WO2022121907A1 - 硅丙烯腈类化合物及其制备方法与应用 - Google Patents

硅丙烯腈类化合物及其制备方法与应用 Download PDF

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WO2022121907A1
WO2022121907A1 PCT/CN2021/136159 CN2021136159W WO2022121907A1 WO 2022121907 A1 WO2022121907 A1 WO 2022121907A1 CN 2021136159 W CN2021136159 W CN 2021136159W WO 2022121907 A1 WO2022121907 A1 WO 2022121907A1
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group
alkyl
compound
formula
cycloalkyl
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PCT/CN2021/136159
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English (en)
French (fr)
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程家高
彼得·麦恩斐希
周聪
李忠
邵旭升
徐晓勇
钱旭红
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华东理工大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P5/00—Nematocides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage

Definitions

  • the invention belongs to the field of pesticides, and in particular relates to a silicon acrylonitrile compound and a preparation method and application thereof.
  • the standard of living is crucial.
  • my country has a huge amount of chemical acaricides, insecticides and fungicides, with broad market prospects and strong demand for new products.
  • harmful mites, insects and pathogenic bacteria have developed serious resistance to the existing agricultural protective chemicals, and the ecological and environmental safety problems of the existing pesticides have become increasingly prominent.
  • the object of the present invention is to provide a silico-acrylonitrile compound with excellent acaricidal, insecticidal and bactericidal activities, which has novel structure and excellent effect, and has less toxic and side effects.
  • the first aspect of the present invention provides a compound of formula I, its geometric isomer, stereoisomer, or a pesticide acceptable salt or prodrug thereof,
  • R 1 is selected from the group consisting of substituted or unsubstituted groups: C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy , C 3-6 cycloalkoxy, C 1-6 alkylthio, C 3-6 cycloalkylthio, C 6 -C 10 aryl, 5-10-membered heteroaryl, 4-10-membered heterocyclyl ; Wherein, described replacement refers to be replaced by one or more Ra ;
  • R 2 , R 3 and R 4 are each independently selected from the group consisting of substituted or unsubstituted groups: hydrogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl; wherein, the Substituted means replaced by one or more Ra ;
  • R2 and R3 , R3 and R4, or R2 and R4 together form a group selected from the group consisting of - ( CH2 ) p- , - ( CH2 ) o - O- ( CH2 ) p -O-( CH2 ) o- ; wherein o is independently 0, 1, 2, 3, or 4, and p is 2, 3, 4, 5, or 6;
  • R 5 is selected from the group consisting of substituted or unsubstituted groups: C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy , C 1-6 alkylthio, C 3-6 cycloalkoxy, C 3-6 cycloalkylthio, R 6 and R 7 ; wherein, the substitution refers to being substituted by one or more Ra ;
  • R 6 is a substituted or unsubstituted C 6-14 aryl group; in R 6 , the substitution means that the hydrogen on the group is replaced by 1-5 groups selected from the following group: halogen, C 1- 6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy, C 1-6 alkylthio, C 3-6 cycloalkoxy , C 3-6 cycloalkylthio, -CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 and -SO 2 NR 8 R 9 ;
  • R 7 is an unsubstituted or substituted 5-14-membered heteroaryl group; in R 7 , the substitution means that the hydrogen on the group is replaced by 1-5 groups selected from the following group: halogen, C 1 -6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy, C 1-6 alkylthio, C 3-6 cycloalkoxy group, C 3-6 cycloalkylthio, -CN, NO 2 , SO 2 R 8 , COR 8 , COOR 8 , CONR 8 R 9 and SO 2 NR 8 R 9 ;
  • R 8 and R 9 are each independently selected from the group consisting of substituted or unsubstituted groups: hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl, C 6-14 aryl , 5-14-membered heteroaryl; or, R 8 and R 9 together with the N atom to which they are attached form a substituted or unsubstituted 3-6-membered heterocyclic group; wherein, the substitution refers to being replaced by one or more R a replace;
  • Each X is independently selected from the group consisting of hydrogen, halogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl, halogenated C 1-6 alkoxy, -CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 and -SO 2 NR 8 R 9 ;
  • Z is selected from: CRbRc , oxygen, sulfur or NRd ;
  • the H in (CH 2 ) n can be replaced by Ra ;
  • Z-(CH 2 ) n -R 1 moiety is selected from the group consisting of substituted or unsubstituted groups: C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl, C 6- 14 -aryl, 5-14-membered heteroaryl; wherein, the substitution refers to being substituted by one or more R a ;
  • R b , R c are each independently selected from the group consisting of hydrogen, halogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl, halogenated C 1-6 alkoxy , -CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 and -SO 2 NR 8 R 9 ;
  • R d is selected from the group consisting of hydrogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl;
  • R a is selected from the group consisting of hydrogen, halogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl, halogenated C 1-6 alkoxy, -CN, -NO 2 , oxo group, C 3-6 cycloalkyl, 3-6 membered heterocyclic group, -SO 2 R 10 , -COR 10 , -COOR 10 , -CONR 10 R 11 and -SO 2 NR 10 R 11 ;
  • R 10 and R 11 are each independently selected from the group consisting of hydrogen, C 1-6 alkyl, halogenated C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl, C 6-14 aryl, 5-14 membered heteroaryl;
  • n 0, 1, 2, 3 or 4.
  • R 1 is selected from the following group: C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy , C 3-6 cycloalkoxy, C 1-6 alkylthio, C 3-6 cycloalkylthio, phenyl, 4-10-membered heterocyclic group.
  • R 5 is selected from the group consisting of substituted or unsubstituted groups: C 6-14 aryl and 5-14-membered heteroaryl, wherein the substitution means that the hydrogen on the group is replaced by Substituted with 1-5 groups selected from the group consisting of halogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkane Oxy group, C 1-6 alkylthio, C 3-6 cycloalkoxy, C 3-6 cycloalkylthio, -CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 and -SO 2 NR 8 R 9 ; wherein, R 8 and R 9 are each independently selected from the group consisting of hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 membered heterocyclic group.
  • R 7 is a group selected from the group consisting of substituted or unsubstituted: thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridyl, thiomorpholine-S-oxide , thiomorpholine-S,S-oxide, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazolyl, furanyl, pyrrolyl , pyrazolyl, imidazolyl, triazolyl; in R 7 , the substitution means that the hydrogen on the group is replaced by 1-4 groups selected from the following group: halogen, C 1-6 alkyl , C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy, C 1-6 alkylthio
  • the compound of formula I its geometric isomers, stereoisomers, or agrochemically acceptable salts or prodrugs thereof have the structure shown in formula II or formula III
  • X, m, R 1 , R 2 , R 3 , R 4 , R 5 , Z and n are as defined above.
  • R 5 is selected from substituted or unsubstituted lower groups Group: phenyl, naphthyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridyl, thiomorpholine-S-oxide, thiomorpholine-S,S-oxide, pyrimidine base, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl; wherein, Said substitution means that the hydrogen on the group is replaced by 1-5 groups selected from the group consisting of halogen, C 1-6 alkyl, C 2-6 alkenyl, C 2
  • R 5 is selected from the following group:
  • g is independently 0, 1, 2, 3, 4, or 5;
  • Each R' is independently selected from the group consisting of halogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy, C 1-6 alkylthio, C 3-6 cycloalkoxy, C 1-6 alkylthio, C 3-6 cycloalkylthio, CN, NO 2 , SO 2 R 8 , COR 8 , COOR 8 , CONR 8 R 9 , and SO 2 NR 8 R 9 ; R 8 and R 9 are each independently selected from the group consisting of hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl.
  • R 5 is selected from the following group:
  • the (CH 2 ) n -R 1 moiety is selected from substituted or unsubstituted following groups: H, C 1-6 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-6 alkylthio, C 1-6 alkoxy, 3- 6-membered cycloalkyl, C 6 -C 10 -membered aryl, 5-10-membered heteroaryl, 4-10-membered heterocyclyl, (CH 2 )R', R' is selected from: 3-6-membered cycloalkyl, C 6 -C 10 aryl, 5-10-membered heteroaryl, 4-10-membered heterocyclic group; wherein, the substitution refers to being substituted by one or more groups selected from the following group: C 1-6 alkane group, C 1-6 alkoxy, C 1-6
  • R 2 , R 3 and R 4 are independently selected from each other. From the group: C1-6 alkyl, C2-4 alkenyl and C2-4 alkynyl.
  • the compound of formula I its geometric isomers, stereoisomers, or agrochemically acceptable salts or prodrugs thereof have the structures shown in formulas i-xvi
  • R 1 , R 2 , R 3 , R 4 , X, m, n, and Z are as described above.
  • R 1 , R 2 , R 3 , R 4 , X, m, n, and Z correspond to the groups corresponding to the specific compounds in the embodiments.
  • the compound of formula i-xvi, its geometric isomer, stereoisomer, or its pesticide acceptable salt or prodrug, R 1 , R 2 , R 3 , R 4 , X, m, n, Z have the definitions as shown in table a
  • the compound is selected from the compounds shown in the Examples.
  • the second aspect of the present invention provides a preparation method of the compound described in the first aspect, its geometric isomer, stereoisomer, or its agrochemically acceptable salt or prodrug, the method comprising the steps:
  • the compound preparation method of formula I also comprises the steps:
  • step (s1) is: in a solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl alcohol base tert-butyl ether, 1,4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), in a base (Preferably, the base is selected from: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, tert-butanol
  • a solvent preferably, the solvent is selected from: benzene, toluene,
  • step (ii) is: in a solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, ethylene glycol monomethyl) ether, dichloromethane, dichloroethane, tert-butanol, 1,4-dioxane, n-butanol, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, n-heptane, n-hexane, cyclohexane, Petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), in a base (preferably, the base is selected from: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, In the presence of sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine
  • a third aspect of the present invention there is provided a use of the compound described in the first aspect, its geometric isomer, stereoisomer, or a pesticide acceptable salt or prodrug thereof,
  • (i) Can be used to kill and/or control Acarina, Synoptera, Orthoptera, Fusarium, Isoptera, Panicea, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera at least one pest and/or its nymphs and/or its eggs from the Order, Hymenoptera, Diptera, Pleas and plant-parasitic nematodes;
  • compositions or formulations for acaricidal and/or insecticidal and/or bactericidal use For the preparation of compositions or formulations for acaricidal and/or insecticidal and/or bactericidal use.
  • the compound of formula I is used for killing and/or controlling mites and/or for preparing compositions or formulations for insecticidal and/or sterilization.
  • the compound of formula I is used to kill and/or control harmful mites and/or their eggs in agriculture, pastures, lawns and/or indoors.
  • the compound of formula I is used for killing and/or controlling pests and/or fungi in agriculture, pastures, lawns and/or indoors.
  • the mites are harmful mites.
  • the mites are selected from: Tetranychus urticae Koch, Tetranychus viennensis Zacher, Tetranychus truncatus Ehara, Tetranychus cinnabarinus Boisduval), Panonychus ulmi Koch, Panonychus citri McGregor, Bryobia rubrioculus Scheuten, Petrobia latens Muller, Oligonychus ununguis Jacobi ), Brevipalpus obovatus Donnadieu, B.
  • the pests are selected from the group consisting of: Scutigerella immaculat, Acheta domesticus, Gryllotalpa spp., Locusta inigratoria, Melanoplus spp. , Desert Locust (Schistocer cagregaria), Oriental Cockroach (Blatta orientalis), American Cockroach (Periplanet aainericana), Florida Cockroach (Leucophae amaderae), German Cockroach (Blattella gerrnanica), Reticuliterines spp., Pediculus humanuscorporis ), Haematopinus spp., Linognathus spp., Trichodectes spp., Dainalinia spp., Hercinothrips fernoralis, Thrips tabaci (Thrips tabaci), Thrips palmi, Frankliniella occidentalis, Eurygaster spp., Dysdercus interrnedius, Pies
  • Otiorrhynchus sulcatus Banana bulb weevil (Cosinopolites sordidus), Cabbage turtle weevil (Ceuthorrhynchus assimilis), Alfalfa leaf weevil (Hypera postica), Dermestes spp., Trogoderrna spp.), Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp. ), Niptus bololeucus, Gibbium psylloides, Triboliurn spp., Tenebnio rnolitor, Agriotes spp.
  • the examples of the plant diseases include soybean, corn, wheat, melons, rice, strawberries, peanuts, cotton; the examples of the plant diseases include soybean rust, corn rust, wheat powdery mildew , melon powdery mildew, rice sheath blight, wheat sheath blight, strawberry gray mold, peanut white silk, cotton blight, wheat scab, wheat take-all and cucumber target spot, wherein the Cucurbit powdery mildew includes cucumber powdery mildew, etc.; the pathogenic bacteria include Phakopsora pachyrhizi syd., Puccinia sorghi Schw, Blumeria graminis, melon powdery mildew ( Erysiphe cucurbitacearum, Sphaerotheca cucurbitae, Thanatephorus cucumeris, Rhizoctonia cerealis, and Rhizoctonia solani, Botrytis cinerea Pers .), Fusarium graminearum schw., Fusarium
  • a fourth aspect of the present invention provides a composition
  • a composition comprising (i) as an active ingredient the compound of the first aspect, its geometric isomer, stereoisomer, or a pesticide acceptable salt or prodrug thereof ; and (ii) a carrier and/or surfactant.
  • the content of the compound is 0.001-99.999 wt %.
  • the composition is a pesticide composition; preferably, it is an acaricidal composition, an insecticidal composition and a bactericidal composition.
  • a fifth aspect of the present invention provides a method for killing mites, insects and/or bacteria, comprising the steps of: contacting the mites, insects and/or bacteria with an effective amount of the compound described in the first aspect, or its geometric isomers , a stereoisomer, or a pesticidally acceptable salt or prodrug thereof or a composition as described in the fourth aspect.
  • halogen refers to fluorine, chlorine, bromine or iodine.
  • alkyl by itself or as part of another substituent refers to a straight or branched chain hydrocarbon group having the indicated number of carbon atoms (ie, C1-6 represents 1-6 carbons).
  • alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, and the like.
  • alkenyl refers to an unsaturated alkyl group having one or more double bonds.
  • alkynyl refers to an unsaturated alkyl group having one or more triple bonds. Examples of such unsaturated alkyl groups include vinyl, 2-propenyl, crotyl, 2-prenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1, 4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl and higher homologs and isomers.
  • cycloalkyl refers to a saturated or unsaturated cyclic hydrocarbon group having the specified number of ring atoms (eg, C 3-6 cycloalkyl). Examples of such cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, and the like.
  • aryl refers to a polyunsaturated (usually aromatic) hydrocarbon group, which may be monocyclic or polycyclic (up to three rings) fused together or covalently linked.
  • aryl groups include: phenyl.
