CN112300079A - N-difluoromethyl azole selenourea derivative or agriculturally and pharmaceutically acceptable salt and application thereof - Google Patents

N-difluoromethyl azole selenourea derivative or agriculturally and pharmaceutically acceptable salt and application thereof Download PDF

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CN112300079A
CN112300079A CN202011222204.1A CN202011222204A CN112300079A CN 112300079 A CN112300079 A CN 112300079A CN 202011222204 A CN202011222204 A CN 202011222204A CN 112300079 A CN112300079 A CN 112300079A
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alkyl
radical
halo
difluoromethyl
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CN112300079B (en
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汤日元
郭雪莹
黄子豪
徐汉虹
熊兰图
魏林豪
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South China Agricultural University
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    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07D473/00—Heterocyclic compounds containing purine ring systems
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    • C07D473/32—Nitrogen atom
    • C07D473/34—Nitrogen atom attached in position 6, e.g. adenine

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  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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Abstract

The invention discloses an N-difluoromethyl azole selenourea derivative or an agriculturally and pharmaceutically acceptable salt and application thereof. The structure of the N-difluoromethyl azole selenourea derivative is shown as a general formula (I) or a general formula (II), and the definition of each substituent group in the formula is shown in the specification. The compound of the general formula (I) or the general formula (II) shows insecticidal activity on pests in agriculture and forestry and other fields, and the compound of the general formula (I) or the general formula (II) is used as an insecticide, namely the compound of the general formula (I) or the general formula (II) is used for preparing a medicament for preventing and treating the pests in the agriculture and forestry or other fields. Particularly, the insecticidal composition has excellent insecticidal activity against lepidopteran (Lepidotera) chewing mouthparts pests such as Plutella xylostella (Plutella xylostella), Spodoptera frugiperda (Spodoptera frugiperda), beet armyworm (S.exigua) and Spodoptera litura (S.litura).

Description

N-difluoromethyl azole selenourea derivative or agriculturally and pharmaceutically acceptable salt and application thereof
Technical Field
The invention belongs to the field of agricultural pesticides, and particularly relates to an N-difluoromethyl azole selenourea derivative or an agriculturally and pharmaceutically acceptable salt and application thereof.
Background
The nitrogen heterocyclic pesticide has the advantages of high insecticidal activity, broad spectrum, low toxicity and the like, and becomes an advantageous framework created by new pesticides. In recent years, the newly developed pesticides such as cycloxaprid, cyantraniliprole, sulfoxaflor, flonicamid, cyflumetofen, cyenopyrafen, spirotetramat, Flupyrimin and the like are nitrogen heterocyclic derivatives, and are mainly obtained by deriving nitrogen heterocycles such as pyrazole or pyridine. However, the problems of more serious drug resistance and exchange resistance caused by long-term use of the existing pesticide increase the difficulty of pest control. In particular, serious resistance is developed by serious pests such as Plutella xylostella (Plutella xylostella), Spodoptera frugiperda (Spodoptera frugiperda), Spodoptera exigua (S.exigua), Spodoptera litura (S.litura), Meloidogyne incognita (Meloidora) and the like. The development of new target pesticides with high efficiency and low toxicity is urgently needed to solve the current resistance problem. The key of creating new pesticide is to find new skeleton of pesticide with new acting target.
The azole compound has the advantages of variable structure, high selectivity, high efficiency, low toxicity and the like, accords with the development concept and requirements of modern green pesticides, and becomes an advantageous framework created by new pesticides. In the earlier stage, the study finds that the benzimidazolone derivative has insecticidal activity on diamond back moth, spodoptera frugiperda, spodoptera exigua and prodenia litura (patent application number: 202010743473.6), wherein the insecticidal activity effect of the benzimidazolone selenone is good. On the basis, the fluorine-containing group is designed to enhance the activity of the compound, and when the difluoromethyl group is introduced, the compound has obvious influence on the pharmacokinetic properties of the drug, namely membrane permeability, bioavailability, binding affinity, metabolic stability and lipophilicity. According to the analysis of the existing published documents, the N-difluoromethyl oxazole selenourea derivatives are not applied to insecticidal application, and the related reports do not disclose that the compounds have insecticidal activity on diamond back moth, spodoptera frugiperda, spodoptera exigua and prodenia litura.
Disclosure of Invention
In order to develop a novel pesticide lead compound, the invention aims at providing an N-difluoromethyl azole selenourea derivative or an agriculturally and pharmaceutically acceptable salt which can control various agricultural and forestry pests and sanitary pests.
The invention also aims to provide the application of the N-difluoromethyl azole selenourea derivative or the salt acceptable in the agricultural pharmacy in preparing the medicament for preventing and controlling pests in the agricultural or other fields.
The purpose of the invention is realized by the following technical scheme:
an N-difluoromethyl azole selenourea derivative for preventing and treating pests in agriculture and forestry or pests in other fields has a structure shown as a general formula (I) or a general formula (II);
Figure BDA0002762457330000021
the preferable technical scheme of the invention is as follows: in the general formula (I) or (II)
X is selected from C, N; y is selected from C, N;
R1selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, ethyl fluoroacetate, C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy, halo C1-C12Alkoxy radical, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl radical, C2-C12Alkenyl radical, C2-C12Alkynyl, C2-C12Alkenyloxy, halogeno C2-C12Alkenyloxy radical, C2-C12Alkynyloxy, halo C2-C12Alkynyloxy, C1-C12Alkylthio, halo C1-C12Alkylthio radical, C1-C12Alkoxy radical C1-C12Alkyl, halo C1-C12Alkoxy radical C1-C12Alkyl radical, C1-C12Alkylthio group C1-C12Alkyl, halo C1-C12Alkylthio group C1-C12Alkyl, sulfinyl-containing C1-C12Alkyl, halogen-and sulfinyl-containing C1-C12Alkyl radical, containing sulfonyl radical C1-C12Alkyl, halogen-containing and sulphonyl C1-C12Alkyl radical, containing amino group C1-C12Alkyl, amino-containing halogeno C1-C12Alkyl radical, C1-C12Alkoxycarbonyl, CONH2，C1-C12Alkylaminocarbonyl, di (C)1-C12Alkyl) aminocarbonyl, cyano C1-C12Alkoxy radical, C1-C12Alkoxycarbonyl radical C1-C12Alkyl radical, C1-C12Alkylaminocarbonyl radical C1-C12Alkyl, di (C)1-C12Alkyl) aminocarbonyl group C1-C12An alkyl group; or benzyl, pyridine methylene, pyrimidine methylene, thiazole methylene, thiophene methylene, furan methylene, pyrazole methylene; or phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C12Alkyl of (C)1-C12Alkoxy group of (C)1-C12Alkanethiol of (C)1-C12Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C1-C12Alcoxyl acyl radical, C1-C12An acyloxy group;
R2is a substituent at any position shown in the general formula (I) or (II), and can be mono-substituted, same or different groups of di-substituted and tri-substituted;
R2selected from hydrogen, C1-C12Alkyl of (C)1-C12Alkoxy group of (C)1-C12Alkanethiol of (C)1-C12Alkylamino of (C)1-C12Alcoxyl acyl radical, C1-C12Acyloxy, halogeno C1-C12Alkyl, halo C of1-C12Alkoxy, halo C of1-C12Alkanemercapto, halogeno C of1-C12Alkylamino, halogeno C of1-C12Alkoxyacyl, halo C1-C12Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide, or aryl containing one or more substituents,
aryl may be phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, andother heteroaryl groups containing one or more hetero atoms, such as oxygen, sulfur, nitrogen, etc., the substituent being C1-C12Alkyl of (C)1-C12Alkoxy group of (C)1-C12Alkanethiol of (C)1-C12Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C1-C12Alcoxyl acyl radical, C1-C12And (4) acyloxy.
The further preferable technical scheme of the invention is as follows: in the general formula (I) or (II)
X is selected from C, N; y is selected from C, N;
R1selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, ethyl fluoroacetate, C1-C8Alkyl, halo C1-C8Alkyl radical, C1-C8Alkoxy, halo C1-C8Alkoxy radical, C3-C8Cycloalkyl, halo C3-C8Cycloalkyl radical, C2-C8Alkenyl radical, C2-C8Alkynyl, C2-C8Alkenyloxy, halogeno C2-C8Alkenyloxy radical, C2-C8Alkynyloxy, halo C2-C8Alkynyloxy, C1-C8Alkylthio, halo C1-C8Alkylthio radical, C1-C8Alkoxy radical C1-C8Alkyl, halo C1-C8Alkoxy radical C1-C8Alkyl radical, C1-C8Alkylthio group C1-C8Alkyl, halo C1-C8Alkylthio group C1-C8Alkyl, sulfinyl-containing C1-C8Alkyl, halogen-and sulfinyl-containing C1-C8Alkyl radical, containing sulfonyl radical C1-C8Alkyl, halogen-containing and sulphonyl C1-C8Alkyl radical, containing amino group C1-C8Alkyl, amino-containing halogeno C1-C8Alkyl radical, C1-C8An alkoxycarbonyl group, a carbonyl group,CONH2，C1-C8alkylaminocarbonyl, di (C)1-C8Alkyl) aminocarbonyl, cyano C1-C8Alkoxy radical, C1-C8Alkoxycarbonyl radical C1-C8Alkyl radical, C1-C8Alkylaminocarbonyl radical C1-C8Alkyl, di (C)1-C8Alkyl) aminocarbonyl group C1-C8Alkyl, or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8Alkanethiol of (C)1-C8Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C1-C8Alcoxyl acyl radical, C1-C8An acyloxy group;
R2is a substituent at any position shown in a general formula (I) or (II), and can be mono-substituted, same or different groups of di-substituted and tri-substituted;
R2selected from hydrogen, C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8Alkanethiol of (C)1-C8Alkylamino of (C)1-C8Alcoxyl acyl radical, C1-C8Acyloxy, halogeno C1-C8Alkyl, halo C of1-C8Alkoxy, halo C of1-C8Alkanemercapto, halogeno C of1-C8Alkylamino, halogeno C of1-C8Alcoxyl acyl, halogen C1-C8Acyloxy, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethylTrichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8Alkanethiol of (C)1-C8Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C1-C8Alcoxyl acyl radical, C1-C8And (4) acyloxy.
