CN110551148B - Compound containing silicon acyl acetonitrile, preparation method and application thereof - Google Patents

Compound containing silicon acyl acetonitrile, preparation method and application thereof Download PDF

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CN110551148B
CN110551148B CN201910415131.9A CN201910415131A CN110551148B CN 110551148 B CN110551148 B CN 110551148B CN 201910415131 A CN201910415131 A CN 201910415131A CN 110551148 B CN110551148 B CN 110551148B
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CN110551148A (en
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程家高
彼得·迈恩菲什
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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    • 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
    • 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
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • 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
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • 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
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • 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

Abstract

The invention discloses a silicon acyl acetonitrile-containing compound, or a geometric isomer, or a stereoisomer, or a salt 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 compound of the invention has excellent acaricidal activity.

Description

Compound containing silicon acyl acetonitrile, preparation method and application thereof
Technical Field
The invention belongs to the field of insecticides and acaricides, and particularly relates to a silicon acyl acetonitrile compound with insecticidal/acaricidal activity, a preparation method of the compound, and application and a method of the compound as an insecticide and/or acaricide.
Background
Insects and mites often cause great loss to economic crops such as fruits, cotton, vegetables, ornamental plants and the like, the chemical insecticidal and acaricidal agent is used for preventing and controlling the economic crops, the safety of the economic crops is guaranteed, the living standard of people is improved, and the insecticidal and acaricidal agent can bring considerable social and economic benefits. The resistance problem of insects and mites to the existing insecticidal and acaricidal agents and the ecological environment safety problem of the existing insecticidal and acaricidal agents also promote the innovative research of the novel insecticidal and acaricidal agents. However, the existing acaricides have the problems of mite resistance and the like, and the research of the novel acaricides cannot meet the requirement.
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 compound with a novel structure and excellent insecticidal and acaricidal activity.
In a first aspect of the present invention, there is provided a compound comprising a silicon acyl acetonitrile, or a geometric isomer thereof, or a stereoisomer thereof, or a salt thereof, wherein the compound is represented by formula I:
Figure BDA0002064091570000011
in the formula (I), the compound is shown in the specification,
R1selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, R6And R7；
n is 0, 1, 2, 3 or 4;
R2，R3，R4each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C1-6Alkoxy radical, C2-6Alkenyl radical, C2-6Alkynyl, R6And R7；
Or, R2And R3、R3And R4Or R2And R4Together form a group selected from: - (CH)2)p-、-(CH2)o-O-(CH2)p-O-(CH2)o-; wherein each o is independently 0, 1, 2, 3, or 4, and p is 2, 3, 4,5, or 6;
R5selected from the group consisting of: c1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio of, C3-6Cycloalkoxy, C3-6Cycloalkylthio radical, R6And R7；
R6Is substituted or unsubstituted C6-14Aryl (preferably, phenyl); 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 of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical C1-6Alkoxy radical, C1-6Alkylthio of, C3-6Cycloalkoxy, C3-6Cycloalkylthio, CN, -NO2、-SO2R8、-COR8、-COOR8、-CONR8R9and-SO2R8R9；
R7Is unsubstituted or substituted 5-to 14-membered heteroaryl or 4-to 16-membered heterocyclyl (preferably, 5-to 10-membered heteroaryl or 4-to 10-membered heterocyclyl); 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 of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio of C3-6Cycloalkoxy, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2R8R9；
R8And R9Each independently selected from: hydrogen, halogen, C1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio of C3-6Cycloalkoxy, and C3-6Cycloalkylthio (with the proviso that when R is substituted with8Or R9R bound to oxygen when the atom bound is oxygen8And R9Is other than C1-6Alkoxy radical, C3-6Cycloalkoxy groups);
each X is independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6A cycloalkylthio group;
m is 1, 2, 3 or 4;
z is selected from: oxygen, sulfur;
R1，R2，R3，R4，R5，R6，R7，R8，R9and one or more (preferably, 1 to 10; more preferably, 1, 2, 3, 4 or 5) hydrogen atoms in the X group can be further substituted with substituents each 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, and C3-6A cycloalkylthio group.
In another preferred embodiment, the heteroaryl or heterocyclyl (i.e., 5-to 14-membered heteroaryl or 4-to 16-membered heterocyclyl, or 5-to 10-membered heteroaryl or 4-to 10-membered heterocyclyl) contains 1 to 5 heteroatoms; preferably, the heteroatoms are selected from: oxygen, nitrogen, sulfur.
In another preferred embodiment, R2And R3、R3And R4Or R2And R4Together form a group selected from:
-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-OCH2CH2CH2O-、-OCH2CH2CH2CH2O-、-OCH2CH2CH2CH2CH2O-、-CH2CH2CH2O-、-CH2CH2CH2CH2O-、-CH2CH2OCH2CH2-, and-CH2OCH2CH2-。
In another preferred embodiment, the 5-to 14-membered heteroaryl or 4-to 16-membered heterocyclyl is each independently selected from the group consisting of: quinolyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, benzotriazinyl, purinyl, benzimidazolyl, benzopyrazolyl, benzotriazolyl, benzisoxazolyl, isobenzofuranyl, isoindolyl, indolizinyl, benzotriazinyl, thienopyridinyl, thienopyrimidinyl, pyrazolopyrimidine, imidazopyridine, benzothiazolyl, benzofuranyl, benzothiophenyl, indolyl, quinolyl, isoquinolyl, isothiazolyl, indazolyl, pteridinyl, tetrazolyl, pyrazolidine, butyrolactam, valerolactam, imidazolidinone, hydantoin, dioxolanyl, phthalimidyl, piperidinyl, 1, 4-dioxane, morpholine, thiomorpholine-S-oxide, thiomorpholine-S, S-oxide, piperazine, pyran, pyridone-S-oxide, pyridone-oxide, and pharmaceutically acceptable salts thereof, 3-pyrroline, thiopyran, pyrone, quinuclidinyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, 1, 4-oxathienyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydropyrrolyl, tetrahydrothiazolyl, tetrahydropyrazolyl, tetrahydroimidazolyl, tetrahydrotriazolyl, hexahydropyridyl, pyrrolidinyl, pyrrolidinonyl, oxazolinyl, oxazolinonyl, and hexahydropyranyl.
