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CN103420884B - There is bisamide derivatives and the preparations and applicatio of optical activity and rotamerism - Google Patents

There is bisamide derivatives and the preparations and applicatio of optical activity and rotamerism Download PDF

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CN103420884B
CN103420884B CN201310183112.0A CN201310183112A CN103420884B CN 103420884 B CN103420884 B CN 103420884B CN 201310183112 A CN201310183112 A CN 201310183112A CN 103420884 B CN103420884 B CN 103420884B
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bisamide
propyl
halogen
acid
methyl
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CN103420884A (en
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李正名
周莎
闫涛
周蕴赟
熊丽霞
李永强
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Nankai University
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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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/10—Compounds containing sulfur atoms doubly-bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

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Abstract

本发明涉及一种具有光学活性和几何异构的双酰胺衍生物与制备及应用，结构如通式(I-1)及(I-2)所示，式中各取代基团的定义见说明书。通式(I-1)和(I-2)的化合物具有优异的杀虫活性。本发明是新型手性双酰胺类衍生物不仅改善了原有化合物抗药性，而且提高了杀虫活性和降低了生产成本。包含几何异构体。The present invention relates to a bisamide derivative with optical activity and geometric isomerism and its preparation and application. The structures are shown in the general formulas (I-1) and (I-2). For the definition of each substituent group in the formula, see the description . The compounds of the general formulas (I-1) and (I-2) have excellent insecticidal activity. The invention is a novel chiral bisamide derivative which not only improves the drug resistance of the original compound, but also improves the insecticidal activity and reduces the production cost. Contains geometric isomers.

Description

具有光学活性和几何异构的双酰胺衍生物与制备及应用Bisamide Derivatives with Optical Activity and Geometric Isomerism and Their Preparation and Application

技术领域technical field

本发明涉及一种具有光学活性和几何异构的双酰胺衍生物与制备及应用。The invention relates to a bisamide derivative with optical activity and geometric isomerism, its preparation and application.

背景技术Background technique

近年来，由于市场的不断扩大以及害虫的抗性、药物的使用寿命等问题以及人们对环境的日益重视，需要科学家们不断研究，致力开发出更有效、低成本、低毒、对环境安全和新颖具有独特作用机制的杀虫剂品种。In recent years, due to the continuous expansion of the market, the resistance of pests, the service life of drugs and other issues, as well as people's increasing attention to the environment, scientists need to continue to study and strive to develop more effective, low-cost, low-toxic, environmentally safe and Novel insecticide species with unique mechanism of action.

专利WO2006022225公开如下具有较好杀虫活性的手性双酰胺类化合物。Patent WO2006022225 discloses the following chiral bisamide compounds with good insecticidal activity.

为设计合成具有杀虫生物活性的新衍生物，并改善杀虫剂抗药性和降低生产成本，设计合成了未见文献报道的一类新颖具有光学活性和几何异构的双酰胺类衍生物，生物活性测试表明，此类衍生物表现较高的杀虫活性。In order to design and synthesize new derivatives with insecticidal biological activity, improve insecticide resistance and reduce production costs, a novel class of bisamide derivatives with optical activity and geometric isomerism that has not been reported in the literature was designed and synthesized. Biological activity tests show that such derivatives exhibit high insecticidal activity.

发明内容Contents of the invention

本发明的目的在于提供一种具有光学活性和几何异构的双酰胺衍生物与制备及应用。该化合物能够改善原有化合物抗药性和提高杀虫活性。The object of the present invention is to provide a bisamide derivative with optical activity and geometric isomerism, its preparation and application. The compound can improve the drug resistance of the original compound and improve the insecticidal activity.

本发明提供的具有光学活性和几何异构的双酰胺衍生物具有如下通式：The bisamide derivatives with optical activity and geometric isomerism provided by the present invention have the following general formula:

式中：In the formula:

X是H，卤素，SCN，氰基，硝基，C1-C6烷基，C2-C6烯基，C2-C6炔基，C3-C6环烷基，C1-C6卤代烷基，C1-C4烷氧基烷基，C1-C4羟基烷基，C1-C4烷氧基，C1-C4卤代烷氧基，C1-C4烷硫基，C2-C6烷氧基羰基，C2-C6烷基羰基，C1-C4烷基磺酰基，C1-C4烷基亚磺酰基，C1-C4烷基亚磺酰基亚胺基，C1-C4烷硫基，C1-C4烷氨基，C2-C8二烷基氨基，C3-C6环烷基氨基，C3-C6三烷基甲硅烷基，C2-C6烷基氨基羰基，C3-C8二烷基氨基羰基，苯基，苯氧基，苄基，五元杂芳环或六元杂芳环任选的被1-3个取代基取代，这些取代基各自独立自卤素，SCN，CN，硝基，羟基，C1-C4烷基，C1-C4烷氧基，C1-C6卤代烷基，C1-C4卤代烷氧基，C1-C4烷硫基，C1-C4羟基烷基；X is H, halogen, SCN, cyano, nitro, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 - C 6 haloalkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio radical, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylene Sulfonyl imino, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 3 -C 6 trioxane ylsilyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl, phenyl, phenoxy, benzyl, five-membered heteroaryl ring or six-membered heteroaryl ring optional Substituted with 1-3 substituents each independently selected from halogen, SCN, CN, nitro, hydroxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 6 haloalkyl , C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 hydroxyalkyl;

