suitable for controlling animal pests in the fields of vines, fruits, horticulture, agriculture, animal health, forests, storage products and materials and hygiene.

优选的是，所述吡唑衍生物用于防治选自等足目、倍足目、唇足目、综合目、缨尾目、弹尾目、直翅目、蜚蠊目、革翅目、等翅目、虱目、缨翅目、异翅目、同翅目、鳞翅目、鞘翅目、膜翅目、双翅目、蚤目、蛛形纲和植物寄生线虫中的至少一种。Preferably, the pyrazole derivatives are used to control and control the group selected from the group consisting of Isopoda, Diplopoda, Labiopoda, Synthetia, Thysanidae, Collembola, Orthoptera, Blattella, Dermatoptera, and Isoptera. At least one of the order, Liceps, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Pleas, Arachnids, and plant parasitic nematodes.

所述等足目(Isopoda)，例如栉水虱(Oniscus asellus)、鼠(Armadillidiumvulgare)、球鼠妇(Porcellio scaber)。From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

所述倍足目(Diplopoda)，例如，Blaniulus guttulatus。Said Diplopoda, eg, Blaniulus guttulatus.

所述唇足目(Chilopoda)，例如，Geophilus carpophagus、Scutigera spp.。Said Chilopoda, eg, Geophilus carpophagus, Scutigera spp..

所述综合目(Symphyla)，例如，白松虫(Scutigerella immaculata)。From the Symphyla, for example, the white pine worm (Scutigerella immaculata).

所述缨尾目(Thysanura)，例如，衣鱼(Lepisma saccharina)。From the order of the Thysanura, for example, Lepisma saccharina.

所述弹尾目(Collembola)，例如，武装棘跳虫(Onychiurus armatus)。From the order of the Collembola, for example, Onychiurus armatus.

所述直翅目(Orthoptera)，例如，家蟋(Acheta domesticus)、蝼蛄属(Gryllotalpa spp.)、非洲飞蝗(Locusta migratoria)、黑蝗(Melanoplus spp.)、沙漠蝗(Schistocer cagregaria)。From the order of the Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria, Melanoplus spp., Schistocer cagregaria.

所述蜚蠊目(Blattaria)，例如，东方蟑螂(Blatta orientalis)、美洲蟑(Periplanet aamericana)、佛罗里达蟑螂(Leucophae amaderae)、德国蟑螂(Blattellagermanica)。From the order of the Blattaria, for example, Blatta orientalis, Periplanet aamericana, Leucophae amaderae, Blattellagermanica.

所述革翅目(Dermaptera)，例如，欧洲球螋(Forficula auricularia)。From the order of the Dermaptera, for example, Forficula auricularia.

所述等翅目(Isoptera)，例如，散白蚁属(Reticulitermes spp.)。From the order of the Isoptera, for example, Reticulitermes spp.

所述虱目(Phthiraptera)，例如，人体虱(Pediculus humanuscorporis)、血虱属(Haematopinus spp.)、毛虱属(Linognathus spp.)、嚼虱属(Trichodectes spp.)、畜虱属(Damalinia spp.)。From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp. ).

所述缨翅目(Thysanoptera)，例如，温室条篱蓟马(Hercinothrips femoralis)、烟蓟马(Thrips tabaci)、棕榈蓟马(Thrips palmi)、西花蓟马(Frankliniellaoccidentalis)。From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

所述异翅目(Heteroptera)，例如，扁盾蝽属(Eurygaster spp.)、居间棉红蝽(Dysdercus intermedius)、方背皮蝽(Piesma quadrata)、温带臭虫(Cimexlectularius)、长红锥蝽(Rhodnius prolixus)、锥蝽属(Triatoma spp.)。From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimexlectularius, Tria bug (Cimexlectularius) Rhodnius prolixus), Triatoma spp.

所述同翅目(Homoptera)，例如，白粉虱(Aleurodes brassicae)、烟粉(Bemisiatabaci)、温室粉虱(Trialeurodes vaporariorum)、棉蚜(Aphis gossypii)、甘蓝蚜(Brevicoryne brassicae)、茶藨隐瘤蚜(Cryptomyzus ribis)、黑豆蚜(Aphis fabae)、苹果黄蚜(Aphis pomi)、苹果绵蚜(Eriosoma lanigerum)、梅大尾蚜(Hyalopterusarundinis)、葡萄根瘤蚜(Phylloxera vastatrix)、瘿绵蚜属(Pemphigus spp.)、麦长管蚜(Macrosiphum avenae)、瘤蚜属(Myzus spp.)、忽布疣蚜(Phorodon humuli)、禾谷缢管蚜(Rhopalosiphum padi)、小绿叶蝉属(Empoasca spp.)、Euscelis bilobatus、稻黑尾叶蝉(Nephotettix cincticeps)、介壳虫(Lecanium corni)、榄珠蜡蚧(Saissetia oleae)、灰飞虱(Laodelphax striatellus)、褐飞虱(Nilaparvatalugens)、红圆蚧(Aonidiellaaurantii)、常春藤圆盾蚧(Aspidiotus hederae)、粉蚧属种(Pseudococcus spp.)、木虱属种(Psylla spp.)。From the order of the Homoptera, for example, Aleurodes brassicae, Bemisiatabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Crysoptera Aphid (Cryptomyzus ribis), Black bean aphid (Aphis fabae), Apple yellow aphid (Aphis pomi), Apple cotton aphid (Eriosoma lanigerum), Plum aphid (Hyalopterusarundinis), grape phylloxera (Phylloxera vastatrix), gall aphid ( Pemphigus spp.), Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp. ), Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvatalugens, Aonidiellaaurantii , Ivy round shield scale (Aspidiotus hederae), mealybug genus species (Pseudococcus spp.), psyllid genus species (Psylla spp.).

所述鳞翅目(Lepidoptera)，例如，红铃麦蛾(Pectinophora gossypiella)、松尺蠖(Bupalus piniarius)、冬尺蛾(Cheimatobia brumata)、苹细蛾(Lithocolletisblancardella)、苹果巢蛾(Hyponomeuta padella)、菜蛾(Plutella xylostella)、黄褐天幕毛虫(Malacosoma neustria)、黄毒蛾(Euproctis chrysorrhoea)、毒蛾属(Lymantriaspp.)、棉潜蛾(Bucculatrix thurberiella)、桔潜蛾(Phyllocrnistis citrella)、地老虎属(Agrotis spp.)、切根虫属(Euxoa spp.)、脏切夜蛾属(Feltia spp.)、埃及金刚钻(Earias insulana)、实夜蛾属(Heliothis spp.)、甘蓝夜蛾(Mamestra brassicae)、小眼夜蛾(Panolis flammea)、灰翅夜蛾属(Spodoptera spp.)、粉纹夜蛾(Trichoplusia ni)、苹果小卷蛾(Carpocap sapomonella)、菜粉蝶属(Pieris spp.)、禾草螟属(Chilo spp.)、玉米螟(Pyrausta nubilalis)、地中海粉斑螟(Ephestia kuehniella)、大蜡螟(Galleriamellonella)、幕谷蛾(Tineola bisselliella)、袋谷蛾(Tinea pellionella)、褐织蛾(Hofmannophilap seudospretella)、亚麻黄卷蛾(Cacoecia podana)、枞色卷蛾(Choristoneura fumiferana)、葡萄果蠹蛾(Clysia ambiguella)、茶长卷蛾(Homonamagnanima)、栎绿卷蛾(Tortrix viridana)、稻纵卷叶螟属种(Cnaphalocerus spp.)、水稻负泥虫(Oulema oryzae)。From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantriaspp., Bucculatrix thurberiella, Phyllocrnistis citrella, Cutworm Agrotis spp.), Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae , Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocap sapomonella, Pieris spp., Grass Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Brown weaver (Hofmannophilap seudospretella), Cacoecia podana, Choristoneura fumiferana, Clysia ambiguella, Homonamagnanima, Tortrix viridana, Rice worm Cnaphalocerus spp., Oulema oryzae.