In another preferred embodiment, the 5-to 14-membered heteroaryl or 4-to 16-membered heterocyclyl (preferably, 5-to 10-membered heteroaryl or 4-to 10-membered heterocyclyl) is each independently selected from the group consisting of: pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, 1, 4-oxathiaxinyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydropyrrolyl, tetrahydrothiazolyl, tetrahydropyrazolyl, tetrahydroimidazolyl, tetrahydrotriazolyl, hexahydropyridyl, pyrrolidinyl, pyrrolidinonyl, oxazolinyl, oxazolinonyl, and hexahydropyranyl.
In another preferred embodiment, R7Each independently is unsubstituted or substituted group selected from: pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, 1, 4-oxathiaxinyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydropyrrolyl, tetrakisA hydrotriazolyl, tetrahydropyrazolyl, tetrahydroimidazolyl, tetrahydrotriazolyl, hexahydropyridyl, pyrrolidinyl, pyrrolidinonyl, oxazolinyl, oxazolinonyl, and hexahydropyranyl group; r7Wherein 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, C3-6Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9And SO2R8R9。
In another preferred embodiment, R2，R3，R4Each independently selected from the group consisting of: c1-3Alkyl radical, C1-3Alkoxy radical, C2-4Alkenyl radical, C2-4Alkynyl. In another preferred embodiment, R5Is R6Or R7。
In another preferred embodiment, R6Is substituted or unsubstituted C6-10Aryl (preferably, phenyl); r6Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9、SO2R8R9。
In another preferred embodiment, R8And R9Each independently selected from the group consisting of: hydrogen, halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio (with the proviso that when R is substituted with8Or R9R bound to oxygen when the atom bound is oxygen8And R9Is other than C1-3Alkoxy radical, C3-4Cycloalkoxy) group.
In another preferred embodiment, R1，R2，R3，R4，R5，R6，R7，R8，R9And one or more (preferably, 1 to 10; more preferably, 1, 2, 3, 4 or 5) hydrogen atoms in the X group can be further substituted with substituents each independently selected from the group consisting of: halogen, C1-3Alkyl of (C)2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4A cycloalkylthio group.
In another preferred embodiment, in formula I,
R1selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, R6、R7；
n is 0, 1, 2, 3 or 4;
R2，R3and R4Each independently selected from the group consisting of: c1-3Alkyl radical, C1-3Alkoxy radical, C2-4Alkenyl radical, C2-4An alkynyl group;
R5is R6Or R7；
R6Is substituted or unsubstituted phenyl; r6Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9、SO2R8R9；
R7Is unsubstituted or substituted 5-to 10-membered heteroaryl or 4-to 10-membered heterocyclyl; r7In (1), theSubstituted means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9、SO2R8R9(ii) a And said 5-to 10-membered heteroaryl or 4-to 10-membered heterocyclyl is selected from: pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, 1, 4-oxathiaxinyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydropyrrolyl, tetrahydrothiazolyl, tetrahydropyrazolyl, tetrahydroimidazolyl, tetrahydrotriazolyl, hexahydropyridyl, pyrrolidinyl, pyrrolidinonyl, oxazolinyl, oxazolinonyl, and hexahydropyranyl;
R8and R9Each independently selected from the group consisting of: hydrogen, halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio (with the proviso that when R is substituted with8Or R9R bound to oxygen when the atom bound is oxygen8And R9Is other than C1-3Alkoxy radical, C3-4Cycloalkoxy groups);
each X is independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio of, C3-6Cycloalkoxy, C3-6A cycloalkylthio group;
m is 1, 2, 3 or 4;
z is selected from: oxygen, sulfur;
R1，R2，R3，R4，R5，R6，R7，R8，R9and one or more (preferably, 1 to 10; more preferably, 1, 2, 3, 4 or 5) hydrogen atoms in the X group can be further substituted with substituents each independently selected from the group consisting of: halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4A cycloalkylthio group.
In another preferred embodiment, Z is oxygen.
In another preferred embodiment, in formula I,
R1selected from the group consisting of: c1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6Cycloalkylthio radical, R6、R7；
n is 0, 1, 2, 3 or 4;
R2、R3and R4Each independently selected from the group consisting of: c1-3Alkyl radical, C1-3Alkoxy radical, C2-4Alkenyl radical, C2-4An alkynyl group;
R5is R6Or R7；
R6Is substituted or unsubstituted phenyl; r6Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-3Alkyl of (C)2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9、SO2R8R9；
R7Is unsubstituted or substituted 5-to 10-membered heteroaryl or 4-to 10-membered heterocyclyl; r7Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl radical、C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9、SO2R8R9(ii) a And said 5-to 10-membered heteroaryl or 4-to 10-membered heterocyclyl is selected from: pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, 1, 4-oxathiapinyl, tetrahydrofuryl, tetrahydrothienyl, tetrahydropyrrolyl, tetrahydrothiazolyl, tetrahydropyrazolyl, tetrahydroimidazolyl, tetrahydrotriazolyl, hexahydropyridyl, pyrrolidine, pyrrolidone, oxazoline, oxazolinone, and hexahydropyranyl;
R8and R9Each independently selected from the group consisting of: hydrogen, halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio (with the proviso that when R is substituted with8Or R9R bound to oxygen when the atom bound is oxygen8And R9Is other than C1-3Alkoxy radical, C3-4Cycloalkoxy groups);
each X is independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6A cycloalkylthio group;
m is 1, 2, 3 or 4;
z is oxygen;
R1，R2，R3，R4，R5，R6，R7，R8，R9and one or more (preferably, 1, 2, 3, 4 or 5) hydrogen atoms in the group X can also be substituted with substituents each independently selected from the group consisting of: halogen, C1-3Alkyl group of (A) or (B),C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4A cycloalkylthio group.
