CN114621280A - Silicon acrylonitrile compound and preparation method and application thereof - Google Patents

Silicon acrylonitrile compound and preparation method and application thereof Download PDF

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CN114621280A
CN114621280A CN202011460379.6A CN202011460379A CN114621280A CN 114621280 A CN114621280 A CN 114621280A CN 202011460379 A CN202011460379 A CN 202011460379A CN 114621280 A CN114621280 A CN 114621280A
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radical
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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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East China University of Science and Technology
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Priority to PCT/CN2021/136159 priority patent/WO2022121907A1/en
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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 System
    • 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 System
    • 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

Abstract

The invention discloses a silicon acrylonitrile compound and a preparation method and application thereof. In particular to a compound shown as a formula I, a composition containing the compound shown as the formula I and application of the compound and the composition. The compounds of the present invention have excellent acaricidal, insecticidal and fungicidal activity.

Description

Silicon acrylonitrile compound and preparation method and application thereof
Technical Field
The invention belongs to the field of agricultural pharmacy, and particularly relates to a silicon acrylonitrile compound and a preparation method and application thereof.
Background
Harmful mites, insects and crop pathogenic bacteria often cause great loss to economic crops such as grains, vegetables, fruits, cotton, ornamental plants and the like, and the prevention and control of the harmful mites, the insects and the crop pathogenic bacteria by utilizing chemical acaricides, insecticides and bactericides is vital to ensuring the safety of the economic crops and improving the living standard of people. As a large country of pesticide, China has huge dosage of chemical acaricide, insecticide and bactericide, has wide market prospect and has vigorous demand for new products. However, with the long-term use of large quantities of harmful mites, insects and pathogenic bacteria, the harmful mites, insects and pathogenic bacteria have already developed serious resistance to the existing agricultural protective agents, and the ecological safety problem of the existing pesticides is increasingly highlighted.
Although acrylonitrile compounds having acaricidal, insecticidal and/or fungicidal activities have been disclosed in the prior art, these compounds have problems of serious structural homogeneity, outstanding resistance to pests and the like, and the research progress of novel acaricides has been slow. Therefore, the temperature of the molten metal is controlled,
in view of the above, there is an urgent need in the art to develop a new class of compounds having excellent insecticidal and acaricidal activity.
Disclosure of Invention
The invention aims to provide a silicon acrylonitrile compound with excellent acaricidal, insecticidal and bactericidal activities, novel structure, excellent effect and less toxic and side effects.
In a first aspect of the invention, there is provided a compound of formula I, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof,
Figure BDA0002831327570000011
in the formula (I), the compound is shown in the specification,
R1selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy, C1-6Alkylthio radical, C3-6Cycloalkylthio radical, C6-C10Aryl, 5-10 membered heteroaryl, 4-10 membered heterocyclyl; wherein said substitution is by one or more RaSubstitution;
R2、R3and R4Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6An alkynyl group; wherein said substitution is by one or more RaSubstitution;
or, R2And R3、R3And R4Or R2And R4Together form a group selected from: - (CH)2)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;
R5selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio radical, R6And R7(ii) a Wherein said substitution is by one or more RaSubstitution;
R6is substituted or unsubstituted C6-14An aryl group; r is6Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
R7Is unsubstituted or substituted 5-14 membered heteroaryl; r7Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio, -CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；
R8And R9Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl; or, R8And R9Taken together with the N atom to which they are attached form a substituted or unsubstituted 3-6 membered heterocyclyl; wherein said substitution is by one or more RaSubstitution;
each X is independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
Z is selected from: CRbRcOxygen, sulfur or NRd；
(CH2)nH in (1) may be substituted by RaSubstitution;
or Z- (CH)2)n-R1The moiety is selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl; wherein said substitution is by one or more RaSubstitution;
Rb、Rceach is independentThe land is selected from the following group: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
RdSelected from the group consisting of: hydrogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6An alkyl group;
Raselected from the group consisting of: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2Oxo, C3-6Cycloalkyl, 3-6 membered heterocyclyl, -SO2R10、-COR10、-COOR10、-CONR10R11and-SO2NR10R11(ii) a Wherein R is10、R11Each independently selected from the group consisting of: hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl;
m is 0, 1, 2, 3 or 4; n is 0, 1, 2, 3 or 4.
In another preferred embodiment, R1Selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy, C1-6Alkylthio radical, C3-6Cycloalkylthio, phenyl, 4-10 membered heterocyclyl.
In another preferred embodiment, R5Selected from the group consisting of substituted or unsubstituted: c6-14Aryl and 5-14 membered heteroaryl, wherein said substitution means that the hydrogen on the group is substituted by 1-5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9(ii) a Wherein R is8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl.
In another preferred embodiment, R7Is 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; r7Wherein said substitution means that the hydrogen on the group is substituted with 1 to 4 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C1-6Alkylthio of, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；R8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl.
In another preferred embodiment, the compound of formula I, its geometric isomer, stereoisomer, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, has the structure shown in formula II or formula III
Figure BDA0002831327570000031
In the formula, X, m, R1、R2、R3、R4、R5Z and n are as defined above.
In another preferred embodiment, the compounds of formula I, their geometric isomers, stereoisomers, or agriculturally and pharmaceutically acceptable salts or prodrugs thereof，R5Selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, 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; wherein said substitution is such that the hydrogen on the group is substituted by 1 to 5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C1-6Alkylthio of, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；R8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl.
In another preferred embodiment, the compound of formula I, a geometric isomer, a stereoisomer, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, R5Selected from the group consisting of:
Figure BDA0002831327570000032
Figure BDA0002831327570000033
in the formula (I), the compound is shown in the specification,
g is independently 0, 1, 2, 3,4 or 5;
each R' is independently selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C1-6Alkylthio of, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；R8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl.
In another preferred embodiment, the compound of formula I, a geometric isomer, a stereoisomer, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, R5Selected from the group consisting of:
Figure BDA0002831327570000041
in another preferred embodiment, the compound of formula I, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, (CH)2)n-R1The moiety is selected from the group consisting of substituted or unsubstituted: H. c1-6Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-6Alkylthio radical, C1-6Alkoxy, 3-6 membered cycloalkyl, C6-C10Aryl, 5-10 membered heteroaryl, 4-10 membered heterocyclyl, (CH)2) R ', R' is selected from: 3-6 membered cycloalkyl, C6-C10Aryl, 5-10 membered heteroaryl, 4-10 membered heterocyclyl; wherein said substitution is by one or more groups selected from the group consisting of: c1-6Alkyl radical, C1-6Alkoxy radical, C1-6Alkylthio, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；R8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl.
In another preferred embodiment, the compound of formula I, a geometric isomer, a stereoisomer, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, R2、R3And R4Each independently selected from the group consisting of: c1-6Alkyl radical, C2-4Alkenyl and C2-4Alkynyl.
In another preferred embodiment, the compound of formula I, a geometric isomer, a stereoisomer, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, has the structure shown in formulas I-xvi
Figure BDA0002831327570000051
Figure BDA0002831327570000061
In the formula (I), the compound is shown in the specification,
R1、R2、R3、R4x, m, n, Z are as defined above.
In another preferred embodiment, the compound of formula i-xvi, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, R1、R2、R3、R4X, m, n, Z have the definitions shown in Table a
TABLE a
Figure BDA0002831327570000062
Figure BDA0002831327570000071
Figure BDA0002831327570000081
Figure BDA0002831327570000091
Figure BDA0002831327570000101
Figure BDA0002831327570000111
Figure BDA0002831327570000121
Figure BDA0002831327570000131
Figure BDA0002831327570000141
Figure BDA0002831327570000151
Figure BDA0002831327570000161
Figure BDA0002831327570000171
In another preferred embodiment, the compound is selected from the compounds shown in the examples.
In a second aspect of the present invention, there is provided a process for the preparation of a compound of the first aspect, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, said process comprising the steps of:
Figure BDA0002831327570000172
wherein, m, n, R1、R2、R3、R4、R5X and Z are as defined above;
(s1) reacting compound A with compound B in an inert solvent in the presence of a base to give the compound of formula I.
In another preferred embodiment, the process for preparing the compound of formula I further comprises the steps of:
Figure BDA0002831327570000181
wherein, m, n, R1、R2、R3、R4、R5And X is as defined above;
(s0) reacting compound C with compound D in an inert solvent in the presence of a catalyst to obtain compound A.
In another preferred embodiment, step (s1) is: reacting a compound of formula a and a compound of formula B in a solvent (preferably selected from benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1, 4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethylsulfoxide, or a combination thereof) in the presence of a base (preferably selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or a combination thereof) at 0-25 ℃ or 0 ℃ to reflux temperature to obtain a compound of formula I.
In another preferred embodiment, step (ii) (i.e., the reaction shown in equation 2) is: reacting a compound of formula C with a compound of formula D in the presence of a base (preferably, the base is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or combinations thereof) at 0-25 ℃ or 0 ℃ to reflux temperature 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, dimethylsulfoxide, or combinations thereof) to obtain a compound of formula a.