The invention further preferably adopts the technical scheme that: in the general formula (I) or (II)
X is selected from C, N; y is selected from C;
R1selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, ethyl fluoroacetate, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyloxy, halogeno C2-C6Alkenyloxy radical, C2-C6Alkynyloxy, halo C2-C6Alkynyloxy, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkoxy radical C1-C6Alkyl, halo C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkylthio group C1-C6Alkyl, halo C1-C6Alkylthio group C1-C6Alkyl, sulfinyl-containing C1-C6Alkyl, halogen-and sulfinyl-containing C1-C6Alkyl radicals containing sulfurAcyl radical C1-C6Alkyl, halogen-containing and sulphonyl C1-C6Alkyl radical, containing amino group C1-C6Alkyl, amino-containing halogeno C1-C6Alkyl radical, C1-C6Alkoxycarbonyl, CONH2，C1-C6Alkylaminocarbonyl, di (C)1-C6Alkyl) aminocarbonyl, cyano C1-C6Alkoxy radical, C1-C6Alkoxycarbonyl radical C1-C6Alkyl radical, C1-C6Alkylaminocarbonyl radical C1-C6Alkyl, di (C)1-C6Alkyl) aminocarbonyl group C1-C6Alkyl, or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino of (C)1-C4Alcoxyl acyl radical, C1-C4Acyloxy, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl;
R2is a substituent at any position on an aromatic ring shown in a general formula (I) or (II), and can be mono-substituted, di-substituted and tri-substituted by the same or different groups; r3Selected from hydrogen, C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino of (C)1-C4Alcoxyl acyl radical, C1-C4Acyloxy, halogeno C1-C4Alkyl, halo C of1-C4Alkoxy, halo ofGeneration C1-C4Alkanemercapto, halogeno C of1-C4Alkylamino, halogeno C of1-C4Alcoxyl acyl, halogen C1-C4Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide, or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C1-C4Alcoxyl acyl radical, C1-C4And (4) acyloxy.
Still further preferred technical solution of the present invention is: in the general formula (I) or (II)
X is selected from C; y is selected from C;
R1selected from hydrogen, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, tribromomethyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6Alkenyl, halo C2-C6Alkynyl, C1-C6Ester group, C1-C6Acetoxy, C1-C6Cyano, or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
aryl may be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazoleAnd other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., the substituent may be C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C1-C4Alcoxyl acyl radical, C1-C4An acyloxy group;
R2is a substituent at any position shown in a general formula (I) or (II), and can be mono-substituted, same or different groups of di-substituted and tri-substituted;
R2selected from hydrogen, C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino of (C)1-C4Alcoxyl acyl radical, C1-C4Acyloxy, halogeno C1-C4Alkyl, halo C of1-C4Alkoxy, halo C of1-C4Alkanemercapto, halogeno C of1-C4Alkylamino, halogeno C of1-C4Alkoxyacyl, halo C1-C4Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide, or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, trifluoromethyl,C1-C4alcoxyl acyl radical, C1-C4And (4) acyloxy.
Still further preferred technical solution of the present invention is: in the general formula (I) or (II)
X is C; y is C;
R1selected from hydrogen, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, tribromomethyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6Alkenyl, halo C2-C6Alkynyl, C1-C6Ester group, C1-C6Acetoxy, C1-C6Cyano, or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C1-C4Alcoxyl acyl radical, C1-C4An acyloxy group;
R2is a substituent at any position shown in a general formula (I) or (II), and can be mono-substituted, same or different groups of di-substituted and tri-substituted;
R2selected from hydrogen, C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino of (C)1-C4Alcoxyl acyl radical, C1-C4Acyloxy, halogeno C1-C4Alkyl, halo C of1-C4Alkoxy, halo C of1-C4Alkanemercapto, halogeno C of1-C4Alkylamino, halogeno C of1-C4Alkoxyacyl, halo C1-C4Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide, or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, etc., and the substituent can be C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C1-C4Alcoxyl acyl radical, C1-C4And (4) acyloxy.
The invention also provides a salt formed by the compound shown in the general formula (I) or (II) and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid and the like.
In the definitions given above for compounds (I) or (II), the terms used collectively generally represent the following substituents:
halogen: refers to fluorine, chlorine, bromine or iodine. Alkyl groups: straight-chain or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl or tert-butyl. Cycloalkyl groups: substituted or unsubstituted cyclic alkyl groups, such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen, and the like. Halogenated alkyl groups: straight-chain or branched alkyl radicals, the hydrogen atoms in which may be presentPartially or totally substituted by halogen atoms, for example: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like. Alkoxy groups: straight or branched chain alkyl groups attached to the structure via oxygen atom linkages. Haloalkoxy groups: straight-chain or branched alkoxy groups in which the hydrogen atoms may be partially or completely replaced by halogen atoms. For example: chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like. Alkylthio group: straight or branched chain alkyl groups attached to the structure via a sulfur atom. Haloalkylthio: straight-chain or branched alkylthio groups in which the hydrogen atoms may be partially or fully substituted by halogen atoms, for example: chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like. Alkenyl: straight-chain or branched alkenes, for example ethenyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl also includes polyenes such as 1, 2-allenyl and 2, 4-hexadienyl. Halogenated alkenyl groups: straight-chain or branched alkenes in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynyl: straight-chain or branched alkynes, for example ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. Alkynyl also includes groups consisting of multiple triple bonds, such as 2, 5-hexadiynyl. Halogenated alkynyl group: straight-chain or branched alkynes, in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkenyloxy: linear or branched alkenes linked to the structure via oxygen atoms. Haloalkenyloxy: straight-chain or branched alkenyloxy groups in which the hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynyloxy: straight or branched alkynes, linked to the structure via oxygen atom bonds. Haloalkynyloxy: straight-chain or branched alkynyloxy, in which the hydrogen atoms may be partially or completely substituted by halogen atoms. Alkenyloxycarbonyl radical: such as CH2＝CHCH2OCO-, etc. Alkynyloxycarbonyl group: such as CH ≡ CCH2OCO-, etc. Alkylamino group: straight or branched chain alkyl, linked to the structure via a nitrogen atom.
Halogenated alkylamidosBase: straight-chain or branched alkylamino groups in which the hydrogen atoms may be partially or fully substituted by halogen atoms. Dialkylamino group: for example (CH)3)2NH-，(C2H5)2NH-. Alkylsulfinyl group: straight or branched chain alkyl groups are attached to the structure via a sulfinyl (-SO-) group, such as methylsulfinyl. Cyanoalkoxy group: CN-alkoxy, e.g. CNCH3O，CNC2H5And O. Alkylsulfinyl group: straight or branched chain alkyl groups are attached to the structure via a sulfinyl (-SO-) group, such as methylsulfinyl. Haloalkylsulfinyl group: straight-chain or branched alkylsulfinyl groups in which the hydrogen atoms of the alkyl group may be partially or fully substituted by halogen atoms. An alkylsulfonyl group: straight or branched chain alkyl via sulfonyl (-SO)2-) is attached to a structure, such as a methylsulfonyl group. Haloalkylsulfonyl group: straight-chain or branched alkylsulfonyl wherein the hydrogen atoms of the alkyl group may be partially or wholly substituted by halogen atoms. An alkylcarbonyl group: the alkyl radical being bound to the structure via a carbonyl group, e.g. CH3CO-，CH3CH2 CO-. Halogenated alkylcarbonyl group: the hydrogen atoms of the alkyl group of the alkylcarbonyl group may be partially or fully substituted by halogen atoms, e.g. CF3CO-. Alkoxycarbonyl group: alkyl-O-CO-, such as CH3OCO-, C2H5OCO-. Halogenated alkoxycarbonyl group: the hydrogen atoms of the alkyl group of the alkoxycarbonyl group may be partially or wholly replaced by halogen atoms, e.g. ClCH2CH2OCO-、CF3CH2OCO-, etc. Alkoxycarbonylalkyl groups: alkoxycarbonyl-alkyl-, e.g. CH3OCOCH2-. Alkoxyalkyl groups: alkyl-O-alkyl-, e.g. CH3OCH2-. Haloalkoxyalkyl groups: the hydrogen atoms on the alkyl group of the alkoxyalkyl group may be partially or fully substituted with halogen atoms. Such as ClCH2CH2OCH2-. Alkylthioalkyl: alkyl-S-alkyl-, e.g. CH3SCH2-. Haloalkylthioalkyl: the hydrogen atoms of the alkyl group of an alkylthioalkyl group may be partially or fully substituted by halogen atoms, e.g. ClCH2CH2SCH2-、CF3CH2SCH2-and the like. Alkylaminosulfonyl: alkyl-NH-SO2-. Cycloalkyloxycarbonyl group: such asCyclopropyloxycarbonyl, cyclohexyloxycarbonyl, and the like. Alkylcarbonylalkyl group: alkyl-CO-alkyl-. Alkyl amino carbonyl: alkyl-NH-CO-, for example: CH (CH)3NHCO-、(CH3)2NCO-. Dialkylaminocarbonyl group: (alkyl group)2-NH-CO-, for example: (CH)3)2-N-CO-、(C2H5)2-N-CO-. Alkoxy alkoxycarbonyl group: such as CH3OCH2CH2OCO-, etc. Alkylaminocarbonylalkyl: such as CH3NH2COCH2-. Dialkylaminocarbonylalkyl: for example (CH)3)2NH2COCH2-. Aryl: including phenyl or naphthyl and the like. Heteroaryl group: refers to a five or six membered ring containing 1 or more heteroatoms of N, O, S. For example: pyrrolyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, indolinyl, benzofuryl, benzoxazolyl, benzothienyl, benzothiazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, benzopyrazolyl, quinoxalinyl, and the like. Aryloxy group: including phenoxy and the like. Heteroaryloxy group: including pyridyloxy and the like. (hetero) arylcarbonyl group: such as benzoyl, 4-chlorobenzoyl, picolinoyl, pyrimidoyl, pyrazinoyl and the like. (hetero) aryloxycarbonyl group: such as phenoxycarbonyl, 4-chlorophenoxycarbonyl, 4-nitrophenoxycarbonyl, naphthyloxycarbonyl, pyridyloxycarbonyl, pyrimidyloxycarbonyl and the like. (hetero) arylcarbonylalkyl: such as PhCOCH2-. (hetero) aryloxycarbonylalkyl: such as PhOCOCH2-. (hetero) arylalkyl: such as benzyl, phenethyl, p-chlorobenzyl,
Figure BDA0002762457330000081
And the like. Aryloxyalkyl radicals such as:
Figure BDA0002762457330000082
and the like. Sugar group: it refers to an alcoholic sugar group or an aldehyde sugar group, such as a glucosyl group, a galactosyl group, etc. Amino acids: refers to organic compounds containing amino and carboxyl groups, such as glutamic acid, cysteine, lysine,Proline, valine, arginine, tryptophan, leucine, and the like. Peptide chain: refers to chain or cyclic oligopeptides or polypeptides formed by dehydrating and condensing the same or different amino acids.