In another preferred embodiment, R1Selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6A cycloalkylthio group.
In another preferred embodiment, R5Is R6。
In another preferred embodiment, in formula I,
R1selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6A cycloalkylthio group;
n is 0, 1, 2, 3 or 4;
R2、R3and R4Each independently selected from the group consisting of: c1-3Alkyl radical, C1-3Alkoxy radical, C2-4Alkenyl radical, C2-4An alkynyl group;
R5is R6；
R6Is substituted or unsubstituted phenyl; r6Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio of, C3-4Cycloalkoxy, C3-4Cycloalkylthio, CN, NO2、SO2R8、COR8、COOR8、CONR8R9、SO2R8R9；
R8And R9Each independently selected from the group consisting of: hydrogen, halogen, C1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4Cycloalkylthio (with the proviso that when R is substituted with8Or R9R bound to oxygen when the atom bound is oxygen8And R9Is other than C1-6Alkoxy radical, C3-4Cycloalkoxy groups);
each X is independently selected from the group consisting of: hydrogen, halogen, C1-6Alkyl of (C)2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical, C1-6Alkylthio radical, C3-6Cycloalkoxy, C3-6A cycloalkylthio group;
m is 1, 2, 3 or 4;
z is oxygen;
R1，R2，R3，R4，R5，R6，R8，R9and one or more (preferably, 1 to 10; more preferably, 1, 2, 3, 4 or 5) hydrogen atoms in the X group can be further substituted with substituents each independently selected from the group consisting of: halogen, C1-3Alkyl of (C)2-4Alkenyl radical, C2-4Alkynyl, C3-5Cycloalkyl radical, C1-3Alkoxy radical, C1-3Alkylthio radical, C3-4Cycloalkoxy, C3-4A cycloalkylthio group.
In another preferred embodiment, the compound is selected from the compounds in Table 1 (i.e., compounds 1-361).
7. A process for the preparation of a compound according to claim 1, comprising the steps of:
Figure BDA0002064091570000071
(reaction formula 1)
(i) Reacting a compound of formula II with a compound of formula III to obtain a compound of formula I;
wherein, m, n, R1、R2、R3、R4、R5And X is as defined in claim 1.
In another preferred embodiment, the compound of formula II is prepared by process a or process b,
the method a comprises the following steps:
Figure BDA0002064091570000072
(reaction formula 2)
(a1) Reacting a compound of formula IV with diethyl carbonate (CO (OCH)2CH3)2) Carrying out a reaction to obtain a compound of formula V; and (a2) reacting the formulae V and R1-ZH, thereby obtaining a compound of formula II;
the method b comprises the following steps:
Figure BDA0002064091570000073
(reaction formula 3)
(b1) Reacting a compound of formula IV with a chloroformate (ClCO (CH)2)nR1) The reaction is carried out to obtain the compound of formula II.
In another preferred embodiment, the compound of formula IV is prepared by process c or process d,
the method c comprises the following steps:
Figure BDA0002064091570000074
(reaction formula 4)
(c1) Reacting a compound of formula VI with a catalyst
Figure BDA0002064091570000081
(i.e., sodium cyanoacetate or potassium cyanoacetate) to obtain a compound of formula IV;
the method d comprises the following steps:
Figure BDA0002064091570000082
(reaction formula 5)
(d1) Reacting a compound of formula VII with a catalyst ligand in the presence of a palladium catalyst
Figure BDA0002064091570000083
The reaction is carried out to obtain the compound of formula IV.
In another preferred embodiment, the compound of formula VI is prepared by process e, which comprises the steps of:
Figure BDA0002064091570000084
(reaction formula 6)
(e1) Reacting a compound of formula VIII with
Figure BDA0002064091570000085
The reaction is carried out to give the compound of formula VI.
In another preferred embodiment, step (i) (i.e., the reaction shown in equation 1) is: reacting a compound of formula II and a compound of formula III in a solvent (preferably, the solvent is selected from benzene, toluene, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-heptane, dimethylformamide, or a combination thereof) in the presence of a base (preferably, the base is selected from sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, lithium diisopropylamide, or a combination thereof) at 0-25 ℃ or 0 ℃ to reflux temperature to provide a compound of formula I.
In another preferred embodiment, method a (i.e., the reaction shown in equation 2) is reacting a compound of formula IV and diethyl carbonate in a solvent (preferably, the solvent is selected from the group consisting of benzene, toluene, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-heptane, dimethylformamide, or a combination thereof) in the presence of a base (preferably, the base is selected from the group consisting of sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, lithium diisopropylamide, or a combination thereof) at 0-25 deg.C or 0 deg.C to reflux temperature to obtain a compound of formula V; under the catalysis of sulfuric acid or aluminum isopropoxideReacting a compound of formula V with R1-ZH, thereby obtaining the compound of formula II.