R1是H，C1-C6烷基，C2-C6链烯基，C2-C6炔基或C3-C6环烷基；R 1 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl;

R2是H，C1-C6烷基，C2-C6链烯基，C2-C6炔基或C3-C6环烷基；R 2 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl;

R3是卤素，H，C1-C6烷基，C2-C6链烯基，C2-C6链烯氧基，C2-C6炔基，C3-C6环烷基，C4-C7烷基环烷基，C1-C6卤代烷基，C1-C6卤代烷氧基，C2-C6卤链烯基，C2-C6卤炔基，C3-C6卤环烷基，C4-C7卤烷基环烷基，C2-C6烷氧羰基，C2-C6卤代烷氧羰基；R 3 is halogen, H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl , C 4 -C 7 alkylcycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 haloalkylcycloalkyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 haloalkoxycarbonyl;

R4是卤素，H，C1-C6烷基，C2-C6链烯基，C2-C6链烯氧基，C2-C6炔基，C3-C6环烷基，C4-C7烷基环烷基，C1-C6卤代烷基，C1-C6卤代烷氧基，C2-C6卤链烯基，C2-C6卤炔基，C3-C6卤环烷基，C4-C7卤烷基环烷基，C2-C6烷氧羰基，C2-C6卤代烷氧羰基；R 4 is halogen, H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl , C 4 -C 7 alkylcycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 haloalkylcycloalkyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 haloalkoxycarbonyl;

R5是H，卤素，C1-C6烷基，C2-C6链烯基，C2-C6链烯氧基，C2-C6炔基，C3-C6环烷基，C4-C7烷基环烷基，C1-C6卤代烷基，C1-C6卤代烷氧基，C2-C6卤链烯基，C2-C6卤炔基，C3-C6卤环烷基，C4-C7卤烷基环烷基，C2-C6烷氧羰基，C2-C6卤代烷氧羰基；R 5 is H, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl , C 4 -C 7 alkylcycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 haloalkylcycloalkyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 haloalkoxycarbonyl;

A是C0-C6烷基，C2-C6链烯基，C2-C6链烯氧基，C3-C6环烷基，C4-C7烷基环烷基，C1-C6卤代烷基，C1-C6卤代烷氧基，C2-C6卤代链烯基，C3-C6卤代环烷基，C4-C7卤烷基环烷基；A is C 0 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 2 -C 6 haloalkenyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 haloalkylcycloalkyl;

B是C1-C6烷基，C2-C6烯基，C3-C6环烷基，C2-C6卤代烷基，C1-C4烷氧基，C1-C4卤代烷氧基，C1-C4烷氧基烷基，C1-C4羟基烷基，C1-C4烷硫基，C1-C4烷氨基，C2-C8二烷基氨基，C3-C6环烷基氨基，苯基，五元杂芳环或者六元杂芳环任选的被1-3个取代基取代，这些取代基各自独立自卤素，SCN，CN，硝基，羟基，C1-C4烷基，C1-C4烷氧基，C1-C4卤代烷氧基，C1-C4烷硫基，C1-C4烷氨基，C2-C8二烷基氨基，C3-C6环烷基氨基，C2-C6烷基羰基，C2-C6烷氧羰基，C2-C6烷基氨基羰基，C3-C8二烷基氨基羰基；B is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 cycloalkyl, C 2 -C 6 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkane Oxygen, C 1 -C 4 alkoxyalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, phenyl, five-membered heteroaryl ring or six-membered heteroaryl ring are optionally substituted by 1-3 substituents, each of which is independently selected from halogen, SCN, CN, nitro , hydroxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 di Alkylaminocarbonyl;

W是H，氰基，硝基，卤素，羟基，胍基，硫氰酸基，氰酸基，四氮唑环，噁二唑环，这些杂环任选的被1-3个取代基取代，这些取代基各自独立自卤素，SCN，CN，硝基，羟基，C1-C4烷基，C1-C4烷氧基，C1-C4卤代烷氧基，C1-C4卤代烷基；W is H, cyano, nitro, halogen, hydroxyl, guanidino, thiocyanate, cyanate, tetrazole ring, oxadiazole ring, these heterocycles are optionally substituted by 1-3 substituents , each of these substituents is independently selected from halogen, SCN, CN, nitro, hydroxyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkane base;

M＝O，NR6；M=O, NR 6 ;

R6是H，卤素，氰基，硝基，硫氰酸基，C1-C6烷基，C2-C6链烯基，C2-C6链烯氧基，C2-C6炔基，C3-C6环烷基，C4-C7烷基环烷基，C1-C6卤代烷基，C1-C6卤代烷氧基，C2-C6卤链烯基，C2-C6卤炔基，C3-C6卤环烷基，C2-C6烷基羰基，C2-C6烷氧羰基，C2-C6烷基氨基羰基，苯基，五元杂芳环或者六元杂芳环任选的被1-3个取代基取代，这些取代基各自独立自卤素，SCN，CN，硝基，羟基，C1-C4烷基，C1-C4烷氧基，C1-C4卤代烷氧基，C1-C6卤代烷基，C1-C6卤代烷氧基；R 6 is H, halogen, cyano, nitro, thiocyanato, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 Alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 haloalkoxy, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, phenyl, The five-membered heteroaryl ring or the six-membered heteroaryl ring is optionally substituted by 1-3 substituents, each of which is independently selected from halogen, SCN, CN, nitro, hydroxyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 haloalkoxy;

K＝O或S；n＝0，1。K=O or S; n=0,1.