  • heterocycloalkyl refers to a cycloalkyl group containing one to five heteroatoms selected from N, O and S, wherein the nitrogen and sulfur atoms are optionally oxidized, And the nitrogen atom is optionally quaternized.
  • Heterocycloalkyl can be a monocyclic, bicyclic or polycyclic ring system.
  • heterocycloalkyl examples include pyrrolidine, imidazolidine, pyrazolidine, butyrolactam, valerolactam, imidazolidinone, hydantoin, dioxolane, phthalimide, piperidine, 1,4-dioxane, morpholine, thiomorpholine, thiomorpholine-S-oxide, thiomorpholine-S,S-oxide, piperazine, pyran, pyridone, 3-pyrroline, thiopyran, pyranone, tetrahydrofuran, tetrahydrothiophene, quinuclidine, etc.
  • a heterocycloalkyl group can be attached to the remainder of the molecule through a ring carbon or a heteroatom.
  • cycloalkylalkyl and heterocycloalkylalkyl it is meant that the cycloalkyl or heterocyclyl group is attached to the remainder of the molecule through an alkyl or alkylene linker.
  • heteroaryl refers to an aryl group (or ring) containing 1 to 5 heteroatoms selected from N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atom is either Select to be quaternized.
  • a heteroaryl group can be attached to the remainder of the molecule through a heteroatom.
  • heteroaryl groups include pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, benzene benzotriazinyl, purinyl, benzimidazolyl, benzopyrazolyl, benzotriazolyl, benzisoxazolyl, isobenzofuryl, isoindolyl, Indolizine, benzotriazinyl, thienopyridyl, thienopyrimidinyl, pyrazolopyrimidinyl, imidazopyridine, benzothiazolyl, benzofuranyl, benzothienyl, indolyl, quinoline olinyl, isoquinolinyl, isothiazolyl, pyrazolyl, indazolyl,
  • heteroatom is intended to include oxygen (O), nitrogen (N), sulfur (S), and silicon (Si).
  • a bond from a substituent (usually an R group) to the center of an aromatic ring will be understood to mean a bond that provides a link at any available vertex of the aromatic ring.
  • the description also includes linkages on rings fused to aromatic rings.
  • a bond drawn to the center of the indole benzene moiety would represent a bond to any available vertex of the six- or five-membered ring moiety of the indole.
  • the terms "containing”, “comprising” or “including” mean that the various ingredients can be used together in the mixture or composition of the present invention.
  • the terms “consisting essentially of” and “consisting of” are encompassed by the term “comprising”.
  • the compounds represented by formula I of the present invention include geometric isomers (different configurations represented by Z and E respectively) that can be formed due to carbon-carbon double bonds or carbon-nitrogen double bonds connecting different substituents.
  • the invention includes the Z isomer and the E isomer and mixtures thereof in any ratio.
  • the compounds represented by formula I of the present invention include stereoisomers (different configurations are represented by R and S respectively) due to the connection of different substituents on carbon and nitrogen atoms, and the present invention includes R-type isomers and S-type isomers Isomers and mixtures thereof in any ratio.
  • the compounds represented by formula I of the present invention not only include geometric isomers (Z/E formula) and stereoisomers (R/S formula), but also include mixtures of geometric isomers and stereoisomers in any ratio.
  • an "effective amount” refers to an amount of the compound sufficient to produce acaricidal, insecticidal and fungicidal effects without causing serious adverse effects.
  • the term compound of the present invention refers to a class of silico-acrylonitrile compounds shown in formula I, and the term also includes geometric isomers, or stereoisomers thereof, or salts thereof, and mixtures of various isomers .
  • the present invention provides the silico-acrylonitrile compound shown in formula I,
  • R 1 , R 2 , R 3 , R 4 , R 5 , Z, n, X, and m are defined as described above.
  • the compound has the structure shown in formula II or formula III
  • X, m, R 1 , R 2 , R 3 , R 4 , R 5 , Z and n are as defined above.
  • R 5 is selected from the group consisting of substituted or unsubstituted groups: phenyl, naphthyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridyl, thio Morpholine-S-oxide, thiomorpholine-S,S-oxide, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, oxazolyl, oxadiazolyl, isoxazole base, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl; wherein, the substitution means that the hydrogen on the group is replaced by 1-5 groups selected from the following group: halogen, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alk
  • the Z-(CH 2 ) n -R 1 moiety is selected from the group consisting of substituted or unsubstituted groups: C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 Member Heterocyclic, C 6-14 Aryl, 5-14 Member Heteroaryl, C 1-6 Alkyl O-, C 3-6 Cycloalkyl O-, 3-6 Member Heterocyclic O-, C 6-14 Aryl O-, 5-14 Member Heteroaryl O-, C 1-6 Alkyl S-, C 3-6 Cycloalkyl S-, 3-6 Member Heterocyclyl S-, C 6- 14 -aryl S-, 5-14-membered heteroaryl S-, NR 8 R 9 ;
  • R 8 and R 9 are as defined above.
  • R 2 , R 3 and R 4 are each independently selected from the group consisting of C 1-6 alkyl, C 2-4 alkenyl and C 2-4 alkynyl.
  • R 1 is selected from the group consisting of C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkane Oxy group, C 3-6 cycloalkoxy group, C 1-6 alkylthio group, C 3-6 cycloalkylthio group, phenyl group, 4- to 10-membered heterocyclic group.
  • R 1 is selected from the group consisting of C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 1-6 alkoxy , C 3-6 cycloalkoxy, C 1-6 alkylthio, C 3-6 cycloalkylthio, phenyl;
  • n 0, 1, 2 or 3;
  • R 2 , R 3 and R 4 are each independently selected from the group consisting of C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl;
  • R 2 and R 3 , R 3 and R 4 , or R 2 and R 4 together form a -(CH 2 ) p - group; wherein p is 2, 3, 4, 5, or 6;
  • R 5 is selected from the group consisting of R 6 and R 7 ;
  • R 6 is a substituted or unsubstituted phenyl group; in R 6 , the substitution refers to that the hydrogen on the group is replaced by 1, 2 or 3 groups selected from the following group: halogen, C 1-6 alkane group, C 1-6 alkoxy, CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 , and -SO 2 NR 8 R 9 ;
  • R 7 is an unsubstituted or substituted group selected from the group consisting of thiazolyl, pyridyl, thiomorpholine-S-oxide, thiomorpholine-S,S-oxide, pyridazinyl, pyrazine base, thienyl, furanyl, pyrrolyl, pyrazolyl; in R 7 , the substitution means that the hydrogen on the group is replaced by 1, 2, 3 or 4 groups selected from the following group: halogen , C 1-6 alkyl, C 1-6 alkoxy, CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 , and -SO 2 NR 8 R 9 ;
  • R 8 and R 9 are each independently selected from: hydrogen, C 1-6 alkyl
  • Each X is independently selected from the group consisting of hydrogen, halogen, C 1-6 alkyl;
  • n 1 or 2;
  • Z is selected from: CRbRc , oxygen, sulfur or NRd ;
  • Z-(CH 2 ) n -R 1 moiety is selected from the group consisting of substituted or unsubstituted groups: C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl, C 6- 14 -aryl, 5-14-membered heteroaryl, C 1-6 alkyl O-, C 3-6 cycloalkyl O-, 3-6-membered heterocyclyl O-, C 6-14 aryl O-, 5-14-membered heteroaryl O-, C 1-6 alkyl S-, C 3-6 cycloalkyl S-, 3-6 membered heterocyclyl S-, C 6-14 aryl S-, 5- 14-membered heteroaryl S-, NR 8 R 9 ;
  • R b , R c are each independently selected from the group consisting of hydrogen, halogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl, halogenated C 1-6 alkoxy , -CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 and -SO 2 NR 8 R 9 ;
  • R d is selected from the group consisting of hydrogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl;
  • one or more hydrogen atoms in the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and X groups may also each independently be selected from the group of Substituents substituted: halogen, C 1-3 alkyl.
  • R 1 is selected from the group consisting of C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 3-6 alkoxy base, C 3-6 cycloalkoxy, C 1-6 alkylthio, C 3-6 cycloalkylthio, phenyl;
  • n 0, 1 or 2;
  • R 2 , R 3 and R 4 are each independently selected from the group consisting of C 1-6 alkyl, C 2-4 alkenyl and C 2-4 alkynyl;
  • R 5 is 1,3,4-trimethylpyrazol-5-yl, 2-trifluoromethyl-phenyl, 2-iodo-phenyl, 2-bromo-phenyl, 5-chloro-1,3 -Dimethyl-4-pyrazolyl, 5-fluoro-1,3-dimethyl-4-pyrazolyl, 1-methyl-3-trifluoromethyl-4-pyrazolyl, 1-ethyl yl-3-methyl-5-pyrazolyl, 2-methyl-4-trifluoromethyl-5-thiazolyl, 2-chloro-3-pyridyl, 1,3,5-trimethylpyrazole -4-yl, 2-trifluoromethyl-3-pyridyl, 2-trifluoromethyl-3-pyrazinyl, 2-methyl-3-furyl, 3-methyl-2-thienyl and 1-Methyl-3-difluoromethyl-4-pyrazolyl;
  • Each X is independently selected from the group consisting of hydrogen, halogen and C 1-6 alkyl;
  • n 1 or 2;
  • Z is selected from: CRbRc , oxygen, sulfur or NRd ;
  • Z-(CH 2 ) n -R 1 moiety is selected from the group consisting of substituted or unsubstituted groups: C 1-6 alkyl, C 3-6 cycloalkyl, 3-6 membered heterocyclyl, C 6- 14 -aryl, 5-14-membered heteroaryl, C 1-6 alkyl O-, C 3-6 cycloalkyl O-, 3-6-membered heterocyclyl O-, C 6-14 aryl O-, 5-14-membered heteroaryl O-, C 1-6 alkyl S-, C 3-6 cycloalkyl S-, 3-6 membered heterocyclyl S-, C 6-14 aryl S-, 5- 14-membered heteroaryl S-, NR 8 R 9 ;
  • R b , R c are each independently selected from the group consisting of hydrogen, halogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl, halogenated C 1-6 alkoxy , -CN, -NO 2 , -SO 2 R 8 , -COR 8 , -COOR 8 , -CONR 8 R 9 and -SO 2 NR 8 R 9 ;
  • R d is selected from the group consisting of hydrogen, C 1-6 alkyl, C 1-6 alkoxy, halogenated C 1-6 alkyl;
  • R 8 and R 9 are each independently selected from: hydrogen, C 1-6 alkyl
  • one or more hydrogen atoms in the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and X groups may also each independently be selected from the group of Substituents substituted: halogen, C 1-3 alkyl.
  • the compound of formula I has the structure shown in formula i-xvi
  • R 1 , R 2 , R 3 , R 4 , X, m, n, and Z are as described above.
  • the preparation method of the compound of formula I of the present invention is described in more detail below, but these specific methods do not constitute any limitation of the present invention.
  • the compounds of the present invention can also be conveniently prepared by optionally combining various synthetic methods described in this specification or known in the art, and such combinations can be easily performed by those skilled in the art to which the present invention pertains.
  • the present invention also provides a general method for preparing the compounds of the first aspect, ie compounds of formula I.
  • the method comprises the steps of:
  • the compound preparation method of formula I also comprises the steps:
  • step (s1) is: in a solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl alcohol base tert-butyl ether, 1,4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), in a base (Preferably, the base is selected from: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, tert-butanol
  • a solvent preferably, the solvent is selected from: benzene, toluene,
  • step (ii) is: in a solvent (preferably, the solvent is selected from: benzene, toluene, ethyl acetate, acetonitrile, ethylene glycol monomethyl) ether, dichloromethane, dichloroethane, tert-butanol, 1,4-dioxane, n-butanol, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, n-heptane, n-hexane, cyclohexane, Petroleum ether, dimethylformamide, dimethyl sulfoxide, or a combination thereof), in a base (preferably, the base is selected from: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, In the presence of sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine
  • the present invention also provides the compound represented by formula I or the agricultural composition comprising the silicoacrylonitrile compound represented by formula I and uses thereof.
  • the silicoacrylonitrile compound represented by formula I of the present invention has excellent acarid control activity against various pests in agriculture or other fields, especially against arachnida (Arachnida) acarina (Acarina), such as two-spotted leaves Mites (Tetranychus urticae Koch), Tetranychus viennensis Zacher, Tetranychus truncatus Ehara, Tetranychus cinnabarinus Boisduval, Panonychus ulmi Koch, Panonychus citrus ( Panonychus citri McGregor), Bryobia rubrioculus Scheuten, Petrobia latens Muller, Oligonychus ununguis Jacobi, Brevipalpus obovatus Donnadieu, Shorthair mite Liu's (B.lewisi McGregor), Tenuipalpus taonicas Ma et Yuan, Tenuipalpus zhizhilashviliae Reck, C.vitis
  • Mite control means acaricidal activity at each stage of the mite life cycle (egg, larvae, adult). Therefore, the technical solution of the present invention also includes the use of the silico-acrylonitrile compound represented by formula I as an acaricide in agriculture or other fields.
  • the silico-acrylonitrile compound shown in the formula I of the present invention is also suitable for preventing and treating Synthetia, Orthoptera, Fusarium, Isoptera, Pancreata, Thysanoptera, Heteroptera, Homoptera, Lepidoptera in agriculture or other fields. At least one pest of the order Ptera, Coleoptera, Hymenoptera, Diptera, Flea and plant parasitic nematodes.
  • Syrnphyla for example, Scutigerella immaculat and the like.
  • Orthoptera for example, house cricket (Acheta domesticus), mole cricket (Gryllotalpa spp.), African locust (Locusta inigratoria), black locust (Melanoplus spp.), desert locust (Schistocer cagregaria) etc.;
  • the Blattaria for example, Blatta orientalis, Periplanet aainericana, Leucophae amaderae, Blattella gerrnanica and the like.
  • the Isoptera for example, Reticuliterines spp. and the like.
  • Phthiraptera From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Dainalinia spp. )Wait.
  • Thysanoptera for example, Hercinothrips fernoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis and the like.
  • Said Heteroptera for example, Eurygaster spp., Dysdercus interrnedius, Piesrna quadrata, Cimxiectularius, Tria bug (Cimxiectularius) Rhodnius prolixus), Triatoma spp., etc.
  • Said Hoinoptera for example, whitefly (Aleurodes brassicae), tobacco powder (Beinisia tabaci), greenhouse whitefly (Trialeurodes vaporariorum), cotton aphid (Aphis gossypii), cabbage aphid (Brevicoryne brassicae), Cryptomyzus ribis, Aphis fabae, Aphis poini, Eriosoma lanigerum, Hyalopterus aruninis, Phylloxera vastatrix, Slime Aphid (Pernphigus spp.), Macrosiphurn avenae, Myzus spp., Phorodon humuli, Rhopalos iphuin padi, Green leafhopper (Einpoasca spp.), Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lug
  • Attagenus spp. Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus bololeucus, Gibbium psylloides, Triboliurn spp., Tenebnio rnolitor, Agriotes spp., Conoderus spp., Melololontha inelolontha, Potato gills Horned beetles (Ainphimallon solstitialis), brown New Zealand rib-winged beetles (Costelytra zealandica), rice root elephants (Li s sorhoptrus oryzophilus), etc.