In a third aspect of the invention, there is provided a use of a compound according to the first aspect, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof,
(i) useful for killing and/or controlling at least one pest from the orders Acarina, Symphenoptera, Orthoptera, Blattaria, Isoptera, Anoploptera, Thysanoptera, Heteroptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and plant parasitic nematodes and/or their nymphs and/or their eggs;
(ii) can be used for preventing and treating at least one plant disease of anthracnose, leaf spot, rust disease, powdery mildew, banded sclerotial blight, leaf blight, gray mold, southern blight, damping off, gibberellic disease, full rot and target spot caused by infection of rhizoctonia, sclerotinia, pseudoperonospora, monascus, phaeophyceae, pythium and the like;
(iii) for the preparation of a composition or formulation for killing and/or controlling mites and/or their eggs;
(iv) for insecticidal and/or bactericidal use; and/or
(v) For the production of compositions or preparations for acaricidal and/or insecticidal and/or fungicidal use.
In another preferred embodiment, the compounds of the formula I are used for combating and/or controlling mites and/or for preparing compositions or preparations for combating pests and/or killing bacteria.
In another preferred embodiment, the compounds of the formula I are used for combating and/or controlling harmful acarids and/or their eggs in agriculture, in pastures, on lawns and/or indoors.
In another preferred embodiment, the compounds of the formula I are used for combating and/or controlling pests and/or bacteria in agriculture, in pastures, on lawns and/or indoors.
In another preferred embodiment, the mites are harmful mites.
In another preferred embodiment, the mites are selected from the group consisting of: tetranychus urticae (Tetranychus urticae Koch), Tetranychus urticae (Tetranychus viennensis Zacher), Tetranychus truncatus (Tetranychus truncatus Ehara), Tetranychus cinnabarinus (Tetranychus cinnabarinus Boisdruval), Panonychus ulmi (Panychus ulmi Koch), Panonychus citri (Panychus citri McGregor), Carex orchidus (Bryobia rubrus Scheuten), Trionycis tritici (Petrobia latifolia Muller), Tetranychus brachypus (Oligonchus uneguensis Jacobius), Brevibacterium ovatus (Brevitus ovatus Donnadei), and Brevibacterium flavus (B. leii McGregor), oriental peach blossom mites (Tenuipipus taonicas Ma et Yuan), Diospyros kaki Thunb (Tenuipipus zhizhizhi huas Viliae Reck), vitis vinifera Hemsl (C. vitas Pagentecher), Steinwedeli Keifer (A. stepwedeli Keifer), Lycium chinense Purpus (A. macroodonis Keifer), Pyricularia pyrifolia (Eriophenous pyrus Pagent), Ruscus aculeatus (Epitrimerus pirifolia Keifer), Tarsonemus laterosomus (Polyphalaovorus lateus Linnaeus Banks), Tridax merus (Penthanus major Duges), and Rhizopyrus taro (Rhizogylus calcoactus caerutemens).
In another preferred embodiment, the pests are selected from: white pine (Scutigerella immaculata), cricket (Acheta domestica), Gryllotalpa (Gryllotalpa sp.), African migratory locust (Locusta inigera), Black locust (Melanoplus spp.), desert locust (Schistocher cagregaria), oriental cockroach (Blatta orientalis), American cockroach (Periplaneta), Florida (Leucopia amadorae), German cockroach (Blattella gernanica), Anthrix (Reticuloruliginis spp.), Pediculus humanus (Pediculus hunculus), Haematophagus (Haematophagus spp.), Phthirius (Linognatus spp.), Phthirius (Trichophyton trichia, Triplophyta (Trichophyton), Triplophyta (Trichophyton trichopterus), Triplophyta (Trichophyton trichopteris), Triplophyta (Trichophyton trichophyta), Thraustria spp), Thrombus (Trichophyton trichophyta), Thraustria spp (Trichophyton trichophyta), Trichophyton trichophyta (Trichophyton, Thraustria spp), Thraustria spp (Trichophyton trichophyta), Periplus spp), Periplaneta (Trichophyta trichophyta (Herpyris), Periplaneta (Herpyris), Periplaneta (Herpyris (Hericium spp), Periplaneta (Hericium falciparum spp), Periplaneta (Hericium falcatus spp), Periplaneta (Hericium falcatum spp), Periplum falcatum spp (Hericium spp), Periplum falcatum spp (Hericium falcatum spp), Periplum spp (Hericium falcatum spp (Thunbergii (Hericium spp), Periplum spp (Hericium spp), Periplum falcatum spp (Hericium spp), Periplum spp (Thunberg (Hericium spp), Periplum spp (Frankinium spp), Periplum spp (Hericium spp), Periplum spp (Thunbergii (Frankinium spp), Periplum spp (Frankinium spp), Periplum falcatum spp), Periple (Hericium spp (Herpyritum (Hericium spp), Periple (Herpyritum (Thunberg (Herpyri (Hericium spp), Periple (Herpyritum (Herpyri (Thunberg (Herpyri) and Periplum spp), Haplophorum spp), Periplum spp), Periple (Mipalum spp), Periplum spp), Periple (Herpyri (Haplophorum spp), Periplum spp), Periple (Herpyri (Herpyritum (Herpyri, Whitefly (Aleurodeses brasticae), powdered tobacco (Beirisia tabaci), Trialeurodes grisea (Trialeurodes vaporariorum), Aphis gossypii (Aphis gossypii), Aphis brassicae (Brevicornus brassiccus), Aphis virginiana (Cryptomyces striatus), Aphis nigricans (Aphis fabae), Aphis citrina (Aphis flavus), Aphis pomorum (Eriosoma lanigerum), Aphis metformis (Hyalophorus grandiflorus), Aphis viticola (Phyllotreta), Aphis gossypii (Perothrix), Aphis graminicola (Phyllocerulosa), Aphis gramineus (Phyllocerulosa), Phyllocerulosa viridiplus viridans (Pholiota), Phyllocercus nigra, Phyllocerulosa viridans (Pholiota), Phyllocercus carotovorax (Pholiota), Phyllocerus spp), Phyllocercospora (Pholiota), Phyllocercospora viridae (Leporus), Phyllocerotis spp), Phyllochavicia viridae (Leporus spp), Phyllochaetes spp), Phyllochavicia viride (Leporus spp), Phyllochavicia spp (Leporus spp), Phyllochavicia spp (Pyrus spp), Phyllochavicia spp (Pholiota), Phyllochavicia spp (Leporus spp (Pyrus spp), Phyllochavicia spp (Nephophora, Phyllochavicia spp), and Myospiriella spp (Nephophora spp), Phyllochavicia spp) Red bell wheat moth (Petrophora gossypiella), looper (Bupalus piniarius), winter striped moth (Cheirnathia braunia), apple moth (Lithocolletis blancardella), apple moth (Hypomelia padella), cabbage moth (Plutella xylostella), yellow brown tenella ((Malacola neostia), yellow moth (Euproctitis chrysomyrea), moth (Lyinantia spp.), cotton sneaker (Bucclusix thyteriella), orange sneaker (Phycrythris ostreatus), cutworm (Eudragia sp.), Spoloptera Spodoptera, Spodoptera, Spodoptera (Spodoptera), Spodoptera frugiperda (Spodoptera), Spodoptera) Spodoptera (Spodoptera), Spodoptera (Spodoptera), Spodoptera (Spodoptera) Spodoptera, Spodoptera (Spodoptera) Spodoptera, Spodoptera (Spodoptera, Spodoptera (Spodoptera) and Spodoptera) Spodoptera (Spodoptera, Spodoptera (Spodoptera) and Spodoptera) Spodoptera (Spodoptera) Spodoptera, Spodoptera (Spodoptera) Spodoptera, Spodoptera (Spodoptera) of Spodoptera, Spodopter, Corn borer (Pyrausta nubilalis), mediterranean meal borer (Ephestia kuehniella), pyralida (Galleria mellonella), avenae sinensis (Tineola bisselella), Botrytis cinerea (Tineola pellionella), Botrytis cinerea (Men pellionella), Bombycis fulva (Hofrna nigrospora septemella), Sphaeria linonella (Cacoecia podana), Sphaeria punctata (Choristoneura fulica), Botrytis cinerea (Clysidia albuginella), Sphaeria virescens (Homona rnana), Pieris virescens (Todara virida), Philasia punctifera (Cnaphalocrocis), Photinus pyralis (Cnaphalocrocis niponensis), Sphaeria serotina (Photinus), Sphaemaphila palea (Photinus), Sphaemaphila (Pieris terrestris indica), Sphaemaphila (Pieris), Piper falva (Piper) and Sphaemaphysalis (Piper, Sphaemaphysalis), Sphaemaphila (Piper spp), Sphaemaphysalis (Photinus sp) Goodynia mangostana (Oryzaphidia suta), Ceratophylla spp (Anthonomus spp.), Rhynchophylla (Sitophilus spp.), Aleuryphylus nigratus (Oclernchus Sulcatus), Scyphylla sativa (Cosinopoloides sondus sordidus), Ceratophylla brassicae (Ceratophyllus assiliensis), Ceratophyllus purpureus (Hypera pottica), Sclerotis (Desmesspps spp.), Rhynchophorus maculatus (Trogopterus spp.), Rhynchophorus orbiculatus ((Anthronus spp.), bark beetle pis (Atlantana spp.), Ceratopterus (Atgenophycus spp.), Ceratophyllus (Lyctus spp.), Ceratophyllum spicatula (Meyloides), Ceratophyllopodium purpurea spica (Melothuropterocarpus spp.), Melothria spp.), Melothrix (Melothrix spp.), Melothrix Spiropsis spp.), Melothrix (Melothrix spp.), Melothrix Spirosporum (Melothrix spp.), Melothrix spp (Melothrix spp.), Melothrix spp. (Melothrix spp.), or Melothrix spp (Melothrix spp.), Melothrix spp (Melothrix spp.), Melothrix spp (Melothrix spp), Melothrix