In another preferred embodiment, method b (i.e., the reaction shown in equation 3) is: a compound of formula IV is reacted with a chloroformate (ClCOZ (CH) in a solvent (preferably selected from the group consisting of benzene, toluene, ethyl acetate, dichloromethane, tetrahydrofuran, n-heptane, dimethylformamide, or combinations thereof) in the presence of a base (preferably selected from the group consisting of sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, lithium diisopropylamide, n-butyllithium, or combinations thereof) at 0-25 deg.C or 0 deg.C to reflux temperature2)nR1) The reaction is carried out to produce the compound of formula II.
In another preferred embodiment, phosgene or triphosgene and R are used in a solvent (preferably, the solvent is selected from the group consisting of benzene, toluene, methylene chloride, tetrahydrofuran, diethyl ether, or a combination thereof)1(CH2)nZH reaction to obtain chloroformic ester ClCOZ (CH)2)nR1。
In another preferred embodiment, the method c (i.e., the reaction shown in equation 4) is: in a solvent (preferably, the solvent is selected from the group consisting of benzene, toluene, trimethylbenzene, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-heptane, dimethylformamide, or a combination thereof), in a palladium catalyst (preferably, the palladium catalyst is selected from the group consisting of tetratriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, allyl palladium chloride, bis (tri-tert-butylphosphino) palladium, palladium chloride, or a combination thereof) and in a ligand (preferably, the ligand is selected from the group consisting of triphenylphosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, 2-dicyclohexylphosphine-2 ',6' -diisopropyl-1, 1 ' -biphenyl, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene, or a combination thereof) with sodium or potassium cyanoacetate at 0-25 deg.c or 0 to reflux temperature to produce a compound of formula iv.
In another preferred embodiment, method d (i.e., the reaction shown in equation 5) is: in a solvent (preferably, the solventThe agent is selected from the group consisting of: benzene, toluene, trimethylbenzene, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-heptane, 1, 3-dimethylpropyleneurea, dimethylformamide, dimethylsulfoxide, or a combination thereof) in a palladium catalyst (preferably, the palladium catalyst is selected from the group consisting of: tetrakistriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, allylpalladium chloride, bis (tri-tert-butylphosphine) palladium, palladium chloride) and a ligand (preferably, the ligand is selected from the group consisting of: triphenylphosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, 2-dicyclohexylphosphine-2 ',6' -diisopropyl-1, 1 ' -biphenyl, diphenyl-2-pyridylphosphine, 2- (di-tert-butylphosphine) biphenyl, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene, or a combination thereof, in the presence of a base (preferably, the base is selected from the group consisting of: sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium fluoride, lithium acetate, or combinations thereof) at 0-25 ℃ or 0 to reflux temperature2R3R4Substituted disilanes (i.e.
Figure BDA0002064091570000091
) And reacting to obtain the compound shown in the formula IV.
In another preferred embodiment, method e (i.e., the reaction shown in equation 6) is: reacting a compound of formula VII and R in a solvent (preferably selected from the group consisting of benzene, toluene, ethyl acetate, tetrahydrofuran, diethyl ether, n-heptane, dimethylformamide, or combinations thereof) in the presence of a base (preferably n-butyllithium) at a temperature of-78-0 ℃ or-78 ℃ to reflux temperature2R3R4Substituted chlorosilanes
Figure BDA0002064091570000092
And reacting to obtain the compound of formula VI.
In a second aspect of the invention, there is provided the use of a compound according to the first aspect,
(i) for killing and/or controlling mites and/or their eggs; (ii) for the preparation of a composition or formulation for killing and/or controlling mites and/or their eggs; (iii) for insecticidal and/or bactericidal use; and/or (iv) for the preparation of a composition or formulation for insecticidal and/or bactericidal 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 example, the mites are harmful mites; preferably, the mites comprise: tetranychus urticae, tetranychus cinnabarinus, tetranychus urticae, panonychus citri, tetranychus cinnabarinus, tetranychus urticae, and rust citrus mites, or a combination thereof.
In a third aspect of the invention there is provided a composition comprising (i) as active ingredient a compound as claimed in claim 1, 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 an acaricidal composition.
In a fourth aspect of the invention there is provided a method of killing mites, comprising the steps of: contacting the mite with an effective amount of a compound as described in the first aspect or a composition as described in the second aspect.
In a fifth aspect the present invention provides a method of combating and/or killing bacteria, comprising the steps of: contacting insects and/or bacteria in need of killing with an effective amount of a compound according to the first aspect or a composition according to the second aspect.
In another preferred embodiment, the insects and/or bacteria to be killed include: diamondback moth, broad bean single cell rust fungus.
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.
Detailed Description
The inventor has conducted extensive and intensive studies and unexpectedly found a class of silicon acyl acetonitrile-containing compounds (shown in formula I) with a novel structure, and the compounds have excellent insecticidal and acaricidal activity. 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 sufficient to produce insecticidal and acaricidal effects without causing serious adverse 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.
Compound containing silicon acyl acetonitrile
Although some acyl acetonitrile compounds with acaricidal activity are disclosed in the prior art, the compounds have the problem of acarid resistance, and the research progress of the novel acaricide is slow. Therefore, through continuous innovative search, the inventor unexpectedly finds a plurality of silicon acyl acetonitrile compounds with novel structures and excellent acaricidal and insecticidal activities, and compared with the existing compounds, the compounds (i.e. the compounds shown in the formula I) have similar or even more excellent technical effects.
As used herein, the term compound of the present invention refers to a class of silicon-containing acetonitrile compounds represented by formula I, which term also includes geometric isomers, or stereoisomers thereof, or salts, and mixtures of isomers thereof.
Specifically, the invention provides a silicon acyl acetonitrile-containing compound shown as a formula I, which can show excellent acaricidal and insecticidal activity at an extremely high concentration.
Figure BDA0002064091570000131
The groups in formula I are as defined in the first aspect.