The term "acceptable salt" refers to salts whose cations or anions are known and which are useful in forming uses in the art.
Suitable salts with bases are, for example: salts formed from compounds of formula (I) or (II) containing a carboxyl group include salts of alkali metals (e.g., sodium and potassium), alkaline earth metals (e.g., calcium and magnesium), ammonium and amines.
Suitable salts with addition of acid groups, such as salts formed from compounds of formula (I) or (ii) containing amino groups, include salts with inorganic acids, such as hydrochloride, sulfate, sulfite, phosphate, hydrogen phosphate and nitrate, and salts with organic acids, such as acetic, malic, tartaric, citric, lactic, salicylic and oxalic acids, and the like.
Some of the compounds of the present invention are exemplified by the specific compounds listed below, but the present invention is not limited to these compounds.
Figure BDA0002762457330000091
Figure BDA0002762457330000101
Figure BDA0002762457330000111
The reaction path of the compound of the general formula (I) or (II) is shown as the formulas (1) and (2), wherein X1Is Cl or Br or I.
The preparation methods of the compounds I-1 to I-37 are shown in the reaction path (1); the production methods of the compounds II-1 to II-37 are shown in the reaction scheme (2).
(1)
Figure BDA0002762457330000121
(2)
Figure BDA0002762457330000122
X in the formula1Refers to chlorine, bromine or iodine.
The alkali is potassium carbonate or potassium tert-butoxide.
The compounds of the present invention are useful for controlling and exterminating a wide range of agricultural and forestry pests, hygiene pests and pests that are harmful to the health of animals. In the present specification, "pesticide" is a general term for a substance having an effect of controlling all the pests mentioned above. Examples of pests include, but are not limited to: lepidopteran (Lepidoptera) insects: for example, Plutella xylostella (Plutella xylostella), Spodoptera frugiperda (Spodoptera frugiperda), Spodoptera exigua (s.exigua), Spodoptera litura (s.litura), gypsy moth (Lymantria dispar), trichosanthis tenuis (malacomonas campestris), southern cottoniana (Diaphania persica persicaria), gloriosa gigas (Diaphania persicaria), gloriosa gigantea (Clania variegata), yellow spiny moth (cnidocapa flaugesens), red pine moth (Dendrolimus puncatus), ancient poisonous moth (Orgyia anticaqua), poplar piercing through moth (Paranthrene tabaniformis), Chilo suppressalis (Chisupppressalis), corn borer (Ostrinia nubilalis), pink moth (Ostrinia), Ostrinia (Ostrinia), Ostrinia nubilalis (Ostrinia nubilalis), oriental moth (Ostrinia nubilalis), oriental armyworm (Ostrinia nubila, etc.; coleopteran (Coleoptera) insects: for example, elephants of corn (Sitophilus zeamais), Tribophytes castanea (Tribolum castaneum), Harpagophytum procumbens (Henosapillaria virginiana), Iris pusilla (H. sparsa), Elaeagnus microphylla (Agriotes fusciplis), Rhynchophylla rubra (Anamala cuprina), Rhynchophylla quadrifarina (Popilia squaruta), Rhizoma equi (Monocyclopia hippophylla), Rhizophora bellifera (Monocyclopia hippophaga), Monochamus alternatus (Monochamus alternatus), Rhizoctonia oryzae (Basidiotota biosignata), Tagetes bullosa (Anoplophora chinensis), Morus alba (Apropora geri), Abrus umbilicalis (Sophora zea), or Verticillicularia (Agileria brasiliensis, etc.; hemipteran (Hemiptera) insects: for example, Nephrosic brevicoryza sativa (Stephanitis nashi), Nezara viridula oryzae (Nezara viridula), Pirardinus sasaiana (Poecilocoris latis), Pirardinus oryzae (Cletus punctiger), Orthosiphon aristatus (Dimorphopipterus japonicus), Pirardinus gossypii (Dysdercus cingulatus), and the like; homoptera (Homoptera) insects: for example, leafhopper nigricans (Nephotettix cincticeps), arrowhead scales (Unaspis yanonensis), green peach aphids (Myzus persicae), cotton aphids (Aphis gossydii), whitefly (Bemisia tabaci), Laodelphax striatellus (Laodelphax striatellus), Nilaparvata lugens, Sogatella furcifera (Sogatella furcifera), etc.; orthoptera (Orthoptera) insects: for example, mole cricket in africa (Gryllotalpa africana), locusta migratoria asiatica (Locus migratoria), etc.; hymenoptera (Hymenoptera) insects: for example, Solenopsis invicta (Solenopsis invicta), bracon versicolor (Tremex fusceronis), and the like; insects of the order blattaria: for example, german cockroach (Blattella germanica), american cockroach (Periplaneta americana), termite (copoters for mosamuus), etc.; diptera (Diptera) insects: for example, houseflies (Musca domestica), Aedes aegypti (Aedes aegypti), seed flies (Delia platura), Culex mosquitoes (Culex mosquitoes), Anopheles sinensis (Anopheles sinensis), and the like; plant parasitic nematodes: such as root-knot nematodes, root-rot nematodes, aphelenchoides besseyi, bursaphelenchus xylophilus, and the like. Pests that pose a health hazard to animals include Boophilus microplus (Boophilus microplus), Haemaphysalis longicornis (Haemaphysalis longicornis), Hyalomma microphyllum (Hyalomma anaticum), Dermata bovis (Hypoderma bovis), Fasciola hepatica (Facilia hepatica), Monizzia beijerincana (Moniezia blanchard), Protozoa (Trypanosoma enansi), Babesia bigemina (Babesia bigemina), and the like.
The compounds of the general formula (I) or (II) show control effects on pests in the field of agricultural technology. Therefore, another technical scheme of the invention relates to the application of the compound shown in the general formula (I) or (II) as a pesticide, namely the application of the compound shown in the general formula (I) or (II) in preparing pesticides for controlling pests in agriculture or other fields.
In particular, the preferred compounds of the general formula (I) or (II) show better poisoning effect on chewing mouthparts pests such as diamondback moth, spodoptera frugiperda, beet armyworm and prodenia litura.
An insecticidal composition comprises active components (compounds of general formula (I) or (II)) and agriculturally acceptable carriers, wherein the weight percentage of the active components in the composition is 0.01-99.99%;
a process for the preparation of a composition as defined above: mixing a compound of formula (I) or (II) with a carrier. The active ingredient in such compositions may comprise a single compound or a mixture of several compounds according to the invention.
The above compositions may be administered in the form of a formulation. The compounds of formula (I) or (II) as active ingredients are dissolved or dispersed in a carrier or formulated so as to be more easily dispersed for use as insecticides. For example: the chemical preparation can be prepared into powder, wettable powder, missible oil, concentrated emulsion and microemulsion, suspension emulsion, granule, oil solution and ultra-low volume spray, smoke type, slow release agent and other pesticide dosage forms. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added.
The carrier in the composition of the present invention is a substance satisfying the following conditions: it is formulated with the active ingredient so as to be conveniently applied to the locus to be treated, which may be, for example, a plant, seed or soil; or to facilitate storage, transport or handling. The carrier may be a solid or a liquid, including materials which are normally gaseous but which have been compressed to form a liquid, and carriers which are normally used in formulating insecticidal compositions may be used.
The agricultural composition can be used in pesticide for killing or preventing agricultural and forestry pests, sanitary pests or pests harmful to animal health.
The use according to the above, characterised in that the insecticide is applied to the pests or to the medium on which the pests are growing.
For certain applications, for example in agriculture, one or more other types of insecticides, nematicides, acaricides, bactericides, herbicides, plant growth regulators or fertilizers and the like can be added to the insecticide composition of the invention, whereby additional advantages and effects can be brought about.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the compound of the general formula (I) or (II) shows insecticidal activity to pests in agriculture and forestry and other fields, and the compound of the general formula (I) or (II) is used as an insecticide, namely the compound of the general formula (I) or (II) is used for preparing a medicament for preventing and controlling the pests in the agriculture and forestry or other fields. In particular has better poisoning effect on lepidoptera pests such as plutella xylostella, spodoptera frugiperda, spodoptera exigua, spodoptera litura and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.
Synthesis example 1: preparation of Compound I-10
Figure BDA0002762457330000141
The method comprises the following steps: benzimidazole (0.40mmol), K was added to the sealed tube2CO3(0.80mmol) and dissolved in 2mL acetonitrile (MeCN), followed by the addition of 3-bromo-2-butanone (0.60mmol), the reaction tube was sealed and placed in an 80 ℃ oil bath and stirred for 8 h. After TLC monitoring of the reaction, the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, the organic phases combined and purified over anhydrous Na2SO4After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow oily product with a yield of 67.8%.
Step two: add the product of step one (0.20mmol), selenium powder (0.40mmol), potassium tert-butoxide (KTB) (0.40mmol) to a sealed tube and dissolve in 2mL acetonitrile (MeCN), then add bromofluoroacetate (0.50mmol), seal the tube and place in a 100 ℃ oil bath and stir for 24 h. After the TLC monitoring reaction is finished, the reaction mixture is ready to be reactedCooling to room temperature, extracting with ethyl acetate, and mixing the organic phases over anhydrous Na2SO4After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a colorless oily product with a yield of 42.7%.
Compounds I-1 to I-37 were prepared by the method of reference compound I-10.
Synthesis example 2: preparation of Compound II-5
Figure BDA0002762457330000151
To a sealed tube were added 1-isopropylimidazole (0.20mmol), selenium powder (0.40mmol), potassium tert-butoxide (KTB) (0.40mmol) and dissolved in 2mL of acetonitrile (MeCN), followed by addition of ethyl bromofluoroacetate (0.50mmol), and the reaction tube was sealed and placed in a 100 ℃ oil bath and stirred for reaction for 24 hours. After TLC monitoring of the reaction, the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, and the combined organic phases were dried over anhydrous Na2SO4After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a brown liquid product with a yield of 60.0%.