spp. sp. sp.sp. sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.P (Melothrix), Melothrix spp.), and Melothrix spp.), or Melothrix spp. (Melothrix spp.), Melothrix spp. (Melothrix spp.), or Melothrix spp. sp.sp.sp.sp.albus (Melothrix spp.), or Melothrix spp. sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.sp.T.sp.sp.sp.sp.sp.sp.sp.sp.sp., The genus Trichophyton ((Dipnion spp.), Ceratoptera (Hoplocpap spp.), the genus Trichophyton (Lasius spp.), the genus Microptera (Monononium pharaonis), the genus Vespa (Vespa spp.), the genus Aedes (Aedes spp.), the genus Anopheles (Anopheles spp.), the genus Culex (Culex spp.), the genus Drosophila melanogaster (Drosophila melanogaster), the genus Musca spp.), the genus Fannia spp, the genus Rhododendron virginalis (Callica), the genus Lucilia (Lucilia spp.), the genus Chrysomyzilla (Chrysomyia spp.), the genus Flabellosa (Cuebra spp.), the genus Gastrophania (Phymatopsis spp.), the genus Paralichia (Ostreta), the genus Paralichia (Phormidis), the genus Paralichia spp.), the genus Paralichia (Ostrex spp.), the genus Ostreta (Ostrematophagia spp.), the genus Paralichia (Phormidis), the genus Paralichia spp.), the genus Ostrex spp.), the genus Chrysomyia (Ostrematodinia spp.), the genus Chrysomyia (Ostrex spp.), the genus Paralichia spp.), the genus Ostrematodinia (Pholidocarpa, the genus Paralichia (Pholidae (Phormidis), the genus Ostrex spp.), the genus Paralichia spp.), the genus Paralichia (Phormidis), the genus Paralichia (Pilatus spp.), the genus Paralichia (Pikeramis (Pilatus (Pikeramis (Pilatus spp.), the genus Pikeramis (Pilatus (Pilat) and the genus, the genus Pikeramis (Pilat) of the genus, the genus of the genus Pikeramis (Pikeramis), the genus Pikeramis (Pikermasia (Pikeramis) of the genus Pikeramis (Pikeramis), the genus Pikeramis (Pikeramis), the genus Pilat), the genus Pikeramis (Pilatus (Pikeramis), the genus Pikeramis (Pikeramis), the genus Pikersfor the genus Pikeramis), the genus Pikeramis (Pikeramis) of the genus Pikeramis (Pikersfor the genus, the genus Pikeramis), the genus Pikersfor the genus Pikeramis (Pilat) of the genus Pilat), the genus Pikeramis (Pikersf, The species bactrocera olivaceus (Dacus oleae), the species aedes europe (Tipula paludosa), the genus melanophora (hylemia spp.), the species bactrocera maculata (Liriotnyza spp.), the species xenorhabdus volvatus (Xenopsylla cheopis), the species ceratophus (Ceratophyllus spp.), the species Pratylenchus spp, the species nematodiasis (Radopholus spp.), the species setaria ciliata (Ditylenchus difolia, Ditylenchus semipenetrans), the species xenorhabdus (tylenchus spp.), the species Heterodera (Heterodera spp.), the species Heterodera globosa (Globodera spp.), the species Meloidogyne spp.), the species setaria spp (melodiophora spp.), the species carotojejunipes spp, the species carotovorax spp (trichoderma spp.), the species nematodia (trichoderma spp.), the species trichoderma spp.).
In another preferred embodiment, examples of the plant having the plant disease include soybean, corn, wheat, melon, rice, strawberry, peanut, cotton; examples of the plant diseases include soybean rust, corn rust, wheat powdery mildew, melon powdery mildew, rice sheath blight, wheat sharp eyespot, strawberry gray mold, peanut southern blight, cotton rhizoctonia rot, wheat scab, wheat take all and cucumber target spot, wherein the melon powdery mildew includes cucumber powdery mildew and the like; the pathogenic bacteria include Phakopsora pachyrhizi (Phakopsora pachyrhizi system.), Puccinia zeae (Puccinia sorghi Schw), Erysiphe necator (Blumeria graminis), Erysiphe cucurbitaceae (Erysiphe cucurbita), Erysiphe cucurbitae (Sphaerotheca cucurbitae), dermataceae (thanatephora cuscutaris), rhizoctonia graminis (rhizoctonia solani), and rhizoctonia solani (rhizoctonia solani), Botrytis cinerea (Botrytis cinerea per), Fusarium graminearum (Fusarium graminearum Schw.), Fusarium avenae (Fusarium avenaceum), moniliforme (Fusarium moniliforme), pythomonas oryzae (phomophilus), Pythium purpurea (phoma niponicum). Preferably the plant disease is caused by rust pseudomonas fabae, phytophthora capsici, pythium and the like.
In a fourth aspect of the present invention, there is provided a composition comprising (i) as active ingredient a compound according to the first aspect, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof; and (ii) a carrier and/or surfactant.
In another preferred embodiment, the compound is present in the composition in an amount of 0.001 to 99.999 wt%.
In another preferred embodiment, the composition is a pesticide composition; preferably, the composition is a miticidal composition, an insecticidal composition and a bactericidal composition.
In a fifth aspect of the present invention, there is provided a method of killing mites, insects and/or bacteria, comprising the steps of: contacting the mites, insects and/or bacteria with an effective amount of a compound as described in the first aspect, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof or a composition as described in the fourth aspect.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
Is free of
Detailed Description
The inventors have extensively and intensively studied and unexpectedly found a class of silicon-containing acrylonitrile-based compounds (represented by formula I) having a novel structure, which have excellent acaricidal and/or insecticidal and/or fungicidal activities. Based on this, the inventors have completed the present invention.
Term(s) for
As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.
Unless otherwise defined, the term "alkyl" by itself or as part of another substituent refers to a straight or branched chain hydrocarbon radical having the indicated number of carbon atoms (i.e., C)1-6Representing 1-6 carbons). Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, and the like.
Unless otherwise indicated, the term "alkenyl" refers to an unsaturated alkyl group having one or more double bonds. Similarly, the term "alkynyl" refers to an unsaturated alkyl group having one or more triple bonds. Examples of such unsaturated alkyl groups include ethenyl, 2-propenyl, crotyl, 2-isopentenyl, 2- (butadienyl), 2, 4-pentadienyl, 3- (1, 4-pentadienyl), ethynyl, 1-and 3-propynyl, 3-butynyl, and higher homologs and isomers.
Unless otherwise defined, the term "cycloalkyl" refers to a ring having the indicated number of ring atoms (e.g., C)3-6Cycloalkyl) saturated or unsaturated cyclic hydrocarbon groups. Examples of such cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, and the like.
Unless otherwise indicated, the term "aryl" denotes a polyunsaturated (usually aromatic) hydrocarbon group which may be a single ring or multiple rings (up to three rings) which are fused together or linked covalently. Examples of aryl groups include: a phenyl group.
Unless otherwise defined, the term "heterocycloalkyl" or "heterocyclyl" 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. The heterocycloalkyl group can be a monocyclic, bicyclic, or polycyclic ring system. Non-limiting examples of heterocycloalkyl groups include pyrrolidine, imidazolidine, pyrazolidine, butyrolactam, valerolactam, imidazolidinone, hydantoin, dioxolane, phthalimide, piperidine, 1, 4-dioxane, morpholine, thiomorpholine-S-oxide, thiomorpholine-S, S-oxide, piperazine, pyran, pyridone, 3-pyrroline, thiopyran, pyrone, tetrahydrofuran, tetrahydrothiophene, quinuclidine, and the like. The heterocycloalkyl group can be attached to the rest of the molecule via a ring carbon or a heteroatom. By terms such as 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.
Unless otherwise defined, the term "heteroaryl" refers to an aryl (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 atoms are optionally quaternized. The heteroaryl group may be attached to the rest of the molecule through a heteroatom. Non-limiting examples of heteroaryl groups include pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, benzotriazinyl (benzotriazinyl), purinyl, benzimidazolyl, benzpyrazolyl, benzotriazolyl, benzisoxazolyl, isobenzofuranyl, isoindolyl, indolizinyl, benzotriazinyl, thienopyridyl, thienopyrimidinyl, pyrazolopyrimidyl, imidazopyridine, benzothiazolyl, benzofuranyl, benzothienyl, indolyl, quinolinyl, isoquinolinyl, isothiazolyl, pyrazolyl, indazolyl, pteridinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiadiazolyl, pyrrolyl, thiazolyl, furanyl, thienyl, and the like.
As used herein, the term "heteroatom" is meant to include oxygen (O), nitrogen (N), sulfur (S), and silicon (Si).