Y是苯基，苄基，苯氧基，苯甲酰基，苯氨基，5或6元杂环芳环基，萘基或芳族的8，9或10元稠合的杂双环体系，每个环或者环系任选的被1-5个各自独立的取代基所取代，这些取代基各自独立自卤素，SCN，氰基，硝基，C1-C6烷基，C2-C6烯基，C2-C6炔基，C3-C6环烷基，C1-C6卤代烷基，C1-C4烷氧基烷基，C1-C4羟基烷基，C1-C4烷氧基，C1-C4卤代烷氧基，C1-C4烷硫基，C2-C6烷氧基羰基，C2-C6烷基羰基，C1-C4烷基磺酰基，C1-C4烷基亚磺酰基，C1-C4烷基亚磺酰基亚胺基，C1-C4烷硫基，C1-C4烷氨基，C2-C8二烷基氨基，C3-C6环烷基氨基，C3-C6三烷基甲硅烷基，C2-C6烷基羰基，C2-C6烷氧羰基，C2-C6烷基氨基羰基，C3-C8二烷基氨基羰基；Y is phenyl, benzyl, phenoxy, benzoyl, anilino, 5- or 6-membered heterocyclic aromatic ring group, naphthyl or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each The ring or ring system is optionally substituted with 1-5 independently selected substituents independently selected from halogen, SCN, cyano, nitro, C 1 -C 6 alkyl, C 2 -C 6 alkene C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 4 alkoxyalkyl, C 1 -C 4 hydroxyalkyl, C 1 - C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, C 1 -C 4 alkyl Sulfonyl, C 1 -C 4 Alkylsulfinyl, C 1 -C 4 Alkylsulfinylimino, C 1 -C 4 Alkylthio, C 1 -C 4 Alkylamino, C 2 -C 8 Dialkylamino, C 3 -C 6 cycloalkylamino, C 3 -C 6 trialkylsilyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 Alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl;

在上述化合物的定义中，所用术语不论单独使用还是用在复合词中，代表如下取代基：In the definitions of the compounds above, the terms used, whether used alone or in compound words, represent the following substituents:

卤素：氟、氯、溴或碘；Halogen: fluorine, chlorine, bromine or iodine;

烷基：直链或支链烷基，例如甲基、乙基、丙基、异丙基或者叔丁基；Alkyl: straight chain or branched chain alkyl, such as methyl, ethyl, propyl, isopropyl or tert-butyl;

卤代烷基：直链或者支链烷基，在这些烷基上的氢原子可部分或者全部被卤原子所取代，例如，卤代烷基诸如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基或者三氟甲基。Haloalkyl: straight chain or branched chain alkyl, the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl group, difluoromethyl or trifluoromethyl.

烯基：直链或支链并可在任何位置上存在有双键，例如乙烯基或烯丙基；Alkenyl: straight or branched chain with double bonds at any position, such as vinyl or allyl;

炔基：直链或支链并可在任何位置上存在有三键，例如乙炔基或炔丙基；Alkynyl: straight or branched chain with triple bonds at any position, such as ethynyl or propargyl;

五元或六元杂环中杂原子为N，O或S；The heteroatom in the five-membered or six-membered heterocycle is N, O or S;

可选地，X是H，卤素，硫氰酸基，氰基，硝基，甲基，乙基，正丙基，异丙基，正丁基，异丁基，仲丁基，叔丁基，正戊基，异戊基，正己基，环己基，三氯甲基，氯甲基，二氯甲基，氟甲基，二氟甲基，三氟甲基，七氟异丙基，1-羟基六氟异丙基，甲氧基，氯甲氧基，二氯甲氧基，氟甲氧基，二氟甲氧基，三氟甲氧基，三氯甲氧基，乙氧基，全氟乙氧基，四氟乙氧基，2，2，2-三氟乙氧基，1，2，2-三氟乙氧基，1，1，2-三氟乙氧基，正丙氧基，异丙氧基，氨基，甲胺基，乙胺基，正丙胺基，乙酰胺基，甲酰胺基，三氟乙酰胺基，甲磺酰胺基，甲硫基，甲亚磺酰亚胺基，甲醛基，乙酰基，丙酰基，C1-C6烷胺基羰基或卤代烷胺基羰基，甲磺酰酯基；Alternatively, X is H, halogen, thiocyanato, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl , n-pentyl, isopentyl, n-hexyl, cyclohexyl, trichloromethyl, chloromethyl, dichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, heptafluoroisopropyl, 1 -Hydroxyhexafluoroisopropyl, methoxy, chloromethoxy, dichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, trichloromethoxy, ethoxy, Perfluoroethoxy, tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 1,2,2-trifluoroethoxy, 1,1,2-trifluoroethoxy, n-propyl Oxygen, isopropoxy, amino, methylamino, ethylamino, n-propylamino, acetamido, formamido, trifluoroacetamido, methylsulfonamido, methylthio, methylsulfinyl Amino, formaldehyde, acetyl, propionyl, C 1 -C 6 alkylaminocarbonyl or haloalkylaminocarbonyl, methylsulfonyl ester group;