所述鞘翅目(Coleoptera)，例如，家具窃蠹(Anobium punctatum)、谷蠹(Rhizopertha dominica)、恶条豆象(Bruchidius obtectus)、菜豆象(Acanthoscelidesobtectus)、北美家天牛(Hylotrupes bajulus)、杨树萤叶甲(Agelastica alni)、马铃薯甲虫(Leptinotarsa decemlineata)、辣根猿叶虫(Phaedon cochleariae)、叶甲属(Diabrotica spp.)、油菜金头跳甲(Psylliodes chrysocephala)、墨西哥豆瓢虫(Epilachna varivestis)、Atomaria spp.、锯谷盗(Oryzaephilus surinamensis)、花象属种(Anthonomus spp.)、谷象属(Sitophilus spp.)、黑葡萄耳象(Otiorrhynchussulcatus)、香蕉球茎象甲(Cosmopolites sordidus)、白菜龟象(Ceuthorrhynchusassimilis)、紫苜蓿叶象(Hypera postica)、皮蠹属(Dermestes spp.)、斑皮蠹属(Trogoderma spp.)、圆皮蠹属(Anthrenus spp.)、毛皮蠹属(Attagenus spp.)、粉蠹属(Lyctus spp.)、油菜花露尾甲(Meligethes aeneus)、蛛甲属(Ptinus spp.)、黄蛛甲(Niptus bololeucus)、裸蛛甲(Gibbium psylloides)、拟谷盗属(Tribolium spp.)、黄粉虫(Tenebrio molitor)、叩甲属(Agriotes spp.)、宽胸叩头虫属(Conoderus spp.)、西方五月鳃角金龟(Melolontha melolontha)、马铃薯鳃角金龟(Amphimallon solstitialis)、褐新西兰肋翅鳃角金龟(Costelytra zealandica)、稻根象(Lissorhoptrusoryzophilus)。From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Poplar firefly Leaf beetle (Agelastica alni), potato beetle (Leptinotarsa decemlineata), horseradish beetle (Phaedon cochleariae), leaf beetle (Diabrotica spp.), rape beetle (Psylliodes chrysocephala), Mexican bean lady beetle (Epilachna varivestis) ), Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchussulcatus, Banana bulb weevil (Cosmopolites sordidus), Cabbage Turtle Elephant (Ceuthorrhynchus assimilis), Alfalfa Leaf Elephant (Hypera postica), Dermestes (Dermestes spp.), Trogoderma spp., Anthrenus spp., Attagenus spp.), Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus bololeucus, Gibbium psylloides, Psyllium Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Potato beetle (Amphimallon solstitialis), brown New Zealand rib-winged beetle (Costelytra zealandica), rice root elephant (Lissorhoptrusoryzophilus).

所述膜翅目(Hymenoptera)，例如，松叶蜂属(Diprion spp.)、实叶蜂属(Hoplocampa spp.)、毛蚁属(Lasius spp.)、小家蚁(Monomorium pharaonis)、胡蜂属(Vespa spp.)。From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa (Vespa spp.).

所述双翅目(Diptera)，例如，伊蚊属(Aedes spp.)、按蚊属(Anopheles spp.)、库蚊属(Culex spp.)、黑腹果蝇(Drosophila melanogaster)、家蝇属(Musca spp.)、厕蝇属(Fannia spp.)、红头丽蝇(Calliphora vicina)、绿蝇属(Lucilia spp.)、金蝇属(Chrysomyia spp.)、黄蝇属(Cuterebra spp.)、胃蝇属(Gastrophilus spp.)、虱蝇属(Hyppobosca spp.)、螫蝇属(Stomoxys spp.)、狂蝇属(Oestrus spp.)、皮蝇属(Hypodermaspp.)、虻属(Tabanus spp.)、花园毛蚊(Bibio hortulanus)、瑞典麦秆蝇(Oscinellafrit)、草种蝇属(Phorbia spp.)、藜泉蝇(Pegomyia hyoscyami)、地中海蜡实蝇(Ceratitis capitata)、橄榄大实蝇(Dacus oleae)、欧洲大蚊(Tipula paludosa)、黑蝇属(Hylemyia spp.)、斑潜蝇属(Liriomyza spp.)。From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca domestica (Musca spp.), Fannia spp., Calliphora vicina, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp. ), Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Olive fruit fly ( Dacus oleae), Tipula paludosa, Hylemyia spp., Liriomyza spp.

所述蚤目(Siphonaptera)，例如，印鼠客蚤(Xenopsylla cheopis)、角叶蚤属(Ceratophyllus spp.)。From the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp.

所述蛛形纲(Arachnida)，例如，中东金蝎(Scorpio maurus)、黑寡妇蜘蛛(Latrodectus mactans)、粗脚粉螨(Acarus siro)、锐缘蜱属种(Argas spp.)、钝缘蜱属(Ornithodoros spp.)、鸡皮刺螨(Dermanyssus gallinae)、茶藨瘿螨(Erio phyesribis)、桔芸锈螨(Phyllocoptruta oleivora)、牛蜱属(Boophilus spp.)、扇头蜱属(Rhipicephalus spp.)、花蜱属(Amblyomma spp.)、璃眼蜱属(Hyalomma spp.)、硬蜱属(Ixodes spp.)、痒螨属(Psoroptes spp.)、皮螨属(Chorioptes spp.)、疥螨属(Sarcoptesspp.)、跗线螨属(Tarsonemus spp.)、苜蓿苔螨(Bryobia praetiosa)、全爪螨属(Panonychus spp.)、叶螨属(Tetranychus spp.)、半跗线螨属(Hemitarsonemus spp.)、短须螨属(Brevipalpus spp.)。Said Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithocarpus Genus (Ornithodoros spp.), Dermanyssus gallinae, Erio phyesribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp. ), Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Scabies Genus Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp.), Brevipalpus spp..

所述植物寄生线虫包括，例如，短体线虫属(Pratylenchus spp.)、相似穿孔线虫(Radopholus similis)、起绒草茎线虫(Ditylenchus dipsaci)、半穿刺线虫(Tylenchulussemipenetrans)、异皮线虫属(Heterodera spp.)、球异皮线虫属(Globodera spp.)、根结线虫属(Meloidogyne spp.)、滑刃线虫属(Aphelenchoides spp.)、长针线虫属(Longidorus spp.)、剑线虫属(Xiphinema spp.)、毛刺线虫属(Trichodorus spp.)、伞滑刃线虫属(Bursaphelenchus spp.)。The plant parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp.), Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp.), Trichodorus spp., Bursaphelenchus spp.

附图说明Description of drawings

图1为化合物251的单晶衍射图。Figure 1 is a single crystal diffraction pattern of compound 251.