For the compounds provided herein, a bond from a substituent (typically an R group) to the center of an aromatic ring (e.g., benzene, pyridine, etc.) will be understood to refer to a bond that provides attachment at any available vertex of the aromatic ring. In some embodiments, the description also includes a link on a ring fused to the aromatic ring. For example, 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 portion of the indole.
As used herein, the terms "comprising," "including," or "including" mean that the various ingredients may be used together in a mixture or composition of the invention. Thus, the terms "consisting essentially of and" consisting of are encompassed by the term "comprising.
Unless otherwise specified, the compounds of formula I of the present invention include geometric isomers (Z and E represent different configurations, respectively) that may be formed due to the attachment of different substituents to a carbon-carbon double bond or a carbon-nitrogen double bond, and the present invention includes Z-type and E-type isomers and mixtures thereof in any proportion. The compound shown in the formula I comprises stereoisomers (R and S respectively represent different configurations) which can be formed by connecting different substituents on a carbon-nitrogen atom, and the invention comprises R-type isomers, S-type isomers and mixtures thereof in any proportion. The compound shown in the formula I of the invention not only comprises geometric isomers (Z/E formula) and stereoisomers (R/S formula), but also comprises a mixture of the geometric isomers and the stereoisomers in any proportion.
As used herein, "effective amount" refers to: the amount of the compound is enough to produce the effect of killing mites, insects and bacteria without causing serious negative effects.
As used herein, for example, "1 to 5" means 1, 2, 3,4, or 5, and "1-10" means 1, 2, 3,4, 5, 6, 7, 8, 9, or 10.
Silicon-containing acrylonitrile compound
As used herein, the term compound of the present invention refers to a class of silacrylonitrile compounds represented by formula I, which term also includes geometric isomers, or stereoisomers thereof, or salts, or mixtures of isomers thereof.
Specifically, the invention provides a silicon acrylonitrile compound shown in a formula I,
Figure BDA0002831327570000231
in the formula I, R1、R2、R3、R4、R5Z, n, X and m are as defined above.
Preferably, the compound has a structure represented by formula II or formula III
Figure BDA0002831327570000232
X、m、R1、R2、R3、R4、R5Z and n are as defined above.
Preferably, in the formulae I-III, R5Selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, 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; wherein said substitution is such that the hydrogen on the group is substituted by 1 to 5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radicals、C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C1-6Alkylthio of, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；R8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl.
Preferably, in the formulae I to III, Z- (CH)2)n-R1The moiety is selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl, C1-6Alkyl O-, C3-6Cycloalkyl O-, 3-6 membered heterocyclyl O-, C6-14Aryl O-, 5-14 membered heteroaryl O-, C1-6Alkyl radical S-, C3-6Cycloalkyl S-, 3-6 membered heterocyclyl S-, C6-14Aryl S-, 5-14 membered heteroaryl S-, NR8R9；
Wherein R is8And R9Is as defined above.
Preferably, in the formulae I-III, R2、R3And R4Each independently selected from the group consisting of: c1-6Alkyl radical, C2-4Alkenyl and C2-4Alkynyl.
Preferably, in the formulae I-III, R1Selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy, C1-6Alkylthio radical, C3-6Cycloalkylthio, phenyl, 4-to 10-membered heterocyclyl.
Preferably, in formula I, R1Selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy, C1-6Alkylthio radical, C3-6Cycloalkylthio, phenyl;
n is 0, 1, 2 or 3;
R2、R3and R4Each independently selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6An alkynyl group;
or, R2And R3、R3And R4Or R2And R4Together form- (CH)2)p-a group of (a); wherein p is 2, 3,4, 5, or 6;
R5selected from the group consisting of: r6And R7；
R6Is substituted or unsubstituted phenyl; r6Wherein said substitution means that the hydrogen on the group is substituted by 1, 2 or 3 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C1-6Alkoxy, CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
R7Is an unsubstituted or substituted radical selected from the group consisting of: thiazolyl, pyridyl, thiomorpholine-S-oxide, thiomorpholine-S, S-oxide, pyridazinyl, pyrazinyl, thienyl, furyl, pyrrolyl, pyrazolyl; r7Wherein said substitution means that the hydrogen on the group is substituted by 1, 2, 3 or 4 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C1-6Alkoxy, CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
Wherein R is8And R9Each independently selected from: hydrogen, C1-6An alkyl group;
each X is independently selected from the group consisting of: hydrogen, halogen, C1-6An alkyl group;
m is 1 or 2;
z is selected from: CRbRcOxygen, sulfur or NRd；
Or Z- (CH)2)n-R1The moiety is selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl、C6-14Aryl, 5-14 membered heteroaryl, C1-6Alkyl O-, C3-6Cycloalkyl O-, 3-6 membered heterocyclyl O-, C6-14Aryl O-, 5-14 membered heteroaryl O-, C1-6Alkyl radical S-, C3-6Cycloalkyl S-, 3-6 membered heterocyclyl S-, C6-14Aryl S-, 5-14 membered heteroaryl S-, NR8R9；
Rb、RcEach independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
RdSelected from the group consisting of: hydrogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6An alkyl group;
and R is1、R2、R3、R4、R5、R6、R7、R8、R9And one or more hydrogen atoms in the group X may also each independently be substituted with a substituent selected from the group consisting of: halogen, C1-3Alkyl group of (1).
Preferably, in formula I, R1Selected from the group consisting of: c1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C3-6Alkoxy radical, C3-6Cycloalkoxy, C1-6Alkylthio radical, C3-6Cycloalkylthio, phenyl;
n is 0, 1 or 2;
R2、R3and R4Each independently selected from the group consisting of: c1-6Alkyl radical, C2-4Alkenyl and C2-4Alkynyl;
-SiR2R3R4the substitution site of (b) is 3-or 4-position;
R5is 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-pyrazolyl1-methyl-3-trifluoromethyl-4-pyrazolyl, 1-ethyl-3-methyl-5-pyrazolyl, 2-methyl-4-trifluoromethyl-5-thiazolyl, 2-chloro-3-pyridyl, 1,3, 5-trimethylpyrazol-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 C1-6An alkyl group;
m is 1 or 2;
z is selected from: CRbRcOxygen, sulfur or NRd；
Or Z- (CH)2)n-R1The moiety is selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl, C1-6Alkyl O-, C3-6Cycloalkyl O-, 3-6 membered heterocyclyl O-, C6-14Aryl O-, 5-14 membered heteroaryl O-, C1-6Alkyl radical S-, C3-6Cycloalkyl S-, 3-6 membered heterocyclyl S-, C6-14Aryl S-, 5-14 membered heteroaryl S-, NR8R9；
Rb、RcEach independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
RdSelected from the group consisting of: hydrogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6An alkyl group;
R8and R9Each independently selected from: hydrogen, C1-6An alkyl group;
and R is1、R2、R3、R4、R5、R6、R7、R8、R9And one or more hydrogen atoms in the group X may also each independently be substituted with a substituent selected from the group consisting of: halogen, C1-3Alkyl group of (1).
Preferably, the compound of formula I has a structure represented by formula I-xvi
Figure BDA0002831327570000261
Figure BDA0002831327570000271
In the formula (I), the compound is shown in the specification,
R1、R2、R3、R4x, m, n, Z are as defined above.
Preferably, in the compounds of formula i-xvi, R1、R2、R3、R4X, m, n, Z are as defined in Table a
TABLE a
Figure BDA0002831327570000272
Figure BDA0002831327570000281
Figure BDA0002831327570000291
Figure BDA0002831327570000301
Figure BDA0002831327570000311
Figure BDA0002831327570000321
Figure BDA0002831327570000331
Figure BDA0002831327570000341
Figure BDA0002831327570000351
Figure BDA0002831327570000361
Figure BDA0002831327570000371
Figure BDA0002831327570000381
Process for the preparation of the compounds of the invention
The process for the preparation of the compounds of formula I according to the invention is described in more detail below, but these particular processes do not constitute any limitation of the invention. The compounds of the present invention may also be conveniently prepared by optionally combining various synthetic methods described in the present specification or known in the art, and such combinations may be readily carried out by those skilled in the art to which the present invention pertains.
The present invention also provides a general process for the preparation of a compound according to the first aspect, i.e. a compound of formula I.
Preferably, the method comprises the steps of:
Figure BDA0002831327570000382
wherein, m, n, R1、R2、R3、R4、R5X and Z are as described above;
(s1) reacting compound A with compound B in an inert solvent in the presence of a base to give the compound of formula I.
In another preferred embodiment, the process for preparing the compound of formula I further comprises the steps of:
Figure BDA0002831327570000391
wherein, m, n, R1、R2、R3、R4、R5And X is as defined above;
(s0) reacting compound C with compound D in an inert solvent in the presence of a catalyst to obtain compound A.
In another preferred embodiment, step (s1) is: reacting a compound of formula a and a compound of formula B in a solvent (preferably selected from benzene, toluene, ethyl acetate, acetonitrile, dichloromethane, dichloroethane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1, 4-dioxane, PEG400, n-heptane, n-hexane, cyclohexane, petroleum ether, dimethylformamide, dimethylsulfoxide, or a combination thereof) in the presence of a base (preferably selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or a combination thereof) at 0-25 ℃ or 0 ℃ to reflux temperature to obtain a compound of formula I.