Process for preparing compounds II-1 to II-37 reference compounds II-5
Nuclear magnetic data for some compounds (except where noted, the remaining compounds:1H NMR,500MHz；13c NMR,125MHz, internal standard TMS, solvent: CDCl3) The following were used:
compound I-1: pink solid.13H NMR(500MHz,CD3COCD3):δH 8.27(t,J＝58.38Hz,1H),7.64(m,2H),7.43(dtd,J＝1.13,7.60,21.79,2H),4.49(m,1H),1.79(m,1H),1.73(m,2H),1.04(m,1H),1.02(m,1H)；13C NMR(125MHz,CD3COCD3):δC 166.99(t,JC-F＝3.62Hz,1C),133.67,129.47,125.59,124.87,113.36(t,JC-F＝248.23Hz,1C),111.80(t,JC-F＝2.88Hz,1C),111.26,45.23,36.44,26.43,22.42(2C).
Compound I-2: pink solidAnd (3) a body. DeltaH 8.18(t,J＝58.48Hz,1H),7.60(d,J＝7.50Hz,1H),7.24–7.33(m,3H),5.27(t,J＝6.67Hz,1H),5.07(d,J＝6.66Hz,1H)；δC 166.22(t,JC-F＝3.60Hz,1C),137.89,132.98,129.23,124.74,124.19,116.90,112.51(t,JC-F＝250.16Hz,1C),111.63(t,JC-F＝2.71Hz,1C),110.22,45.02,25.55,18.57.
Compound I-3: yellow oil. DeltaH 8.16(t,J＝58.45Hz,1H),7.61(d,J＝7.63Hz,1H),7.38–7.27(m,3H),5.86(ddt,J＝17.07,10.19,6.87Hz,1H),5.21–4.97(m,2H),4.58–4.32(m,2H),2.63(dd,J＝14.77,7.27Hz,2H)；δC 166.32(t,J＝3.68Hz,1C),133.44,133.05,129.05,124.77,124.21,118.10,112.33(t,JC-F＝250.18Hz,1C),111.66(t,JC-F＝2.73Hz,1C),110.70,109.92,45.77,31.69.
Compound I-4: a pale pink solid. DeltaH 8.17(t,J＝58.47Hz,1H),7.61(d,J＝7.74Hz,1H),7.40–7.22(m,3H),5.85(ddt,J＝16.78,10.18,6.48Hz,1H),5.14–4.98(m,2H),4.44–4.33(m,2H),2.22(q,J＝7.07Hz,2H),2.02–1.90(m,2H)；δC 166.27(t,JC-F＝3.42Hz,1C),136.74,133.02,129.11,124.76,124.20,115.81,111.67(t,JC-F＝2.61Hz,1C),112.36(t,JC-F＝250.16Hz,1C),109.79,45.82,30.67,26.42.
Compound I-5: a pale yellow solid. DeltaH 8.17(t,J＝58.49Hz,1H),7.61(d,J＝7.63Hz,1H),7.32(m,3H),5.79(m,1H),5.01(m,2H),4.39(m,2H),2.15(q,J＝7.13Hz,2H),1.89(m,2H),1.56(m,2H)；δC166.33(t,J＝3.65Hz,1C),137.87,133.08,129.17,124.78,124.20,115.14,114.40,112.41,111.73,111.71,111.69,110.42,109.83,77.25,77.00,76.75,46.27,40.99,33.15,27.36,26.94,25.94,25.89.
Compound I-6: yellow oil. DeltaH 8.18(t,J＝58.49Hz,1H),7.61(d,J＝7.69Hz,1H),7.37–7.27(m,3H),4.44–4.31(m,2H),1.85(dt,J＝15.43,7.64Hz,2H),1.46–1.18(m,11H),0.87(d,J＝13.84Hz,3H)；δC 166.20(t,J＝3.51Hz,1C),133.08,129.13,124.73,124.14,113.39(d,JC-F＝251.13Hz,1C),111.65(d,JC-F＝2.63Hz,1C),109.84,46.46,31.66,29.09,29.01,27.50,26.75,22.51,13.97.
Compound I-7: a pale pink solid.13H NMR(500MHz,CD3COCD3):δH 8.30(t,J＝58.34Hz,1H),7.69(dd,J＝9.95,3.90Hz,2H),7.47–7.38(m,4H),7.31(t,J＝7.46Hz,2H),7.27–7.22(m,1H),6.85(d,J＝15.97Hz,1H),6.44(dt,J＝15.96,6.21Hz,1H),5.33(dd,J＝6.2,1.3Hz,2H)；13C NMR(125MHz,CD3COCD3):δC 167.65(t,JC-F＝3.85Hz,1C),136.75,134.75,133.78,129.55,129.14,128.55,127.07,125.65,124.99,122.28,113.48(t,JC-F＝248.38Hz,1C),111.85(t,JC-F＝2.89Hz,1C),111.72,48.60.
Compound I-8: pink solid. DeltaH 8.14(t,J＝58.38Hz,1H),7.61(d,J＝7.95Hz,1H),7.45(d,J＝7.89Hz,1H),7.34(dt,J＝15.38,8.01Hz,2H),4.66(t,J＝7.05Hz,2H),3.67(s,3H),2.99(t,J＝7.05Hz,2H)；δC 171.20,166.52(t,J＝3.68Hz,1C),132.99,129.06,124.91,124.41,112.22(t,JC-F＝250.38Hz,1C),111.66(t,JC-F＝2.76Hz,1C),110.30,52.04,42.01,31.91.
Compound I-9: pink solid. DeltaH 8.14(t,J＝58.38Hz,1H),7.62(d,J＝7.70Hz,1H),7.39–7.29(m,2H),7.17(d,J＝8.61Hz,1H),5.08(s,2H),1.47(s,9H)；δC 168.41(t,JC-F＝3.81Hz,1C),164.90,133.16,128.97,125.03,124.46,112.43(t,JC-F＝250.56Hz,1C),111.81(t,JC-F＝2.73Hz,1C),109.69,83.58,47.88,27.95.
Compound I-10: a colorless oil. DeltaH 8.17(t,J＝58.29Hz,1H),7.65(d,J＝7.69Hz,1H),7.38–7.26(m,2H),7.10(d,J＝7.82Hz,1H),6.26(dd,J＝13.99,6.91Hz,1H),2.08(s,3H),1.65(d,J＝7.20Hz,3H)；203.15,168.13,131.20,129.36,125.13,124.64,112.76(t,JC-F＝251.29Hz,1C),112.10(t,JC-F＝2.81Hz,1C),110.77,62.56,27.15,12.77.
Compound I-11: a pale pink solid. DeltaH 8.09(t,J＝58.26Hz,1H),7.63(d,J＝7.84Hz,1H),7.49–7.30(m,3H),4.65(t,J＝6.71Hz,2H),3.05(t,J＝6.70Hz,2H)；δC 166.68(t,J＝3.50Hz,1C),132.57,128.90,125.24,124.82,116.87,111.99(t,JC-F＝250.92Hz,1C),111.86(t,JC-F＝2.77Hz,1C),109.72,41.92,16.24.
Compound I-12: yellow solid. DeltaH 8.13(t,J＝58.37Hz,1H),7.62(t,J＝7.58Hz,1H),7.40-7.31(m,3H),4.80(m,2H),3.51(m,2H)；δC 166.53(t,JC-F＝3.62Hz,1C),132.93,129.15,125.10,124.57,113.28(t,JC-F＝250.76Hz,1C),111.90(t,JC-F＝2.58Hz,1C),109.75,46.89(d,JC-F＝79.10Hz,1C),25.67(d,JC-F＝269.12Hz,1C).
Compound I-13: a pale yellow solid. DeltaH 8.21(t,J＝58.40Hz,1H),7.73(d,J＝7.59Hz,1H),7.63(d,J＝7.94Hz,1H),7.39–7.27(m,2H),6.06(m,J＝9.19Hz,1H),3.05–2.85(m,2H),2.65–2.44(m,2H),2.15–1.92(m,2H)；δC 166.29(t,J＝3.48Hz,1C),132.27,129.62,124.35,124.05,112.74(t,JC-F＝250.71Hz,1C),111.97(t,JC-F＝2.95Hz,1C),111.24,52.41,27.36,14.56.
Compound I-14: yellow solid. DeltaH 8.19(t,J＝58.48Hz,1H),7.60(d,J＝8.13Hz,1H),7.35–7.28(m,3H),4.21(d,J＝7.44Hz,2H),2.15(m,1H),1.69(m,5H),1.18(m,5H)；δC166.80(t,J＝3.50Hz,1C),133.78,128.98,124.63,124.07,112.47(t,JC-F＝250.18Hz,1C),111.56(t,JC-F＝2.68Hz,1C),110.29,52.43,36.76,30.88,30.71,26.03,25.54.
Compound I-15: a pale yellow solid. DeltaH 8.17(t,J＝58.40Hz,1H),7.60(d,J＝7.73Hz,1H),7.47(d,J＝7.81Hz,1H),7.39–7.27(m,2H),5.34(t,J＝4.32Hz,1H),4.62(d,J＝4.34Hz,2H),4.04–3.97(m,2H),3.93–3.87(m,2H)；δC 167.77(t,J＝3.72Hz,1C),133.73,128.96,124.80,124.32,112.48(t,JC-F＝250.43Hz,1C),111.43(t,JC-F＝2.72Hz,1C),111.16,100.96,65.19(2C),48.86.
Compound I-16: a white solid. DeltaH 8.20(t,J＝58.3Hz,1H),7.81(d,J＝14.1Hz,1H),7.70(d,J＝8.1Hz,1H),7.42–7.33(m,1H),7.33–7.20(m,3H),6.85(d,J＝8.0Hz,1H)δC 168.11(t,J＝3.73Hz,1C),162.02(d,JCF＝251.34Hz,1C),135.61(d,JC-F＝10.19Hz,1C),135.24(d,JC-F＝8.59Hz,1C),133.39,129.08,125.28,124.88,119.30(d,JC-F＝22.14Hz,1C),118.67(d,JC-F＝24.41Hz,1C),117.51(d,JC-F＝4.04Hz,1C),112.33(t,JC-F＝251.13Hz,1C),111.78(t,JC-F＝2.68Hz,1C),110.45.
Compound I-17: a tan solid. DeltaH 8.14(t,J＝58.32Hz,1H),7.69–7.59(m,1H),7.38–7.28(m,2H),7.26–7.18(m,1H),5.71(s,2H)；δC 168.05(t,JC-F＝3.71Hz,1C),146.41(ddt,JC-F＝3.89,7.79,11.69Hz,1C),144.42(ddt,JC-F＝3.95,7.93,11.85Hz,1C),140.69(m,1C),138.62(ddd,JC-F＝2.54,10.16,18.48Hz,1C),132.64,129.03,125.10,124.68,112.37(t,JC-F＝250.95Hz,1C),111.91(t,JC-F＝2.74Hz,1C),109.62,107.80(td,JC-F＝3.98,16.13Hz,1C),39.04.