R1，R2均为H，甲基，烯丙基；R 1 and R 2 are both H, methyl, allyl;

R3，R4，R5均为H，卤素，甲基，乙基，正丙基，异丙基，正丁基，异丁基，仲丁基，叔丁基，正己基，环己基，三氟甲基，三氯甲基，氯甲基，二氯甲基，氟甲基，二氟甲基，三氟甲氧基，甲氧基，氯甲氧基，二氯甲氧基，氟甲氧基，二氟甲氧基，三氟甲氧基，三氯甲氧基，乙氧基，全氟乙氧基，正丙氧基，异丙氧基；R 3 , R 4 , R 5 are all H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, Trifluoromethyl, trichloromethyl, chloromethyl, dichloromethyl, fluoromethyl, difluoromethyl, trifluoromethoxy, methoxy, chloromethoxy, dichloromethoxy, fluorine Methoxy, difluoromethoxy, trifluoromethoxy, trichloromethoxy, ethoxy, perfluoroethoxy, n-propoxy, isopropoxy;

A是甲基，卤代甲基，乙基，丙基，卤代乙基，卤代乙烯基；A is methyl, halomethyl, ethyl, propyl, haloethyl, halovinyl;

B是甲基，乙基，正丙基，异丙基，正丁基，异丁基，仲丁基，叔丁基，正戊基，异戊基，正己基，环己基，甲氧基，三氟甲氧基，乙氧基，正丙氧基，异丙氧基，苯基，苄基，呋喃环基，吡啶环基，噻唑环基，吡咯环基，其中芳香环可以任意被1-3个取代基取代，这些取代基是氰基，硝基，卤素，甲基，乙基，异丁基，三氟甲氧基，三氟甲基，三氯甲氧基，三氯甲基；B is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, methoxy, Trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, phenyl, benzyl, furyl ring, pyridine ring, thiazole ring, pyrrole ring, wherein the aromatic ring can be optionally 1- Substituted by 3 substituents, these substituents are cyano, nitro, halogen, methyl, ethyl, isobutyl, trifluoromethoxy, trifluoromethyl, trichloromethoxy, trichloromethyl;

W是H，氰基，硝基，卤素，羟基，胍基，硫氰酸基，氰酸基，四氮唑环，3-甲基噁二唑环，3-三氟甲基噁二唑环；W is H, cyano, nitro, halogen, hydroxyl, guanidino, thiocyanate, cyanate, tetrazole ring, 3-methyloxadiazole ring, 3-trifluoromethyloxadiazole ring ;

M＝O，NR6：M=O, NR 6 :

R6是H，卤素，氰基，硝基，硫氰酸基，叔丁基二甲基硅基，乙酰基，三氟乙酰基，三氟磺酰基，苯基，五元杂芳环或者六元杂芳环任选的被1-3个取代基取代，这些取代基是氰基，硝基，卤素，甲基，乙基，异丁基，三氟甲氧基，三氟甲基，三氯甲氧基，三氯甲基等；R6 is H, halogen, cyano, nitro, thiocyanato, tert-butyldimethylsilyl, acetyl, trifluoroacetyl, trifluorosulfonyl, phenyl, five-membered heteroaromatic ring or six The membered heteroaromatic ring is optionally substituted with 1-3 substituents, which are cyano, nitro, halogen, methyl, ethyl, isobutyl, trifluoromethoxy, trifluoromethyl, trifluoromethyl, Chloromethoxy, trichloromethyl, etc.;

K＝O或S；K=O or S;

n＝0，1：n=0,1:

Y是苯基、苄基、苯氧基、苯甲酰基、苯氨基、5或6元杂环芳环基、萘基或芳族的8，9或10元稠合的杂双环体系，每个环或者环系任选的被1-5个各自独立的取代基所取代，这些取代基各自独立自卤素，SCN，氰基，硝基，甲基，乙基，正丙基，异丙基，正丁基，异丁基，仲丁基，叔丁基，正戊基，异戊基，正己基，环己基，三氯甲基，氯甲基，二氯甲基，氟甲基，二氟甲基，三氟甲基，七氟异丙基，1-羟基六氟异丙基，甲氧基，氯甲氧基，二氯甲氧基，氟甲氧基，二氟甲氧基，三氟甲氧基，三氯甲氧基，乙氧基，全氟乙氧基，四氟乙氧基，2，2，2-三氟乙氧基，1，2，2-三氟乙氧基，1，1，2-三氟乙氧基，正丙氧基，异丙氧基，氨基，甲胺基，乙胺基，正丙胺基，乙酰胺基，甲酰胺基，三氟乙酰胺基，甲磺酰胺基，甲硫基，甲亚磺酰亚胺基，甲醛基，乙酰基，丙酰基。Y is phenyl, benzyl, phenoxy, benzoyl, anilino, 5 or 6 membered heterocyclic aromatic ring group, naphthyl or aromatic 8, 9 or 10 membered fused heterobicyclic ring system, each The ring or ring system is optionally substituted by 1-5 independent substituents, each of which is independently selected from halogen, SCN, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, trichloromethyl, chloromethyl, dichloromethyl, fluoromethyl, difluoro Methyl, trifluoromethyl, heptafluoroisopropyl, 1-hydroxyhexafluoroisopropyl, methoxy, chloromethoxy, dichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy Fluoromethoxy, trichloromethoxy, ethoxy, perfluoroethoxy, tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 1,2,2-trifluoroethoxy , 1,1,2-trifluoroethoxy, n-propoxy, isopropoxy, amino, methylamino, ethylamino, n-propylamino, acetamido, formamido, trifluoroacetamido , Methanesulfonamide, Methylthio, Methanesulfinimide, Formaldehyde, Acetyl, Propionyl.