In one embodiment, the present invention provides a compound of formula I including, but not limited to, the compounds in the following compound table (i.e., Table 1):
table 1 compound list 1
Figure BDA0002064091570000132
Figure BDA0002064091570000133
Figure BDA0002064091570000141
Figure BDA0002064091570000151
Figure BDA0002064091570000161
Figure BDA0002064091570000171
Figure BDA0002064091570000181
Figure BDA0002064091570000191
Figure BDA0002064091570000201
Figure BDA0002064091570000211
Figure BDA0002064091570000221
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.
In one embodiment, the compound of formula I is prepared by the following reaction:
reaction formula 1:
Figure BDA0002064091570000222
reaction formula 2:
Figure BDA0002064091570000223
reaction formula 3:
Figure BDA0002064091570000231
reaction formula 4:
Figure BDA0002064091570000232
reaction formula 5:
Figure BDA0002064091570000233
reaction formula 6:
Figure BDA0002064091570000234
the compound of formula I (reaction formula 1) is prepared by reacting the compounds of formula II and formula III in the presence of alkali sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide and lithium diisopropylamide in solvents of benzene, toluene, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-heptane and dimethylformamide at 0-25 ℃ or up to the reflux temperature of the solvents, and the related experimental methods can refer to the synthetic methods in the prior art or the methods in the examples of the application;
reacting a compound of a formula II (reaction formula 2) with diethyl carbonate in a solvent of benzene, toluene, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-heptane and dimethylformamide in the presence of alkali sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide and lithium diisopropylamide at 0-25 ℃ or above to the reflux temperature of the solvent to obtain a compound of a formula V; the compound of formula V and R are catalyzed by sulfuric acid or aluminum isopropoxide1(CH2)nThe ZH reaction produces the compound of formula II, and the related experimental method can refer to the synthetic method in the prior art or the method in the embodiment of the application; or
Formula IIThe compound (reaction formula 3) is prepared in a solvent of benzene, toluene, dichloromethane, tetrahydrofuran, diethyl ether and by using phosgene or triphosgene R1(CH2)nZH reaction to obtain ClCOZ (CH)2)nR1(ii) a Then, in the presence of benzene, toluene, ethyl acetate, dichloromethane, tetrahydrofuran, n-heptane and dimethylformamide as solvents, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide, sodium ethoxide, lithium diisopropylamide and n-butyllithium as bases, reacting the compound with a formula IV at 0-25 ℃ or at a temperature as high as the reflux temperature of the solvents to obtain a compound with a formula II, wherein the related experimental method can refer to the synthetic method in the prior art or the method in the embodiment of the application;
the compound of formula IV (reaction formula 4) is prepared by the reaction of the compound of formula VI with sodium cyanoacetate or potassium cyanoacetate in the solvent of benzene, toluene, trimethylbenzene, ethyl acetate, dichloromethane, tetrahydrofuran, diethyl ether, n-heptane, dimethylformamide in the presence of palladium catalyst of palladium tetrakistriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, allylpalladium chloride, bis (tri-tert-butylphosphino) palladium, palladium chloride and the combination of ligand triphenylphosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, 2-dicyclohexylphosphine-2 ',6' -diisopropyl-1, 1 ' -biphenyl, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene at 0-25 ℃ or up to the solvent reflux temperature Reference may be made to synthetic methods in the prior art or to the methods in the examples of the present application; or
A compound of formula IV (reaction formula 5) is prepared in the presence of a palladium catalyst of palladium tetrakistriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, allylpalladium chloride, bis (tri-tert-butylphosphino) palladium, palladium chloride and in the presence of a ligand of triphenylphosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, 2-dicyclohexylphosphine-2 ',6' -diisopropyl-1, 1 ' -biphenyl, diphenyl-2-pyridylphosphine, 2- (di-tert-butylphosphino) biphenyl, 4, 5-bis (diphenylphosphino) -9, in the presence of a combination of 9-dimethylxantheneUsing a compound of formula VII and R in the presence of an alkali selected from the group consisting of sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium fluoride, lithium acetate at a temperature of from 0 to 25 ℃ or up to the reflux temperature of the solvent2R3R4Substituted disilanes are reacted to produce the compound of formula IV, and the related experimental methods can be found in the synthesis methods of the prior art or in the examples of the present application;
a compound of formula VI (equation 6) is prepared from a compound of formula VII and R in the presence of n-butyllithium in the solvents of benzene, toluene, ethyl acetate, tetrahydrofuran, diethyl ether, n-heptane and dimethylformamide at-78-0 deg.C or up to the reflux temperature of the solvent2R3R4Substituted chlorosilane is reacted to prepare the compound shown in the formula VI, and the related experimental method can refer to a synthetic method in the prior art or a method in the embodiment of the application;
R1，R2，R3，R4，R5m, n, X are as defined in the first aspect.
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 acyl acetonitrile compound shown in the formula I and application thereof.
The compound containing the silicon acyl acetonitrile shown in the formula I shows excellent mite control activity on various pest mites in agriculture or other fields, such as cotton leaf mites, tetranychus cinnabarinus (Carmine spider mite), tetranychus urticae (two-spotted spider mite), Citrus red mite (Citrus red mite), tetranychus cinnabarinus (Kanzawa spider mite), tea midtarsal mite (Broad mite) and Citrus rust mite (Pink Citrus rust mite) 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 compound containing the silicon acyl acetonitrile shown in the formula I as the acaricide in agriculture or other fields.
The compound of the invention shown in formula I and containing the silicon acyl acetonitrile can be prepared into an acaricide composition by a conventional method. 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, attapulgite, 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 present invention of the compound of formula I can be made into a mixture with other active compounds in their commercial formulations or from these formulations prepared using dosage forms, these other active compounds are insecticides, bactericides, fungicides, herbicides, growth control agents, etc. Insecticides include, for example, phosphates, carbamates, chlorinated hydrocarbons, and substances produced by microorganisms, such as avermectins, etc., and fungicides include strobilurins, amides, triazoles, etc.