Compound I-18: a pale pink solid. DeltaH 8.11(t,J＝58.27Hz,1H),7.72(s,1H),7.64(d,J＝8.95Hz,1H),7.42–7.30(m,3H),5.72(s,2H)；δC 153.53,141.44,133.04,132.11,129.30,125.27,124.91,113.32(t,JC-F＝251.04Hz,1C),112.33,112.19(t,JC-F＝2.70Hz,1C),109.52,99.95,42.29.
Compound I-19: a white solid. DeltaH 8.21(t,J＝58.38Hz,1H),7.63(dd,J＝18.71,8.06Hz,1H),7.43(d,J＝8.58Hz,2H),7.30(m,2H),7.20–7.16(m,3H),5.67(s,2H)；δC 167.95,149.08,132.94,132.88,129.34,129.14(2C),125.08,124.63,121.39,112.64,111.93,110.30,49.11.
Compound I-20: a pale pink solid. DeltaH 8.23(t,J＝58.45Hz,1H),7.62(d,J＝7.91Hz,1H),7.30-7.18(5H),7.14(d,J＝7.14Hz,2H),5.63(s,2H),2.31(s,3H)；δC 167.69(t,J＝3.94Hz,1C),138.07,133.10,131.26,129.58,127.58,124.89,124.36,112.72(t,JC-F＝250.46Hz,1C),111.73(t,JC-F＝2.65Hz,1C),110.65,49.81,21.11.
Compound I-21: a white solid. DeltaH 8.25(t,J＝58.44Hz,1H),7.65(d,J＝7.85Hz,1H),7.55(d,J＝8.44Hz,4H),7.44(m,4H),7.36-7.22(m,4H),5.72(s,2H)；δC 167.85(t,J＝3.46Hz,1C),141.24,140.38,133.22,133.09,129.36,128.79,128.01,127.64,127.50,127.03,124.98,124.47,112.71(t,JC-F＝250.46Hz,1C),111.81(t,JC-F＝2.61Hz,1C),110.62,49.71.
Compound I-22: yellow solid.13H NMR(500MHz,CD3COCD3):δH 8.49–8.20(m,3H),7.89(d,J＝8.81Hz,1H),7.51(d,J＝7.46Hz,2H),7.35(dt,J＝26.15,7.20Hz,3H),5.89(s,2H)；13C NMR(125MHz,CD3COCD3):δC 172.05(t,JC-F＝3.40Hz,1C),145.85,135.11,129.45(2C),128.77,128.26(2C),120.97,113.38(t,JC-F＝250.73Hz,1C),111.97(t,JC-F＝3.38Hz,1C),107.23,50.07.
Compound I-23: yellow solid. DeltaH 8.48(s,1H),8.19(d,J＝58.23Hz,1H),8.19(dd,J＝8.82,2.10Hz,1H),7.38–7.32(m,5H),7.22(d,J＝8.90Hz,1H),5.70(s,2H):δC 172.01(t,JC-F＝3.42Hz,1C),144.47,137.16,133.36,129.22(2C),129.16,128.74,127.52(2C),121.18,113.35(t,JC-F＝252.62Hz,1C),110.04,107.42(t,JC-F＝3.11Hz,1C),50.29.
Compound I-24: pink solid. DeltaH 8.16(t,J＝58.33Hz,1H),7.50–7.42(m,1H),7.40–7.31(m,5H),6.96(dd,J＝9.04,6.57Hz,1H),5.62(s,2H)；δC 169.24,149.43(dd,JC-F＝14.38,63.44Hz,1C),147.46(dd,JC-F＝14.38,63.44Hz,1C),133.51,129.15(2C),129.10,128.61,127.50(2C),127.41,112.40(t,JC-F＝251.50Hz,1C),101.19(d,JC-F＝24.34Hz,1C),99.79(d,JC-F＝23.78Hz,1C),50.26.
Compound I-25: a pale pink solid. DeltaH 8.16(t,J＝58.45Hz,1H),7.18(dd,J＝30.19,39.04Hz,2H),6.94(d,J＝2.33,8.85Hz,1H),3.87(s,3H),3.84(s,3H)；δC 165.77,157.56,129.80,127.88,112.62,112.42(t,JC-F＝250.25Hz,1C),110.25,96.70(t,JC-F＝2.75Hz,1C),56.03,32.99.
Compound I-26: a pale pink solid. DeltaH 8.13(t,J＝58.58Hz,1H),7.38(s,1H),7.05(s,1H),3.83(s,3H),2.35(d,J＝6.40Hz,6H)；δC 165.53,134.05,133.58,132.01,127.28,112.40(t,JC-F＝249.53Hz,1C),112.26(t,JC-F＝2.53Hz,1C),110.35,32.88,20.26,20.14.
Compound I-27: a pale pink solid. DeltaH 8.11(t,J＝58.36Hz,1H),7.50–7.38(m,3H),3.84(s,3H)；δC168.22(t,JC-F＝3.33Hz,1C),134.84,128.12,127.37,118.38,112.93,112.65(t,JC-F＝2.88Hz,1C),112.25(t,JC-F＝250.93Hz,1C),32.99.
Compound I-28 (XLT-52): brick red solid. DeltaH 8.19(t,J＝58.55Hz,1H),7.40(s,1H),7.28(s,1H),5.79(m,1H),2.36(s,3H),2.34(s,3H),1.60(d,J＝7.05Hz,6H).δC＝164.29,133.34,133.19,129.80,128.15,112.83(t,JC-F＝250.26Hz,1C),112.43(t,JC-F＝2.77Hz,1C),112.09,51.40,20.39,20.04,19.66(2C).
Compound I-29: yellow solid. DeltaH 8.41(s,1H),8.23(dd,J＝9.01,1.68Hz,1H),8.14(t,J＝58.55Hz,1H),7.62(d,J＝9.02Hz,1H),5.80(m,1H),1.62(d,J＝7.22Hz,6H).δC＝170.10,143.75,135.65,129.45,120.38,112.30(t,JC-F＝252.42Hz,1C),110.66,107.12(t,JC-F＝3.20Hz,1C),51.82,19.45(2C).
Compound I-30: yellow solid. DeltaH 8.36(d,J＝1.94Hz,1H),8.22(dd,J＝8.92,2.03Hz,1H),8.16(t,J＝58.39Hz,1H),7.70(d,J＝8.91Hz,1H),5.78(m,1H),1.65(d,J＝7.18Hz,6H).δC＝169.53,144.37,133.69,131.44,119.76,112.28(t,JC-F＝252.47Hz,1C),111.14(t,JC-F＝3.14Hz,1C),106.59,51.90,19.43(2C).
Compound I-31: a white solid. DeltaH 8.17(t,J＝58.33Hz,1H),7.65(d,J＝1.55Hz,1H),7.49(d,J＝8.62Hz,1H),7.42(dd,J＝8.63,1.67Hz,1H),5.79(m,1H),1.60(d,J＝7.14Hz,6H).δC＝167.02,132.63,128.83,126.95,117.79,114.30,112.78(t,JC-F＝2.97Hz,1C),112.63(t,JC-F＝251.52Hz,1C),51.62,19.58(2C).
Compound I-32: a white solid. DeltaH 8.17(t,J＝58.33Hz,1H),7.77(s,1H),7.43(dd,J＝8.71,1.71Hz,1H),7.37(d,J＝8.7Hz,1H),5.79(m,1H),1.59(d,J＝7.11Hz,6H).δC＝166.65,130.78,130.60,127.44,117.45,114.93(t,JC-F＝3.22Hz,1C),112.58(t,JC-F＝250.87Hz,1C),112.29,51.66,19.62(2C).
Compound I-33: yellow solid. DeltaH 8.18(t,J＝58.39Hz,1H),7.55(dt,J＝15.41,7.70Hz,1H),7.24(dd,J＝8.66,2.21Hz,1H),7.05(td,J＝9.00,2.30Hz,1H),5.81(m,1H),1.60(d,J＝7.14Hz,6H)；δC 167.30,159.86(d,J＝243.74Hz),132.02(d,J＝12.21Hz),112.73(d,J＝250.87Hz),112.45(dt,J＝9.83,3.11Hz),111.38(d,J＝24.85Hz),99.24(d,J＝28.94Hz),51.58,19.49(2C).
Compound I-34: yellow solid. DeltaH 8.19(t,J＝58.34Hz,1H),7.45(dd,J＝8.98,4.26Hz,1H),7.36(m,1H),7.06(td,J＝9.00,2.48Hz,1H),5.80(m,1H),1.61(d,J＝7.12Hz,6H)；δC166.61,159.70(d,J＝244.61Hz),130.32(d,J＝12.7Hz),127.95,112.63(d,J＝251.2Hz),112.02(2C),111.87(d,J＝13.37Hz),99.90(dt,J＝28.89,3.09Hz),51.67,19.67(2C).
Compound I-35: a yellow-brown solid. DeltaH 8.16(t,J＝58.45Hz,1H),7.69(s,1H),7.58(s,1H),5.75(m,1H),1.59(d,J＝7.14Hz,6H).δC＝167.86,130.75,128.87,128.49,114.39,112.91(t,JC-F＝3.26Hz,1C),112.39(t,JC-F＝251.73Hz,1C),112.33,51.65,19.51(2C).
Compound I-36: a pale pink solid. DeltaH 8.44(s,1H),8.40(t,J＝58.97Hz,1H),7.38–7.28(m,5H),5.78(s,1H),4.86(t,J＝5.48Hz,2H),3.83(s,3H)；δC 167.75(t,JC-F＝4.09Hz,1C),154.70,151.37,146.92,137.64,128.84(2C),127.70,127.29(2C),111.77(t,JC-F＝249.31Hz,1C),106.55,45.20,31.97.
Compound I-37: pink solid. DeltaH 8.48(s,1H),8.44(t,J＝58.99Hz,1H),7.66(m,2H),7.40–7.30(s,8H),5.80(t,J＝4.34Hz,1H),5.65(s,2H),4.87(d,J＝5.48Hz,2H)；δC167.70,154.76,151.94,146.91,137.66,137.10,134.51,129.11,128.84,128.54,128.30,127.69,127.30,111.95(t,JC-F＝249.49Hz,1C),106.70,48.50,45.20.