所述的具有光学活性的双酰胺衍生物及其几何异构体的制备方法包括的步骤：The preparation method of the optically active bisamide derivatives and geometric isomers thereof includes the steps:

具有光学活性和几何异构的双酰胺衍生物(I-1)合成：Synthesis of bisamide derivatives (I-1) with optical activity and geometric isomerism:

通式II化合物与通式III化合物(摩尔比为1∶1)溶于有机溶剂中，然后加入适量的酸或碱，在温度为-10℃到沸点下反应0.5-48小时制得目标化合物IV；通式化合物IV在冰浴条件下溶于有机碱的有机溶剂中，然后加入通式化合物V，在温度为0℃至室温条件下反应3-24小时得到通式化合物I-1。The compound of the general formula II and the compound of the general formula III (the molar ratio is 1:1) are dissolved in an organic solvent, then an appropriate amount of acid or base is added, and the target compound IV is obtained by reacting at a temperature ranging from -10°C to the boiling point for 0.5-48 hours The compound IV of the general formula is dissolved in the organic solvent of the organic base under ice-bath conditions, then the compound V of the general formula is added, and the compound I-1 is obtained by reacting at a temperature ranging from 0°C to room temperature for 3-24 hours.

所述的有机溶剂选自二氯甲烷、氯仿、四氯化碳、苯、甲苯、二甲苯、环己烷、正己烷、乙酸乙酯、四氢呋喃、1，4-二氧六环、N，N-二甲基甲酰胺或二甲基亚砜。Described organic solvent is selected from dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, cyclohexane, n-hexane, ethyl acetate, tetrahydrofuran, 1,4-dioxane, N,N - dimethylformamide or dimethylsulfoxide.

所述的酸(酸和通式II化合物摩尔比0.001-0.1∶1)选自：甲基磺酸、苯磺酸、对甲基苯磺酸、乙酸、磷酸酯，或盐酸、硫酸或磷酸。The acid (the molar ratio of the acid to the compound of formula II is 0.001-0.1:1) is selected from: methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, phosphoric acid ester, or hydrochloric acid, sulfuric acid or phosphoric acid.

所述的碱选自有机碱(碱和通式II化合物摩尔比0.001-0.1)：三乙胺、吡啶、1，8-二氮杂-双环(5，4，O)十一碳烯-7或N，N-二甲基苯胺，或无机碱：氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、甲醇钠、叔丁醇钠或叔丁醇钾。The base is selected from organic bases (the molar ratio of the base to the compound of formula II is 0.001-0.1): triethylamine, pyridine, 1,8-diaza-bicyclo(5,4,O)undecene-7 or N,N-dimethylaniline, or inorganic bases: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide.

所述的氧化剂有高锰酸钾、间氯过氧苯甲酸(mCPBA)、NaIO4/RuO2、H2O2、臭氧。The oxidizing agent includes potassium permanganate, m-chloroperoxybenzoic acid (mCPBA), NaIO 4 /RuO 2 , H 2 O 2 , and ozone.

所述的有机溶剂选自二氯甲烷、氯仿、四氯化碳、苯、甲苯、二甲苯、环己烷、正己烷、乙酸乙酯、四氢呋喃、1，4-二氧六环、N，N-二甲基甲酰胺或二甲基亚砜。Described organic solvent is selected from dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, cyclohexane, n-hexane, ethyl acetate, tetrahydrofuran, 1,4-dioxane, N,N - dimethylformamide or dimethylsulfoxide.

通式I-2化合物制备如同通式I-1化合物。Compounds of general formula I-2 are prepared like compounds of general formula I-1.

本发明所述的具有光学活性的双酰胺衍生物及其几何异构体用于制备农用化学杀虫剂。特别是用于东方粘虫，小菜蛾和甜菜夜蛾等昆虫的防治。The optically active bisamide derivatives and their geometric isomers described in the invention are used to prepare agricultural chemical insecticides. Especially for the control of insects such as oriental armyworm, diamondback moth and beet armyworm.

在本发明的光学活性化合物中，同时硫氮双键连接不同的取代基而存在非对应异构体，本发明还包含顺反异构体、光学异构体、非对应异构体、消旋体或任何比例的它们的混合物；或对应它们的在农业中使用的盐。In the optically active compound of the present invention, diastereoisomers exist at the same time when sulfur and nitrogen double bonds are connected to different substituents. The present invention also includes cis-trans isomers, optical isomers, diastereoisomers, racemic or their mixtures in any proportion; or their corresponding salts for use in agriculture.

本发明提供的具有光学活性的双酰胺衍生物及其几何异构体作为活性成分配以农业可以接受的助剂组成的农药组合物用于防治昆虫的用途。The present invention provides an optically active bisamide derivative and its geometric isomer as an active ingredient and an agriculturally acceptable adjuvant for controlling insects.