  • Hymenoptera for example, Dipnion spp., Hoplocampa spp., Lasius spp., Monornonium pharaonis, Vespa spp., etc.;
  • 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., Stornoxy (spp.), Oestrus spp., Hypoderrna spp., Horseflies ( Tabanus spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyarni, Ceratitis capitata, Olive Dacus oleae, Tipula paludosa, Hylemyia spp., Liriotnyza spp., etc.
  • Siphonaptera for example, Xenopsylla cheopis, Ceratophyllus spp. and the like.
  • the plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus sernipenetrans, Heterodera ( Heterodera spp.), Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Sword nematodes ( Xiphinerna spp.), Trichodorus spp., Bursaphelenchus (Bursaphelenchus spp.), etc. Therefore, the technical solution of the present invention also includes the silicic acrylonitrile compound shown in formula I in agriculture or other field use as a pesticide.
  • the silico-acrylonitrile compound shown in the formula I of the present invention is also suitable for preventing and treating anthrax caused by the infection of Rhizoctonia, Sporobacterium, Pseudomonas, Pseudomonas, Laminaria, Pythium, etc. Disease, leaf spot, rust, powdery mildew, sheath blight, leaf blight, botrytis cinerea, white smut, blight, scab, total rot and target spot disease at least one plant disease.
  • Examples of the plant fungal diseases include soybean, corn, wheat, melon, rice, strawberry, peanut, cotton; examples of the plant fungal disease include soybean rust, corn rust, wheat powdery mildew, and melon powdery mildew , rice sheath blight, wheat sheath blight, strawberry gray mold, peanut white silk, cotton blight, wheat scab, wheat take-all and cucumber target spot, wherein the melon powdery mildew includes Cucumber powdery mildew, etc.; the pathogenic bacteria include Phakopsora pachyrhizi syd., Puccinia sorghi Schw, Blumeria graminis, Erysiphe cucurbitacearum, melon Sphaerotheca cucurbitae, Thanatephorus cucumeris, Rhizoctonia cerealis, and Rhizoctonia solani, Botrytis cinerea Pers., Cereal Fusarium graminearum schw., Fusarium avenace
  • the technical solution of the present invention also includes the use of the silico-acrylonitrile compound represented by formula I as a fungicide in agriculture or other fields.
  • the silicic acrylonitrile compound represented by formula I of the present invention can be prepared into acaricide and/or insecticide and/or fungicide composition by conventional methods.
  • the active compounds can be formulated into customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substances, in polymeric Microcapsules in cigarettes, coating formulations for seeds, and formulations for use with combustion devices such as smoking cartridges, smoking pots, and smoking trays, as well as ULV Cold mist and Warm mist mist) preparations.
  • formulations can be produced by known methods, for example, by mixing the active compounds with extenders, which are liquid or liquefied gas or solid diluents or carriers, optionally with surfactants, ie emulsifiers and/or Dispersants and/or foam formers.
  • extenders which are liquid or liquefied gas or solid diluents or carriers, optionally with surfactants, ie emulsifiers and/or Dispersants and/or foam formers.
  • surfactants ie emulsifiers and/or Dispersants and/or foam formers.
  • organic solvents can also be used as auxiliaries.
  • liquid solvents When using liquid solvents as diluents or carriers, it is basically suitable, such as: aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons such as cyclohexane or paraffins such as mineral oil fractions; alcohols such as ethanol or ethylene glycol and their ethers and lipids; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or unusual polar solvents such as dimethylformamide and dimethylsulfoxide, and water.
  • aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or dichlor
  • a diluent or carrier for a liquefied gas refers to a liquid that will become a gas at normal temperature and pressure, such as aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
  • the solid carrier may be ground natural minerals, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth; and ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicates.
  • Solid supports for granules are ground and graded natural zircon such as calcite, marble, pumice, sepiolite and dolomite, as well as granules synthesized from inorganic and organic coarse powders, and organic materials such as sawdust, coconut shells, Particles of corn cobs and tobacco stems, etc.
  • Nonionic and anionic emulsifiers can be used as emulsifiers and/or foam formers.
  • polyoxyethylene-fatty acid esters polyoxyethylene-fatty alcohol ethers, such as alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and white protein hydrolysate.
  • Dispersants include lignin sulfite waste liquor and methyl cellulose.
  • Binders such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or emulsions such as acacia, polyvinyl alcohol and polyvinyl acetate can be used in the formulation.
  • Colorants such as inorganic dyes such as iron oxide, cobalt oxide and Prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes; and trace nutrients such as iron, manganese, boron, copper, cobalt, aluminum can be used and zinc salts, etc.
  • the silico-acrylonitrile compounds represented by formula I of the present invention can be made into a mixture with other active compounds and exist in their commercial preparations or in the dosage forms prepared from these preparations.
  • These other active compounds are insecticides, bactericidal pesticides, fungicides, herbicides, growth control agents, etc.
  • Insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons and substances produced by microorganisms, such as abamectin, etc.
  • Fungicides include methoxyacrylates, amides, triazoles Wait.
  • the silico-acrylonitrile compounds represented by the formula I of the present invention can also be made into a mixture with synergists to be present in their commercial preparations or in the dosage forms prepared from these preparations, and these synergists are to increase the active compound The acting compound, since the active compound itself is active, also does not need to add synergist.
  • formulations generally contain from 0.001 to 99.99% by weight, preferably from 0.01 to 99.9% by weight, more preferably from 0.05 to 90% by weight of the active compound of the invention, based on the total weight of the pesticidal composition.
  • concentration of active compound in the commercial formulation or in the dosage form for use can vary within wide limits.
  • concentration of active compound in the dosage form used may be from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1% (g/v) It should be clear that, within the scope defined by the claims of the present invention, Various changes and modifications can be made.
  • the compound of the present invention also has excellent insecticidal and bactericidal activity
  • the compounds of the present invention have excellent acaricidal, insecticidal and bactericidal activities, and have little impact on the environment.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid with a yield of 84.2%. Subsequently, the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise to react at room temperature.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid with a yield of 84.2%. Subsequently, the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and isobutyryl chloride (1.25 g, 12.5 mmol) was added dropwise to react at room temperature.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid with a yield of 84.2%. Subsequently, the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and benzoyl chloride (1.75 g, 12.5 mmol) was added dropwise to react at room temperature.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid with a yield of 84.2%. Then the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and 2-methoxy chloroformate (1.73 g, 12.5 mmol) was added dropwise to react at room temperature.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid with a yield of 84.2%. Subsequently, the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and dimethylcarbamoyl chloride (1.34 g, 12.5 mmol) was added dropwise to react at room temperature.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure and column chromatography gave a brown oil in 71.8% yield. Subsequently, the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise to react at room temperature.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid with a yield of 82.8%. Subsequently, the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise to react at room temperature.
  • Extract with ethyl acetate (20 mL ⁇ 3) combine the organic phases, wash with saturated sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was removed under reduced pressure, and n-heptane was added to the residue to precipitate a white solid with a yield of 87.9%. Subsequently, the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise to react at room temperature.
  • reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. . The solvent was removed under reduced pressure to give a white solid in 74.8% yield.
  • the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and isobutyryl chloride (1.25 g, 12.5 mmol) was added dropwise to react at room temperature. After the reaction, the solvent was removed under reduced pressure, washed with ethyl acetate and filtered, and the filtrate was concentrated and purified by column chromatography to obtain the target compound with a yield of 84.2%.
  • reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. . The solvent was removed under reduced pressure to give a white solid in 84.2% yield.
  • the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise to react at room temperature. After the reaction, the solvent was removed under reduced pressure, washed with ethyl acetate and filtered, and the filtrate was concentrated and purified by column chromatography to obtain the target compound in a yield of 74.8%.
  • reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. . The solvent was removed under reduced pressure to give a white solid in 84.2% yield.
  • reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. . The solvent was removed under reduced pressure to give a white solid in 84.2% yield.
  • the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and benzoyl chloride (1.75 g, 12.5 mmol) was added dropwise to react at room temperature. After the reaction, the solvent was removed under reduced pressure, washed with ethyl acetate and filtered, and the filtrate was concentrated and purified by column chromatography to obtain the target compound in a yield of 64.6%.
  • the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. .
  • the solvent was removed under reduced pressure to give the crude product.
  • the crude product was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, stirred at room temperature for 10 min, pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise, and the reaction was carried out at room temperature.
  • the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. .
  • the solvent was removed under reduced pressure to give the crude product.
  • the crude product was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, stirred at room temperature for 10 min, pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise, and the reaction was carried out at room temperature.
  • the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. .
  • the solvent was removed under reduced pressure to give the crude product.
  • the crude product was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, stirred at room temperature for 10 min, pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise, and the reaction was carried out at room temperature.
  • the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. .
  • the solvent was removed under reduced pressure to give the crude product.
  • the crude product was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, stirred at room temperature for 10 min, pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise, and the reaction was carried out at room temperature.
  • reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. . The solvent was removed under reduced pressure to give a white solid in 75.8% yield.
  • the white solid was dissolved in 20 ml of dichloromethane, triethylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise to react at room temperature. After the reaction, the solvent was removed under reduced pressure, washed with ethyl acetate and filtered, and the filtrate was concentrated and purified by column chromatography to obtain the target compound in a yield of 79.5%.
  • the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was added with dilute hydrochloric acid to adjust to acidity, extracted with ethyl acetate (20 mL ⁇ 3), the organic phases were combined, washed with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. .
  • the solvent was removed under reduced pressure to give the crude product.
  • the crude product was dissolved in 20 ml of dichloromethane, diisopropylamine (1.01 g, 10 mmol) was added, and the mixture was stirred at room temperature for 10 min, and pivaloyl chloride (1.50 g, 12.5 mmol) was added dropwise to react at room temperature.
  • test compound was dissolved in dimethyl sulfoxide, it was diluted with triton aqueous solution to different test concentrations, and the liquid was sprayed evenly on the front and back of the bean leaf cuttings. After the liquid was dried, the mixed individuals of Tetranychus two-spotted mites were connected to the cuttings of bean leaves, and the base number was recorded. Observe in a standard observation room (23-25°C, RH40-60%), conduct investigation after 192 hours, and record the number of live insects on bean leaves. The commercial pesticide Cyenopyrafen was used as the control, and the aqueous solution of triton was used as the blank control. Table 2 shows the results of the determination of the activity of some compounds against Tetranychus 2-spotted mites.
  • the compounds of the present invention have basically equivalent acaricidal activity to the reference substance, and even at lower concentrations (such as 50 ppm), most compounds still have 100% acaricidal activity, such as compound i-4 , i-5, i-6, i-7, i-19, i-24, i-27, i-36, i-37, i-39, i-43, i-55, i-58, i -67, i-70, i-88, i-91, etc.
  • the compound of the present invention has excellent insecticidal activity.
  • the compounds to be tested were prepared into a 100 ppm concentration test liquid with N,N-dimethylformamide (DMF) containing 0.1% Tween 80.
  • the greenhouse live pot method was used to measure, the test crops were placed on a sprayer for foliar spray treatment, the crops after the chemical treatment were placed in a cool place, and the spores of pathogenic bacteria were inoculated after 24 hours, and 3 repetitions were set. ) is the control, and another blank control is set.
  • the inoculated crops were cultured in an artificial climate chamber, and the control effects were investigated after culturing the above diseases for 7 days and 10 days respectively.
  • the compounds to be tested were prepared into a 100 ppm concentration test liquid with N,N-dimethylformamide (DMF) containing 0.1% Tween 80.
  • the greenhouse live potted method was used to measure, the test crops were placed on a sprayer for foliar spray treatment, the crops after the chemical treatment were placed in a cool place, and the spores of pathogenic bacteria were inoculated after 24 hours, and 3 repetitions were set. Cyenopyrafen) was used as a control, and a blank control was also set up.
  • the inoculated crops were cultured in an artificial climate chamber, and the control effects were investigated after culturing the above diseases for 7 days and 10 days respectively.
  • the compounds to be tested were prepared into a 100 ppm concentration test liquid with N,N-dimethylformamide (DMF) containing 0.1% Tween 80.
  • the greenhouse live pot method was used to measure, the test crops were placed on a sprayer for foliar spray treatment, the crops after the chemical treatment were placed in a cool place, and the spores of pathogenic bacteria were inoculated after 24 hours, and 3 repetitions were set. ) is the control, and another blank control is set.
  • the inoculated crops were cultivated in an artificial climate chamber, and the control effects were investigated after culturing the above diseases for 7 days and 10 days respectively.
  • the compounds of the present invention have excellent bactericidal activity compared with the reference compounds.
  • compounds i-4, i-5, i-6, i-7, i-19, i-24, i-27, i-36, i-37, i-39, i-43, i-51 The performance of i-55, i-58, i-67, i-70, i-71, i-83, i-88, i-91, i-102, etc. on Faba bean rust, Phytophthora capsici, and Pythium A good control effect was obtained, and the overall control effect was better than that of the control fenpyroxifen.