Compound II-1: a white solid. DeltaH 8.09(t,J＝58.30Hz,1H),7.34–7.27(m,5H),5.77(s,2H),3.93(s,3H),3.76(s,3H)；δC 164.56(t,J＝3.55Hz,1C),157.71,157.64,134.57,128.66(2C),128.25,127.85(2C),125.47,124.84,111.52(t,J＝257.65Hz,1C),53.69,53.15,51.11.
Compound II-2: brown solid. DeltaH 7.73(t,J＝59.55Hz,1H),7.13(d,J＝2.48Hz,1H),6.91(d,J＝2.36Hz,1H),3.68(s,3H)；δC 158.39,121.54,113.95,110.39(t,JC-F＝251.41Hz),36.30.
Compound II-3: a yellow liquid. DeltaH 7.79(t,J＝59.58Hz,1H),7.15(d,J＝2.51Hz,1H),6.93(d,J＝2.44Hz,1H),4.18(q,J＝7.32Hz,2H),1.41(t,J＝7.32Hz,3H)；δC 157.45,119.77,114.28,110.33(t,JC-F＝251.38Hz),44.17,13.97.
Compound II-4: a yellow liquid. DeltaH 7.79(t,J＝59.59Hz,1H),7.15(d,J＝2.50Hz,1H),6.90(d,J＝2.45Hz,1H),4.17–4.01(m,2H),1.91–1.76(m,2H),0.98(t,JC-F＝7.42Hz,3H)；δC 157.83(t,JC-F＝3.24Hz,1C),120.53,114.06,110.38(d,J＝251.35Hz),50.63,22.04,10.95.
Compound II-5: a brown liquid. DeltaH 7.85(t,J＝59.63Hz,1H),7.17(d,J＝2.55Hz,1H),6.96(d,J＝2.53Hz,1H),5.24(dt,J＝13.57,6.78Hz,1H),1.41(d,J＝6.80Hz,6H)；δC156.92,116.76,114.54,110.19(t,JC-F＝251.42Hz),50.50,21.64(2C).
Compound II-6: a yellow liquid. DeltaH 7.76(t,J＝59.62Hz,1H),7.12(t,J＝7.19Hz,1H),6.90(d,J＝2.45Hz,1H),4.10(m,2H),1.75(m,2H),1.34(m,2H),0.93(m,3H)；δC 157.59(t,JC-F＝3.21Hz,1C),120.44,113.99,110.28(t,JC-F＝251.34Hz,1C),48.74,30.58,19.55,13.44.
Compound II-7: brown solid. DeltaH 7.98(t,J＝59.83Hz,1H),7.11(d,J＝2.66Hz,1H),7.08(d,J＝2.64Hz,1H),1.88(s,9H)；δC 159.72,118.51,113.19,110.11(t,JC-F＝251.48Hz),61.18,28.47(3C).
The compound II-8: a yellow liquid. DeltaH 7.78(t,J＝59.60Hz,1H),7.14(d,J＝2.47Hz,1H),6.90(d,J＝2.46Hz,1H),4.16–4.03(m,2H),1.91–1.69(m,2H),1.41–1.25(m,6H),0.87(t,J＝6.83Hz,3H)；δC 157.77,120.44,114.03,110.37(t,JC-F＝251.37Hz),49.12,31.18,28.60,26.05,22.37,13.86.
Compound II-9: a yellow liquid. DeltaH 7.79(t,J＝59.60Hz,1H),7.14(d,J＝2.44Hz,1H),6.90(d,J＝2.41Hz,1H),4.16–4.05(m,2H),1.86–1.71(m,2H),1.39–1.16(m,15H),0.86(d,J＝13.65Hz,2H)；δC 157.80(t,JC-F＝4.43Hz,1C),120.43,114.03,110.38(t,JC-F＝251.36Hz),49.13,31.78,29.40,29.34,29.18,29.04,28.65,26.41,22.58,14.01.
Compound II-10: pink solid. DeltaH 7.83(t,J＝59.45Hz,1H),7.62(dd,J＝15.99,8.93Hz,1H),7.19(s,2H),5.32(dd,J＝15.99,2.12Hz,1H),5.14(dd,J＝8.93,2.13Hz,1H)；δC 159.54,130.43,116.58,115.09,109.92(t,JC-F＝252.04Hz),104.04.
Compound II-11: a yellow liquid. DeltaH 7.80(t,J＝59.54Hz,1H),7.16(d,J＝2.54Hz,1H),6.92(d,J＝2.50Hz,1H),5.93(ddt,J＝16.44,10.21,6.16Hz,1H),5.34(ddd,J＝18.02,13.64,0.97Hz,2H),4.77(d,J＝6.15Hz,2H)；δC 158.39,130.65,120.51,120.13,114.27,110.44(t,JC-F＝251.57Hz),51.31.
Compound II-12: a yellow liquid. DeltaH 7.79(t,J＝59.58Hz,1H),7.15(d,J＝2.46Hz,1H),6.90(d,J＝2.42Hz,1H),5.80(ddt,J＝16.87,10.20,6.57Hz,1H),5.06(ddd,J＝13.68,11.17,1.19Hz,2H),4.23–4.05(m,2H),2.14(dd,J＝14.12,7.11Hz,2H),2.02–1.82(m,2H)；δC 157.99(t,JC-F＝3.46Hz,1C),136.64,120.56,116.00,114.11,110.39(t,JC-F＝251.55Hz),48.51,30.36,27.66.
Compound II-13: a yellow liquid. DeltaH 7.79(t,J＝59.59Hz,1H),7.14(d,J＝2.43Hz,1H),6.90(d,J＝2.38Hz,1H),5.77(ddt,J＝16.93,10.17,6.70Hz,1H),5.00(ddd,J＝13.65,11.05,1.06Hz,2H),4.13(t,J＝7.52Hz,2H),2.11(q,J＝7.08Hz,2H),1.90–1.73(m,2H),1.46(dt,J＝15.02,7.45Hz,2H)；δC 157.94,137.77,120.39,115.25,114.13,110.40(d,JC-F＝251.41Hz),48.92,33.04,28.07,25.60.
Compound II-14: a yellow liquid. DeltaH 7.81(t,J＝59.45Hz,1H),7.18(d,J＝2.57Hz,1H),7.07(d,J＝2.53Hz,1H),5.52(s,2H),3.42(s,3H)；δC 159.49(t,JC-F＝3.75Hz,1C),119.70,114.76,110.13(t,JC-F＝251.89Hz),79.10,57.61.
Compounds II to 15: brown solid. DeltaH 7.68(t,J＝59.25Hz,1H),7.24(d,J＝2.62Hz,1H),7.15(d,J＝2.57Hz,1H),5.14(s,2H)；δC 160.89(t,JC-F＝2.48Hz,1C),119.46,115.33,112.71,110.29(t,JC-F＝253.1Hz),36.54.
Compound II-16: a yellow liquid. DeltaH 7.73(t,J＝59.48Hz,1H),7.17(d,J＝2.57Hz,1H),7.01(d,J＝2.52Hz,1H),4.96(s,2H),4.26(q,J＝7.14Hz,2H),1.30(t,J＝7.15Hz,3H)；δC166.34,160.29,121.28,114.13,110.48(t,JC-F＝251.91Hz),62.24,49.54,14.02.
Compounds II to 17: a yellow liquid. DeltaH 7.80(t,J＝59.61Hz,1H),7.14(d,J＝2.46Hz,1H),6.86(d,J＝2.40Hz,1H),3.96(d,J＝7.41Hz,2H),2.03–1.85(m,1H),1.78–1.61(m,4H),1.34–1.11(m,4H),1.09–0.95(m,2H)；δC 158.26,121.37,113.78,110.46(t,JC-F＝251.51Hz),55.10,36.99,30.42(2C),26.08,25.43(2C).
Compound II-18: a yellow liquid. DeltaH 7.80(t,J＝59.57Hz,1H),7.33–7.16(m,5H),7.02(d,J＝2.43Hz,1H),6.53(d,J＝2.35Hz,1H),4.36(t,J＝7.29Hz,2H),3.13(t,J＝7.28Hz,2H)；δC 157.82,137.10,128.89(2C),128.78(2C),126.99,121.05,113.60,110.36(t,J＝251.43Hz),50.67,34.53.
Compounds II to 19: a white solid. DeltaH 7.83(t,J＝59.57Hz,1H),7.23(d,J＝8.00Hz,2H),7.18(d,J＝7.95Hz,2H),7.10(d,J＝2.52Hz,1H),6.74(d,J＝2.46Hz,1H),5.28(s,2H),2.35(s,3H)；δC＝158.54(t,JC-F＝2.48Hz,1C),138.64,131.28,129.75(2C),128.59(2C),120.16,114.26,110.49(t,JC-F＝251.55Hz),52.24,21.13.
Compound II-20: a white solid. DeltaH 7.83(t,J＝59.56Hz,1H),7.41(d,J＝8.15Hz,2H),7.30(d,J＝8.13Hz,2H),7.12(d,J＝2.55Hz,1H),6.77(d,J＝2.52Hz,1H),6.70(dd,J＝17.60,10.89Hz,1H),5.76(d,J＝17.58Hz,1H),5.32(s,2H),5.28(d,J＝10.90Hz,1H)；δC158.78(t,JC-F＝3.15Hz,1C),138.05,135.96,133.69,128.77(2C),126.84(2C),120.16,114.85,114.37,110.50(t,JC-F＝251.68Hz),52.14.
The compound II-21: a white solid. DeltaH 7.81(t,J＝59.51Hz,1H),7.35(d,J＝8.39Hz,2H),7.29(d,J＝8.35Hz,2H),7.14(d,J＝2.40Hz,1H),6.78(d,J＝2.02Hz,1H),5.31(s,2H)；δC159.08(t,JC-F＝3.16Hz,1C),134.72,132.91,129.81(2C),129.28(2C),120.06,114.60,110.50(t,JC-F＝251.91Hz),51.60.
Compound II-22: brown solid. DeltaH 7.81(t,J＝59.51Hz,1H),7.39(d,J＝8.45Hz,2H),7.22(d,J＝8.21Hz,2H),7.15(d,J＝2.26Hz,1H),6.81(d,J＝2.06Hz,1H),5.36(s,2H)；δC159.27(t,JC-F＝3.12Hz,1C),149.37(d,JC-F＝1.68Hz,1C),133.17,129.93(2C),121.49(2C),120.34(q,JC-F＝257.85Hz,1C),120.09,114.68,110.53(t,JC-F＝251.91Hz,1C),51.46.