In another preferred embodiment, step (ii) (i.e., the reaction shown in equation 2) is: reacting a compound of formula C with a compound of formula D in the presence of a base (preferably, the base is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, triethylamine, dimethylaminopyridine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, diisopropylethylamine, pyridine, or combinations thereof) at 0-25 ℃ or 0 ℃ to reflux temperature 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, dimethylsulfoxide, or combinations thereof) to obtain a compound of formula a.
Combinations comprising the Compounds of the invention and uses of the Compounds of the invention and compositions thereof
The invention also provides a compound shown in the formula I or an agricultural composition containing the silicon acrylonitrile compound shown in the formula I and application thereof.
The silacrylonitrile compound represented by formula I of the present invention shows excellent mite-controlling activity against various pests in agriculture or other fields, particularly spider mites (Arachnida) order (Acarina) mites, such as Tetranychus urticae (Koch), Tetranychus urticae (Zanthopanax vinensis Zacher), Tetranychus truncatus (Tetranychus truncatus Ehara), Tetranychus cinnabarinus (Boisdduval), Tetranychus apple (Panychus ulmi Koch), Tetranychus citrullus (Panychus citri McGregor), Bryomyces bryoides (Bryobia rubrus Scheutenu) Deutus (Bryoides), Triphytes tritici (Petrobius ovatus), Tetranyensis (Tyrophus ovatus), Tetranychii (Tyrophus ovatus), Tetranychus ovatus (Tyrophus ovatus), Tetranychus urticae (Tyrophus ovatus), Lycium chinense (Tyrophus chinensis) Gray, Lycium chinense (Tyropoides), Lycium chinense (Tyrophus chinensis) Gray, et Rust pyricularis (Epitrimerus pirifolia Keifer), Tarsonemus laterospinus (Polygonatum latus Banks), Dermatophagoides meretrix (Penthaleus major Duges), Rhizopus tararicus (Rhizoglyhus calluses Oudemans), and the like. "mite control" means that the mite has acaricidal activity at each stage (egg, larva, adult) of the mite's life cycle. Therefore, the technical scheme of the invention also comprises the application of the silicon acrylonitrile compound shown in the formula I as an acaricide in agriculture or other fields.
The silacrylonitrile compounds of formula I of the present invention are also suitable for controlling at least one pest of the general, orthoptera, blattaria, isoptera, phthiraptera, thysanoptera, heteroptera, homoptera, lepidoptera, coleoptera, hymenoptera, diptera, siphonaptera, and plant parasitic nematodes in agriculture or other fields.
The synthetic order (Syrnphyla) is, for example, white pine moth (Scutigerella immaculate) or the like.
The order Orthoptera (Orthoptera), for example, cricket-tree (Acheta domesticus), mole cricket genus (Gryllotalpa spp.), African migratory locust (Locusta migratoria), black locust (Melanoplus spp.), desert locust (Schistocer cagregaria), and the like;
the Blattaria (Blattaria), for example, Oriental Blatta (Blatta orientalis), American Blatta (Periplanet aainecana), Florida Blatta (Leucophae amaderae), German Blatta (Blattella gernanica), and the like.
The Isoptera (Isoptera), for example, Reticulitermes spp.
From the order of the Anoplura (Phthiraptera), for example, Pediculus humanus (Pediculus humanus corpporus), Hematophthirus (Haematopinus spp.), Phthirius spp (Linoganathus spp.), Phthirius spp (Trichodectenes spp.), Phthirius spp., and the like are mentioned.
From the order of the Thysanoptera (Thysanoptera), for example, Thrips palmi (Hercinothrips pernoralis), Thrips tabaci (Thrips tabaci), Thrips palmi (Thrips palmi), Thrips occidentalis (Frankliniella occidentalis), etc.
The Heteroptera (Heteroptera), for example, Douglas bugs (Eurygaster spp.), Meristus intermedia (Dysdercus internus), Piriscus quadratus (Piesna quadrata), Cimicifuga fascicularis (Cimexicanus), Primatus rudis (Rhodnius prolixus), Primatus rudis (Triatoma spp.), and the like.
From the order of the Hoinoptera (Hoinoptera), for example, whitefly (Aleurodes brassicae), tobacco powder (Beinisia tabaci), whitefly (Trialeurodes vaporariorum), cotton aphid (Aphis gossypii), cabbage aphid (Brevicyne brassiccus), Cryptophycus aurantiaca (Cryptomyces rius), Aphis nigricans (Aphis fabae), Aphis citricola (Aphis pygium), Aphis citricola (Aphis punctiferum), Aphis woolla (Eriosoma lanigerum), cercospora mume (Hyalophorus arundinis), Rhizopus vitis (Phyllophora botrys), Aphis graminearum (Phyllostachys), Aphis leptosporum (Perphugineus spp.), Aphis gramineus (Phyllospora), Aphis gramineus (Phyllocerulophycus), Phytophaga canus, Phytophilus viridula (Phyllophora), Phytophus nilotica (Phytophus nilotica), Phytopsis (Phytophus niloti ludina), Phytopsis (Phytopsis), Phytopsis (Phytophaga ludinaria), Phytopsis (Phytophaga), Phytophaga peregrina), Phytophilus (Phytophaga), Phytophaga peregrina), Phytophaga (Leporella viridotus (Leporus), Phytophaga), Phytophagi (Leporus spp), Phytophaga (Leporus spp), Phytophagi), Phytophaga (Leporella viridotus spp), Phytophaga (Leporus spp), Phytophagi), Phytophaga (Leporus spp) Pediculosis species (Psylla spp.) and the like.
The Lepidoptera (Lepidoptera), for example, Henochloropsis (Pectinophora gossypiella), Trichoplusia (Bupalus piniarius), Dipper cutworm (Cheirnathia braurita), Spirocha (Lithocolletia blanca), apple armyworm (Hypomeuta padelila), Plutella xylostella (Plutella xylostella), Trichoplusia fusca ((Malaconia neosteria), yellow moth (Euproctis chrysospora), Spodoptera (Lyinanria spp.), cotton snezoea (Bucculus thyridularia), orange snezoea (Phyllanthus reticulata), Sporidia (Sporidia spp.), Sporidia (Sporidia) and Sporidia (Sporidia spp.), Sporidia (Sporidia) Sporidia (Sporidia) and Sporidia (Sporidia) Sporidia (Sporidia), Sporidia (Sporidia), Sporidia (Sporidia) and Sporidia (Sporidia) Sporidia (Sporidia) Sporidia (Sporidia) Sporidia (Sporidia) or Sporidia (Sporidia) including Sporidia) and Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia) of Sporidia (Sporidia, The species Cnaphalocrocis (Chilo spp.), Cnaphalocrocis medinalis (Pyrausta nubilalis), Diatraea medinalis (Ephemeta kuehniella), Ceramia furnacalis (Galleria mellonella), Pleiobolus (Tineola bisselella), Baboea (Tinea pellionella), Bombycina (Menllionella), Brown looper (Hofrnannophiap Seudospermella), Linnaeus (Cacoecia podana), Plectoid moth (Choristoneura furifera), Stachys vinifera (Clysia ambigua), Camellia sinensis (Hooma moniganna irna), Tortoise viridis (Tortrix viridana), Cnaphalocrocis (Cnaphalotrus spp.), and Nepholida oryzae (Ohiophaga nivea).
The Coleoptera (Coleoptera), for example, bark beetles (Anobium puncatus), bark beetles (rhizoperthos dominica), yellowhorn beetles (Bruchidius obesus), bean weevils (acathoscopes), horsebeans (Acanthoscelides obtectus), longicorn beetles (hylolus bajulus), yellowhorn beetles (agrastica annuus), potato beetles (leprosus), horsetail beetles (Phaedon cochleariae), phyllanthus (Diabrotica spp.), stemona beetles (pseudopteris chrysospora), coccinella varivestis (phylinicola), coccinella (epilinum), sabdariae, globeformis, globeformes (nigripes), globeformes (cornus), grapevis (nigripes), brassica (purpureus), grapevis (purpureus sp), grapevis (nigra), grapevis (nigripes (purpureus), picea sp Rape pollen beetle (Meligethes aeneus), spider beetle (Ptinus spp.), yellow spider beetle (Niptus bololeuus), naked spider beetle (Gibbium psiyloides), pseudogluta sp (Triboliur spp.), yellow mealworm (Tenebnio rnolitor), click beetle (Agriotes spp.), broad chest click beetle (Conoderus spp.), Western Holotrichia gilles (Melolontha inlolontha), potato gill horn (Aihimalalon solstialis), brown New Zealand gill horn golden tortoise (Costelytra zea), rice root weevil (Li soloryphulus syzobius), and the like.
From the order Hymenoptera ((Hymenoptera), for example, genus lobela ((Dipnion spp.), genus euglena (hoplocampapa spp.), genus trichomes (Lasius spp.), genus calomel (monarnonis), genus vespid (Vespa spp.), etc.;
the Diptera (Diptera), for example, the present invention relates to a composition for treating insect pests, such as, for example, autographa, aleurodermia, Drosophila melanogaster, muscsca, Drosophila lata, Fannia spp, callimastra, Drosophila rubra, Drosophila viridans, Drosophila, chrysomyzia spp, xanthomyza, bactenaria, Drosophila, pythium spp, diaposira spp, diaposia spp, Drosophila sting, stonoxy, spenopsis, ostrinia.