Furthermore, the silicon acyl acetonitrile-containing compounds 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, or 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 of the invention has excellent acaricidal activity.
(b) The compounds of the invention also have insecticidal and fungicidal 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 provided by the invention has remarkable structural innovation.
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 Compound 4
(1) Preparation of trimethylsilyl bromobenzene:
Figure BDA0002064091570000261
2.9g of p-dibromobenzene is weighed into a Schlenk reaction bottle, 100ml of anhydrous THF is added for dissolution, 5ml of n-BuLi (2.5M) is slowly dripped after stirring at-78 ℃, stirring is continued at-78 ℃ after dripping is finished, and then 1.8ml of trimethylchlorosilane is dripped. Gradually increasing to room temperature, adding saturated NH4After the Cl solution, extraction was performed with ethyl acetate (30 mL. times.3), and 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 and purified by column chromatography to give the title compound as a colorless oil in 74.7% yield.1H NMR(400MHz,Chloroform-d)δ7.48(d,J＝8.2Hz,2H),7.37(d,J＝8.3Hz,2H),0.25(s,9H)ppm。
(2) Preparation of p-trimethylsilylbenzacetonitrile:
Figure BDA0002064091570000271
37mg of allylpalladium chloride, 123mg of 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl and 800mg of sodium cyanoacetate were weighed into a two-necked flask. After purging with argon for three times, 1.15g of p-trimethylsilylbenzene and 10ml of mesitylene were added by a syringe, and the mixture was stirred at room temperature and then heated at 140 ℃ to react. After the reaction is finished, the reaction product is cooled to room temperature and purified by column chromatography to obtain yellow oily matter with the yield of 73.2 percent.1H NMR(400MHz,Chloroform-d)δ7.53(d,J＝8.1Hz,2H),7.32(d,J＝8.1Hz,2H),3.74(s,2H),0.27(s,9H)ppm。
(3) Preparation of ethyl 2- (4-trimethylsilylbenzene) -cyanoacetate:
Figure BDA0002064091570000272
weighing 600mg NaH in a 50ml two-mouth bottle, adding 30ml THF, and stirring and dispersing uniformly under ice bath; 1.9g of p-trimethylsilylphenylacetonitrile was weighed out and added dropwise to a suspension of NaH in THF. After further stirring for 20min, 1.5g of diethyl carbonate were added dropwise and reacted at 46 ℃. 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 purified by column chromatography to give the title compound as an orange oil with a yield of 72.8%.1H NMR(400MHz,Chloroform-d)δ7.57(d,J＝8.2Hz,2H),7.44(d,J＝8.0Hz,2H),4.70(s,1H),4.31–4.18(m,2H),1.29(t,J＝7.1Hz,3H),0.27(s,9H)ppm。
(4) Preparation of 2- (4-trimethylsilylbenzene) -cyanoacetic acid-2-methoxyisopropyl ester:
Figure BDA0002064091570000273
600mg of 2- (4-trimethylsilylphenyl) -cyanoacetic acid ethyl ester is weighed and dissolved in 15ml of isopropanol, two drops of concentrated sulfuric acid are added dropwise as a catalyst, and the reaction is carried out for 12 hours at 100 ℃. The reaction mixture was poured into 30mL of water, extracted with ethyl acetate (20 mL. times.3), and the organic phases were combined and saturatedAnd sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and purified by column chromatography to give the title compound as an orange oil with a yield of 85.3%.1H NMR(400MHz,Chloroform-d)δ7.44(d,J＝8.2Hz,2H),7.31(d,J＝8.0Hz,2H),4.98–4.87(m,1H),4.55(s,1H),1.14(d,J＝13.0Hz,6H),0.15(s,9H)ppm。
(5) Preparation of (RS) -isopropyl 2- (4-trimethylsilylphenyl) 2-cyano-3-oxo-3- (. alpha., -trifluoro-o-tolyl) propionate:
Figure BDA0002064091570000281
weighing 220mg of NaH (60%) in a single-mouth bottle, adding 10ml of THF, stirring and dispersing uniformly in an ice bath, weighing 800mg of 2- (4-tert-butyl benzene) -cyanoacetic acid 2-methoxyethyl ester, dropwise adding the solution into a THF suspension of the NaH in the ice bath, stirring and reacting for half an hour, weighing 800mg of 2-trifluoromethyl benzoyl chloride, dropwise adding the solution into the reaction solution, slowly heating to room temperature, and reacting overnight. After the reaction was completed, the reaction was quenched by adding a small amount of water under ice-bath. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. Removing solvent under reduced pressure, and purifying by column chromatography to obtain the target compound, white solid compound, melting point 109.8-113.4 deg.C, and yield 70.4%. 1H NMR (400MHz, Chloroform-d) δ 7.64(d, J ═ 7.9Hz,1H),7.48(s,5H),7.32(d, J ═ 15.2Hz,1H),6.95(d, J ═ 7.8Hz,1H),5.00(hept, J ═ 6.2Hz,1H),1.19(d, J ═ 6.3Hz,3H),1.14(d, J ═ 6.3Hz,3H),0.15(s,9H) ppm.