Compound II-23: brown solid. DeltaH 8.21(d,J＝8.69Hz,2H),7.78(t,J＝59.44Hz,1H),7.50(d,J＝8.67Hz,2H),7.20(d,J＝2.51Hz,1H),6.89(d,J＝2.42Hz,1H),5.48(s,2H)；δC159.87(t,JC-F＝3.36Hz,1C),147.91,141.57,128.90(2C),124.19(2C),120.19,115.01,110.50(t,JC-F＝252.28Hz),51.32.
Compound II-24: a white solid. DeltaH 8.00–7.71(m,5H),7.55–7.47(m,2H),7.43(dd,J＝8.44,1.68Hz,1H),7.11(d,J＝2.56Hz,1H),6.78(d,J＝2.52Hz,1H),5.49(s,2H)；δC158.86(t,JC-F＝3.10Hz,1C),133.16,133.14,131.76,129.13,127.85,127.74,126.63,125.78,120.23,114.39,110.51(t,JC-F＝251.72Hz),108.51,52.55.
Compounds II to 25:a white solid. DeltaH 7.85(t,J＝59.56Hz,1H),7.61–7.56(m,4H),7.49–7.39(m,4H),7.37(t,J＝7.35Hz,1H),7.14(d,J＝2.44Hz,1H),6.83(d,J＝2.36Hz,1H),5.38(s,2H)；δC158.83,141.63,140.19,133.26,129.93(2C),128.81(2C),127.74(2C),127.60,127.01(2C),120.24,114.40,110.51(t,JC-F＝251.74Hz),52.07.
Compounds II to 26: yellow solid. DeltaH 8.41(s,1H),7.77(m,2H),7.33(d,J＝8.25Hz,1H),7.17(d,J＝2.56Hz,1H),6.88(d,J＝2.51Hz,1H),5.36(s,2H)；δC 159.57(t,JC-F＝3.39Hz,1C),151.97,149.19,139.02,129.43,124.71,120.94,114.98,110.44(t,JC-F＝252.31Hz,1C),48.85.
Compound II-27: brown solid. DeltaH 7.75(t,J＝59.48Hz,1H),7.64(s,1H),7.18(d,J＝2.51Hz,1H),6.97(d,J＝2.42Hz,1H),5.47(s,2H)；δC 159.05(t,JC-F＝3.34Hz,1C),153.93,141.40,133.44,119.68,114.98,110.33(t,JC-F＝252.36Hz,1C),44.80.
Compound II-28: brown solid. DeltaH 7.97–7.67(m,2H),7.31–7.26(m,2H),7.19–7.14(m,1H),6.98(d,J＝2.49Hz,1H)；δC 162.65–160.66(d,JC-F＝251.45Hz,1C),160.88,137.38–137.30(d,JC-F＝9.19Hz,1C),134.95–134.88(d,JC-F＝8.52Hz,1C),121.59,119.17–118.99(d,JC-F＝22.81Hz 1C),118.22–118.02(d,JC-F＝24.80Hz,1C),116.36–116.32(d,JC-F＝3.85Hz,1C),114.70,110.52(t,JC-F＝252.52Hz,1C).
Compound II-29: a yellow liquid. DeltaH 7.86(t,J＝59.61Hz,1H),7.43–7.28(m,5H),7.14–7.06(m,1H),6.80–6.71(m,1H),6.46–6.35(m,1H),1.77(d,J＝7.10Hz,3H)；δC 158.01(t,JC-F＝3.46Hz,1C),138.62,128.93(2C),128.48,127.09(2C),118.02,114.46,110.36(t,JC-F＝251.55Hz),56.52,18.83.
The compound II-30: yellow solid. DeltaH 8.13(s,1H),7.58(t,J＝59.57Hz,1H),7.49(m,2H),7.40–7.33(m,3H),5.48(s,2H)；δC 160.99(t,JC-F＝2.77Hz,1C),136.63,133.79,128.88(2C),128.77(2C),128.66,109.63(t,JC-F＝254.57Hz,1C),53.47.
Compound II-31: yellow solid. DeltaH 7.83(td,J＝59.60,1.6Hz,1H),7.39–7.32(m,5H),7.11(d,J＝2.58Hz,1H),6.77(t,J＝2.52Hz,1H),5.33(s,1H)；δC 158.80(t,JC-F＝3.14Hz,1C),134.34,129.06(2C),128.66,128.49(2C),120.20,114.34,110.50(t,JC-F＝252.30Hz,1C),52.37.
Compounds II to 32: yellow solid. DeltaH 7.74(t,J＝59.80Hz,1H),7.57–7.48(m,4H),7.43(t,J＝7.20Hz,1H),7.08(d,J＝2.20Hz,1H),6.90(d,J＝2.0Hz,1H)；δC 164.61,136.78,129.25(2C),128.88,125.90(2C),119.92,112.10,109.17(t,JC-F＝250.75Hz,1C).
Compound II-33: brown solid. DeltaH 7.93–7.81(m,2H),7.84(t,J＝59.50Hz,1H),7.32(d,J＝2.50Hz,1H),7.06(s,1H),2.66(s,3H).δC 195.4,161.1,156.6(d,JC-F＝255.20Hz,1C),139.80(d,JC-F＝6.00Hz,1C),130.2,128.70(d,JC-F＝12.40Hz,1C),124.50(d,JC-F＝3.70Hz,1C),121.80(t,JC-F＝2.40Hz,1C),116.80(d,JC-F＝20.50Hz,1C),114.90,110.50(t,JC-F＝253.20Hz,1C),26.70.
Compound II-34: brown solid. DeltaH 9.32(d,J＝8.62Hz,1H),8.80(s,1H),8.14(dd,J＝8.63,2.23Hz,1H),7.92(t,J＝59.48Hz,1H),7.85(d,J＝2.69Hz,1H),7.29(d,J＝2.71Hz,1H)；δC 158.92(t,JC-F＝3.49Hz),151.66,145.86(q,JC-F＝4.08Hz),135.44(q,JC-F＝3.34Hz),126.32(q,JC-F＝33.73Hz),122.99(q,JC-F＝272.55Hz),120.15,118.69,114.75,110.22(t,JC-F＝252.75Hz).
Compounds II to 35: a white solid. DeltaH 8.09(t,J＝58.03Hz,1H),7.45–7.41(m,3H),7.37–7.35(m,2H),7.08(s,1H),5.32(s,2H)；δC 164.31,133.20,129.41(2C),129.26,128.82(2C),122.83(q,J＝5.0Hz),119.72(q,J＝44.51Hz),118.36(q,J＝268.6Hz),111.52(t,J＝256.5Hz),53.18.
Chemical combinationSubstance II-36: brown solid. DeltaH 8.05(t,J＝58.29Hz,1H),7.29,5.73,3.94,3.80；δC164.53,157.76,157.52,134.22,133.11,129.44,128.82,126.00,123.98,111.42(t,J＝257.76Hz,1H),53.80,53.23,50.40.
Compound II-37: yellow oil. DeltaH 7.78(t,J＝59.61Hz,1H),7.47(d,J＝8.42Hz,1H),7.43(d,J＝2.01Hz,1H),7.33(dd,J＝8.30,1.94Hz,1H),7.28(d,J＝8.41Hz,2H),7.12(d,J＝8.43Hz,2H),7.09(d,J＝2.51Hz,1H),6.95(d,J＝2.43Hz,1H),5.26(dd,J＝8.61,3.60Hz,1H),4.57(dd,J＝14.00,3.61Hz,1H),4.42(d,J＝11.72Hz,1H),4.24(d,J＝11.73Hz,1H),4.20(dd,J＝14.03,8.64Hz,1H)；δC 159.12,135.43,135.01,134.41,133.82,129.80,129.10,128.74,128.61,127.72,122.30,113.32,110.43(t,JC-F＝251.61Hz,1C),75.00,70.51,52.70.
Examples of measurement of biological Activity
The compound of the invention shows good activity to various pests in the agricultural field. The results of the insecticidal activity measurement are shown in the following examples.
Example 3: evaluation of insecticidal Activity of partial Compounds on Plutella xylostella
The tested insects are lepidoptera plutella xylostella, and the sensitive strains are raised indoors. The 3-instar middle and later stage larvae of the plutella xylostella are taken as test objects, and the test method is a leaf soaking method.
The operation process is as follows: accurately weighing each sample, respectively adding acetone to prepare 10g/L mother liquor, and diluting the mother liquor to 500ppm by using a Tween 80 aqueous solution containing 0.5 thousandth. Preparing clean leaf dish with 1.0cm diameter puncher, soaking in the medicinal liquid for 10s, taking out, air drying, and transferring into clean container. Inoculating 3-year-old and middle-and-later-stage larvae of plutella xylostella with consistent growth into a vessel, inoculating 10 test insects for each treatment, and feeding at constant temperature of 28 ℃. Assuming 3 replicates, the control group was treated with an aqueous solution containing an equal amount of 0.5% tween 80 acetone. After 48h the test results were observed and the mortality (%) was calculated according to the formula. The death rate (%) < dead insect number/test insect number x 100%. The test results are shown in Table 1.
Example 4: evaluation of insecticidal activity of partial compounds on Spodoptera frugiperda
The tested insects were Lepidoptera Spodoptera frugiperda, and the sensitive strains were raised indoors. The late stage 2 instar larvae of Spodoptera frugiperda are used as test objects, and the test method is a leaf soaking method.
The operation process is as follows: accurately weighing each sample, respectively adding acetone to prepare 10g/L mother liquor, and diluting the mother liquor to 500ppm by using a Tween 80 aqueous solution containing 0.5 thousandth. Making clean corn leaves into leaf disks by using a puncher with the diameter of 1.0cm, soaking the leaf disks into the liquid medicine, taking out the leaves after 10 seconds, naturally drying the leaves, and transferring the leaves into a clean vessel. Inoculating 2-instar late stage Spodoptera frugiperda larvae with consistent growth into a vessel, inoculating 10 test insects for each treatment, and feeding at constant temperature of 28 ℃. Assuming 3 replicates, the control group was treated with an aqueous solution containing an equivalent amount of 0.5% tween 80 in acetone. After 48h the test results were observed and the mortality (%) was calculated according to the formula. The death rate (%) < dead insect number/test insect number x 100%. The test results are shown in Table 1.