The Siphonaptera (Siphonaptera), for example, Xenopsylla cheopis (Xenopsylla cheopis), Ceratophyllus spp (Ceratophyllus spp.) and the like.
Such plant parasitic nematodes include, for example, Pratylenchus spp, Radopholus similis, hedyotis herbacea (Ditylenchus dipsaci), hemithora nematoda (Tylenchus seropenetrans), Heterodera (Heterodera spp), Globodera (Globodera spp), Meloidogyne (Meloidogyne spp), Globodera (Aphelenchus spp), Longodiscus (Looidorus spp.), Trigonella spp, Globodera (Xeronium spp), and the like.
The silicoacrylonitrile compound shown in the formula I is also suitable for preventing and treating at least one plant disease of anthracnose, leaf spot, rust disease, powdery mildew, banded sclerotial blight, leaf blight, gray mold, southern blight, damping off, gibberellic disease, full rot and target spot caused by infection of rhizoctonia, sporisorium, pseudoperonospora, monascus, phaeophycus, phaeophythora and the like. Examples of the plant having the plant fungal disease include soybean, corn, wheat, melons, rice, strawberry, peanut, cotton; examples of the plant fungal diseases include soybean rust, corn rust, wheat powdery mildew, melon powdery mildew, rice sheath blight, wheat sharp eyespot, strawberry gray mold, peanut southern blight, cotton rhizoctonia rot, wheat scab, wheat take-all and cucumber target spot, wherein the melon powdery mildew includes cucumber powdery mildew and the like; the pathogenic bacteria include Phakopsora pachyrhizi (Phakopsora pachyrhizi system.), Puccinia zeae (Puccinia sorghi Schw), Erysiphe necator (Blumeria graminis), Erysiphe cucurbitaceae (Erysiphe cucurbita), Erysiphe cucurbitae (Sphaerotheca cucurbitae), dermataceae (thanatephora cuscutaris), rhizoctonia graminis (rhizoctonia solani), and rhizoctonia solani (rhizoctonia solani), Botrytis cinerea (Botrytis cinerea per), Fusarium graminearum (Fusarium graminearum Schw.), Fusarium avenae (Fusarium avenaceum), moniliforme (Fusarium moniliforme), pythomonas oryzae (phomophilus), Pythium purpurea (phoma niponicum).
Therefore, the technical scheme of the invention also comprises the application of the silicon acrylonitrile compound shown in the formula I as a bactericide in agriculture or other fields.
The silicoacrylonitriles of formula I according to the invention can be prepared in a conventional manner into acaricide and/or insecticide and/or fungicide compositions. These active compounds can be formulated in the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active substance, microcapsules in polymers, coating compositions for seeds, and formulations for use with combustion devices, such as smoking cartridges, smoking pots and smoking trays, and ULV Cold mist (Cold mist) and hot mist (Warm mist) formulations.
These formulations can be produced by known methods, for example by mixing the active compounds with extenders, that is, liquid or liquefied gas or solid diluents or carriers, and optionally surfactants, that is, emulsifiers and/or dispersants and/or foam formers. Organic solvents may also be used as adjuvants, for example when water is used as extender.
When a liquid solvent is used as the diluent or carrier, it is basically suitable, for example: 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, for example 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 less commonly polar solvents such as dimethylformamide and dimethylsulfoxide, and water.
Liquid gas diluents or carriers refer to liquids that will become gases at normal temperature and pressure, such as aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
The solid carrier may be a finely divided natural mineral such as kaolin, clay, talc, quartz, floridin, montmorillonite, or diatomaceous earth; and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates. Solid carriers for granules are crushed and classified natural zircon, such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic coarse powders, and granules of organic materials, such as sawdust, coconut shells, corn cobs and tobacco stalks, and the like.
Nonionic and anionic emulsifying trains may be used as emulsifiers and/or foam formers. Such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and albumin hydrolysates. The dispersant comprises lignin sulfite waste liquor and methyl cellulose.
Binders such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or emulsions, for example gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
Colorants such as inorganic dyes, e.g., iron oxide, cobalt oxide, and prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes; and with trace nutrients such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc, and the like.
The silicon acrylonitrile compounds of formula I of the present invention may be present in their commercial preparations as a mixture with other active compounds such as insecticides, bactericides, fungicides, herbicides, growth control agents, etc., or in the dosage forms prepared from these preparations. Insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms, such as avermectins, etc., and fungicides include strobilurins, amides, triazoles, etc.
In addition, the silicon acrylonitriles of the formula I according to the invention can also be present in their commercial preparations in a mixture with synergists, which are compounds which increase the action of the active compounds, in the use forms prepared from these preparations, it being possible for no synergists to be added, since the active compounds themselves are active.
These 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 according to the invention, based on the total weight of the pesticidal composition. The concentration of the active compound in the commercial preparations or dosage forms to be used can vary within wide limits. The concentration of the active compound in the dosage form to be used may vary from 0.0000001 to 100% (g/v), preferably between 0.0001 and 1% (g/v), and variations and modifications are possible within the scope of the invention as defined in the claims.
The main advantages of the invention include:
(a) the compound has excellent acaricidal activity;
(b) the compound also has excellent insecticidal and bactericidal activity;
(c) the compound of the invention has short synthesis steps and better total yield;
(d) compared with the existing compounds of the same type, the compound has remarkable structural innovation;
(f) the compound has excellent acaricidal, insecticidal and bactericidal activities and has small influence on the environment.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight.
EXAMPLE 1 preparation of Compounds i-7
Figure BDA0002831327570000441
Weighing NaH (500mg, 12.5mmol) in a 50ml two-mouth bottle, adding 30ml THF, and stirring and dispersing uniformly under ice bath; trimethylsilylphenylacetonitrile (1.89g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue was taken up in n-heptane to precipitate a white solid in 84.2% yield. The white solid was then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 2 preparation of Compounds i-4
Figure BDA0002831327570000442
Weighing NaH (500mg, 12.5mmol) in a 50ml two-mouth bottle, adding 30ml THF, and stirring and dispersing uniformly under ice bath; trimethylsilylphenylacetonitrile (1.89g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue was taken up in n-heptane to precipitate a white solid in 84.2% yield. The white solid is subsequently dissolved in 20ml of dichloromethane and triethyl chloride is addedAfter stirring amine (1.01g,10mmol) at room temperature for 10min, isobutyryl chloride (1.25g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 3 preparation of Compounds i-24
Figure BDA0002831327570000451
Weighing NaH (500mg, 12.5mmol) in a 50ml two-mouth bottle, adding 30ml THF, and stirring and dispersing uniformly under ice bath; trimethylsilylphenylacetonitrile (1.89g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue was taken up in n-heptane to precipitate a white solid in 84.2% yield. The white solid was then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, benzoyl chloride (1.75g, 12.5mmol) was added dropwise and the reaction was carried out at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 4 preparation of Compounds i-39
Figure BDA0002831327570000452
NaH (500mg, 12.5mmol) was weighed into a 50ml two-necked flask and added30ml of THF, stirring and dispersing evenly under ice bath; trimethylsilylphenylacetonitrile (1.89g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue was taken up in n-heptane to precipitate a white solid in 84.2% yield. The white solid was then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added thereto, and the mixture was stirred at room temperature for 10min, and ethyl 2-methoxychloroformate (1.73g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 38.4%.1H NMR(400MHz,CDCl3)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).
EXAMPLE 5 preparation of Compounds i-58
Figure BDA0002831327570000461
Weighing NaH (500mg, 12.5mmol) into a 50ml two-mouth bottle, adding 30ml THF, and stirring and dispersing uniformly under ice bath; trimethylsilylphenylacetonitrile (1.89g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue was taken up in n-heptane to precipitate a white solid in 84.2% yield. The white solid was then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added thereto, the mixture was stirred at room temperature for 10min, and dimethylcarbamoyl chloride (1.34g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the pressure is reducedRemoving the solvent, washing with ethyl acetate, filtering, concentrating the filtrate, and purifying by column chromatography to obtain the target compound with a yield of 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).
EXAMPLE 6 preparation of Compounds i-71
Figure BDA0002831327570000462
Weighing NaH (500mg, 12.5mmol) in a 50ml two-mouth bottle, adding 30ml THF, and stirring and dispersing uniformly under ice bath; paradimethylvinylsilylphenylacetonitrile (2.01g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and column chromatography gave a brown oil in 71.8% yield. The white solid was then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, and the target compound is obtained after the filtrate is concentrated and purified by column chromatography, wherein the yield is 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).