具体实施方式Detailed ways

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。The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to these specific embodiments. Those skilled in the art should realize that the present invention covers all alternatives, modifications and equivalents that may be included within the scope of the claims.

一、化合物制备1. Compound preparation

实施例1、中间体制备Embodiment 1, intermediate preparation

(1)中间体1-乙基-3-甲基-5-吡唑甲酸乙酯合成(1) Synthesis of intermediate 1-ethyl-3-methyl-5-pyrazolecarboxylic acid ethyl ester

Figure BDA0001285920250001081
Figure BDA0001285920250001081

将154.1g(1mol)中间体A加入到1000ml的烧瓶中，加入500ml乙腈和138g碳酸钾，然后加入1mol硫酸二乙酯，体系搅拌加热回流反应，板层析跟踪大约3hr反应完成，体系过滤，母液用旋转蒸发仪蒸干，残留物进行减压蒸馏得140g的中间体B，收率为77.0％。154.1g (1mol) of Intermediate A was added to a 1000ml flask, 500ml of acetonitrile and 138g of potassium carbonate were added, then 1mol of diethyl sulfate was added, the system was stirred and heated to reflux for reaction, followed by plate chromatography for about 3hr to complete the reaction, and the system was filtered, The mother liquor was evaporated to dryness with a rotary evaporator, and the residue was distilled under reduced pressure to obtain 140 g of Intermediate B with a yield of 77.0%.

(2)中间体1-乙基-3-甲基-4-氯-5-吡唑甲酸乙酯合成(2) Synthesis of intermediate 1-ethyl-3-methyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester

Figure BDA0001285920250001091
Figure BDA0001285920250001091

将18.2g(0.1mol)中间体B加入到100ml的烧瓶中，加入50ml二氯乙烷和138g碳酸钾，然后加入0.11mol磺酰氯，体系搅拌加热回流反应，板层析跟踪大约2.5hr反应完成，母液蒸干，残留物不处理直接用于下一步反应。Add 18.2g (0.1mol) of intermediate B to a 100ml flask, add 50ml of dichloroethane and 138g of potassium carbonate, then add 0.11mol of sulfonyl chloride, the system is stirred and heated to reflux for reaction, and the reaction is completed by plate chromatography tracking about 2.5hr , the mother liquor was evaporated to dryness, and the residue was directly used in the next reaction without treatment.

(3)中间体1-乙基-3-甲基-4-甲基-5-吡唑甲酸乙酯合成(3) Synthesis of intermediate 1-ethyl-3-methyl-4-methyl-5-pyrazolecarboxylic acid ethyl ester

Figure BDA0001285920250001092
Figure BDA0001285920250001092

中间体D参考JP2001342178A提供方法制得。Intermediate D was prepared with reference to the method provided in JP2001342178A.

(4)中间体1-甲基-3-甲基-4-甲基-5-吡唑甲酸乙酯合成(4) Synthesis of intermediate 1-methyl-3-methyl-4-methyl-5-pyrazolecarboxylic acid ethyl ester

Figure BDA0001285920250001093
Figure BDA0001285920250001093

中间体D-1参考JP2001342178A提供方法制得。Intermediate D-1 was prepared by referring to the method provided in JP2001342178A.

(5)中间体1-甲基-3-甲基-4-氯-5-吡唑甲酸乙酯合成(5) Synthesis of intermediate 1-methyl-3-methyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester

Figure BDA0001285920250001101
Figure BDA0001285920250001101

中间体C-1制备方法同中间体C。The preparation method of intermediate C-1 is the same as that of intermediate C.

(6)中间体F制备(6) Preparation of Intermediate F

Figure BDA0001285920250001102
Figure BDA0001285920250001102

常规操作：将取代醛与催化量氯化锌在反应器中搅拌均匀，在冷却下缓慢滴加取代酰氯，滴加完毕后在低温下继续搅拌1-2hr,然后升温，继续反应5hr，然后通过减压蒸馏方式提纯。Routine operation: stir the substituted aldehyde and the catalytic amount of zinc chloride in the reactor evenly, slowly add the substituted acid chloride dropwise under cooling, continue stirring at low temperature for 1-2hr after the dropwise addition, then heat up, continue the reaction for 5hr, and then pass Purified by vacuum distillation.

中间体乙酸氯代甲酯制备：Preparation of intermediate chloromethyl acetate:

Figure BDA0001285920250001103
Figure BDA0001285920250001103

在冷却到0℃下将50g(0.6mol)乙酰氯滴加到85g多聚甲醛和1.75g氯化锌混和物中，大约2hr滴加完毕，然后反应体系升至室温，反应1hr，然后加热到90℃继续反应10hr，冷却，过滤去除固体，减压蒸馏得中间体F-1 45g。50g (0.6mol) acetyl chloride was added dropwise to the mixture of 85g paraformaldehyde and 1.75g zinc chloride under cooling to 0°C, the dropwise addition was completed in about 2hr, then the reaction system was raised to room temperature, reacted for 1hr, and then heated to The reaction was continued at 90° C. for 10 hr, cooled, filtered to remove solids, and distilled under reduced pressure to obtain 45 g of intermediate F-1.

(7)中间体H制备(7) Preparation of intermediate H

Figure BDA0001285920250001104
Figure BDA0001285920250001104

常规操作：在冷却下将氯甲酸氯代酯缓慢滴加到取代醇和三乙胺溶液中，滴加完毕后在低温下继续搅拌1-2hr,然后升温，室温继续反应1hr，然后过滤，蒸出溶剂，然后通过减压蒸馏方式提纯得中间体H。Routine operation: slowly add chloroformate chloroformate dropwise to the substituted alcohol and triethylamine solution under cooling, continue to stir at low temperature for 1-2hr after the dropwise addition, then heat up, continue to react at room temperature for 1hr, then filter and steam out solvent, and then purified by distillation under reduced pressure to obtain intermediate H.

中间体H-1制备：Preparation of Intermediate H-1:

Figure BDA0001285920250001111
Figure BDA0001285920250001111

在冷却到0℃下将71.5g(0.5mol)1-氯乙基氯甲酸酯滴加到40g和52.0g三乙胺250ml甲苯溶液中，大约2hr滴加完毕，然后反应体系升至室温，反应1hr，过滤去除固体，减压蒸馏得中间体H-1为78.5g。71.5g (0.5mol) of 1-chloroethyl chloroformate was added dropwise to 40g and 52.0g of triethylamine in 250ml of toluene solution under cooling to 0°C, the dropwise addition was completed in about 2hr, and then the reaction system was raised to room temperature, The reaction was carried out for 1 hr, the solid was removed by filtration, and 78.5 g of intermediate H-1 was obtained by distillation under reduced pressure.

(8)中间体TA-1制备(8) Preparation of intermediate TA-1

Figure BDA0001285920250001112
Figure BDA0001285920250001112

将17.3g对叔丁基苯乙腈溶入70ml无水THF中，体系冷却到-5℃加入等摩尔固体甲醇钠，然后在搅拌下滴入等摩尔中间体B,2hr滴加完毕，继续搅拌1.5hr，然后升到室温，继续搅拌反应2hr,反应完成后蒸出THF，残留物用水溶解，用盐酸中和到pH为4左右，用乙酸乙酯萃取，用无水硫酸钠干燥，蒸出乙酸乙酯得中间体TA-1，不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylbenzeneacetonitrile into 70ml of anhydrous THF, cool the system to -5°C and add equimolar solid sodium methoxide, then dropwise equimolar Intermediate B under stirring, after 2hr dropwise addition, continue to stir for 1.5 hr, then rise to room temperature, continue to stir the reaction for 2hr, steam THF after the reaction is completed, the residue is dissolved in water, neutralized to pH 4 with hydrochloric acid, extracted with ethyl acetate, dried with anhydrous sodium sulfate, and steamed with acetic acid. The ethyl ester obtains the intermediate TA-1, which is directly used in the next step without purification.