本发明提供的具有光学活性的双酰胺衍生物及其几何异构体表现较高的杀虫活性。不仅改善了原有化合物抗药性，也提高了杀虫活性和降低了生产成本。The optically active bisamide derivatives and geometric isomers provided by the invention exhibit higher insecticidal activity. It not only improves the drug resistance of the original compound, but also improves the insecticidal activity and reduces the production cost.

具体实施方式Detailed ways

以下结合实施例来进一步说明本发明，其目的是能更好的理解本发明的内容乃体现本发明的实质性特点，因此所举之例不应视为对本发明保护范围的限制。The present invention is further described below in conjunction with embodiment, and its purpose is that content of the present invention can be better understood and embodies substantive characteristics of the present invention, so the example given should not be considered as limiting the protection scope of the present invention.

实施例1Example 1

N-[1-(S-甲基-N-氰基硫代羰基)-2-丙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺(衍生物83)的合成：N-[1-(S-methyl-N-cyanothiocarbonyl)-2-propyl]-3-iodo-N'-(3-trifluoromethylphenyl)-1,2-benzyl Synthesis of diamide (derivative 83):

步骤A：制备3-碘代邻苯二甲酸Step A: Preparation of 3-iodophthalic acid

将水(100mL)、3-硝基邻苯二甲酸(21.10g)和、氢氧化钠(9.2g)、2g六水合三氯化铁、8g活性碳和80％水合肼(12.5g)混合加热，制得3-氨基邻苯二甲酸。3-氨基邻苯二甲酸(18.1g)溶于浓硫酸和水混合液中，保持低温，依次加入亚硝酸钠(10.4g)、碘化钾溶液(25g)，后处理得固体3-碘代邻苯二甲酸。Water (100mL), 3-nitrophthalic acid (21.10g), sodium hydroxide (9.2g), 2g ferric chloride hexahydrate, 8g activated carbon and 80% hydrazine hydrate (12.5g) were mixed and heated , to produce 3-aminophthalic acid. 3-Aminophthalic acid (18.1g) was dissolved in a mixture of concentrated sulfuric acid and water, and kept at low temperature, sodium nitrite (10.4g) and potassium iodide solution (25g) were added successively, and post-treatment was performed to obtain solid 3-iodo-o-phthalic acid Diformic acid.

步骤B：制备3-碘代邻苯二甲酸酐Step B: Preparation of 3-iodophthalic anhydride

3-碘代邻苯二甲酸(29.2g)和乙酸酐(30mL)混合后加热微沸后处理得固体3-碘代邻苯二甲酸酐。3-iodophthalic acid (29.2 g) and acetic anhydride (30 mL) were mixed, heated and slightly boiled, and treated to obtain solid 3-iodophthalic anhydride.

步骤C：制备(S)-1-甲硫基-2-丙胺Step C: Preparation of (S)-1-methylthio-2-propanamine

(S)-1-甲硫基-2-丙醇(7.51g)和氯磺酸(11.65g)溶于乙二醇二甲醚，保持温度低于50℃。得到的(S)-1-甲硫基-2-丙醇的硫酸酯、NaOH(4g)和甲硫醇钠(70.09g)溶液混合，加热得到(S)-1-甲硫基-2-丙胺。(S)-1-Methylthio-2-propanol (7.51 g) and chlorosulfonic acid (11.65 g) were dissolved in ethylene glycol dimethyl ether keeping the temperature below 50°C. The obtained (S)-1-methylthio-2-propanol sulfate, NaOH (4g) and sodium thiomethoxide (70.09g) solution were mixed and heated to obtain (S)-1-methylthio-2- Propylamine.

步骤D：制备(S)-2-碘-6-羧基-N-(1-甲硫基-2-丙基)苯甲酰胺Step D: Preparation of (S)-2-iodo-6-carboxy-N-(1-methylthio-2-propyl)benzamide

室温下，3-碘代邻苯二甲酸酐(2.74g)、(S)-1-甲硫基-2-丙胺(1.05g)和三乙胺(1.00g)混合入二氯甲烷溶液，得固体2-碘-6-羧基-N-(1-甲硫基-2-丙基)苯甲酰胺。At room temperature, 3-iodophthalic anhydride (2.74g), (S)-1-methylthio-2-propylamine (1.05g) and triethylamine (1.00g) were mixed into dichloromethane solution to obtain 2-Iodo-6-carboxy-N-(1-methylthio-2-propyl)benzamide as a solid.

步骤E：制备N-(1-甲硫基-2-丙基)-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺Step E: Preparation of N-(1-methylthio-2-propyl)-3-iodo-N'-(3-trifluoromethylphenyl)-1,2-benzenediamide

2-碘-6-羧基-N-(1-甲硫基-2-丙基)苯甲酰胺(1.90g)和三乙胺(0.50g)溶于二氯甲烷溶剂，保持低温下依次加入甲磺酰氯(0.57g)、间三氟甲基苯胺(0.806g)，后处理得固体N-(1-甲硫基-2-丙基)-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺。2-iodo-6-carboxy-N-(1-methylthio-2-propyl)benzamide (1.90g) and triethylamine (0.50g) were dissolved in dichloromethane solvent, and methyl Sulfonyl chloride (0.57g), m-trifluoromethylaniline (0.806g), post-treatment to give solid N-(1-methylthio-2-propyl)-3-iodo-N'-(3-trifluoromethyl phenyl)-1,2-phthalamide.