EXAMPLE 7 preparation of Compounds i-134
Figure BDA0002831327570000471
NaH (500mg, 12.5mmol) was weighed into 50ml, adding 30ml of THF into a two-mouth bottle, and stirring and dispersing uniformly under ice bath; paradimethyl tert-butylsilylphenylacetonitrile (2.31g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue was taken up in n-heptane to precipitate a white solid in 82.8% yield. The white solid was then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 8 preparation of Compounds i-313
Figure BDA0002831327570000472
Weighing NaH (500mg, 12.5mmol) in a 50ml two-mouth bottle, adding 30ml THF, and stirring and dispersing uniformly under ice bath; m-trimethylsilylphenylacetonitrile (1.89g,10mmol) was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, ethyl 2-trifluoromethylbenzoate (2.18g,10mmol) was added dropwise and reacted at 60 ℃. After the reaction is finished, adding a small amount of water under ice bath to quench the reaction, and adding diluted hydrochloric acid to adjust the reaction to be acidic. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the residue was taken up in n-heptane to precipitate a white solid in 87.9% yield. The white solid was then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, and ethyl acetateWashing and filtering the ester, concentrating the filtrate, and purifying by column chromatography to obtain the target compound with the yield of 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).
EXAMPLE 10 preparation of Compounds ii-4
Figure BDA0002831327570000473
A two-necked flask was charged with ethyl 1,3, 4-trimethylpyrazole-5-carboxylate (1.82g,10mmol), p-trimethylsilylacetonitrile (1.89g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, isobutyryl chloride (1.25g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 9 preparation of Compounds ii-7
Figure BDA0002831327570000481
Adding 1,3, 4-trimethylpyrazole-5-ethyl formate (1.82g,10mmol), p-trimethylsilylbenzacetonitrile (1.89g,10mmol), n-hexane 30ml, ethylene glycol monoethyl ether5ml of dimethyl ether were added, followed by a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 11 preparation of Compounds ii-39
Figure BDA0002831327570000482
A two-necked flask was charged with ethyl 1,3, 4-trimethylpyrazole-5-carboxylate (1.82g,10mmol), p-trimethylsilylacetonitrile (1.89g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20mL × 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added thereto, and the mixture was stirred at room temperature for 10min, and ethyl 2-methoxychloroformate (1.73g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, decompressing to remove the solvent, washing and filtering by ethyl acetate, concentrating the filtrate, purifying by column chromatography to obtain the target compound,the yield was 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).
EXAMPLE 12 preparation of Compounds ii-24
Figure BDA0002831327570000491
A two-necked flask was charged with ethyl 1,3, 4-trimethylpyrazole-5-carboxylate (1.82g,10mmol), p-trimethylsilylacetonitrile (1.89g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, benzoyl chloride (1.75g, 12.5mmol) was added dropwise and the reaction was carried out at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained, wherein the yield is 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).
EXAMPLE 13 preparation of Compounds ii-308
Figure BDA0002831327570000492
A two-necked flask was charged with ethyl 1,3, 4-trimethylpyrazole-5-carboxylate (1.82g,10mmol), 5-fluoro-3-trimethylsilylphenylacetonitrile (2.07g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, 110Reflux at C for 2 hours, then cool to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 14 preparation of Compounds ii-313
Figure BDA0002831327570000501
A two-necked flask was charged with ethyl 1,3, 4-trimethylpyrazole-5-carboxylate (1.82g,10mmol), m-trimethylsilylacetonitrile (1.89g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 15 preparation of Compounds iii-7
Figure BDA0002831327570000502
A two-necked flask was charged with ethyl 1-ethyl-3, 4-trimethylpyrazole-5-carboxylate (1.82g,10mmol), p-trimethylsilylphenylacetonitrile (1.89g,10mmol), n-hexane 30ml, and 1, 4-dioxane 5ml, followed by addition of a water separator and a condenser reflux tube. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 16 preparation of Compounds iii-313
Figure BDA0002831327570000503
A two-necked flask was charged with ethyl 1-ethyl-3, 4-trimethylpyrazole-5-carboxylate (1.82g,10mmol), m-trimethylsilylphenylacetonitrile (1.89g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, a sodium methoxide solution (2M, 6ml, 12.0 mmol). After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 17 preparation of Compounds vi-313
Figure BDA0002831327570000511
Two-necked flask was charged with 2-iodo-benzoic acid ethyl ester (2.76g,10mmol), m-trimethylsilylacetonitrile (1.89g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, triethylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and reacted at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and purified by column chromatography, and the target compound is obtained with the yield of 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).
EXAMPLE 18 preparation of Compound xv-7
Figure BDA0002831327570000512
Two-necked flask was charged with 3-methylthiophenezole-2-carboxylic acid ethyl ester (1.70g,10mmol), p-trimethylsilylphenylacetonitrile (1.89g,10mmol), n-hexane 30ml, and ethylene glycol monomethyl ether 5ml, followed by addition of a water separator and a reflux condenser. After the nitrogen replacement of the reaction system, the reaction system was refluxed at 110 ℃ for 2 hours and then cooled to 100 ℃. After the temperature had stabilized, sodium methoxide solution (2M, 6ml, 12.0mmol) was added dropwise. After the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the aqueous phase was acidified by adding dilute hydrochloric acid, extracted with ethyl acetate (20 mL. times.3), the organic phases were combined, washed with a 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 then dissolved in 20ml of dichloromethane, diisopropylamine (1.01g,10mmol) was added and the mixture was stirred at room temperature for 10min, pivaloyl chloride (1.50g, 12.5mmol) was added dropwise and the reaction was carried out at room temperature. After the reaction is finished, the solvent is removed under reduced pressure, ethyl acetate is used for washing and filtering, the filtrate is concentrated and then is purified by column chromatography, and the target compound is obtained, wherein the yield is 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).
Other example compounds were also prepared from different starting materials with reference to the above preparation methods, and the example compounds of the present invention are shown in table 1; other silicon acrylonitrile compounds of the present invention, represented by formula I, can also be prepared using suitable starting materials, by reference to the methods of the examples described above:
table 1 structural characterization of compounds of some examples
Figure BDA0002831327570000521
Figure BDA0002831327570000531
Figure BDA0002831327570000541
Figure BDA0002831327570000551
Figure BDA0002831327570000561
Figure BDA0002831327570000571
Figure BDA0002831327570000581
Figure BDA0002831327570000591
Figure BDA0002831327570000601
Figure BDA0002831327570000611
Figure BDA0002831327570000621
Figure BDA0002831327570000631
Figure BDA0002831327570000641
Examples of biological Activity assays
Evaluation of acaricidal Activity against Tetranychus urticae (Tetranychus urticae)
After the compound to be tested is dissolved by dimethyl sulfoxide, the solution is diluted to different test concentrations by a water solution of triton, and the liquid medicine is uniformly sprayed on the front and back surfaces of the bean leaf cutting pieces. After the liquid medicine is dried, the mixed individuals of the tetranychus urticae are connected to the bean leaf cut pieces, and the base number is recorded. The number of live insects on the bean leaves was recorded after 192 hours of observation in a standard observation room (23-25 ℃ C., RH 40-60%). Commercial pesticide Cyenopyrafen (Cyenopyrafen) is used as a control, and a water solution of Triton is used as a blank control. The results of the activity assay of some compounds on tetranychus urticae are shown in table 2.
Table 2 partial compound tetranychus urticae activity determination results
Figure BDA0002831327570000651
Figure BDA0002831327570000661
Figure BDA0002831327570000671
Figure BDA0002831327570000681
From the above experimental results it can be seen that: the compounds of the present invention have acaricidal activity substantially equivalent to that of the control, even at lower concentrations (e.g., 50ppm) most of the compounds have 100% acaricidal activity, e.g., compounds 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.
Evaluation of insecticidal Activity against Plutella xylostella (Plutella xylostella)
Taking a culture dish, covering a layer of filter paper at the bottom of the culture dish, and dropwise adding a proper amount of tap water for moisturizing. After removing the surface wax layer from the cabbage leaves, a cabbage leaf dish having a diameter of about 6cm was prepared, and the leaf was placed in a petri dish with the back side upward. After a compound to be tested is dissolved by dimethyl sulfoxide (DMSO), the solution is diluted to different test concentrations by a water solution of Qula, and liquid medicine is uniformly sprayed on the front and back surfaces of the leaves. After the leaves are naturally dried in the shade, 1-instar larvae of the plutella xylostella are inoculated, 3 times of repetition are carried out, a commercialized pesticide Cyenopyrafen (Cyenopyrafen) is used as a control, and a water solution of Triton is used as a blank control. The dishes were transferred to a standard observation chamber (23-25 ℃, RH 40-60%). And (4) carrying out test investigation 72 hours after treatment, recording the number of dead insects and live insects of the test insects, and calculating the death rate. The results of the activity assay of some compounds on diamond back moth are shown in Table 3.
TABLE 3 determination of Plutella xylostella Activity of some Compounds
Figure BDA0002831327570000682
Figure BDA0002831327570000691
From the above experimental results it can be seen that: compared with a control compound, the compound has excellent insecticidal activity. For example, compounds 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-313, xiii-260, xv-260, xvi-260 show better or superior plutella xylostella activity at 200ppm, the contrast medicine cyenopyrafen does not show related insecticidal activity, and the compound has broad insecticidal spectrum.