(9)中间体TA-2制备(9) Preparation of intermediate TA-2

Figure BDA0001285920250001113
Figure BDA0001285920250001113

将17.3g对叔丁基苯乙腈溶入70ml无水THF中，体系冷却到-5℃加入等摩尔固体叔丁醇钾，然后在搅拌下滴入等摩尔中间体C,2.5hr滴加完毕，继续搅拌2.0hr，然后升到室温，继续搅拌反应2hr,反应完成后蒸出THF，残留物用水溶解，用盐酸中和到pH为4左右，用乙酸乙酯萃取，用无水硫酸钠干燥，蒸出乙酸乙酯得中间体TA-2，不需提纯直接用于下一步反应。17.3g of p-tert-butylbenzeneacetonitrile was dissolved in 70ml of anhydrous THF, the system was cooled to -5°C and equimolar solid potassium tert-butoxide was added, and then equimolar intermediate C was added dropwise under stirring, and the dropwise addition was completed in 2.5hr, Continue to stir for 2.0hr, then rise to room temperature, continue to stir and react for 2hr, steam THF after the reaction is completed, the residue is dissolved in water, neutralized with hydrochloric acid to a pH of about 4, extracted with ethyl acetate, and dried with anhydrous sodium sulfate, The ethyl acetate was distilled off to obtain the intermediate TA-2, which was directly used in the next reaction without purification.

(10)中间体TA-3制备(10) Preparation of intermediate TA-3

Figure BDA0001285920250001121
Figure BDA0001285920250001121

将17.3g对叔丁基苯乙腈溶入70ml甲基叔丁基醚中，体系冷却到-5℃加入等摩尔固体叔丁醇钾，然后在搅拌下滴入等摩尔中间体D,3.0hr滴加完毕，继续搅拌2.0hr，然后升到室温，继续搅拌反应2hr,反应完成后蒸出甲基叔丁基醚，残留物用水溶解，用盐酸中和到pH为4左右，用乙酸乙酯萃取，用无水硫酸钠干燥，蒸出乙酸乙酯得中间体TA-3，不需提纯直接用于下一步反应。Dissolve 17.3g of p-tert-butylbenzeneacetonitrile in 70ml of methyl tert-butyl ether, cool the system to -5°C and add equimolar solid potassium tert-butoxide, then add equimolar intermediate D under stirring, dropwise in 3.0hr After adding, continue to stir for 2.0hr, then rise to room temperature, continue to stir and react for 2hr, steam methyl tert-butyl ether after the reaction is completed, the residue is dissolved in water, neutralized with hydrochloric acid to a pH of about 4, and extracted with ethyl acetate , dried with anhydrous sodium sulfate, and evaporated the ethyl acetate to obtain the intermediate TA-3, which was directly used in the next reaction without purification.

(11)中间体TA-4制备(11) Preparation of intermediate TA-4

Figure BDA0001285920250001122
Figure BDA0001285920250001122

将17.3g对叔丁基苯乙腈溶入70ml无水THF中，体系冷却到-5℃加入等摩尔固体甲醇钠，然后在搅拌下滴入等摩尔中间体M,2hr滴加完毕，继续搅拌1.5hr，然后升到室温，继续搅拌反应2hr,反应完成后蒸出THF，残留物用水溶解，用盐酸中和到pH为4左右，用乙酸乙酯萃取，用无水硫酸钠干燥，蒸出乙酸乙酯得中间体TA-1，不需提纯直接用于下一步反应。17.3g of p-tert-butylbenzeneacetonitrile was dissolved in 70ml of anhydrous THF, the system was cooled to -5°C, and equimolar solid sodium methoxide was added, and then equimolar intermediate M was added dropwise under stirring. hr, then rise to room temperature, continue to stir the reaction for 2hr, steam THF after the reaction is completed, the residue is dissolved in water, neutralized to pH 4 with hydrochloric acid, extracted with ethyl acetate, dried with anhydrous sodium sulfate, and steamed with acetic acid. The ethyl ester obtains the intermediate TA-1, which is directly used in the next step without purification.

中间体TA-5制备：Preparation of intermediate TA-5:

Figure BDA0001285920250001131
Figure BDA0001285920250001131

将17.3g对叔丁基苯乙腈溶入70ml无水THF中，体系冷却到-5℃加入等摩尔固体叔丁醇钾，然后在搅拌下滴入等摩尔中间体C,2.5hr滴加完毕，继续搅拌2.0hr，然后升到室温，继续搅拌反应2hr,反应完成后蒸出THF，残留物用水溶解，用盐酸中和到pH为4左右，用乙酸乙酯萃取，用无水硫酸钠干燥，蒸出乙酸乙酯得中间体TA-5，不需提纯直接用于下一步反应。17.3g of p-tert-butylbenzeneacetonitrile was dissolved in 70ml of anhydrous THF, the system was cooled to -5°C and equimolar solid potassium tert-butoxide was added, and then equimolar intermediate C was added dropwise under stirring, and the dropwise addition was completed in 2.5hr, Continue to stir for 2.0hr, then rise to room temperature, continue to stir and react for 2hr, steam THF after the reaction is completed, the residue is dissolved in water, neutralized with hydrochloric acid to a pH of about 4, extracted with ethyl acetate, and dried with anhydrous sodium sulfate, The ethyl acetate was distilled off to obtain the intermediate TA-5, which was directly used in the next reaction without purification.

中间体TA-6制备：Preparation of intermediate TA-6:

Figure BDA0001285920250001132
Figure BDA0001285920250001132

将17.3g对叔丁基苯乙腈溶入70mlTHF中，体系冷却到-5℃加入等摩尔固体叔丁醇钾，然后在搅拌下滴入等摩尔中间体D-1,3.0hr滴加完毕，继续搅拌2.0hr，然后升到室温，继续搅拌反应2hr,反应完成后蒸出甲基叔丁基醚，残留物用水溶解，用盐酸中和到pH为4左右，用乙酸乙酯萃取，用无水硫酸钠干燥，蒸出乙酸乙酯得中间体TA-3，不需提纯直接用于下一步反应。Dissolve 17.3g p-tert-butylbenzene acetonitrile in 70ml THF, cool the system to -5°C and add equimolar solid potassium tert-butoxide, then dropwise equimolar intermediate D-1 under stirring, after 3.0hr dropwise addition, continue Stir for 2.0 hr, then rise to room temperature, continue to stir and react for 2 hr, steam methyl tert-butyl ether after the reaction is completed, the residue is dissolved in water, neutralized with hydrochloric acid to a pH of about 4, extracted with ethyl acetate, and dried with anhydrous It was dried over sodium sulfate, and the ethyl acetate was distilled off to obtain the intermediate TA-3, which was directly used in the next reaction without purification.