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Abstract

本发明公开了一种硅丙烯腈类化合物及其制备方法与应用。具体地，本发明涉及一种如式I所示的化合物、含式I化合物的组合物、及它们的用途。本发明的化合物具有优异的杀螨、杀虫和杀菌活性。

Description

硅丙烯腈类化合物及其制备方法与应用 技术领域
本发明属于农药学领域，具体涉及一种硅丙烯腈类化合物及其制备方法与应用。
背景技术
害螨、昆虫以及作物病原菌常对粮食、蔬菜、水果、棉花和观赏植物等经济作物造成重大损失，利用化学杀螨剂、杀虫剂以及杀菌剂对其进行防治对保证经济作物安全，提高人们生活水平至关重要。我国作为农药大国，化学杀螨剂、杀虫剂以及杀菌剂用量巨大，市场前景广阔，对新产品需求旺盛。但随着长期大量使用，害螨、昆虫以及病原菌已经对现有农用防护药剂产生严重的抗性，并且现有农药的生态环境安全问题也日益凸显。
现有技术中虽公开了一些具有杀螨、杀虫和/或杀菌活性的丙烯腈类化合物，但这些化合物存在结构同质化严重，害虫抗性突出等问题，并且新型杀螨剂研究进程缓慢。因此，
综上所述，本领域迫切需要开发一类新的具有优异杀虫杀螨活性的化合物。
发明内容
本发明目的是提供一种具有极佳地，兼具杀螨、杀虫、杀菌活性的硅丙烯腈类化合物，其结构新颖效果优异，且毒副作用较小。
本发明的第一方面，提供一种式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，
Figure PCTCN2021136159-appb-000001
式中，
R 1选自取代或未取代的下组基团：C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 3-6环烷氧基、C 1-6烷硫基、C 3-6环烷硫基、C 6-C 10芳基、5-10元杂芳基、4-10元杂环基；其中，所述取代是指被一个或多个R a取代；
R 2、R 3和R 4各自独立地选自取代或未取代的下组基团：氢、C 1-6烷基、C 2-6烯基、C 2-6炔基；其中，所述取代是指被一个或多个R a取代；
或者，R 2和R 3、R 3和R 4、或R 2和R 4共同形成选自下组的基团：-(CH 2) p-、-(CH 2) o-O-(CH 2) p-O-(CH 2) o-；其中，o独立地为0、1、2、3、或4，p为2、3、4、5、或6；
R 5选自取代或未取代的下组基团：C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 3-6环烷硫基、R 6和R 7；其中，所述取代是指被一个或多个R a取代；
R 6为取代或未取代的C 6-14芳基；R 6中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 3-6环烷硫基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
R 7为未取代或取代的5-14元杂芳基；R 7中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 3-6环烷硫基、-CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9和SO 2NR 8R 9；
R 8和R 9各自独立选自取代或未取代的下组基团：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基；或者，R 8和R 9与其连接的N原子共同形成取代或未取代的3-6元杂环基；其中，所述取代是指被一个或多个R a取代；
X各自独立地选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
Z选自：CR bR c、氧、硫或NR d；
(CH 2) n中的H可以被R a取代；
或者Z-(CH 2) n-R 1部分选自取代或未取代的下组基团：C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基；其中，所述取代是指被一个或多个R a取代；
R b、R c各自独立地选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
R d选自下组：氢、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基；
R a选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、氧代基、C 3-6环烷基、3-6元杂环基、-SO 2R 10、-COR 10、-COOR 10、-CONR 10R 11和-SO 2NR 10R 11；其中，R 10、R 11各自独立地选自下组：氢、C 1-6烷基、卤代C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基；
m为0、1、2、3或4；n为0、1、2、3或4。
在另一优选例中，R 1选自下组：C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 3-6环烷氧基、C 1-6烷硫基、C 3-6环烷硫基、苯基、4-10元杂环基。
在另一优选例中，R 5选自取代或未取代的下组基团：C 6-14芳基和5-14元杂芳基，其中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 3-6环烷硫基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；其中，R 8和R 9各自独立选自下组基团：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
在另一优选例中，R 7为选自取代或未取代的下组基团：噻唑基、噻二唑基、异噻唑基、 四唑基、吡啶基、硫代吗啉-S-氧化物、硫代吗啉-S,S-氧化物、嘧啶基、哒嗪基、吡嗪基、三嗪基、噻吩基、噁唑基、噁二唑基、异噁唑基、呋喃基、吡咯基、吡唑基、咪唑基、三唑基；R 7中，所述的取代是指基团上的氢被选自下组的1-4个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 1-6的烷硫基、C 3-6环烷硫基、CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9、和SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
在另一优选例中，所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其具有式II或式III所示的结构
Figure PCTCN2021136159-appb-000002
式中，X、m、R 1、R 2、R 3、R 4、R 5、Z和n的定义如上所述。
在另一优选例中，所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，R 5选自取代或未取代的下组基团：苯基、萘基、噻唑基、噻二唑基、异噻唑基、四唑基、吡啶基、硫代吗啉-S-氧化物、硫代吗啉-S,S-氧化物、嘧啶基、哒嗪基、吡嗪基、三嗪基、噻吩基、噁唑基、噁二唑基、异噁唑基、呋喃基、吡咯基、吡唑基、咪唑基、三唑基；其中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 1-6的烷硫基、C 3-6环烷硫基、CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9、和SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
在另一优选例中，所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，R 5选自下组：
Figure PCTCN2021136159-appb-000003
Figure PCTCN2021136159-appb-000004
式中，
g独立地为0、1、2、3、4或5；
各R'独立地选自下组：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 1-6的烷硫基、C 3-6环烷硫基、CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9、和SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂 环基。
在另一优选例中，所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，R 5选自下组：
Figure PCTCN2021136159-appb-000005
在另一优选例中，所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，(CH 2) n-R 1部分选自取代或未取代的下组基团：H、C 1-6烷基、C 2-4烯基、C 2-4炔基、C 1-6烷硫基、C 1-6烷氧基、3-6元环烷基、C 6-C 10芳基、5-10元杂芳基、4-10元杂环基、(CH 2)R'，R'选自：3-6元环烷基、C 6-C 10芳基、5-10元杂芳基、4-10元杂环基；其中，所述的取代是指被选自下组一个或多的基团取代：C 1-6烷基、C 1-6烷氧基、C 1-6烷硫基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
在另一优选例中，所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，R 2、R 3和R 4各自独立地选自下组：C 1-6烷基、C 2-4烯基和C 2-4炔基。
在另一优选例中，所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其具有式i-xvi所示的结构
Figure PCTCN2021136159-appb-000006
Figure PCTCN2021136159-appb-000007
式中，
R 1、R 2、R 3、R 4、X、m、n、Z的定义如上所述。
在另一优选例中，R 1、R 2、R 3、R 4、X、m、n、Z对应实施例中各具体化合物所对应基团。
在另一优选例中，所述式i-xvi的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，R 1、R 2、R 3、R 4、X、m、n、Z具有如表a所示定义
表a
Figure PCTCN2021136159-appb-000008
Figure PCTCN2021136159-appb-000009
Figure PCTCN2021136159-appb-000010
Figure PCTCN2021136159-appb-000011
Figure PCTCN2021136159-appb-000012
Figure PCTCN2021136159-appb-000013
Figure PCTCN2021136159-appb-000014
Figure PCTCN2021136159-appb-000015
Figure PCTCN2021136159-appb-000016
Figure PCTCN2021136159-appb-000017
Figure PCTCN2021136159-appb-000018
Figure PCTCN2021136159-appb-000019
在另一优选例中，所述化合物选自实施例中所示化合物。
本发明第二方面，提供一种第一方面所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药的制备方法，所述方法包括步骤：
Figure PCTCN2021136159-appb-000020
其中，m、n、R 1、R 2、R 3、R 4、R 5、X和Z的定义如上所述；
(s1)在惰性溶剂中，碱存在下，化合物A与化合物B反应，得到式I化合物。
在另一优选例中，式I化合物制备方法还包括步骤：
Figure PCTCN2021136159-appb-000021
其中，m、n、R 1、R 2、R 3、R 4、R 5和X的定义如上所述；
(s0)在惰性溶剂中，催化剂存在下，化合物C与化合物D发生反应，得到化合物A。
在另一优选例中，步骤(s1)为：在溶剂(较佳地，所述溶剂选自：苯、甲苯、乙酸乙酯、乙腈、二氯甲烷、二氯乙烷、四氢呋喃、乙醚、甲基叔丁基醚、1,4-二氧六环、PEG400、正庚烷、正己烷、环己烷、石油醚、二甲基甲酰胺、二甲亚砜，或其组合)中，在碱(较佳地，所述碱选自：氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、氢化钠、甲醇钠、乙醇钠、三乙胺、二甲氨基吡啶、叔丁醇钠、叔丁醇钾、二异丙基氨基锂、二异丙基乙胺、吡啶，或其组合)的存在下，于0-25℃或0℃至回流温度下，使式A化合物和式B化合物进行反应，从而得到式I化合物。
在另一优选例中，步骤(ii)(即反应式2所示反应)为：在溶剂(较佳地，所述溶剂选自：苯、甲苯、乙酸乙酯、乙腈、乙二醇单甲醚、二氯甲烷、二氯乙烷、叔丁醇、1,4-二氧六环、正丁醇、四氢呋喃、乙醚、甲基叔丁基醚、正庚烷、正己烷、环己烷、石油醚、二甲基甲酰胺、二甲亚砜，或其组合)中，在碱(较佳地，所述碱选自：氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、氢化钠、甲醇钠、乙醇钠、三乙胺、二甲氨基吡啶、叔丁醇钠、叔丁醇钾、二异丙基氨基锂、二异丙基乙胺、吡啶，或其组合)的存在下，于0-25℃或0℃至回流温度下，使式C化合物与式D化合物进行反应，从而得到式A化合物。
本发明第三方面，提供一种如第一方面所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药的用途，
(i)可用于杀灭和/或防治蜱螨目、综合目、直翅目、蜚镰目、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、蚤目和植物寄生线虫中的至少一种害虫和/或其若虫和/或其卵；
(ii)可用于防治因丝核菌属、孢盘菌属、假霜霉属、单胞锈菌属、层锈菌属、腐霉菌属等侵染造成的炭疽病、叶斑病、锈病、白粉病、纹枯病、叶枯病、灰霉病、白绢病、立枯病、赤霉病、全蚀病和靶斑病中至少一种植物病害；
(iii)用于制备用于杀灭和/或防治螨类和/或其卵的组合物或制剂；
(iv)用于杀虫和/或杀菌；和/或
(v)用于制备用于杀螨和/或杀虫和/或杀菌的组合物或制剂。
在另一优选例中，式I化合物用于杀灭和/或防治螨类和/或用于制备用于杀虫和/或杀菌的组合物或制剂。
在另一优选例中，式I化合物用于在农业，牧场，草坪和/或室内杀灭和/或防治有害螨类和/或其卵。
在另一优选例中，式I化合物用于在农业，牧场，草坪和/或室内杀灭和/或防治害虫和/或菌。
在另一优选例中，所述的螨类为有害螨类。
在另一优选例中，所述的螨类选自：二斑叶螨(Tetranychus urticae Koch)、山楂叶螨 (Tetranychus viennensis Zacher)、截形叶螨(Tetranychus truncatus Ehara)、朱砂叶螨(Tetranychus cinnabarinus Boisduval)、苹果全爪螨(Panonychus ulmi Koch)、柑橘全爪螨(Panonychus citri McGregor)、果苔螨(Bryobia rubrioculus Scheuten)、麦岩螨(Petrobia latens Muller)、针叶小爪螨(Oligonychus ununguis Jacobi)、卵形短须螨(Brevipalpus obovatus Donnadieu)、刘氏短须螨(B.lewisi McGregor)、桃细须螨(Tenuipalpus taonicas Ma et Yuan)、柿细须螨(Tenuipalpus zhizhilashviliae Reck)、葡萄缺节瘿螨(C.vitis Pagenstecher)、斯氏尖叶瘿螨(A.steinwedeni Keifer)、枸杞瘿螨(A.macrodonis Keifer)、梨叶肿瘿螨(Eriophyes pyri Pagenst)、梨叶锈螨(Epitrimerus pirifolia Keifer)、侧多食跗线螨(Polyphagotarsonemus latus Banks)、麦叶爪螨(Penthaleus major Duges)、水芋根螨(Rhizoglyphus callae Oudemans)。