Evaluation of fungicidal Activity against Puccinia fabarum (Uromyces viciae-fabae)
The test compound was prepared into a test solution at a concentration of 100ppm using N, N-Dimethylformamide (DMF) containing 0.1% Tween 80. The method comprises the steps of adopting a greenhouse living potted plant method for determination, placing test crops on a sprayer for carrying out foliage spray treatment, placing the crops after being treated by a medicament in a shade place, inoculating pathogenic bacteria spores after 24 hours, and setting 3 times of repetition, wherein a commercialized pesticide Cyenopyrafen (Cyenopyrafen) is used as a control and a blank control is additionally arranged. The inoculated crops are cultured in an artificial climate chamber, the control effect is investigated after the crops are cultured for 7d and 10d respectively, and the determination result of the activity of part of compounds on the broad bean single cell rust fungus is shown in table 4.
Evaluation of fungicidal Activity against Phytophthora capsici (Phytophthora capsicii)
The test compound was prepared into a test solution at a concentration of 100ppm using N, N-Dimethylformamide (DMF) containing 0.1% Tween 80. The method comprises the steps of adopting a greenhouse living potted plant method for determination, placing a test crop on a sprayer for carrying out foliage spray treatment, placing the crop after being treated by a medicament in a shade place, inoculating pathogenic bacteria spores after 24 hours, setting 3 times of repetition, setting a commercialized pesticide Cyenopyrafen (Cyenopyrafen) as a control, and setting a blank control. The inoculated crops are cultured in a climatic chamber, the control effect is investigated after the crops are cultured for 7d and 10d respectively, and the activity determination result of part of compounds on the phytophthora capsici is shown in table 4.
Evaluation of fungicidal Activity against Pythium (Pythium)
The test compound was prepared into a test solution at a concentration of 100ppm using N, N-Dimethylformamide (DMF) containing 0.1% Tween 80. The method comprises the steps of adopting a greenhouse living potted plant method for determination, placing test crops on a sprayer for carrying out foliage spray treatment, placing the crops after being treated by a medicament in a shade place, inoculating pathogenic bacteria spores after 24 hours, and setting 3 times of repetition, wherein a commercialized pesticide Cyenopyrafen (Cyenopyrafen) is used as a control and a blank control is additionally arranged. The inoculated crops are cultured in a climatic chamber, the control effect is investigated after the crops are cultured for 7d and 10d respectively, and the determination result of the activity of part of compounds on the pythium is shown in table 4.
TABLE 4 determination of fungicidal Activity at 100ppm of some Compounds
Figure BDA0002831327570000701
Figure BDA0002831327570000711
Figure BDA0002831327570000721
Figure BDA0002831327570000731
From the above experimental results it can be seen that: compared with a control compound, the compound has excellent bactericidal activity. For example, the 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, i-55, i-58, i-67, i-70, i-71, i-83, i-88, i-91, i-102 and the like have good control effects on rust pseudomonas fabae, phytophthora capsici and pythium aphanidermatum, and the overall control effect is better than that of the control cyenopyrafen.
All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the appended claims of the present application.

Claims (11)

1. A compound of formula I, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof,
Figure FDA0002831327560000011
in the formula (I), the compound is shown in the specification,
R1selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C3-6Cycloalkoxy, C1-6Alkylthio radical, C3-6Cycloalkylthio radical, C6-C10Aryl, 5-10 membered heteroaryl, 4-10 membered heterocyclyl; wherein said substitution is by one or more RaSubstitution;
R2、R3and R4Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6An alkynyl group; wherein said substitution is by one or more RaSubstitution;
or, R2And R3、R3And R4Or R2And R4Together form a group selected from: - (CH)2)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;
R5selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio radical, R6And R7(ii) a Wherein said substitution is by one or more RaSubstitution;
R6is substituted or unsubstituted C6-14An aryl group; r6Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
R7Is unsubstituted or substituted 5-14 membered heteroaryl; r7Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio, -CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；
R8And R9Each independently selected from the group consisting of substituted or unsubstituted: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl; or, R8And R9Taken together with the N atom to which they are attached form a substituted or unsubstituted 3-6 membered heterocyclyl; wherein said substitution is by one or more RaSubstitution;
each X is independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
Z is selected from: CRbRcOxygen, sulfur or NRd；
(CH2)nH in (3) can be replaced by RaSubstitution;
or Z- (CH)2)n-R1The moiety is selected from the group consisting of substituted or unsubstituted: c1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl; wherein said substitution is by one or more RaSubstitution;
Rb、Rceach independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2NR8R9；
RdSelected from the group consisting of: hydrogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6An alkyl group;
Raselected from the group consisting of: hydrogen, halogen, C1-6Alkyl radical, C1-6Alkoxy, halo C1-6Alkyl, halo C1-6Alkoxy, -CN, -NO2Oxo, C3-6Cycloalkyl, 3-6 membered heterocyclyl, -SO2R10、-COR10、-COOR10、-CONR10R11and-SO2NR10R11(ii) a Wherein R is10、R11Each independently selected from the group consisting of: hydrogen, C1-6Alkyl, halo C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl, C6-14Aryl, 5-14 membered heteroaryl;
m is 0, 1, 2, 3 or 4; n is 0, 1, 2, 3 or 4.
2. A compound of formula I according to claim 1, having the structure of formula II or formula III, geometric isomers, stereoisomers, or agriculturally pharmaceutically acceptable salts or prodrugs thereof
Figure FDA0002831327560000021
In the formula, X, m, R1、R2、R3、R4、R5Z and n are as defined in claim 1.
3. The compound of formula I, its geometric isomers, stereoisomers, or an agriculturally acceptable salt or prodrug thereof, according to claim 1, wherein R is5Selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, 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; wherein said substitution means that the hydrogen on the group is substituted by 1 to 5 groups selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C1-6Alkylthio of, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；R8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl.
4. A compound of formula I, as claimed in claim 1, wherein R is a geometric isomer, a stereoisomer, or an agriculturally acceptable salt or prodrug thereof5Selected from the group consisting of:
Figure FDA0002831327560000022
Figure FDA0002831327560000031
in the formula (I), the compound is shown in the specification,
g is independently 0, 1, 2, 3,4 or 5;
each R' is independently selected from the group consisting of: halogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C1-6Alkylthio of, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2NR8R9；R8And R9Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C3-6Cycloalkyl, 3-6 membered heterocyclyl; .
5. The compound of formula I, its geometric isomers, stereoisomers, or an agriculturally acceptable salt or prodrug thereof, according to claim 1, wherein R is2、R3And R4Each independently selected from the group consisting of: c1-6Alkyl radical, C2-4Alkenyl and C2-4Alkynyl.
6. The compound of formula I, its geometric isomers, stereoisomers, or agriculturally acceptable salts or prodrugs thereof according to claim 1, characterized in that it has the structure shown in formula I-xvi
Figure FDA0002831327560000032
Figure FDA0002831327560000041
In the formula (I), the compound is shown in the specification,
R1、R2、R3、R4x, m, n, Z are as defined in claim 1.
7. The compound, its geometric isomers, stereoisomers, or an agriculturally acceptable salt or prodrug thereof of claim 6, wherein R is1、R2、R3、R4X, m, n, Z have the definitions shown in Table a
TABLE a
Figure FDA0002831327560000051
Figure FDA0002831327560000061
Figure FDA0002831327560000071
Figure FDA0002831327560000081
Figure FDA0002831327560000091
Figure FDA0002831327560000101
Figure FDA0002831327560000111
Figure FDA0002831327560000121
Figure FDA0002831327560000131
Figure FDA0002831327560000141
Figure FDA0002831327560000151
Figure FDA0002831327560000161
8. A process for preparing a compound of claim 1, a geometric isomer, a stereoisomer, or an agriculturally pharmaceutically acceptable salt or prodrug thereof, comprising the steps of:
Figure FDA0002831327560000162
wherein, m, n, R1、R2、R3、R4、R5X and Z are as defined in claim 1;
(s1) reacting compound A with compound B in an inert solvent in the presence of a base to give the compound of formula I.
9. Use of a compound according to any one of claims 1 to 7, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof,
(i) can be used for killing and/or controlling at least one pest of Acarina, Symphyta, Orthoptera, Blattaria, Isoptera, Anoploptera, Thysanoptera, Isoptera, Homoptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Siphonaptera and plant parasitic nematodes and/or nymphs and/or eggs thereof;
(ii) can be used for preventing and treating at least one plant disease of anthracnose, leaf spot, rust disease, powdery mildew, banded sclerotial blight, leaf blight, gray mold, southern blight, damping off, gibberellic disease, full rot and target spot caused by infection of rhizoctonia, sclerotinia, pseudoperonospora, monascus, phaeophyceae, pythium and the like;
(iii) for the preparation of a composition or formulation for killing and/or controlling mites and/or their eggs;
(iv) for insecticidal and/or bactericidal use; and/or
(v) For the production of compositions or preparations for acaricidal and/or insecticidal and/or fungicidal use.
10. A composition comprising (i) as an active ingredient a compound according to any one of claims 1 to 7, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof; and (ii) a carrier and/or surfactant.
11. A method of killing mites, insects and/or bacteria comprising the steps of: contacting mites, insects and/or bacteria with an effective amount of a compound of any one of claims 1-7, a geometric isomer, a stereoisomer thereof, or an agriculturally pharmaceutically acceptable salt or prodrug thereof or a composition of claim 10.
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