实施例2、目标化合物制备Example 2. Preparation of target compound

(1)目标化合物226(1) Target compound 226

Figure BDA0001285920250001141
Figure BDA0001285920250001141

将0.31g(0.001mol)中间体TA-1和0.12g(0.0011mol)中间体F-1，0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中，然后加热回流反应7hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物0.32g，收率为84％。0.31g (0.001mol) of intermediate TA-1 and 0.12g (0.0011mol) of intermediate F-1, 0.15g of sodium carbonate and catalytic amount of sodium iodide were added to 25ml of acetonitrile, then heated to reflux for 7hr, followed by plate chromatography The reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.32 g of the product with a yield of 84%.

(2)目标化合物251(2) Target compound 251

Figure BDA0001285920250001142
Figure BDA0001285920250001142

将31g(0.1mol)中间体TA-1和13g(0.11mol)中间体F-2，15碳酸钠以及催化量碘化钠加入到250ml乙腈中，然后加热回流反应10hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物35.1g，收率为89％。31g (0.1mol) of intermediate TA-1 and 13g (0.11mol) of intermediate F-2, 15 sodium carbonate and catalytic amount of sodium iodide were added to 250ml of acetonitrile, then heated to reflux for 10hr, and plate chromatography followed the reaction to complete , the reaction system was cooled to room temperature, the solid was removed by filtration, the acetonitrile was evaporated, and the residue was purified by column chromatography to obtain 35.1 g of the product with a yield of 89%.

(3)目标化合物259(3) Target compound 259

Figure BDA0001285920250001151
Figure BDA0001285920250001151

将0.31g(0.001mol)中间体TA-1和0.13g(0.0011mol)中间体F-3，0.15碳酸钠以及催化量碘化钠加入到25ml丙酮中，然后加热回流反应12hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物0.28g，收率为66％。Add 0.31g (0.001mol) of intermediate TA-1 and 0.13g (0.0011mol) of intermediate F-3, 0.15g of sodium carbonate and catalytic amount of sodium iodide to 25ml of acetone, then heated under reflux for 12hr, followed by plate chromatography The reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, the acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.28 g of the product with a yield of 66%.

(4)目标化合物326(4) Target compound 326

Figure BDA0001285920250001152
Figure BDA0001285920250001152

将0.34g(0.001mol)中间体TA-2和0.13g(0.0011mol)中间体F-2，0.15碳酸钠以及催化量碘化钠加入到25N,N-二甲基甲酰胺中，然后加热70℃反应4hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，减压蒸出溶剂，残留物柱层析提纯得产物0.24g，收率为56％。0.34g (0.001mol) of intermediate TA-2 and 0.13g (0.0011mol) of intermediate F-2, 0.15 g of sodium carbonate and a catalytic amount of sodium iodide were added to 25N,N-dimethylformamide, and then heated for 70 The reaction was carried out at °C for 4 hr, followed by plate chromatography to complete the reaction, the reaction system was cooled to room temperature, the solid was removed by filtration, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 0.24 g of the product with a yield of 56%.

(5)目标化合物401(5) Target compound 401

Figure BDA0001285920250001161
Figure BDA0001285920250001161

将0.32g(0.001mol)中间体TA-2和0.13g(0.0011mol)中间体F-2，0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中，然后加热回流反应11hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，减压蒸出溶剂，残留物柱层析提纯得产物0.29g，收率为71％。0.32g (0.001mol) of intermediate TA-2 and 0.13g (0.0011mol) of intermediate F-2, 0.15g of sodium carbonate and catalytic amount of sodium iodide were added to 25ml of acetonitrile, then heated under reflux for 11hr, followed by plate chromatography The reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 0.29 g of the product with a yield of 71%.

(6)目标化合物105(6) Target compound 105

Figure BDA0001285920250001162
Figure BDA0001285920250001162

将0.33g(0.1mol)中间体TA-5和0.18g(0.11mol)中间体F-4，0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中，然后加热回流反应11hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物0.25g，收率为55％。0.33g (0.1mol) of intermediate TA-5 and 0.18g (0.11mol) of intermediate F-4, 0.15g of sodium carbonate and catalytic amount of sodium iodide were added to 25ml of acetonitrile, then heated under reflux for 11hr, followed by plate chromatography The reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was evaporated, and the residue was purified by column chromatography to obtain 0.25 g of the product with a yield of 55%.

(7)目标化合物4(7) Target compound 4

Figure BDA0001285920250001163
Figure BDA0001285920250001163

将0.295g(0.1mol)中间体TA-4和0.15g(0.11mol)中间体F-6，0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中，然后加热回流反应5hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物0.31g，收率为78％。0.295g (0.1mol) of intermediate TA-4 and 0.15g (0.11mol) of intermediate F-6, 0.15g of sodium carbonate and catalytic amount of sodium iodide were added to 25ml of acetonitrile, then heated to reflux for 5hr, followed by plate chromatography The reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.31 g of the product with a yield of 78%.

(8)目标化合物91(8) Target compound 91

Figure BDA0001285920250001171
Figure BDA0001285920250001171

将0.33g(0.1mol)中间体TA-5和0.18g(0.11mol)中间体F-4，0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中，然后加热回流反应11hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物0.25g，收率为55％。0.33g (0.1mol) of intermediate TA-5 and 0.18g (0.11mol) of intermediate F-4, 0.15g of sodium carbonate and catalytic amount of sodium iodide were added to 25ml of acetonitrile, then heated under reflux for 11hr, followed by plate chromatography The reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was evaporated, and the residue was purified by column chromatography to obtain 0.25 g of the product with a yield of 55%.

(9)目标化合物548(9) Target compound 548

Figure BDA0001285920250001172
Figure BDA0001285920250001172

将0.31g(0.001mol)中间体TA-1和0.16g(0.0011mol)中间体H-1，0.15碳酸钠以及催化量碘化钠加入到25ml乙腈中，然后加热回流反应6hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物0.33g，收率为78％。Add 0.31g (0.001mol) of intermediate TA-1 and 0.16g (0.0011mol) of intermediate H-1, 0.15g of sodium carbonate and catalytic amount of sodium iodide to 25ml of acetonitrile, then heated to reflux for 6hr, followed by plate chromatography The reaction was completed, the reaction system was cooled to room temperature, the solid was removed by filtration, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.33 g of the product with a yield of 78%.

(10)目标化合物739(10) Target compound 739

Figure BDA0001285920250001181
Figure BDA0001285920250001181

将0.34g(0.001mol)中间体TA-2和0.13g(0.0011mol)中间体H-2，0.15碳酸钾以及催化量碘化钠加入到25N,N-二甲基甲酰胺中，然后加热70℃反应5hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，减压蒸出溶剂，残留物柱层析提纯得产物0.28g，收率为65％。0.34g (0.001mol) of intermediate TA-2 and 0.13g (0.0011mol) of intermediate H-2, 0.15g of potassium carbonate and catalytic amount of sodium iodide were added to 25N,N-dimethylformamide, then heated for 70 The reaction was carried out at °C for 5 hr, followed by plate chromatography to complete the reaction, the reaction system was cooled to room temperature, the solid was removed by filtration, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 0.28 g of the product with a yield of 65%.