EXAMPLE 2 preparation of Compound 6
(1) Preparation of 2- (4-trimethylsilylbenzene) -2-methoxyisobutyl cyanoacetate:
Figure BDA0002064091570000282
600mg of 2- (4-trimethylsilylphenyl) -cyanoacetic acid ethyl ester is weighed and dissolved in 15ml of isobutanol, two drops of concentrated sulfuric acid are added dropwise as a catalyst, and the reaction is carried out for 12 hours at 100 ℃. The reaction mixture was poured into 30mL of water, extracted with ethyl acetate (20 mL. times.3)The organic phases are combined and washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. Removing the solvent under reduced pressure, and purifying by column chromatography to obtain the target compound, light yellow oily substance, with a yield of 82.2%;1H NMR(400MHz,Chloroform-d)δ7.44(d,J＝8.1Hz,2H),7.31(d,J＝8.0Hz,2H),4.02(ddd,J＝29.5,10.5,6.5Hz,2H),2.09–1.94(m,1H),0.95(d,J＝6.7Hz,6H),0.30(s,9H)ppm。
(2) preparation of isobutyl (RS) -2- (4-trimethylsilylphenyl) 2-cyano-3-oxo-3- (. alpha., -trifluoro-o-tolyl) propionate:
Figure BDA0002064091570000291
200mg of NaH (60%) is weighed in a single-mouth bottle, 10ml of THF is added to the single-mouth bottle, the mixture is stirred and dispersed evenly under ice bath, 800mg of 2- (4-tert-butyl benzene) -cyanoacetic acid 2-methoxyethyl ester is weighed and dripped into THF suspension of the NaH under ice bath, after stirring and reacting for half an hour, 800mg of 2-trifluoromethyl benzoyl chloride is weighed and dripped into the reaction liquid, the temperature is slowly raised to the room temperature, and the reaction is carried out overnight. After the reaction was completed, the reaction was quenched by adding a small amount of water under ice-bath. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. Removing solvent under reduced pressure, and purifying by column chromatography to obtain the target compound, white solid compound, melting point 109.8-113.4 deg.C, and yield 78.4%.1H NMR(400MHz,Chloroform-d)δ7.64(d,J＝7.9Hz,1H),7.48(s,5H),7.32(d,J＝15.2Hz,1H),6.95(d,J＝7.8Hz,1H),5.00(hept,J＝6.2Hz,1H),1.19(d,J＝6.3Hz,3H),1.14(d,J＝6.3Hz,3H),0.15(s,9H)ppm.
EXAMPLE 3 preparation of Compound 23
(1) Preparation of allyl 2- (4-trimethylsilylbenzene) -cyanoacetate:
Figure BDA0002064091570000292
15mL of anhydrous THF was added to the dried Schlenk reaction tube, and 4mL of LDA (1.5M) was added dropwise in an ice bath; then 1.1g of trimethylsilylbenzacetonitrile was added dropwise in an ice bath and slowly increased toAfter room temperature, 650mg of allyl chloroformate was added dropwise while cooling on ice, and the temperature was slowly raised to room temperature. 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 purified by column chromatography to give an orange-yellow oil with a yield of 72.8%.1H NMR(400MHz,Chloroform-d)δ7.45(d,J＝8.1Hz,2H),7.32(d,J＝8.0Hz,2H),5.83–5.68(m,1H),5.14(d,J＝11.6Hz,1H),4.62(s,1H),4.55(d,J＝5.8Hz,2H),0.15(s,9H)ppm。
(2) Preparation of allyl (RS) -2- (4-trimethylsilylphenyl) 2-cyano-3-oxo-3- (. alpha.,. alpha. -trifluoro-o-tolyl) propionate
Figure BDA0002064091570000301
Weighing 220mg of NaH (60%) in a single-mouth bottle, adding 10ml of THF, stirring and dispersing uniformly in an ice bath, weighing 800mg of 2- (4-tert-butyl benzene) -cyanoacetic acid 2-methoxyethyl ester, dropwise adding the solution into a THF suspension of the NaH in the ice bath, stirring and reacting for half an hour, weighing 800mg of 2-trifluoromethyl benzoyl chloride, dropwise adding the solution into the reaction solution, slowly heating to room temperature, and reacting overnight. After the reaction was completed, the reaction was quenched by adding a small amount of water under ice-bath. Extraction with ethyl acetate (20 mL. times.3), combining the organic phases, washing with saturated sodium chloride solution, and drying over anhydrous sodium sulfate. Removing solvent under reduced pressure, and purifying by column chromatography to obtain white solid compound with melting point of 90.2-91.6 and yield of 73.8%.1H NMR(400MHz,Chloroform-d)δ7.63(d,J＝7.9Hz,1H),7.49(s,5H),7.32(t,J＝7.6Hz,1H),6.95(d,J＝7.8Hz,1H),5.83–5.69(m,1H),5.28–5.12(m,2H),4.71–4.56(m,2H),0.15(s,9H)ppm.
The compounds in table 2 were also prepared with different starting materials with reference to the above preparation method; other silicon acyl acetonitrile-containing compounds of formula I of the present invention may also be prepared using suitable starting materials by reference to the methods of the above examples:
table 2 compounds of some examples
Figure BDA0002064091570000302
Figure BDA0002064091570000311
Figure BDA0002064091570000321
Figure BDA0002064091570000331
Examples of biological Activity assays
In the bioassay example, the acaricidal activity, the insecticidal activity and the bactericidal activity of the compound are tested, and the result shows that the compound has good acaricidal activity and certain insecticidal activity and bactericidal activity.
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%). The activity results were evaluated on four scales of 100, 80, 50, 0 (100 indicating complete lethality, 80 indicating significant lethality, 50 indicating partial lethality, 0 indicating no activity). Commercial Cyflumetofen (a commercial miticide) is taken as a positive control, and a water solution of Trifloxate is taken as a blank control. The results of the activity assay of some compounds against Tetranychus urticae are shown in Table 3.