步骤F：制备N-[1-(S-甲基-N-氰基硫代羰基)-2-丙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺(衍生物78和360)的合成：Step F: Preparation of N-[1-(S-methyl-N-cyanothiocarbonyl)-2-propyl]-3-iodo-N'-(3-trifluoromethylphenyl)-1, Synthesis of 2-phthalamides (derivatives 78 and 360):

保持室温以下，N-(1-甲硫基-2-丙基)-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺(0.52g)、单氰氨(0.063g)和醋酸碘代苯(0.322g)混合溶于1，4-二氧六环溶剂中，后处理得固体N-[1-(S-甲基-N-氰基硫代羰基)-2-丙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺。Keep below room temperature, N-(1-methylthio-2-propyl)-3-iodo-N'-(3-trifluoromethylphenyl)-1,2-benzenediamide (0.52g), Cyanamide (0.063g) and iodobenzene acetate (0.322g) were mixed and dissolved in 1,4-dioxane solvent, and post-treated to obtain solid N-[1-(S-methyl-N-cyanothio (carbonyl)-2-propyl]-3-iodo-N'-(3-trifluoromethylphenyl)-1,2-benzenediamide.

实施例2Example 2

N-[1-(S-甲基-N-三氟乙酰基硫代羰基)-2-丙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺(衍生物77)的合成：N-[1-(S-methyl-N-trifluoroacetylthiocarbonyl)-2-propyl]-3-iodo-N'-(3-trifluoromethylphenyl)-1,2- Synthesis of phthalamide (derivative 77):

保持室温以下，N-[1，1-二甲基-2-(S-甲基-N-氰基硫代羰基)乙基]-3-碘-N’-(3-三氟甲基苯基苯基)-1，2-苯甲二酰胺(0.56g)和三氟乙酸酐(0.63g)溶于二氯甲烷中，得固体N-[1，1-二甲基-2-(S-甲基-N-三氟乙酰基硫代羰基)乙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺。Keep below room temperature, N-[1,1-dimethyl-2-(S-methyl-N-cyanothiocarbonyl)ethyl]-3-iodo-N'-(3-trifluoromethylbenzene phenyl)-1,2-phthalic diamide (0.56g) and trifluoroacetic anhydride (0.63g) were dissolved in dichloromethane to give solid N-[1,1-dimethyl-2-(S -Methyl-N-trifluoroacetylthiocarbonyl)ethyl]-3-iodo-N'-(3-trifluoromethylphenyl)-1,2-phthalamide.

实施例3Example 3

N-[1-(S-甲基-N-氰基硫代羰基)亚砜基-2-丙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺(衍生物79)的合成：N-[1-(S-methyl-N-cyanothiocarbonyl)sulfoxide-2-propyl]-3-iodo-N'-(3-trifluoromethylphenyl)-1,2 - Synthesis of phthalamide (derivative 79):

冰浴下，间氯过氧苯甲酸(0.26g)、碳酸钾(1.24g)水溶液和N-[1-(S-甲基-N-氰基硫代羰基)-2-丙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺(0.56g)溶于乙醇溶液，后处理得固体N-[1-(S-甲基-N-氰基硫代羰基)亚砜基-2-丙基]-3-碘-N’-(3-三氟甲基苯基)-1，2-苯甲二酰胺。Under ice bath, m-chloroperoxybenzoic acid (0.26g), potassium carbonate (1.24g) aqueous solution and N-[1-(S-methyl-N-cyanothiocarbonyl)-2-propyl]-3 -Iodo-N'-(3-trifluoromethylphenyl)-1,2-benzenediamide (0.56g) was dissolved in ethanol solution, and post-treated to obtain solid N-[1-(S-methyl-N -cyanothiocarbonyl)sulfoxide-2-propyl]-3-iodo-N'-(3-trifluoromethylphenyl)-1,2-phthalamide.

现将根据以上实施例的制备方法而采用不同的原料制备的手性双酰胺类类衍生物：01～562，部分衍生物1HNMR(BrukerAV400spectrometerusingtetramethylsilaneastheinternalstandard)数据列入表2。The chiral bisamide derivatives: 01-562, partial derivatives 1 HNMR (Bruker AV400 spectrometer using tetramethylsilaneas the internal standard) data prepared according to the preparation method of the above examples and using different raw materials are listed in Table 2.

表1aTable 1a

表1bTable 1b

表1cTable 1c

表1dTable 1d

表2Table 2

实施例5Example 5

利用本发明提供的具有光学活性的双酰胺衍生物及其几何异构体进行测试，验证对害虫生物活性评价：Utilize the optically active bisamide derivatives provided by the present invention and their geometric isomers to test and verify the biological activity evaluation of pests:

将本发明提供的任一种具有光学异构和几何异构双酰胺类衍生物(01～562)溶于溶剂、水和表面活性剂，混合成为均一水相，使用时可用水稀释至任何所需的浓度，测试对象和测试方法如下：Dissolve any bisamide derivatives (01-562) with optical isomerism and geometric isomerism provided by the present invention in solvent, water and surfactant, mix to form a uniform water phase, and dilute with water to any desired The required concentration, test object and test method are as follows:

1)对东方粘虫的生物活性评价：供试昆虫是东方粘虫(MythimnaseparataWalker)，室内用玉米叶饲养的正常群体。采用浸叶法，浸渍苗期玉米叶于已配置好的溶液中，晾干后放入直径7cm培养皿中，接入4龄幼虫，每个浓度重复3次；对照用丙酮溶液浸渍玉米叶饲养幼虫；24小时、48小时、72小时后观察试验结果；1) Evaluation of biological activity against Mythimna separata Walker: The tested insects are Mythimnaseparata Walker, a normal group raised indoors with corn leaves. Using the method of soaking leaves, soak the corn leaves at the seedling stage in the prepared solution, put them into a 7cm-diameter petri dish after drying, and insert the 4th instar larvae, and repeat 3 times for each concentration; for the control, soak the corn leaves with acetone solution and raise Larvae; observe the test results after 24 hours, 48 hours, and 72 hours;

2)对小菜蛾的生物活性评价：供试昆虫是小菜蛾2龄幼虫(Plutellaxylostella(L.))，为室内正常饲养的正常群体；采用浸叶法，用镊子浸渍甘蓝叶片于已配置好的溶液中，时间2--3秒，甩掉余液；每次1片，每个样品共3片；待药液干后，放入10cm长的直型试管内，接入2龄小菜蛾幼虫，用纱布盖好管口；将试验处理置于标准处理室内，24小时、48小时、72小时后观察试验结果；2) Evaluation of the biological activity of Plutella xylostella: The insects to be tested are the 2nd instar larvae of Plutella xylostella (Plutellaxylostella (L.)), which is a normal population that is normally reared indoors; the leaf dipping method is used to dip the cabbage leaves into the prepared leaves with tweezers. In the solution, the time is 2-3 seconds, shake off the remaining liquid; 1 tablet each time, a total of 3 tablets for each sample; after the liquid medicine is dry, put it into a 10cm long straight test tube, and insert the 2nd instar diamondback moth larvae , cover the nozzle with gauze; place the test treatment in a standard treatment room, and observe the test results after 24 hours, 48 hours, and 72 hours;

3)对甜菜夜蛾的生物活性评价：供试昆虫是甜菜夜蛾3龄幼虫(LaphygmaexiguaHubner)，为室内正常饲养的正常群体；采用浸叶法，用镊子浸渍甘蓝叶片于已配置好的溶液中，时间2--3秒，甩掉余液；每次1片，每个样品共3片；待药液干后，放入直径7cm培养皿中，接入甜菜夜蛾3龄幼虫，将试验处理置于标准处理室内，24小时、48小时、72小时后观察试验结果；3) Evaluation of the biological activity of Spodoptera exigua: The insects to be tested are 3rd instar larvae of Spodoptera exigua (Laphygmaexigua Hubner), which is a normal population raised indoors; the leaves of cabbage are dipped in the prepared solution with tweezers by the leaf dipping method , time 2--3 seconds, shake off the remaining liquid; 1 tablet each time, a total of 3 tablets for each sample; after the liquid medicine is dry, put it into a 7cm-diameter petri dish, insert the 3rd instar larvae of beet armyworm, and test The treatment is placed in a standard treatment room, and the test results are observed after 24 hours, 48 hours, and 72 hours;

上述试验的部分测试结果如表3所示。Some test results of the above tests are shown in Table 3.

表3table 3

对部分同一结构式的两种光学体R/S生物活性对比，如表4所示：The comparison of the R/S bioactivity of two optical bodies with the same structural formula is shown in Table 4:

表4Table 4

表中死亡率等级：A级为100％-90％；B级为90％-70％；C级为70％-50％；D级为50％-0％。Mortality grades in the table: grade A is 100%-90%; grade B is 90%-70%; grade C is 70%-50%; grade D is 50%-0%.

由表6所示，手性S体双酰胺类衍生物比R体双酰胺类衍生物表现更优异的生物活性：甜菜夜蛾(LaphygmaexiguaHubner)和小菜蛾(Plutellaxylostella(L.))，两者均表现非常优异的活性，对于东方粘虫(MythimnaseparataWalker)，S体的生物活性更好。As shown in Table 6, the chiral S-body bisamide derivatives show more excellent biological activity than the R-body bisamide derivatives: beet armyworm (LaphygmaexiguaHubner) and diamondback moth (Plutellaxylostella (L.)), both Show very excellent activity, for Mythimnaseparata Walker, the biological activity of S body is better.

Claims (2)

1.一种双酰胺衍生物，具有如下结构式： 1. A bisamide derivative has the following structural formula: 其中，R1＝H，R2＝H、CH3，A＝CH2，B＝CH3；n是0、1；Q是CN、COCF3；X是3-Cl、3-Br、3-I；Y是苯基，C是苯基上的2-CH3-4-CF(CF3)2取代基。 Wherein, R 1 =H, R 2 =H, CH 3 , A=CH 2 , B=CH 3 ; n is 0, 1; Q is CN, COCF3; X is 3-Cl, 3-Br, 3-I ; Y is a phenyl group, and C is a 2-CH 3 -4-CF(CF 3 ) 2 substituent on the phenyl group. 2.权利要求1所述的双酰胺衍生物作为活性成分配以农业可以接受的助剂组成的农药组合物，用于防治昆虫的用途。 2. The bisamide derivative as claimed in claim 1 is used as an active ingredient in a pesticide composition composed of an agriculturally acceptable adjuvant for controlling insects.
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