(11)目标化合物835(11) Target compound 835

Figure BDA0001285920250001182
Figure BDA0001285920250001182

将0.31g(0.001mol)中间体TA-6和0.13g中间体H-3，0.15碳酸钾以及催化量碘化钠加入到25mlTHF中，然后加热回流反应10hr，板层析跟踪反应完成，反应体系冷却到室温，过滤去固体，蒸出乙腈，残留物柱层析提纯得产物0.25g，收率为61％。0.31g (0.001mol) of intermediate TA-6 and 0.13g of intermediate H-3, 0.15g of potassium carbonate and catalytic amount of sodium iodide were added to 25ml of THF, then heated to reflux for 10hr, the plate chromatography tracking reaction was completed, and the reaction system After cooling to room temperature, the solid was filtered off, acetonitrile was distilled off, and the residue was purified by column chromatography to obtain 0.25 g of the product with a yield of 61%.

二、制剂配制2. Preparation of preparations

以下实施例按照质量配比配制。The following examples are prepared according to the mass ratio.

实施例3、30％悬浮剂Example 3, 30% suspending agent

Figure BDA0001285920250001183
Figure BDA0001285920250001183

Figure BDA0001285920250001191
Figure BDA0001285920250001191

将化合物251及其它组分充分混和，由此得到的30％悬浮剂。用水稀释得到30％悬浮剂可得到任何所需浓度的稀释液。Compound 251 and other components were mixed well, and the thus obtained 30% suspending agent. Dilution with water to give a 30% suspension can give any desired concentration of dilution.

实施例4、30％乳油Example 4, 30% EC

Figure BDA0001285920250001192
Figure BDA0001285920250001192

将亚磷酸溶解在甲苯中，加入化合物548和乙氧基化甘油三酸酯，得到透明的溶液，即30％乳油。Phosphorous acid was dissolved in toluene, compound 548 and ethoxylated triglycerides were added to give a clear solution, a 30% emulsifiable concentrate.

实施例5、60％可湿粉剂Example 5, 60% wettable powder

Figure BDA0001285920250001193
Figure BDA0001285920250001193

将化合物91、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得60％可湿粉剂。Compound 91, sodium dodecylnaphthalene sulfonate, sodium lignosulfonate and siliceous clay are mixed together, and pulverized in a pulverizer until the particles reach the standard to obtain a 60% wettable powder.

三、生物活性测试3. Biological activity test

实施例6、对朱砂叶螨卵活性测定Example 6. Determination of the activity of the eggs of Tetranychus cinnabarinus

根据待测化合物的溶解性，原药用N,N-二甲基甲酰胺溶解，然后用含1‰吐温80水溶液配制成所需浓度的待测液，N,N-二甲基甲酰胺在溶液中的含量不超过10％。According to the solubility of the compound to be tested, the original drug was dissolved with N,N-dimethylformamide, and then an aqueous solution containing 1‰ Tween 80 was used to prepare the test solution of the required concentration, N,N-dimethylformamide. The content in the solution does not exceed 10%.

采用喷雾法。将蚕豆叶片带柄剪下，插于加水的瓶中。接一定数量的雌成螨，24h后去除成螨，除去成螨24h后进行喷雾处理，试验重复3次，并设空白对照，置于观察室(26±2℃、湿度70％～80％、16h光照/d)内培养，待空白对照孵化后调查结果。调查时以未孵化为死亡。Use spray method. Cut the broad bean leaves with handles and insert them into a bottle with water. Connect a certain number of female adult mites, remove the adult mites after 24 hours, and spray the adult mites 24 hours later. 16h light/d), and the results were investigated after the blank control hatched. At the time of investigation, it was regarded as dead without hatching.

按照上述方法，活性测定发现本发明如下化合物1-17、26-72、76-92、101-117、151-167、176-192、226-242、251-267、301-317、326-342、376-392、401-417、451-454、456、457、458、460、467、468、471、474、476、477、480、481、483-486、488、489、490、492、494、499、500、503、506、508、509、512、513、574-548、549、550、552、553、554、556、558、563、564、567、570、572、573、576、577、579-582、584、585、586、588、590、595、596、599、606、602、604、606、608、609、643-646、648、649、650、652、654、659、660、663、666、668、669、972、673、675-678、680、681、682、684、691、692、695、698、700、701、704、705、739-742、744、745、746、748、750、755、757、759、762、764、765、768、769、771-774、776、777、778、780、782、787、788、791、794、796、797、801、835-838、840、841、842、844、846、851、853、855、858、860、862、864、865、867-870、872、873、874、876、878、883、884、887、890、892、894、896、897、931-934、936、937、938、940、942、947、948、951、956、958、961、960、963-966、968、969、970、972、974、978、980、986、988、983、989、992、993、1158、1172、1293、1318、1323、1468在浓度5mg/L下等于或优于90％杀卵活性。与PCT专利申请WO01/68589相比，PCT专利申请WO01/68589中公开的化合物8-1，8-2，8-3，8-4在浓度5mg/L下杀卵活性小于30％。According to the above method, the activity assay found the following compounds of the present invention 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342 , 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494 , 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577 , 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660 , 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746 , 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835 -838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890 , 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974 , 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468 were equal to or better than 90% ovicidal activity at a concentration of 5 mg/L. Compared with PCT patent application WO01/68589, the ovicidal activity of compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 is less than 30% at a concentration of 5 mg/L.

按照上述方法，活性测定发现本发明如下化合物230、234、226、227、251、252、254、255、259、301、302、305、309、326、327、401、402、409、405、547、548、549、550、553、570、579、580、585、602、771、772、780、931、932、933、940、937、963、964和969在浓度2mg/L下等于或优于90％杀卵活性。与PCT专利申请WO01/68589相比，PCT专利申请WO01/68589中公开的化合物8-1，8-2，8-3，8-4在浓度2mg/L下杀卵活性为0％。According to the above method, the activity assay found the following compounds of the present invention: , 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969 at a concentration of 2 mg/L equal to or better than 90% ovicidal activity. Compared with PCT patent application WO01/68589, compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 had 0% ovicidal activity at a concentration of 2 mg/L.

按照上述方法，选取化合物226、227、230、234、251、252、254、255、301、302、547、585、771、772、931、932和937与PCT专利申请WO01/68589中公开的化合物8-1、8-2、8-3和8-4进行杀卵活性的平行测定，试验结果见表4；According to the above method, compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 and the compounds disclosed in PCT patent application WO01/68589 were selected. 8-1, 8-2, 8-3 and 8-4 carry out parallel determination of ovicidal activity, and the test results are shown in Table 4;

表4Table 4

Figure BDA0001285920250001211
Figure BDA0001285920250001211

Figure BDA0001285920250001221
Figure BDA0001285920250001221

实施例7、对朱砂叶螨成螨活性的测定Example 7. Determination of the adult mite activity of Tetranychus cinnabarinus

根据待测化合物的溶解性，原药用N,N-二甲基甲酰胺溶解，然后用含1‰吐温80水溶液配制成所需浓度的待测液，N,N-二甲基甲酰胺在溶液中的含量不超过10％。According to the solubility of the compound to be tested, the original drug was dissolved with N,N-dimethylformamide, and then an aqueous solution containing 1‰ Tween 80 was used to prepare the test solution of the required concentration, N,N-dimethylformamide. The content in the solution does not exceed 10%.