Example 5: evaluation of insecticidal Activity of partial Compounds on beet armyworm
The tested insects are lepidoptera spodoptera exigua, and sensitive strains are raised indoors. The 1 st-instar metaphase larva of beet armyworm is taken as a test object, and the test method is a leaf soaking method.
The operation process is as follows: accurately weighing each sample, respectively adding acetone to prepare 10g/L mother liquor, and diluting the mother liquor to 500ppm by using a Tween 80 aqueous solution containing 0.5 thousandth. Preparing clean leaf dish with 1.0cm diameter puncher, soaking in the medicinal liquid for 10s, taking out, air drying, and transferring into clean container. Inoculating 1-instar metaphase larva of beet armyworm with consistent growth into a vessel, inoculating 10 test insects for each treatment, and feeding in a constant temperature incubator at 28 ℃. Assuming 3 replicates, the control group was treated with an aqueous solution containing an equivalent amount of 0.5% tween 80 in acetone. After 48h the test results were observed and the mortality (%) was calculated according to the formula. The death rate (%) < dead insect number/test insect number x 100%. The test results are shown in Table 1.
Example 6: evaluation of insecticidal Activity of partial Compounds on Spodoptera litura
The tested insects are Lepidoptera prodenia litura, and sensitive strains are raised indoors. The final stage larva of the 1 st age of prodenia litura is taken as a test object, and the test method is a leaf soaking method.
The operation process is as follows: accurately weighing each sample, respectively adding acetone to prepare 10g/L mother liquor, and diluting the mother liquor to 500ppm by using a Tween 80 aqueous solution containing 0.5 thousandth. Preparing clean leaf dish with 1.0cm diameter puncher, soaking in the medicinal liquid for 10s, taking out, air drying, and transferring into clean container. Inoculating 1-th-instar late-stage spodoptera litura larvae with consistent growth into a vessel, inoculating 10 test insects for each treatment, and feeding at constant temperature of 28 ℃. Assuming 3 replicates, the control group was treated with an aqueous solution containing an equivalent amount of 0.5% tween 80 in acetone. After 48h the test results were observed and the mortality (%) was calculated according to the formula. The death rate (%) < dead insect number/test insect number x 100%. The test results are shown in Table 1.
Table 1 insecticidal activity test of some of the compounds of the present invention against 4 lepidopteran pests
Figure BDA0002762457330000261
Figure BDA0002762457330000271
Figure BDA0002762457330000281
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. An N-difluoromethyl azole selenourea derivative for preventing and treating pests in agriculture and forestry or pests in other fields has a structure shown as a general formula (I) or a general formula (II);
Figure FDA0002762457320000011
in the general formula (I) or the general formula (II)
X is C or N; y is C or N;
R1selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, ethyl fluoroacetate, C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy, halo C1-C12Alkoxy radical, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl radical, C2-C12Alkenyl radical, C2-C12Alkynyl, C2-C12Alkenyloxy, halogeno C2-C12Alkenyloxy radical, C2-C12Alkynyloxy, halo C2-C12Alkynyloxy, C1-C12Alkylthio, halo C1-C12Alkylthio radical, C1-C12Alkoxy radical C1-C12Alkyl, halo C1-C12Alkoxy radical C1-C12Alkyl radical, C1-C12Alkylthio group C1-C12Alkyl, halo C1-C12Alkylthio group C1-C12Alkyl, sulfinyl-containing C1-C12Alkyl, halogen-and sulfinyl-containing C1-C12Alkyl radical, containing sulfonyl radical C1-C12Alkyl, halogen-containing and sulphonyl C1-C12Alkyl radical, containing amino group C1-C12Alkyl, amino-containing halogeno C1-C12Alkyl radical, C1-C12Alkoxycarbonyl, CONH2，C1-C12Alkylaminocarbonyl, di (C)1-C12Alkyl) aminocarbonyl, cyano C1-C12Alkoxy radical, C1-C12Alkoxycarbonyl radical C1-C12Alkyl radical, C1-C12Alkylaminocarbonyl radical C1-C12Alkyl, di (C)1-C12Alkyl) aminocarbonyl group C1-C12An alkyl group; or benzyl, pyridineMethylene, pyrimidylmethylene, thiazolylmethylene, thiophenylmethylene, furanmethylene, pyrazolylmethylene; or phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms selected from oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
aryl is phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms selected from oxygen, sulfur, and nitrogen, and the substituent is C1-C12Alkyl of (C)1-C12Alkoxy group of (C)1-C12Alkanethiol of (C)1-C12Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C1-C12Alcoxyl acyl radical, C1-C12An acyloxy group;
R2is a substituent at any position on an aromatic ring shown in the general formula (I) or the general formula (II), and is mono-substituted, same or different and is bi-substituted or tri-substituted;
R2selected from hydrogen, C1-C12Alkyl of (C)1-C12Alkoxy group of (C)1-C12Alkanethiol of (C)1-C12Alkylamino of (C)1-C12Alcoxyl acyl radical, C1-C12Acyloxy, halogeno C1-C12Alkyl, halo C of1-C12Alkoxy, halo C of1-C12Alkanemercapto, halogeno C of1-C12Alkylamino, halogeno C of1-C12Alkoxyacyl, halo C1-C12Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide, or aryl containing one or more substituents,
the aryl group can be phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and others containing oxygen, sulfur, and nitrogenHeteroaryl of one or more hetero atoms, the substituents being C1-C12Alkyl of (C)1-C12Alkoxy group of (C)1-C12Alkanethiol of (C)1-C12Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C1-C12Alkoxyacyl or C1-C12And (4) acyloxy.
2. The N-difluoromethyl azole selenourea derivative for pest control in agriculture and forestry or other fields as claimed in claim 1,
x is C or N; y is C or N;
R1selected from hydrogen, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, tribromomethyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6Alkenyl, halo C2-C6Alkynyl, C1-C6Ester group, C1-C6Acetoxy, C1-C6A cyano group; or benzyl, pyridine methylene, pyrimidine methylene, thiazole methylene, thiophene methylene, furan methylene, pyrazole methylene; or phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms selected from oxygen, sulfur, nitrogen, or aryl groups containing one or more substituents,
aryl is phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms selected from oxygen, sulfur, and nitrogen, and the substituent is C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloroMethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C1-C4Alkoxyacyl or C1-C4An acyloxy group;
R2is substituent at any position on an aromatic ring shown in the general formula (I) or the general formula (II), and is mono-substituted, same or different;
R2selected from hydrogen, C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino of (C)1-C4Alcoxyl acyl radical, C1-C4Acyloxy, halogeno C1-C4Alkyl, halo C of1-C4Alkoxy, halo C of1-C4Alkanemercapto, halogeno C of1-C4Alkylamino, halogeno C of1-C4Alkoxyacyl, halo C1-C4Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide, or aryl containing one or more substituents,
aryl is phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms selected from oxygen, sulfur, and nitrogen, and the substituent is C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C1-C4Alkoxyacyl or C1-C4And (4) acyloxy.
3. The N-difluoromethyl azole selenourea derivative for pest control in agriculture and forestry or other fields as claimed in claim 1,
x is C; y is C;
R1selected from hydrogen, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, dibromomethyl, tribromomethyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, halo C2-C6Alkenyl, halo C2-C6Alkynyl, C1-C6Ester group, C1-C6Acetoxy, C1-C6Cyano, or phenyl, pyridyl, pyrimidinyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms selected from oxygen, sulfur, and nitrogen, or aryl groups containing one or more substituents;
aryl is phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms such as oxygen, sulfur, nitrogen, and the like, and the substituent is C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C1-C4Alkoxyacyl or C1-C4An acyloxy group;
R2is a substituent at any position on an aromatic ring shown in the general formula (I) or the general formula (II), and is mono-substituted, same or different and is bi-substituted or tri-substituted;
R2selected from hydrogen, C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino of (C)1-C4Alcoxyl acyl radical, C1-C4Acyloxy, halogeno C1-C4Alkyl, halo C of1-C4Alkoxy, halo C of1-C4An alkanemercapto group of,Halogen substituted C1-C4Alkylamino, halogeno C of1-C4Alkoxyacyl, halo C1-C4Acyloxy, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, glycosyl, amino acid, polypeptide, or aryl containing one or more substituents,
aryl is phenyl, pyridyl, pyrimidyl, thiazolyl, thienyl, furyl, pyrazolyl, and other heteroaryl groups containing one or more heteroatoms selected from oxygen, sulfur, and nitrogen, and the substituent is C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkanethiol of (C)1-C4Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, C1-C4Alkoxyacyl or C1-C4And (4) acyloxy.
4. The N-difluoromethyl azole selenourea derivative for controlling pests in agriculture and forestry or pests in other fields as claimed in claim 1, wherein the structural formula of the N-difluoromethyl azole selenourea derivative is as follows:
Figure FDA0002762457320000041
Figure FDA0002762457320000051
Figure FDA0002762457320000061
5. an N-difluoromethyl azole selenourea derivative is characterized in that the structural formula of the N-difluoromethyl azole selenourea derivative is as follows:
Figure FDA0002762457320000071
Figure FDA0002762457320000081
Figure FDA0002762457320000091
6. an N-difluoromethyl azole selenourea derivative or an agriculturally pharmaceutically acceptable salt thereof, which is a salt of the N-difluoromethyl azole selenourea derivative according to any one of claims 1 to 5 with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid, or citric acid.
7. Use of the N-difluoromethyl azole selenourea derivative according to any one of claims 1 to 5 or the N-difluoromethyl azole selenourea derivative according to claim 6 as an agriculturally pharmaceutically acceptable salt for the preparation of a medicament for controlling pests.
8. The use according to claim 7, wherein the pests are lepidopteran insects, coleopteran insects, hemipteran insects, homopteran insects, orthopteran insects, hymenopteran insects, blattaria insects, dipteran insects, plant-parasitic nematodes, calf ticks, haemaphysalis longicornis, vitreomys microplus, dermomya bovis, fasciola hepatica, Monitz cestodes bei, protozoa, and Babesia.
9. The use as claimed in claim 7, wherein the pests are plutella xylostella, spodoptera frugiperda, spodoptera exigua, spodoptera litura.
10. An insecticidal composition comprising an active ingredient and an agriculturally acceptable carrier, wherein the weight percentage of the active ingredient in the composition is 0.01 to 99.99%, and the active ingredient is an N-difluoromethyl azole selenourea derivative according to any one of claims 1 to 5 or an agriculturally acceptable salt of the N-difluoromethyl azole selenourea derivative according to claim 6.
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