在另一优选例中，所述害虫选自：白松虫(Scutigerella immaculat)、家蟋(Acheta domesticus)、蝼蛄属(Gryllotalpa spp.)、非洲飞蝗(Locusta inigratoria)、黑蝗(Melanoplus spp.)、沙漠蝗(Schistocer cagregaria)、东方蟑螂(Blatta orientalis)、美洲蟑螂(Periplanet aainericana)、佛罗里达蟑螂(Leucophae amaderae)、德国蟑螂(Blattella gerrnanica)、散白蚁属(Reticuliterines spp.)、人体虱(Pediculus humanuscorporis)、血虱属(Haematopinus spp.)、毛虱属(Linognathus spp.)、嚼虱属(Trichodectes spp.)、畜虱属(Dainalinia spp.)、温室条篱蓟马(Hercinothrips fernoralis)、烟蓟马(Thrips tabaci)、棕搁蓟马(Thrips palmi)、西花蓟马(Frankliniella occidentalis)、扁盾蝽属(Eurygaster spp.)、居间棉红蝽(Dysdercus interrnedius)、方背皮蝽(Piesrna quadrata)、温带臭虫(Cimexiectularius)、长红锥蝽(Rhodnius prolixus)、锥蝽属(Triatoma spp.)、白粉虱(Aleurodes brassicae)、烟粉(Beinisia tabaci)、温室粉虱(Trialeurodes vaporariorum)、棉蚜(Aphis gossypii)、甘蓝蚜(Brevicoryne brassicae)、茶蕉隐瘤蚜(Cryptomyzus ribis)、黑豆蚜((Aphis fabae)、苹果黄蚜(Aphis poini)、苹果绵蚜(Eriosoma lanigerum)、梅大尾蚜(Hyalopterus arundinis)、葡萄根瘤蚜(Phylloxera vastatrix)、瘦绵蚜属(Pernphigus spp.)、麦长管蚜(Macrosiphurn avenae)、瘤蚜属(Myzus spp.)、忽布疣蚜(Phorodon humuli)、禾谷缘管蚜(Rhopalos iphuin padi)、小绿叶蝉属(Einpoasca spp.)、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(Nilaparvata lugens)、红圆蚧(Aonidiella aurant ii)、常春藤圆盾蚧(Aspidiotus hederae)、粉蚧属种(Pseudococcus spp.)、木虱属种(Psylla spp.)、红铃麦蛾(Pectinophora gossypiella)、松尺蠖(Bupalus piniarius)、冬尺蛾(Cheirnatobia brurnata)、苹细蛾(Lithocolletis blancardella)、苹果巢蛾(Hyponomeuta padella)、菜蛾(Plutella xylostella)、黄褐天幕毛虫((Malacosoina neustria)、黄毒蛾(Euproctis chrysorrhoea)、毒蛾属(Lyinantria spp.)、棉潜娥(Bucculatrix thurberiella)、桔潜娥(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(Mainestra brassicae)、小眼夜娥(Panolis flarnmea)、斜纹夜蛾(Spodoptera litura)、草地贪夜蛾(Spodoptera frugiperda)、灰翅夜娥属(Spodoptera spp.)、粉纹夜蛾(Trichoplusia ni)、苹果小卷蛾(Carpocap saporiionella)、 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(Galleria mellonella)、幕谷娥(Tineola bisselliella)、袋谷娥(Tinea pellionella)、褐织蛾(Hofrnannophilap seudospretella)、亚麻黄卷蛾(Cacoecia podana)、极色卷蛾(Choristoneuna fuiniferana)、葡萄果蠢蛾(Clysia ambiguella)、茶长卷蛾(Homona rnagnan irna)、栋绿卷蛾(Tortrix viridana)、稻纵卷叶螟属种(Cnaphalocerus spp.)、水稻负泥虫(Oulema oryzae)、家具窃蠹虫(Anobium punctatuin)、谷蠹(Rhizopertha dominica)、恶条豆象(Bruchidius obtectus)、菜豆象(Acanthoscelides obtectus)、北美家天牛((Hylotrupes bajulus)、杨树萤叶甲(Agelastica alni)、马铃薯甲虫(Lept inotarsa deceml ineata)、辣根猿叶虫(Phaedon cochleariae)、叶甲属(Diabrotica spp.)、油菜金头跳甲(Psylliodes chrysocephal)、墨西哥豆瓢虫(Epilachna vanivestis)、锯谷盗(Oryzaephilus suninamensis)、花象属(Anthonomus spp.)、谷象属(Sitophilus spp.)、黑葡萄耳象(Otiorrhynchus sulcatus)、香蕉球茎象甲(Cosinopolites sordidus)、白菜龟象(Ceuthorrhynchus assimilis)、紫苜蓿叶象(Hypera postica)、皮囊属(Dermestes spp.)、斑皮蠹属(Trogoderrna 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(Triboliurn spp.)、黄粉虫(Tenebnio rnolitor)、叩甲属((Agriotes spp.)、宽胸叩头虫属(Conoderus spp.)、西方五月鳃角金龟(Melolontha inelolontha)、马铃薯鳃角金龟(Ainphimallon solstitialis)、褐新西兰肋翅鳃角金龟(Costelytra zealandica)、稻根象(Li s sorhoptrus oryzophilus)、松叶蜂属((Dipnion spp.)、实叶蜂属(Hoplocampa spp.)、毛蚁属(Lasius spp.)、小家蚁(Monornonium pharaonis)、胡蜂属(Vespa spp.)、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(Stornoxy、spp.)、狂蝇属(Oestrus spp.)、皮蝇属((Hypoderrna spp.)、虻属(Tabanus spp.)、花园毛蚊(Bibio hortulanus)、瑞典麦秆蝇(Oscinella frit)、草种蝇属(Phorbia spp.)、藜泉蝇(Pegomyia hyoscyarni)、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(Liriotnyza spp.)、印鼠客蚤(Xenopsylla cheopis)、角叶蚤属(Ceratophyllus spp.)、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(Tylenchulus sernipenetrans)、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(Xiphinerna spp.)、毛刺线虫属(Trichodorus spp.)、伞滑刃线虫属((Bursaphelenchus spp.)。
在另一优选例中，所述的植物病害的植物的实例包括大豆、玉米、小麦、瓜类、水稻、草莓、花生、棉花；所述的植物病害实例包括大豆锈病、玉米锈病、小麦白粉病、瓜类白 粉病、水稻纹枯病、小麦纹枯病、草莓灰霉病、花生白绢病、棉花立枯病、小麦赤霉病、小麦全蚀病和黄瓜靶斑病，其中所述的瓜类白粉病包括黄瓜白粉病等；所述的病原菌包括豆薯砌孢层锈菌(Phakopsora pachyrhizi syd.)、玉米柄锈菌(Puccinia sorghi Schw)、白粉菌(Blumeria graminis)、瓜白粉菌(Erysiphe cucurbitacearum)、瓜单囊壳白粉菌(Sphaerotheca cucurbitae)、瓜亡革菌(Thanatephorus cucumeris)、谷丝核菌(Rhizoctoniacerealis)、和立枯丝核菌(Rhizoctoniasolani)、灰葡萄孢菌(Botrytis cinerea Pers.)、禾谷镰袍(Fusarium graminearum schw.)、燕麦镰孢(Fusarium avenaceum)、串珠镰孢(Fusarium moniliforme sheld.)、单胞锈菌(Uromyces)、疫霉菌(Phytophthora)、腐霉菌(Pythium)。优选地为植物病害由蚕豆单胞锈菌、辣椒疫霉菌、腐霉菌等引起。
本发明第四方面，提供一种组合物，包括(i)作为活性成分的如第一方面的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药；和(ii)载体和/或表面活性剂。
在另一优选例中，所述的组合物中，所述化合物的含量为0.001-99.999wt％。
在另一优选例中，所述组合物为农药组合物；较佳地，为杀螨组合物，杀虫组合物和杀菌组合物。
本发明第五方面，提供一种杀灭螨、虫和/或菌的方法，包括步骤：使螨、虫和/或菌接触有效量的如第一方面所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药或如第四方面所述的组合物。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
具体实施方式
发明人经过广泛而深入地研究，意外发现了一类具有新颖结构的含硅丙烯腈类化合物(如式I所示)，这些化合物具有优异的杀螨和/或杀虫和/或杀菌活性。基于此，发明人完成了本发明。
术语
如本文所用，术语“卤素”是指氟、氯、溴或碘。
除非另有定义，术语“烷基”本身或作为另一取代基的一部分是指具有指定碳原子数的直链或支链烃基(即，C 1-6表示1-6个碳)。烷基的例子包括：甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基、仲丁基、正戊基、正己基等。
除非另有表述，术语“烯基”指具有一个或多个双键的不饱和烷基。类似地，术语“炔基”指具有一个或多个三键的不饱和烷基。此类不饱和烷基的例子包括乙烯基、2-丙烯基、巴豆基、2-异戊烯基、2-(丁二烯基)、2,4-戊二烯基、3-(1,4-戊二烯基)、乙炔基、1-和3-丙炔基、3-丁炔基和更高级的同系物和异构体。
除非另有定义，术语“环烷基”是指具有指定环原子数(例如，C 3-6环烷基)的饱和或者不饱和环烃基。此类环烷基的例子包括(但不限于)环戊基、环己基等。
除非另有表述，术语“芳基”表示多不饱和的(通常芳香性)的烃基，其可以是单环或稠合在一起或共价连接的多环(最多三环)。芳基的例子包括：苯基。
除非另有有定义，术语“杂环烷基”或“杂环基”是指含有一至五个选自N、O和S的杂原子的环烷基，其中氮和硫原子任选被氧化，且氮原子任选被季铵化。杂环烷基可以是单环、双环或多环体系。杂环烷基的非限制性例子包括吡咯烷、咪唑烷、吡唑烷、丁内酰胺、戊内酰胺、咪唑烷酮、乙内酰脲、二氧戊环、苯邻二甲酰亚胺、哌啶、1,4-二噁烷、吗啉、硫代吗啉、硫代吗啉-S-氧化物、硫代吗啉-S,S-氧化物、哌嗪、吡喃、吡啶酮、3-吡咯啉、噻喃、吡喃酮、四氢呋喃、四氢噻吩、奎宁环等。杂环烷基可以经环碳或杂原子连接于分子的其余部分。对于诸如环烷基烷基和杂环烷基烷基的术语，是指环烷基或杂环基通过烷基或亚烷基连接体连接到分子的其余部分。
除非另有定义，术语"杂芳基"是指含有1至5个选自N、O、和S的杂原子的芳基(或环)，其中氮和硫原子任选被氧化，氮原子任选被季铵化。杂芳基可通过杂原子连接于分子的其余部分。杂芳基的非限制性例子包括吡啶基、哒嗪基、吡嗪基、嘧啶基、三嗪基、喹啉基、喹喔啉基、喹唑啉基、噌啉基、酞嗪基、苯并三嗪基(benzotriazinyl)、嘌呤基、苯并咪唑基、苯并吡唑基、苯并三唑基、苯并异噁唑基、异苯并呋喃基(isobenzofuryl)、异吲哚基、中氮茚基、苯并三嗪基、噻吩并吡啶基、噻吩并嘧啶基、吡唑并嘧啶基、咪唑并吡啶、苯并噻唑基、苯并呋喃基、苯并噻吩基、吲哚基、喹啉基、异喹啉基、异噻唑基、吡唑基、吲唑基、蝶啶基、咪唑基、三唑基、四唑基、噁唑基、异噁唑基、噻二唑基、吡咯基、噻唑基、呋喃基、噻吩基等等。
如本文所用，术语“杂原子”意在包括氧(O)、氮(N)、硫(S)和硅(Si)。
对于本文提供的化合物，从取代基(通常为R基团)到芳香环(例如苯，吡啶等)的中心的键将被理解为是指在芳香环的任何可用顶点提供连接的键。在一些实施例中，该描述也包括稠合在芳环上的环上的连接。例如，绘制到吲哚苯部分的中心的键将表示与吲哚的六元或五元环部分的任何可用顶点连接的键。
如本文所用，术语“含有”、“包含”或“包括”表示各种成分可一起应用于本发明的混合物或组合物中。因此，术语“主要由...组成”和“由...组成”包含在术语“含有”中。
除非特别说明，本发明式I所示的化合物包括由于碳碳双键或碳氮双键连接不同取代基而可以形成的几何异构体(分别以Z和E来表示不同的构型)，本发明包括Z型异构体和E型异构体及其任何比例的混合物。本发明式I所示的化合物包括由于碳氮原子上连接不同取代基而可以形成立体异构体(分别以R和S来表示不同的构型)，本发明包括R型异构体和S型异构体及其任何比例的混合物。本发明式I所示的化合物不仅包括几何异构体(Z/E式)和立体异构体(R/S式)，还包括几何异构体和立体异构体任何比例的混合物。
如本文所用，“有效量”指的是：化合物的量足以产生杀螨杀虫杀菌效果，而不至于产生严重的负面影响。
如本文所用，例如“1至5个”是指1、2、3、4或5个，“1-10个”是指1、2、3、4、5、6、7、8、9或10个。
含硅丙烯腈化合物
如本文所用，术语本发明化合物是指如式I所示的一类硅丙烯腈类化合物，该术语还包括几何异构体、或其立体异构体、或其盐、各种异构体混合物。
具体地，本发明提供了如式I所示的硅丙烯腈类化合物，
Figure PCTCN2021136159-appb-000022
式I中，R 1、R 2、R 3、R 4、R 5、Z、n、X、m的定义如上所述。
优选地，所述化合物具有式II或式III所示的结构
Figure PCTCN2021136159-appb-000023
X、m、R 1、R 2、R 3、R 4、R 5、Z和n的定义如上所述。
优选地，式I-III中，R 5选自取代或未取代的下组基团：苯基、萘基、噻唑基、噻二唑基、异噻唑基、四唑基、吡啶基、硫代吗啉-S-氧化物、硫代吗啉-S,S-氧化物、嘧啶基、哒嗪基、吡嗪基、三嗪基、噻吩基、噁唑基、噁二唑基、异噁唑基、呋喃基、吡咯基、吡唑基、咪唑基、三唑基；其中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 1-6的烷硫基、C 3-6环烷硫基、CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9、和SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
优选地，式I-III中，Z-(CH 2) n-R 1部分选自取代或未取代的下组基团：C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基、C 1-6烷基O-、C 3-6环烷基O-、3-6元杂环基O-、C 6-14芳基O-、5-14元杂芳基O-、C 1-6烷基S-、C 3-6环烷基S-、3-6元杂环基S-、C 6-14芳基S-、5-14元杂芳基S-、NR 8R 9；
其中，R 8和R 9的定义如上所述。
优选地，式I-III中，R 2、R 3和R 4各自独立地选自下组：C 1-6烷基、C 2-4烯基和C 2-4炔基。
优选地，式I-III中，R 1选自下组：C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 3-6环烷氧基、C 1-6烷硫基、C 3-6环烷硫基、苯基、4至10元杂环基。
优选地，式I中，R 1选自下组：C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 3-6环烷氧基、C 1-6烷硫基、C 3-6环烷硫基、苯基；
n为0、1、2或3；
R 2、R 3和R 4各自独立地选自下组：C 1-6烷基、C 2-6烯基、C 2-6炔基；
或者，R 2和R 3、R 3和R 4、或R 2和R 4共同形成-(CH 2) p-的基团；其中，p为2、3、4、5、或6；
R 5选自下组：R 6和R 7；
R 6为取代或未取代的苯基；R 6中，所述的取代是指基团上的氢被选自下组的1、2或3个基团所取代：卤素、C 1-6烷基、C 1-6烷氧基、CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9、和-SO 2NR 8R 9；
R 7为未取代或取代的选自下组的基团：噻唑基、吡啶基、硫代吗啉-S-氧化物、硫代吗啉-S,S-氧化物、哒嗪基、吡嗪基、噻吩基、呋喃基、吡咯基、吡唑基；R 7中，所述的取代是指基团上的氢被选自下组的1、2、3或4个基团所取代：卤素、C 1-6烷基、C 1-6烷氧基、CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9、和-SO 2NR 8R 9；
其中，R 8和R 9各自独立选自：氢、C 1-6烷基；
X各自独立地选自下组：氢、卤素、C 1-6烷基；
m为1或2；
Z选自：CR bR c、氧、硫或NR d；
或者Z-(CH 2) n-R 1部分选自取代或未取代的下组基团：C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基、C 1-6烷基O-、C 3-6环烷基O-、3-6元杂环基O-、C 6-14芳基O-、5-14元杂芳基O-、C 1-6烷基S-、C 3-6环烷基S-、3-6元杂环基S-、C 6-14芳基S-、5-14元杂芳基S-、NR 8R 9；
R b、R c各自独立地选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
R d选自下组：氢、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基；
并且R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9和X基团中的一个或多个氢原子还可以各自独立地被选自下组的取代基所取代：卤素、C 1-3的烷基。
优选地，式I中，R 1选自下组：C 1-6的烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 3-6烷氧基、C 3-6环烷氧基、C 1-6烷硫基、C 3-6环烷硫基、苯基；
n为0、1或2；
R 2、R 3和R 4各自独立地选自下组：C 1-6烷基、C 2-4烯基和C 2-4炔基；
-SiR 2R 3R 4的取代位点为3位或4位；
R 5为1,3,4-三甲基吡唑-5-基、2-三氟甲基-苯基、2-碘-苯基、2-溴-苯基、5-氯-1,3-二甲 基-4-吡唑基、5-氟-1,3-二甲基-4-吡唑基、1-甲基-3-三氟甲基-4-吡唑基、1-乙基-3-甲基-5-吡唑基、2-甲基-4-三氟甲基-5-噻唑基、2-氯-3-吡啶基、1,3,5-三甲基吡唑-4-基、2-三氟甲基-3-吡啶基、2-三氟甲基-3-吡嗪基、2-甲基-3-呋喃基、3-甲基-2-噻吩基和1-甲基-3-二氟甲基-4-吡唑基；
X各自独立地选自下组：氢、卤素和C 1-6烷基；
m为1或2；
Z选自：CR bR c、氧、硫或NR d；
或者Z-(CH 2) n-R 1部分选自取代或未取代的下组基团：C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基、C 1-6烷基O-、C 3-6环烷基O-、3-6元杂环基O-、C 6-14芳基O-、5-14元杂芳基O-、C 1-6烷基S-、C 3-6环烷基S-、3-6元杂环基S-、C 6-14芳基S-、5-14元杂芳基S-、NR 8R 9；
R b、R c各自独立地选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
R d选自下组：氢、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基；
R 8和R 9各自独立选自：氢、C 1-6烷基；
并且R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9和X基团中的一个或多个氢原子还可以各自独立地被选自下组的取代基所取代：卤素、C 1-3的烷基。
优选地，所述的式I化合物具有式i-xvi所示的结构
Figure PCTCN2021136159-appb-000024
Figure PCTCN2021136159-appb-000025
式中，
R 1、R 2、R 3、R 4、X、m、n、Z的定义如上所述。
优选地，式i-xvi化合物中，R 1、R 2、R 3、R 4、X、m、n、Z的定义如表a所示
表a
Figure PCTCN2021136159-appb-000026