取两片真叶菜豆苗，接种朱砂叶螨成螨并调查基数后，用手持喷雾器进行整株喷雾处理，每处理3次重复，处理后置于标准观察室，48h后调查存活螨数，计算死亡率。Two true-leaf bean sprouts were taken, inoculated with Tetranychus cinnabarinus adult mites and the base number was investigated, then sprayed the whole plant with a hand-held sprayer, repeated 3 times for each treatment, and placed in a standard observation room after treatment. .

按照上述方法，活性测定发现本发明化合物1-17、26-72、76-92、101-117、151-167、176-192、226-242、251-267、301-317、326-342、376-392、401-417、451-454、456、457、458、460、467、468、471、474、476、477、480、481、483-486、488、489、490、492、494、499、500、503、506、508、509、512、513、574-548、549、550、552、553、554、556、558、563、564、567、570、572、573、576、577、579-582、584、585、586、588、590、595、596、599、606、602、604、606、608、609、643-646、648、649、650、652、654、659、660、663、666、668、669、972、673、675-678、680、681、682、684、691、692、695、698、700、701、704、705、739-742、744、745、746、748、750、755、757、759、762、764、765、768、769、771-774、776、777、778、780、782、787、788、791、794、796、797、801、835-838、840、841、842、844、846、851、853、855、858、860、862、864、865、867-870、872、873、874、876、878、883、884、887、890、892、894、896、897、931-934、936、937、938、940、942、947、948、951、956、958、961、960、963-966、968、969、970、972、974、978、980、986、988、983、989、992、993、1158、1172、1293、1318、1323、1468在浓度2.5mg/L下等于或优于90％杀成螨活性。与PCT专利申请WO01/68589相比，PCT专利申请WO01/68589中公开的化合物8-1，8-2，8-3，8-4在浓度2.5mg/L下成螨活性活性小于80％。According to the above method, the activity assay found that the compounds of the present invention 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835- 838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468 were equal to or better than 90% acaricidal activity at a concentration of 2.5 mg/L. Compared with PCT patent application WO01/68589, the mite-forming activity of compounds 8-1, 8-2, 8-3, and 8-4 disclosed in PCT patent application WO01/68589 is less than 80% at a concentration of 2.5 mg/L.

按照上述方法，活性测定发现本发明化合物230、234、226、227、251、252、254、255、259、301、302、305、309、326、327、401、402、409、405、547、548、549、550、553、570、579、580、585、602、771、772、780、931、932、933、940、937、963、964和969在浓度1.25mg/L下等于或优于90％杀成螨活性。与PCT专利申请WO01/68589相比，PCT专利申请WO01/68589中公开的化合物8-1，8-2，8-3，8-4在浓度1.25mg/L下成螨活性低于50％。According to the above method, the activity assay found that the compounds of the present invention 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964 and 969 equal to or better than 1.25 mg/L 90% kill adult mite activity. Compared with PCT patent application WO01/68589, the mite-forming activities of compounds 8-1, 8-2, 8-3, and 8-4 disclosed in PCT patent application WO01/68589 are lower than 50% at a concentration of 1.25 mg/L.

按照上述方法，选取化合物226、227、230、234、251、252、254、255、301、302、547、585、771、772、931、932和937与PCT专利申请WO01/68589中公开的化合物8-1、8-2、8-3和8-4进行成螨活性的平行测定，试验结果见表5。According to the above method, compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 and the compounds disclosed in PCT patent application WO01/68589 were selected. 8-1, 8-2, 8-3 and 8-4 were used for parallel determination of mite-forming activity, and the test results are shown in Table 5.

表5table 5

Figure BDA0001285920250001231
Figure BDA0001285920250001231

Figure BDA0001285920250001241
Figure BDA0001285920250001241

实施例8、对朱砂叶螨若螨活性的测定Example 8. Determination of the activity of Tetranychus cinnabarinus nymphs

根据待测化合物的溶解性，原药用N,N-二甲基甲酰胺溶解，然后用含1‰吐温80水溶液配制成所需浓度的待测液，N,N-二甲基甲酰胺在溶液中的含量不超过10％。According to the solubility of the compound to be tested, the original drug was dissolved with N,N-dimethylformamide, and then an aqueous solution containing 1‰ Tween 80 was used to prepare the test solution of the required concentration, N,N-dimethylformamide. The content in the solution does not exceed 10%.

将蚕豆叶片带柄剪下，插于加水的小瓶中，接一定数量体色鲜艳、行动活泼的雌成螨，24h后，去除成螨，去除卵量不足的叶片。待卵孵化，长至若螨后进行喷雾处理，试验重复3次，并设空白对照，置于观察室(26±2℃、湿度70％～80％、16h光照/d)内培养，48h后调查结果。调查时轻触虫体，没有反应视为死虫。Cut faba bean leaves with handles, insert them into a small bottle with water, and connect a certain number of female adult mites with bright body color and lively action. After 24 hours, remove the adult mites and remove the leaves with insufficient eggs. After the eggs hatched, they were sprayed when they grew to nymphs. The experiment was repeated 3 times, and a blank control was set. The eggs were placed in an observation room (26±2°C, humidity 70%-80%, 16h light/d) for cultivation, and after 48h survey results. When investigating, touch the worm body lightly, and if there is no response, it is regarded as a dead worm.

按照上述方法，活性测定发现本发明化合物1-17、26-72、76-92、101-117、151-167、176-192、226-242、251-267、301-317、326-342、376-392、401-417、451-454、456、457、458、460、467、468、471、474、476、477、480、481、483-486、488、489、490、492、494、499、500、503、506、508、509、512、513、574-548、549、550、552、553、554、556、558、563、564、567、570、572、573、576、577、579-582、584、585、586、588、590、595、596、599、606、602、604、606、608、609、643-646、648、649、650、652、654、659、660、663、666、668、669、972、673、675-678、680、681、682、684、691、692、695、698、700、701、704、705、739-742、744、745、746、748、750、755、757、759、762、764、765、768、769、771-774、776、777、778、780、782、787、788、791、794、796、797、801、835-838、840、841、842、844、846、851、853、855、858、860、862、864、865、867-870、872、873、874、876、878、883、884、887、890、892、894、896、897、931-934、936、937、938、940、942、947、948、951、956、958、961、960、963-966、968、969、970、972、974、978、980、986、988、983、989、992、993、1158、1172、1293、1318、1323、1468在浓度2.5mg/L下等于或优于95％杀若螨活性。与PCT专利申请WO01/68589相比，PCT专利申请WO01/68589中公开的化合物8-1，8-2，8-3，8-4在浓度2.5mg/L下若螨活性活性小于80％。According to the above method, the activity assay found that the compounds of the present invention 1-17, 26-72, 76-92, 101-117, 151-167, 176-192, 226-242, 251-267, 301-317, 326-342, 376-392, 401-417, 451-454, 456, 457, 458, 460, 467, 468, 471, 474, 476, 477, 480, 481, 483-486, 488, 489, 490, 492, 494, 499, 500, 503, 506, 508, 509, 512, 513, 574-548, 549, 550, 552, 553, 554, 556, 558, 563, 564, 567, 570, 572, 573, 576, 577, 579-582, 584, 585, 586, 588, 590, 595, 596, 599, 606, 602, 604, 606, 608, 609, 643-646, 648, 649, 650, 652, 654, 659, 660, 663, 666, 668, 669, 972, 673, 675-678, 680, 681, 682, 684, 691, 692, 695, 698, 700, 701, 704, 705, 739-742, 744, 745, 746, 748, 750, 755, 757, 759, 762, 764, 765, 768, 769, 771-774, 776, 777, 778, 780, 782, 787, 788, 791, 794, 796, 797, 801, 835- 838, 840, 841, 842, 844, 846, 851, 853, 855, 858, 860, 862, 864, 865, 867-870, 872, 873, 874, 876, 878, 883, 884, 887, 890, 892, 894, 896, 897, 931-934, 936, 937, 938, 940, 942, 947, 948, 951, 956, 958, 961, 960, 963-966, 968, 969, 970, 972, 974, 978, 980, 986, 988, 983, 989, 992, 993, 1158, 1172, 1293, 1318, 1323, 1468 were equal to or better than 95% nymphicidal activity at a concentration of 2.5 mg/L. Compared with PCT patent application WO01/68589, the compounds 8-1, 8-2, 8-3, 8-4 disclosed in PCT patent application WO01/68589 have less than 80% nymphal activity at a concentration of 2.5 mg/L.