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. Removing surface waxy layer from caulis et folium Brassicae Capitatae leaf, and making into beverageThe cabbage leaves are made into a cabbage leaf dish with a diameter of about 6cm, and the leaves are placed in a culture dish with the back facing upwards. 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 triton, 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 st larva of the plutella xylostella is inoculated, the process is repeated for 3 times, indoxacarb is used as a positive control, and a water solution of the 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 result shows that the compound has certain activity on diamond back moth, for example, the compound 96 is at 500mg L-1The activity to diamondback moth is 100% under the concentration.
Evaluation of fungicidal Activity against Puccinia fabarum (Uromyces viciae-fabae)
Test solutions of different concentrations of the test compound were prepared from 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 medicament treatment in a shade place, inoculating pathogenic bacteria spores after 24 hours, repeating for 3 times, setting azoxystrobin as a positive control, and additionally setting a blank control. And (3) culturing the inoculated crops in an artificial climate chamber, and investigating the control effect after culturing the diseases for 7d and 10d respectively. The result shows that the compound has certain activity on diamond back moth, for example, the compound 96 is 100mg L-1Has 100 percent of inhibitory activity to broad bean monad rust fungus under the concentration.
TABLE 3 Activity assay of Tetranychus urticae for some of the Compounds
Figure BDA0002064091570000341
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and 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 present invention as defined by the appended claims.

Claims (11)

1. A silicon-containing acylacetonitrile compound, or a geometric isomer thereof, or a stereoisomer thereof, or a salt thereof, wherein the compound is represented by formula I:
Figure 28083DEST_PATH_IMAGE001
in the formula (I), the compound is shown in the specification,
R1selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy, phenyl, 4-to 10-membered heterocyclyl;
n is 0, 1, 2, 3 or 4;
R2，R3and R4Each independently selected from the group consisting of: hydrogen, C1-6Alkyl radical, C2-6Alkenyl, and C2-6An alkynyl group;
R5is R6；
R6Is substituted or unsubstituted phenyl; r6Wherein said substitution means that the hydrogen on the group is substituted with 1 to 5 groups selected from the group consisting of: halogen, C1-6An 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: oxygen, sulfur;
R1，R2，R3，R4，R5，R6and one or more hydrogen atoms in the X group can also be substituted with substituents each independently selected from the group consisting of: halogen, C1-6An alkyl group.
2. The compound of claim 1, wherein R is1Selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy radical,Tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyrrolyl, tetrahydrothiazolyl, tetrahydropyrazolyl, tetrahydroimidazolyl, tetrahydrotriazolyl, and hexahydropyridyl.
3. The compound of claim 1, wherein R is6Wherein said substitution means that the hydrogen on the group is substituted by 1, 2 or 3 groups selected from the group consisting of: halogen, C1-6An alkyl group.
4. The compound of claim 1, wherein R is2，R3And R4Each independently selected from the group consisting of: c1-3Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl.
5. The compound of claim 1,
in the formula I, the compound is shown in the specification,
R1selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C3-7Cycloalkyl radical, C1-6Alkoxy, tetrahydrofuryl, tetrahydrothienyl, tetrahydropyrrolyl, tetrahydrothiazolyl, tetrahydropyrazolyl, tetrahydroimidazolyl, tetrahydrotriazolyl, and piperidinyl;
n is 0, 1, 2, 3 or 4;
R2，R3and R4Each independently selected from the group consisting of: c1-3Alkyl radical, C2-4Alkenyl radical, C2-4An alkynyl group;
R5is R6；
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, C1-3An alkyl group;
each X is independently selected from the group consisting of: hydrogen, halogen and C1An alkyl group;
m is 1 or 2;
z is selected from: oxygen;
R1，R2，R3，R4，R5，R6and one or more hydrogen atoms in the X group can also be substituted with substituents each independently selected from the group consisting of: halogen, C1-3An alkyl group.
6. The compound of claim 1,
in the formula I, the compound is shown in the specification,
R1selected from the group consisting of: c1-6Alkyl radical, C2-6Alkenyl radical, C3-7Cycloalkyl radical, C1-6Alkoxy, tetrahydrofuranyl;
n is 0, 1, 2, 3 or 4;
R2、R3and R4Each independently selected from the group consisting of: c1-3Alkyl radical, C2-4Alkenyl radical, C2-4An alkynyl group;
R5is R6；
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, C1-3An alkyl group;
each X is independently selected from the group consisting of: hydrogen, halogen and C1An alkyl group;
m is 1 or 2;
z is oxygen;
R1，R2，R3，R4，R5，R6and one or more hydrogen atoms in the X group can also be substituted with substituents each independently selected from the group consisting of: halogen, C1-3Alkyl group of (1).
7. The compound of claim 1, wherein said compound is selected from the group consisting of compounds of table a below;
Figure 381704DEST_PATH_IMAGE002
Figure 55262DEST_PATH_IMAGE003
。
8. a process for the preparation of a compound according to claim 1, comprising the steps of:
Figure 50900DEST_PATH_IMAGE004
(i) reacting a compound of formula II with a compound of formula III to obtain a compound of formula I;
wherein, m, n, R1、R2、R3、R4、R5Z and X are as defined in claim 1.
9. Use of a compound according to claim 1,
(i) for killing and/or controlling mites and/or their eggs; (ii) for the preparation of a composition or formulation for use in the killing and/or control of mites and/or their eggs; (iii) for insecticidal and/or bactericidal use; and/or (iv) for the preparation of a composition or formulation for insecticidal and/or bactericidal use.
10. A composition comprising (i) a compound according to claim 1 as an active ingredient, and (ii) a carrier and/or surfactant.
11. A method of killing mites comprising the steps of: contacting an acarid with an effective amount of a compound according to claim 1 or a composition according to claim 10.
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