Figure PCTCN2021136159-appb-000027
Figure PCTCN2021136159-appb-000028
Figure PCTCN2021136159-appb-000029
Figure PCTCN2021136159-appb-000030
Figure PCTCN2021136159-appb-000031
Figure PCTCN2021136159-appb-000032
Figure PCTCN2021136159-appb-000033
Figure PCTCN2021136159-appb-000034
Figure PCTCN2021136159-appb-000035
Figure PCTCN2021136159-appb-000036
Figure PCTCN2021136159-appb-000037
本发明化合物的制备方法
下面更具体地描述本发明式I化合物的制备方法，但这些具体方法不对本发明构成任 何限制。本发明化合物还可以任选将在本说明书中描述的或本领域已知的各种合成方法组合起来而方便地制得，这样的组合可由本发明所属领域的技术人员容易地进行。
本发明还提供了一种制备第一方面所述化合物即式I化合物的的通用方法。
优选地，所述方法包括步骤：
Figure PCTCN2021136159-appb-000038
其中，m、n、R 1、R 2、R 3、R 4、R 5、X和Z如上所述；
(s1)在惰性溶剂中，碱存在下，化合物A与化合物B反应，得到式I化合物。
在另一优选例中，式I化合物制备方法还包括步骤：
Figure PCTCN2021136159-appb-000039
其中，m、n、R 1、R 2、R 3、R 4、R 5和X的定义如上所述；
(s0)在惰性溶剂中，催化剂存在下，化合物C与化合物D发生反应，得到化合物A。
在另一优选例中，步骤(s1)为：在溶剂(较佳地，所述溶剂选自：苯、甲苯、乙酸乙酯、乙腈、二氯甲烷、二氯乙烷、四氢呋喃、乙醚、甲基叔丁基醚、1,4-二氧六环、PEG400、正庚烷、正己烷、环己烷、石油醚、二甲基甲酰胺、二甲亚砜，或其组合)中，在碱(较佳地，所述碱选自：氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、氢化钠、甲醇钠、乙醇钠、三乙胺、二甲氨基吡啶、叔丁醇钠、叔丁醇钾、二异丙基氨基锂、二异丙基乙胺、吡啶，或其组合)的存在下，于0-25℃或0℃至回流温度下，使式A化合物和式B化合物进行反应，从而得到式I化合物。
在另一优选例中，步骤(ii)(即反应式2所示反应)为：在溶剂(较佳地，所述溶剂选自：苯、甲苯、乙酸乙酯、乙腈、乙二醇单甲醚、二氯甲烷、二氯乙烷、叔丁醇、1,4- 二氧六环、正丁醇、四氢呋喃、乙醚、甲基叔丁基醚、正庚烷、正己烷、环己烷、石油醚、二甲基甲酰胺、二甲亚砜，或其组合)中，在碱(较佳地，所述碱选自：氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、氢化钠、甲醇钠、乙醇钠、三乙胺、二甲氨基吡啶、叔丁醇钠、叔丁醇钾、二异丙基氨基锂、二异丙基乙胺、吡啶，或其组合)的存在下，于0-25℃或0℃至回流温度下，使式C化合物与式D化合物进行反应，从而得到式A化合物。
含本发明化合物的组合以及本发明化合物及其组合物的用途
本发明还提供了如式I所示化合物或包含如式I所示的硅丙烯腈化合物的农用组合物及其用途。
本发明式I所示的硅丙烯腈化合物对农业或其他领域的多种害虫，特别的对蛛形纲(Arachnida)蜱螨目(Acarina)害螨显示出优异的螨虫防除活性，如二斑叶螨(Tetranychus urticae Koch)、山楂叶螨(Tetranychus viennensis Zacher)、截形叶螨(Tetranychus truncatus Ehara)、朱砂叶螨(Tetranychus cinnabarinus Boisduval)、苹果全爪螨(Panonychus ulmi Koch)、柑橘全爪螨(Panonychus citri McGregor)、果苔螨(Bryobia rubrioculus Scheuten)、麦岩螨(Petrobia latens Muller)、针叶小爪螨(Oligonychus ununguis Jacobi)、卵形短须螨(Brevipalpus obovatus Donnadieu)、刘氏短须螨(B.lewisi McGregor)、桃细须螨(Tenuipalpus taonicas Ma et Yuan)、柿细须螨(Tenuipalpus zhizhilashviliae Reck)、葡萄缺节瘿螨(C.vitis Pagenstecher)、斯氏尖叶瘿螨(A.steinwedeni Keifer)、枸杞瘿螨(A.macrodonis Keifer)、梨叶肿瘿螨(Eriophyes pyri Pagenst)、梨叶锈螨(Epitrimerus pirifolia Keifer)、侧多食跗线螨(Polyphagotarsonemus latus Banks)、麦叶爪螨(Penthaleus major Duges)、水芋根螨(Rhizoglyphus callae Oudemans)等。“螨虫防除”是指在螨虫生命周期的每一阶段(卵，幼虫，成虫)具有杀螨活性。因此，本发明的技术方案还包括式I所示的硅丙烯腈类化合物在农业或其他领域用作杀螨剂的用途。
本发明式I所示的硅丙烯腈化合物也适合防治农业或其他领域的综合目、直翅目、蜚镰目、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、蚤目和植物寄生线虫中的至少一种害虫。
所述综合目(Syrnphyla)，例如，白松虫(Scutigerella immaculat)等。
所述直翅目(Orthoptera)，例如，家蟋(Acheta domesticus)、蝼蛄属(Gryllotalpa spp.)、非洲飞蝗(Locusta inigratoria)、黑蝗(Melanoplus spp.)、沙漠蝗(Schistocer cagregaria)等；
所述蜚蠊目(Blattaria)，例如，东方蟑螂(Blatta orientalis)、美洲蟑螂(Periplanet aainericana)、佛罗里达蟑螂(Leucophae amaderae)、德国蟑螂(Blattella gerrnanica)等。
所述等翅目(Isoptera)，例如，散白蚁属(Reticuliterines spp.)等。
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(Dainalinia spp.)等。
所述缨翅目(Thysanoptera)，例如，温室条篱蓟马(Hercinothrips fernoralis)、烟蓟马(Thrips tabaci)、棕搁蓟马(Thrips palmi)、西花蓟马(Frankliniella occidentalis)等。
所述异翅目(Heteroptera)，例如，扁盾蝽属(Eurygaster spp.)、居间棉红蝽(Dysdercus interrnedius)、方背皮蝽(Piesrna quadrata)、温带臭虫(Cimexiectularius)、长红锥蝽(Rhodnius prolixus)、锥蝽属(Triatoma spp.)等。
所述同翅目(Hoinoptera)，例如，白粉虱(Aleurodes brassicae)、烟粉(Beinisia tabaci)、温室粉虱(Trialeurodes vaporariorum)、棉蚜(Aphis gossypii)、甘蓝蚜(Brevicoryne brassicae)、茶蕉隐瘤蚜(Cryptomyzus ribis)、黑豆蚜((Aphis fabae)、苹果黄蚜(Aphis poini)、苹果绵蚜(Eriosoma lanigerum)、梅大尾蚜(Hyalopterus arundinis)、葡萄根瘤蚜(Phylloxera vastatrix)、瘦绵蚜属(Pernphigus spp.)、麦长管蚜(Macrosiphurn avenae)、瘤蚜属(Myzus spp.)、忽布疣蚜(Phorodon humuli)、禾谷缘管蚜(Rhopalos iphuin padi)、小绿叶蝉属(Einpoasca spp.)、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(Nilaparvata lugens)、红圆蚧(Aonidiella aurant ii)、常春藤圆盾蚧(Aspidiotus hederae)、粉蚧属种(Pseudococcus spp.)、木虱属种(Psylla spp.)等。
所述鳞翅目(Lepidoptera)，例如，红铃麦蛾(Pectinophora gossypiella)、松尺蠖(Bupalus piniarius)、冬尺蛾(Cheirnatobia brurnata)、苹细蛾(Lithocolletis blancardella)、苹果巢蛾(Hyponomeuta padella)、菜蛾(Plutella xylostella)、黄褐天幕毛虫((Malacosoina neustria)、黄毒蛾(Euproctis chrysorrhoea)、毒蛾属(Lyinantria spp.)、棉潜娥(Bucculatrix thurberiella)、桔潜娥(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(Mainestra brassicae)、小眼夜娥(Panolis flarnmea)、斜纹夜蛾(Spodoptera litura)、草地贪夜蛾(Spodoptera frugiperda)、灰翅夜娥属(Spodoptera spp.)、粉纹夜蛾(Trichoplusia ni)、苹果小卷蛾(Carpocap saporiionella)、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(Galleria mellonella)、幕谷娥(Tineola bisselliella)、袋谷娥(Tinea pellionella)、褐织蛾(Hofrnannophilap seudospretella)、亚麻黄卷蛾(Cacoecia podana)、极色卷蛾(Choristoneuna fuiniferana)、葡萄果蠢蛾(Clysia ambiguella)、茶长卷蛾(Homona rnagnan irna)、栋绿卷蛾(Tortrix viridana)、稻纵卷叶螟属种(Cnaphalocerus spp.)、水稻负泥虫(Oulema oryzae)等。
所述鞘翅目(Coleoptera)，例如，家具窃蠹虫(Anobium punctatuin)、谷蠹(Rhizopertha dominica)、恶条豆象(Bruchidius obtectus)、菜豆象(Acanthoscelides obtectus)、北美家天牛((Hylotrupes bajulus)、杨树萤叶甲(Agelastica alni)、马铃薯甲虫(Lept inotarsa deceml ineata)、辣根猿叶虫(Phaedon cochleariae)、叶甲属(Diabrotica spp.)、油菜金头跳甲(Psylliodes chrysocephal)、墨西哥豆瓢虫(Epilachna vanivestis)、锯谷盗(Oryzaephilus suninamensis)、花象属(Anthonomus spp.)、谷象属(Sitophilus spp.)、黑葡萄耳象 (Otiorrhynchus sulcatus)、香蕉球茎象甲(Cosinopolites sordidus)、白菜龟象(Ceuthorrhynchus assimilis)、紫苜蓿叶象(Hypera postica)、皮囊属(Dermestes spp.)、斑皮蠹属(Trogoderrna 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(Triboliurn spp.)、黄粉虫(Tenebnio rnolitor)、叩甲属((Agriotes spp.)、宽胸叩头虫属(Conoderus spp.)、西方五月鳃角金龟(Melolontha inelolontha)、马铃薯鳃角金龟(Ainphimallon solstitialis)、褐新西兰肋翅鳃角金龟(Costelytra zealandica)、稻根象(Li s sorhoptrus oryzophilus)等。
所述膜翅目((Hymenoptera)，例如，松叶蜂属((Dipnion spp.)、实叶蜂属(Hoplocampa spp.)、毛蚁属(Lasius spp.)、小家蚁(Monornonium pharaonis)、胡蜂属(Vespa spp.)等；
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(Stornoxy、spp.)、狂蝇属(Oestrus spp.)、皮蝇属((Hypoderrna spp.)、虻属(Tabanus spp.)、花园毛蚊(Bibio hortulanus)、瑞典麦秆蝇(Oscinella frit)、草种蝇属(Phorbia spp.)、藜泉蝇(Pegomyia hyoscyarni)、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(Liriotnyza spp.)等。
所述蚤目(Siphonaptera)，例如，印鼠客蚤(Xenopsylla cheopis)、角叶蚤属(Ceratophyllus spp.)等。
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(Tylenchulus sernipenetrans)、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(Xiphinerna spp.)、毛刺线虫属(Trichodorus spp.)、伞滑刃线虫属((Bursaphelenchus spp.)等。因此，本发明的技术方案还包括式I所示的硅丙烯腈类化合物在农业或其他领域用作杀虫剂的用途。
本发明式I所示的硅丙烯腈化合物也适合防治因丝核菌属、孢盘菌属、假霜霉属、单胞锈菌属、层锈菌属、腐霉菌属等侵染造成的炭疽病、叶斑病、锈病、白粉病、纹枯病、叶枯病、灰霉病、白绢病、立枯病、赤霉病、全蚀病和靶斑病中至少一种植物病害。所述的植物真菌病的植物的实例包括大豆、玉米、小麦、瓜类、水稻、草莓、花生、棉花；所述的植物真菌病实例包括大豆锈病、玉米锈病、小麦白粉病、瓜类白粉病、水稻纹枯病、小麦纹枯病、草莓灰霉病、花生白绢病、棉花立枯病、小麦赤霉病、小麦全蚀病和黄瓜靶斑病，其中所述的瓜类白粉病包括黄瓜白粉病等；所述的病原菌包括豆薯砌孢层锈菌(Phakopsora pachyrhizi syd.)、玉米柄锈菌(Puccinia sorghi Schw)、白粉菌(Blumeria graminis)、 瓜白粉菌(Erysiphe cucurbitacearum)、瓜单囊壳白粉菌(Sphaerotheca cucurbitae)、瓜亡革菌(Thanatephorus cucumeris)、谷丝核菌(Rhizoctoniacerealis)、和立枯丝核菌(Rhizoctoniasolani)、灰葡萄孢菌(Botrytis cinerea Pers.)、禾谷镰袍(Fusarium graminearum schw.)、燕麦镰孢(Fusarium avenaceum)、串珠镰孢(Fusarium moniliforme sheld.)、单胞锈菌(Uromyces)、疫霉菌(Phytophthora)、腐霉菌(Pythium)。
因此，本发明的技术方案还包括式I所示的硅丙烯腈类化合物在农业或其他领域用作杀菌剂的用途。
可将本发明式I所示的硅丙烯腈类化合物以常规的方法制备成杀螨剂和/或杀虫剂和/或杀菌剂组合物。这些活性化合物可做成常规的制剂，如溶液剂、乳剂、混悬剂、粉剂、泡沫剂、糊剂、颗粒剂、气雾剂、用活性物质浸渍的天然的和合成的材料、在多聚物中的微胶囊、用于种子的包衣复方、和与燃烧装置一块使用的制剂，例如烟熏药筒、烟熏罐和烟熏盘，以及ULV冷雾(Cold mist)和热雾(Warm mist)制剂。
这些制剂可用已知的方法生产，例如，将活性化合物与扩充剂混合，这些扩充剂就是液体的或液化气的或固体的稀释剂或载体，并可任意选用表面活性剂即乳化剂和/或分散剂和/或泡沫形成剂。例如在用水作扩充剂时，有机溶剂也可用作助剂。
用液体溶剂作稀释剂或载体时，基本上是合适的，如：芳香烃类，例如二甲苯、甲苯或烷基萘；氯化的芳香或氯化的脂肪烃类，例如氯苯、氯乙烯或二氯甲烷；脂肪烃类，例如环己烷或石蜡，例如矿物油馏分；醇类，例如乙醇或乙二醇以及它们的醚和脂类；酮类，例如丙酮、甲乙酮、甲基异丁基酮或环已酮；或不常用的极性溶剂，例如二甲基甲酰胺和二甲基亚砜，以及水。
液化气的稀释剂或载体，指的是在常温常压下将成为气体的液体，例如气溶胶推进剂，如卤化的烃类以及丁烷、丙烷、氮气和二氧化碳。
固体载体可用磨碎的天然的矿物质，例如高岭土、粘土、滑石、石英、活性白土、蒙脱土、或硅藻土；和磨碎的合成的矿物质，例如高度分散的硅酸、氧化铝和硅酸盐。供颗粒用的固体载体是碾碎的和分级的天然锆石，例如方解石、大理石、浮石、海泡石和白云石，以及无机和有机粗粉合成的颗粒，和有机材料例如锯木屑、椰子壳、玉米棒子和烟草梗的颗粒等。
非离子的和阴离子的乳化列可用作乳化剂和/或泡沫形成剂。例如聚氧乙烯-脂肪酸酯类，聚氧乙烯-脂肪醇醚类，例如烷芳基聚乙二醇醚类，烷基磺酸酯类，烷基硫酸酯类，芳基磺酸酯类以及白蛋白水解产物。分散剂包括木质素亚硫酸盐废液和甲基纤维素。
在制剂中可以用粘合剂，例如羧甲基纤维素和以粉末、颗粒或乳液形式的天然和合成的多聚物，例如阿拉伯胶、聚乙烯基醇和聚乙烯醋酸酯。
可以用着色剂例如无机染料，如氧化铁、氧化钴和普鲁士蓝；有机染料，如偶氮染料或金属酞菁染料；和用痕量营养剂，如铁、锰、硼、铜、钴、铝和锌的盐等。
本发明式I所示的硅丙烯腈类化合物可与其他活性化合物制成一种混合物存在于它们 的商品制剂中或从这些制剂制备的使用剂型中，这些其他的活性化合物为杀虫剂、杀菌剂、杀真菌剂、除草剂、生长控制剂等。杀虫剂包括，例如磷酸酯类、氨基甲酸酯类、氯化烃类以及由微生物产生的物质，如阿维菌素等，杀真菌剂包括甲氧基丙烯酸酯类、酰胺类、三唑类等。
此外，本发明式I所示的硅丙烯腈类化合物也可与增效剂制成一种混合物存在于它们的商品制剂中或从这些制剂制备的使用剂型中，这些增效剂是提高活性化合物作用的化合物，由于活性化合物本身有活性，也可不必加增效剂。
这些制剂通常含有占所述杀虫剂组合物总重量的0.001-99.99重量％，优选0.01-99.9重量％，更优选0.05-90重量％的本发明的活性化合物。商品制剂或使用剂型中的活性化合物的浓度可在广阔的范围内变动。使用剂型中的活性化合物的浓度可从0.0000001-100％(g/v)，最好在0.0001与1％(g/v)之间应明确的，在本发明的权利要求所限定的范围内，可以进行各种变动和改动。
本发明的主要优点包括：
(a)本发明化合物具有优异的杀螨活性；
(b)本发明化合物还具有优异杀虫及杀菌活性；
(c)本发明化合物合成步骤简短，总收率较好；
(d)本发明化合物与现有同类型化合物相比，具有显著的结构创新性；