按照上述方法，活性测定发现本发明化合物230、234、226、227、251、252、254、255、259、301、302、305、309、326、327、401、402、409、405、547、548、549、550、553、570、579、580、585、602、771、772、780、931、932、933、940、937、963、964和969在浓度0.5mg/L下等于或优于90％杀若螨活性。与PCT专利申请WO01/68589相比，PCT专利申请WO01/68589中公开的化合物8-1，8-2，8-3，8-4在浓度0.5mg/L下若螨活性低于30％。According to the above method, the activity assay found that the compounds of the present invention 230, 234, 226, 227, 251, 252, 254, 255, 259, 301, 302, 305, 309, 326, 327, 401, 402, 409, 405, 547, 548, 549, 550, 553, 570, 579, 580, 585, 602, 771, 772, 780, 931, 932, 933, 940, 937, 963, 964, and 969 equal to or better than 0.5 mg/L 90% nymphicidal activity. Compared with the PCT patent application WO01/68589, the compounds 8-1, 8-2, 8-3, 8-4 disclosed in the PCT patent application WO01/68589 have a nymphalus activity of less than 30% at a concentration of 0.5 mg/L.

按照上述方法，选取化合物226、227、230、234、251、252、254、255、301、302、547、585、771、772、931、932和937与PCT专利申请WO01/68589中公开的化合物8-1、8-2、8-3和8-4进行若螨活性的平行测定，试验结果见表6。According to the above method, compounds 226, 227, 230, 234, 251, 252, 254, 255, 301, 302, 547, 585, 771, 772, 931, 932 and 937 and the compounds disclosed in PCT patent application WO01/68589 were selected. 8-1, 8-2, 8-3 and 8-4 were used for parallel determination of nymphal activity. The test results are shown in Table 6.

表6Table 6

Figure BDA0001285920250001251
Figure BDA0001285920250001251

Figure BDA0001285920250001261
Figure BDA0001285920250001261

Claims (8)

1.一类吡唑衍生物，具有如下通式stru-1：1. A class of pyrazole derivatives having the following general formula stru-1:
Figure FDA0002498284150000011
Figure FDA0002498284150000011
 其中：in: R1、R2、R4、R5为氢；R1, R2, R4, R5 are hydrogen; R3为叔丁基；R3 is tert-butyl; R6为甲基；R6 is methyl; R7选自氢、氯、甲基；R7 is selected from hydrogen, chlorine, methyl; R8为乙基；R8 is ethyl; R9选自氢或甲基；R9 is selected from hydrogen or methyl; L选自氧；L is selected from oxygen; Q为氧；Q is oxygen; R10选自C1-C6烷基、C3-C6环烷基、C2-C6烯基；R10 is selected from C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl; 所述吡唑衍生物为E式吡唑衍生物。The pyrazole derivatives are E-form pyrazole derivatives. 2.按照权利要求1所述的吡唑衍生物，其特征在于：所述吡唑衍生物选自以下结构式所示化合物中的至少一种：2. The pyrazole derivative according to claim 1, wherein the pyrazole derivative is selected from at least one of the compounds represented by the following structural formula:
Figure FDA0002498284150000021
Figure FDA0002498284150000021
 3.一类吡唑衍生物，其特征在于：所述吡唑衍生物选自以下结构式所示化合物中的至少一种：3. A class of pyrazole derivatives, characterized in that: the pyrazole derivatives are selected from at least one of the compounds shown in the following structural formula:
Figure FDA0002498284150000031
Figure FDA0002498284150000031
 4.一种权利要求1所示通式stru-1的吡唑衍生物或权利要求3所示的吡唑衍生物的制备方法，其特征在于：所述方法包括：4. A preparation method of the pyrazole derivative of the general formula stru-1 shown in claim 1 or the pyrazole derivative shown in claim 3, wherein the method comprises:
Figure FDA0002498284150000032
Figure FDA0002498284150000032
 所述X选自卤素，R11为乙基，M为碱中的金属离子，所述碱选自碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾、氢化钠、醇钠和醇钾中的至少一种。The X is selected from halogen, R 11 is an ethyl group, M is a metal ion in the base, and the base is selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium hydride , at least one of sodium alkoxide and potassium alkoxide. 5.按照权利要求4所述的制备方法，其特征在于：5. according to the described preparation method of claim 4, it is characterized in that: 所述酸选自有机酸和无机酸中的至少一种，所述溶剂独立地选自质子性溶剂和非质子性溶剂中的至少一种，催化剂选自碘化钾、碘化钠和相转移催化剂中的至少一种。The acid is selected from at least one of organic acids and inorganic acids, the solvent is independently selected from at least one of protic solvents and aprotic solvents, and the catalyst is selected from potassium iodide, sodium iodide and phase transfer catalysts at least one of. 6.按照权利要求5所述的制备方法，其特征在于：6. according to the described preparation method of claim 5, it is characterized in that: 所述X选自氯、溴或碘，所述酸选自盐酸、硫酸和乙酸中的至少一种，所述溶剂独立地选自丙酮、甲基乙基酮、四氢呋喃、乙腈、N、N-二甲基甲酰胺、甲苯和氯苯中的至少一种。The X is selected from chlorine, bromine or iodine, the acid is selected from at least one of hydrochloric acid, sulfuric acid and acetic acid, and the solvent is independently selected from acetone, methyl ethyl ketone, tetrahydrofuran, acetonitrile, N, N- At least one of dimethylformamide, toluene and chlorobenzene. 7.一种权利要求1或2所示通式stru-1的吡唑衍生物或权利要求3所示的吡唑衍生物的应用，其特征在于：所述吡唑衍生物用于防治作物上的成螨、若螨或螨卵中的至少一种。7. the application of the pyrazole derivative of the general formula stru-1 shown in claim 1 or 2 or the application of the pyrazole derivative shown in claim 3, it is characterized in that: described pyrazole derivative is used for the control on crops At least one of the adult mites, nymphs or mite eggs. 8.一种农用杀螨剂，其特征在于：所述杀螨剂含有0.1～99％质量百分含量的权利要求1或2所述通式stru-1所示化合物或权利要求3所示的吡唑衍生物。8. An agricultural acaricide, characterized in that: the acaricide contains 0.1 to 99% by mass of the compound represented by the general formula stru-1 of claim 1 or 2 or the compound represented by claim 3. Pyrazole derivatives.
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