(f)本发明化合物兼具优异的杀螨、杀虫及杀菌活性，对环境影响较小。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数是重量百分比和重量份数。
实施例1 化合物i-7的制备
Figure PCTCN2021136159-appb-000040
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取对三甲基硅基苯乙腈(1.89g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，残液加入正庚烷析出白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol) 后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率74.2％。 1H NMR(400MHz,Chloroform-d)δ7.68(d,J＝7.6Hz,1H),7.58(d,J＝7.8Hz,1H),7.49(t,J＝7.5Hz,1H),7.43(d,J＝7.6Hz,1H),7.38(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),0.85(s,9H),0.09(s,9H).
实施例2 化合物i-4的制备
Figure PCTCN2021136159-appb-000041
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取对三甲基硅基苯乙腈(1.89g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，残液加入正庚烷析出白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加异丁酰氯(1.25g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率77.6％。 1H NMR(400MHz,Chloroform-d)δ7.68(d,J＝7.6Hz,1H),7.58(d,J＝7.8Hz,1H),7.49(t,J＝7.5Hz,1H),7.43(d,J＝7.6Hz,1H),7.38(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),2.69–2.54(m,1H),0.95(d,J＝6.7Hz,6H),0.28(s,9H).
实施例3 化合物i-24的制备
Figure PCTCN2021136159-appb-000042
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取对三甲基硅基苯乙腈(1.89g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，残液加入正庚烷析出白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加苯甲酰氯(1.75g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率44.2％。 1H NMR(400MHz,Chloroform-d)δ7.68-7.48(m,6H),7.44-7.23(m,3H),7.38(d,J＝8.1Hz,2H), 7.33(d,J＝8.0Hz,2H),0.09(s,9H).
实施例4 化合物i-39的制备
Figure PCTCN2021136159-appb-000043
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取对三甲基硅基苯乙腈(1.89g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，残液加入正庚烷析出白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加2-甲氧基氯甲酸乙酯(1.73g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率38.4％。 1H NMR(400MHz,CDCl 3)δ7.68(d,J＝7.6Hz,1H),7.58(d,J＝7.8Hz,1H),7.49(t,J＝7.5Hz,1H),7.43(d,J＝7.6Hz,1H),7.38(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),4.58–4.39(m,2H),3.64(t,J＝4.8Hz,2H),3.32(s,3H),0.30(s,9H).
实施例5 化合物i-58的制备
Figure PCTCN2021136159-appb-000044
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取对三甲基硅基苯乙腈(1.89g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，残液加入正庚烷析出白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加二甲氨基甲酰氯(1.34g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率54.2％。 1H NMR(400MHz,Chloroform-d)δ7.68(d,J＝7.6Hz,1H),7.58(d,J＝7.8Hz,1H),7.49(t,J＝7.5Hz,1H),7.43(d,J＝7.6Hz,1H),7.38(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),5.00(hept,J＝6.2Hz,1H),3.22(s,6H),0.15(s,9H).
实施例6 化合物i-71的制备
Figure PCTCN2021136159-appb-000045
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取对二甲基乙烯基硅基苯乙腈(2.01g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，柱层析得棕色油状物，产率71.8％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率81.0％。 1H NMR(400MHz,Chloroform-d)δ7.68(d,J＝7.6Hz,1H),7.58(d,J＝7.8Hz,1H),7.49(t,J＝7.5Hz,1H),7.43(d,J＝7.5Hz,1H),7.38(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),6.28(dd,J＝20.0,14.5Hz,1H),6.09(dd,J＝14.5,3.6Hz,1H),5.72(dd,J＝20.2,3.8Hz,1H),0.89(s,9H),0.35(s,6H).
实施例7 化合物i-134的制备
Figure PCTCN2021136159-appb-000046
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取对二甲基叔丁基硅基苯乙腈(2.31g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，残液加入正庚烷析出白色固体，产率82.8％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率74.2％。 1H NMR(400MHz,Chloroform-d)δ7.68(d,J＝7.6Hz,1H),7.58(d,J＝7.8Hz,1H),7.49(t,J＝7.5Hz,1H),7.43(d,J＝7.6Hz,1H),7.38(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),0.89(s,9H),0.86(s,9H),0.30(s,6H).
实施例8 化合物i-313的制备
Figure PCTCN2021136159-appb-000047
称取NaH(500mg，12.5mmol)于50ml两口瓶中，加入30ml THF，冰浴下搅拌分散均匀；称取间三甲基硅基苯乙腈(1.89g,10mmol)滴加入NaH的THF的悬浊液中。继续搅拌20min后，滴加2-三氟甲基苯甲酸乙酯(2.18g,10mmol)，60℃下反应。反应结束后，冰浴下加入少量水淬灭反应，加入稀盐酸调节至酸性。乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，残液加入正庚烷析出白色固体，产率87.9％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率85.2％。 1H NMR(400MHz,Chloroform-d)δ7.85(d,J＝7.6Hz,1H),7.73(d,J＝7.5Hz,1H),7.64(t,J＝7.5Hz,1H),7.58(d,J＝7.1Hz,2H),7.47(dd,J＝17.7,7.5Hz,2H),7.36(t,J＝7.5Hz,1H),0.95(s,9H),0.25(s,9H).
实施例10 化合物ii-4的制备
Figure PCTCN2021136159-appb-000048
两口瓶中加入1,3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，对三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得白色固体，产率74.8％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加异丁酰氯(1.25g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率84.2％。 1H NMR(400MHz,Chloroform-d)δ7.60–7.50(m,4H),3.91(s,3H),2.21(s,3H),2.10(s,3H),2.69–2.54(m,1H),0.95(d,J＝6.7Hz,6H),0.29(s,9H).
实施例9 化合物ii-7的制备
Figure PCTCN2021136159-appb-000049
两口瓶中加入1,3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，对三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加 入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率74.8％。 1H NMR(400MHz,Chloroform-d)δ7.60–7.50(m,4H),3.91(s,3H),2.21(s,3H),2.10(s,3H),1.16(s,9H),0.29(s,9H).
实施例11 化合物ii-39的制备
Figure PCTCN2021136159-appb-000050
两口瓶中加入1,3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，对三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加2-甲氧基氯甲酸乙酯(1.73g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率78.7％。 1H NMR(400MHz,Chloroform-d)δ7.60–7.50(m,4H),4.58–4.39(m,2H),3.91(s,3H),3.64(t,J＝4.8Hz,2H),3.32(s,3H),2.21(s,3H),2.10(s,3H),0.29(s,9H).
实施例12 化合物ii-24的制备
Figure PCTCN2021136159-appb-000051
两口瓶中加入1,3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，对三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得白色固体，产率84.2％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加苯甲酰氯(1.75g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后 柱层析纯化，得目标化合物，产率64.6％。 1H NMR(400MHz,Chloroform-d)δ7.68-7.48(m,6H),7.44-7.23(m,3H),7.38(d,J＝8.1Hz,2H),7.33(d,J＝8.0Hz,2H),2.21(s,3H),2.10(s,3H),1.16(s,9H),0.29(s,9H).
实施例13 化合物ii-308的制备
Figure PCTCN2021136159-appb-000052
两口瓶中加入1,3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，5-氟-3-三甲基硅基苯乙腈(2.07g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得粗产物。随后将粗产物溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率88.2％。 1H NMR(400MHz,Chloroform-d)δ7.85(d,J＝7.6Hz,1H),7.73(d,J＝7.5Hz,1H),7.36(t,J＝7.5Hz,1H),3.32(s,3H),2.21(s,3H),2.10(s,3H),0.95(s,9H),0.25(s,9H).
实施例14 化合物ii-313的制备
Figure PCTCN2021136159-appb-000053
两口瓶中加入1,3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，间三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得粗产物。随后将粗产物溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率75.9％。 1H NMR(400MHz,Chloroform-d)δ7.60(s,1H),7.55(d,J＝7.1Hz,1H),7.47(d,J＝7.9Hz,1H),7.40(t,J＝7.4Hz,1H),3.99(s,3H),3.26(s,3H),2.31(s,3H),1.82(s,9H),0.29(s,9H).
实施例15 化合物iii-7的制备
Figure PCTCN2021136159-appb-000054
两口瓶中加入1-乙基-3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，对三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，1,4-二氧六环5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得粗产物。随后将粗产物溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率69.8％。 1H NMR(400MHz,Chloroform-d)δ7.57(d,J＝7.8Hz,2H),7.49(d,J＝7.8Hz,2H),6.36(s,1H),4.25(q,J＝7.2Hz,2H),2.30(s,3H),1.54(t,J＝7.2Hz,3H),1.14(s,9H),0.28(s,9H).
实施例16 化合物iii-313的制备
Figure PCTCN2021136159-appb-000055
两口瓶中加入1-乙基-3,4-三甲基吡唑-5-甲酸乙酯(1.82g,10mmol)，间三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得粗产物。随后将粗产物溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率74.2％。 1H NMR(400MHz,Chloroform-d)δ7.60(s,1H),7.55(d,J＝7.1Hz,1H),7.47(d,J＝7.9Hz,1H),7.40(t,J＝7.4Hz,1H),6.36(s,1H),4.25(q,J＝7.2Hz,2H),2.30(s,3H),1.54(t,J＝7.2Hz,3H),1.14(s,9H),0.28(s,9H).
实施例17 化合物vi-313的制备
Figure PCTCN2021136159-appb-000056
两口瓶中加入2-碘-苯甲酸乙酯(2.76g,10mmol)，间三甲基硅基苯乙腈(1.89g,10 mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得白色固体，产率75.8％。随后将白色固体溶于20ml二氯甲烷中，加入三乙胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率79.5％。 1H NMR(400MHz,Chloroform-d)δ7.60(s,1H),7.55(d,J＝7.1Hz,1H),7.47(d,J＝7.9Hz,1H),7.40(t,J＝7.4Hz,1H),6.36(s,1H),4.25(q,J＝7.2Hz,2H),2.30(s,3H),1.54(t,J＝7.2Hz,3H),1.14(s,9H),0.28(s,9H).
实施例18 化合物xv-7的制备
Figure PCTCN2021136159-appb-000057
两口瓶中加入3-甲基噻吩唑-2-甲酸乙酯(1.70g,10mmol)，对三甲基硅基苯乙腈(1.89g,10mmol)，正己烷30ml，乙二醇单甲醚5ml，随后添加分水器和冷凝回流管。反应体系氮气置换后，110℃下回流2小时，随后降温至100℃。温度稳定后，滴加甲醇钠溶液(2M，6ml，12.0mmol)。反应结束后，反应液倒入水中，乙酸乙酯萃取，取水相加入稀盐酸调节至酸性，乙酸乙酯萃取(20mL×3)，合并有机相后饱和氯化钠溶液洗涤，无水硫酸钠干燥。减压除去溶剂，得粗产物。随后将粗产物溶于20ml二氯甲烷中，加入二异丙基胺(1.01g,10mmol)后室温搅拌10min，滴加特戊酰氯(1.50g，12.5mmol)，室温反应。反应结束后，减压除去溶剂，乙酸乙酯洗涤过滤，滤液浓缩后柱层析纯化，得目标化合物，产率86.3％。 1H NMR(400MHz,Chloroform-d)δ7.60(s,1H),7.55(d,J＝7.1Hz,1H),7.47(d,J＝7.9Hz,1H),7.40(t,J＝7.4Hz,1H),6.36(s,1H),4.25(q,J＝7.2Hz,2H),2.30(s,3H),1.54(t,J＝7.2Hz,3H),1.14(s,9H),0.28(s,9H).
参考上述制备方法以不同的起始原料还制备了其他实施例化合物，本发明实施例化合物如表1所示；本发明的其他如式I所示的硅丙烯腈化合物也可使用合适的起始材料，参考上述实施例的方法进行制备：
表1 部分实施例化合物结构表征
Figure PCTCN2021136159-appb-000058
Figure PCTCN2021136159-appb-000059
Figure PCTCN2021136159-appb-000060
Figure PCTCN2021136159-appb-000061
Figure PCTCN2021136159-appb-000062
Figure PCTCN2021136159-appb-000063
Figure PCTCN2021136159-appb-000064
Figure PCTCN2021136159-appb-000065
Figure PCTCN2021136159-appb-000066
Figure PCTCN2021136159-appb-000067
Figure PCTCN2021136159-appb-000068
Figure PCTCN2021136159-appb-000069
Figure PCTCN2021136159-appb-000070
Figure PCTCN2021136159-appb-000071
生物活性测定实例
对二斑叶螨(Tetranychus urticae)的杀螨活性评价
待测试化合物用二甲亚砜溶解后，以曲拉通水溶液稀释至不同测试浓度，在豆叶裁片正反面均匀喷洒药液。待药液干燥后，在豆叶裁片接二斑叶螨混合个体，并记录基数。在标准观察室内(23-25℃，RH40-60％)观察，192h后进行调查，记录豆叶上的活虫数。以商品化农药腈吡螨酯(Cyenopyrafen)为对照，曲拉通水溶液为空白对照。部分化合物对二斑叶螨活性测定结果表2所示。
表2 部分化合物二斑叶螨活性测定结果
Figure PCTCN2021136159-appb-000072
Figure PCTCN2021136159-appb-000073
Figure PCTCN2021136159-appb-000074
Figure PCTCN2021136159-appb-000075
从上述实验结果可以看出：本发明化合物具有与对照品基本相当的杀螨活性，甚至在较低浓度下(如50ppm)下，大部分化合物仍具有100％杀螨活性，比如化合物i-4、i-5、i-6、i-7、i-19、i-24、i-27、i-36、i-37、i-39、i-43、i-55、i-58、i-67、i-70、i-88、i-91等。
对小菜蛾(Plutella xylostella)的杀虫活性评价
取培养皿，皿底覆一层滤纸，并滴加适量自来水保湿。从甘蓝叶片除去表面蜡质层后，制成直径约6cm的甘蓝叶碟，叶背向上置于培养皿中。待测试化合物用二甲亚砜(DMSO)溶解后，以曲拉通水溶液稀释至不同测试浓度，在叶片正反面均匀喷洒药液。待叶片自然阴干后，接入小菜蛾1龄幼虫，设3次重复，商品化农药腈吡螨酯(Cyenopyrafen)为对照，曲拉通水溶液为空白对照。将培养皿移至标准观察室内(23-25℃，RH40-60％)。在处理后72小时进行试验调查，记录试虫的死虫与活虫数，计算死亡率。部分化合物对小菜蛾活性测定结果表3所示。
表3 部分化合物小菜蛾活性测定结果
Figure PCTCN2021136159-appb-000076
Figure PCTCN2021136159-appb-000077
从上述实验结果可以看出：相较于对照品化合物，本发明化合物具有优异的杀虫活性。例如化合物i-258、i-260、i-272、i-283、i-289、i-290、i-292、i-298、i-308、i-314、ii-260、ii-265、ii-272、ii-283、ii-292、ii-298、ii-310、ii-311、ii-313、iii-272、iii-283、iii-292、iii-298、iii-310、iii-311、iii-313、ix-260、ix-313、v-313、vi-313、vii-260、viii-260、ix-260、x-313、x-260、xi-260、xii-260、xii-313、xiii-260、xv-260、xvi-260在200ppm下表现出较好或极佳的小菜蛾活性，而对照药品腈吡螨酯未表现出相关杀虫活性，本发明化合物具有杀虫广谱性。
对蚕豆单胞锈菌(Uromyces viciae-fabae)的杀菌活性评价
待测试化合物用含有0.1％吐温80的N，N-二甲基甲酰胺(DMF)，配制成100ppm浓度测试药液。采用温室活体盆栽法测定，将试验作物置于喷雾机上进行叶面喷雾处理，药剂处理后的作物放置阴凉处，于24h后接种病原菌孢子，设3次重复，商品化农药腈吡螨酯(Cyenopyrafen)为对照，另设空白对照。接种后的作物置于人工气候室中培养，对以上病害分别培养7d和10d后调查防效，部分化合物对蚕豆单胞锈菌活性测定结果表4所示。
对辣椒疫霉菌(Phytophthora capsici)的杀菌活性评价
待测试化合物用含有0.1％吐温80的N，N-二甲基甲酰胺(DMF)，配制成100ppm浓度测试药液。采用温室活体盆栽法测定，将试验作物置于喷雾机上进行叶面喷雾处理，药剂处理后的作物放置阴凉处，于24h后接种病原菌孢子，设3次重复，设商品化农药腈吡螨酯(Cyenopyrafen)为对照，另设空白对照。接种后的作物置于人工气候室中培养，对以上病害分别培养7d和10d后调查防效，部分化合物对辣椒疫霉菌活性测定结果表4所示。
对腐霉菌(Pythium)的杀菌活性评价
待测试化合物用含有0.1％吐温80的N，N-二甲基甲酰胺(DMF)，配制成100ppm浓度测试药液。采用温室活体盆栽法测定，将试验作物置于喷雾机上进行叶面喷雾处理，药剂处理后的作物放置阴凉处，于24h后接种病原菌孢子，设3次重复，商品化农药腈吡螨酯(Cyenopyrafen)为对照，另设空白对照。接种后的作物置于人工气候室中培养，对以上病害分别培养7d和10d后调查防效，部分化合物对腐霉菌活性测定结果表4所示。
表4 部分化合物100ppm下杀菌活性测定结果
Figure PCTCN2021136159-appb-000078
Figure PCTCN2021136159-appb-000079
Figure PCTCN2021136159-appb-000080
Figure PCTCN2021136159-appb-000081
从上述实验结果可以看出：相较于对照品化合物，本发明化合物具有优异的杀菌活性。例如化合物i-4、i-5、i-6、i-7、i-19、i-24、i-27、i-36、i-37、i-39、i-43、i-51、i-55、i-58、i-67、i-70、i-71、i-83、i-88、i-91、i-102等对蚕豆单胞锈菌、辣椒疫霉菌、腐霉菌表现出良好的防治作用，整体防效优于对照腈吡螨酯。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (13)

  1. 一种式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，
    Figure PCTCN2021136159-appb-100001
    式中，
    R 1选自取代或未取代的下组基团：C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 3-6环烷氧基、C 1-6烷硫基、C 3-6环烷硫基、C 6-C 10芳基、5-10元杂芳基、4-10元杂环基；其中，所述取代是指被一个或多个R a取代；
    R 2、R 3和R 4各自独立地选自取代或未取代的下组基团：氢、C 1-6烷基、C 2-6烯基、C 2-6炔基；其中，所述取代是指被一个或多个R a取代；
    或者，R 2和R 3、R 3和R 4、或R 2和R 4共同形成选自下组的基团：-(CH 2) p-、-(CH 2) o-O-(CH 2) p-O-(CH 2) o-；其中，o独立地为0、1、2、3、或4，p为2、3、4、5、或6；
    R 5选自取代或未取代的下组基团：C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 3-6环烷硫基、R 6和R 7；其中，所述取代是指被一个或多个R a取代；
    R 6为取代或未取代的C 6-14芳基；R 6中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 3-6环烷硫基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
    R 7为未取代或取代的5-14元杂芳基；R 7中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 3-6环烷硫基、-CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9和SO 2NR 8R 9；
    R 8和R 9各自独立选自取代或未取代的下组基团：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基；或者，R 8和R 9与其连接的N原子共同形成取代或未取代的3-6元杂环基；其中，所述取代是指被一个或多个R a取代；
    X各自独立地选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
    Z选自：CR bR c、氧、硫或NR d；
    (CH 2) n中的H可以被R a取代；
    或者Z-(CH 2) n-R 1部分选自取代或未取代的下组基团：C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基；其中，所述取代是指被一个或多个R a取代；
    R b、R c各自独立地选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；
    R d选自下组：氢、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基；
    R a选自下组：氢、卤素、C 1-6烷基、C 1-6烷氧基、卤代C 1-6烷基、卤代C 1-6烷氧基、-CN、-NO 2、氧代基、C 3-6环烷基、3-6元杂环基、-SO 2R 10、-COR 10、-COOR 10、-CONR 10R 11和-SO 2NR 10R 11；其中，R 10、R 11各自独立地选自下组：氢、C 1-6烷基、卤代C 1-6烷基、C 3-6环烷基、3-6元杂环基、C 6-14芳基、5-14元杂芳基；
    m为0、1、2、3或4；n为0、1、2、3或4。
  2. 如权利要求1所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其特征在于，其具有式II或式III所示的结构
    Figure PCTCN2021136159-appb-100002
    式中，X、m、R 1、R 2、R 3、R 4、R 5、Z和n的定义如权利要求1所述。
  3. 如权利要求1所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其特征在于，R 5选自取代或未取代的下组基团：苯基、萘基、噻唑基、噻二唑基、异噻唑基、四唑基、吡啶基、硫代吗啉-S-氧化物、硫代吗啉-S,S-氧化物、嘧啶基、哒嗪基、吡嗪基、三嗪基、噻吩基、噁唑基、噁二唑基、异噁唑基、呋喃基、吡咯基、吡唑基、咪唑基、三唑基；其中，所述的取代是指基团上的氢被选自下组的1-5个基团所取代：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 1-6的烷硫基、C 3-6环烷硫基、CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9、和SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
  4. 如权利要求1所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，特征在于，R 5选自下组：
    Figure PCTCN2021136159-appb-100003
    Figure PCTCN2021136159-appb-100004
    式中，
    g独立地为0、1、2、3、4或5；
    各R'独立地选自下组：卤素、C 1-6烷基、C 2-6烯基、C 2-6炔基、C 3-7环烷基、C 1-6烷氧基、C 1-6烷硫基、C 3-6环烷氧基、C 1-6的烷硫基、C 3-6环烷硫基、CN、NO 2、SO 2R 8、COR 8、COOR 8、CONR 8R 9、和SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
  5. 如权利要求1所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，特征在于，R 5选自下组：
    Figure PCTCN2021136159-appb-100005
  6. 如权利要求1所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其特征在于，(CH 2) n-R 1部分选自取代或未取代的下组基团：H、C 1-6烷基、C 2-4烯基、C 2-4炔基、C 1-6烷硫基、C 1-6烷氧基、3-6元环烷基、C 6-C 10芳基、5-10元杂芳基、4-10元杂环基、(CH 2)R'，R'选自：3-6元环烷基、C 6-C 10芳基、5-10元杂芳基、4-10元杂环基；其中，所述的取代是指被选自下组一个或多的基团取代：C 1-6烷基、C 1-6烷氧基、C 1-6烷硫基、-CN、-NO 2、-SO 2R 8、-COR 8、-COOR 8、-CONR 8R 9和-SO 2NR 8R 9；R 8和R 9各自独立选自下组：氢、C 1-6烷基、C 3-6环烷基、3-6元杂环基。
  7. 如权利要求1所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其特征在于，R 2、R 3和R 4各自独立地选自下组：C 1-6烷基、C 2-4烯基和C 2-4炔基。
  8. 如权利要求1所述的式I化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其特征在于，其具有式i-xvi所示的结构
    Figure PCTCN2021136159-appb-100006
    Figure PCTCN2021136159-appb-100007
    式中，
    R 1、R 2、R 3、R 4、X、m、n、Z的定义如权利要求1所述。
  9. 如权利要求1-8中任一项所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药，其特征在于，R 1、R 2、R 3、R 4、X、m、n、Z具有如表a所示定义
    表a
    Figure PCTCN2021136159-appb-100008
    Figure PCTCN2021136159-appb-100009
    Figure PCTCN2021136159-appb-100010
    Figure PCTCN2021136159-appb-100011
    Figure PCTCN2021136159-appb-100012
    Figure PCTCN2021136159-appb-100013
    Figure PCTCN2021136159-appb-100014
    Figure PCTCN2021136159-appb-100015
    Figure PCTCN2021136159-appb-100016
    Figure PCTCN2021136159-appb-100017
    Figure PCTCN2021136159-appb-100018
    Figure PCTCN2021136159-appb-100019
  10. 一种如权利要求1所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药的制备方法，其特征在于，所述方法包括步骤：
    Figure PCTCN2021136159-appb-100020
    其中，m、n、R 1、R 2、R 3、R 4、R 5、X和Z如权利要求1中定义；
    (s1)在惰性溶剂中，碱存在下，化合物A与化合物B反应，得到式I化合物。
  11. 一种如权利要求1-9中任一项所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药的用途，其特征在于，
    (i)可用于杀灭和/或防治蜱螨目、综合目、直翅目、蜚镰目、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、蚤目和植物寄生线虫中的至少一种害虫和/或其若虫和/或其卵；
    (ii)可用于防治因丝核菌属、孢盘菌属、假霜霉属、单胞锈菌属、层锈菌属、腐霉菌属等侵染造成的炭疽病、叶斑病、锈病、白粉病、纹枯病、叶枯病、灰霉病、白绢病、立枯病、赤霉病、全蚀病和靶斑病中至少一种植物病害；
    (iii)用于制备用于杀灭和/或防治螨类和/或其卵的组合物或制剂；
    (iv)用于杀虫和/或杀菌；和/或
    (v)用于制备用于杀螨和/或杀虫和/或杀菌的组合物或制剂。
  12. 一种组合物，其特征在于，包括(i)作为活性成分的如权利要求1-9中任一项所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药；和(ii)载体和/或表面活性剂。
  13. 一种杀灭螨、虫和/或菌的方法，其特征在于，包括步骤：使螨、虫和/或菌接触有效量的如权利要求1-9中任一项所述的化合物、其几何异构体、立体异构体、或其农药学上可接受的盐或前药或如权利要求12所述的组合物。
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