An m-diamide compound and its agriculturally acceptable salts, preparation method, composition and application

Abstract

The present application provides a meta-diamide compound represented by formula (I), wherein Q is a substituted or unsubstituted phenyl, naphthyl, etc.; R1 is a substituted or unsubstituted C2-C8 epoxyalkyl group, C3-C9 cycloalkyl group, etc.; R2 is a hydrogen atom, a substituted or unsubstituted C1-C6 alkyl group, etc.; X1 and X2 are each independently selected from a hydrogen atom, a fluorine atom, etc.; Y1 and Y5 are each independently a hydrogen atom, a halogen atom, etc.; Y2 and Y4 are each independently a hydrogen atom, a halogen atom, etc.; Y3 is a C2-C6 haloalkyl group; and W is an oxygen atom or a sulfur atom. This meta-diamide compound has no cross-resistance with existing insecticides, and this compound has the advantages of fast efficacy, low dosage, low toxicity and environmental friendliness against plant pests, and particularly has excellent control effects against rice-resistant Chilo suppressalis, Plutella xylostella, aphids, etc. The present application also provides a preparation method of this meta-diamide compound and its use as a pesticide-acceptable salt, composition and application.

Description

Technical Field

[0001] The present invention relates to the technical field of organic compounds, and particularly relates to a meta-diamide compound, a pesticidally acceptable salt thereof, a preparation method, a composition and an application thereof. Background Art

[0002] In the production processes of agriculture, forestry, greenhouse crops, ornamental plants and nursery crops, insect pests have caused great losses to economic property, and insecticides are widely used in agricultural production and cultivation. With the extensive and long-term use of insecticides, pests have developed resistance to a large number of existing insecticides, and it is necessary to increase the dosage to achieve the original effect, which causes certain problems to agricultural production, the environment and the ecosystem. For example, in the process of rice cultivation, chlorantraniliprole is an efficient insecticide for controlling Chilo suppressalis, but after years of continuous use, serious resistance problems have also emerged in most parts of the world, posing a great threat to global rice production. Therefore, it is necessary to continuously develop new insecticides with high activity, fast efficacy, low toxicity and environmental friendliness. Summary of the Invention

[0003] In view of this, the present application provides a meta-diamide compound and a preparation method thereof. The meta-diamide compound has no cross-resistance with existing insecticides, and has the advantages of fast efficacy, low dosage, low toxicity and environmental friendliness against plant pests, and particularly has excellent control effects against resistant Chilo suppressalis, Plutella xylostella, aphids, etc.

[0004] The first aspect of the present application provides a meta-diamide compound represented by formula (I):

[0005]

[0006] In formula (I), Q is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group; R1 is any one of a substituted or unsubstituted C2-C8 epoxyalkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a substituted C1-C6 alkyl group, a hydrogen atom, a cyano group, an amino group, a hydroxyl group, and a mercapto group; wherein, when R1 is a substituted C1-C6 alkyl group, the substituents are selected from a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinylamino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted -Si(C1-C6 alkyl)3, one or more of them;

[0007] or a group represented by -L1-M-L2, wherein, L1 is selected from a substituted or unsubstituted phenylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C3-C9 cycloalkylene group, a substituted or unsubstituted C1-C6 alkyleneoxy group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C8 epoxyalkylene group, a substituted or unsubstituted C2-C6 alkenylene group, a substituted or unsubstituted C2-C6 alkynylene group, a substituted or unsubstituted C2-C6 alkenyloxy group, and a substituted or unsubstituted C2-C6 alkynyloxy group; M is selected from an oxygen atom, a sulfur atom, a carbonyl group, a sulfone group, a sulfoxide group, and an imino group; L2 is selected from a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, and a substituted or unsubstituted C2-C6 alkynyl group;

[0008] R2 is selected from any one of a hydrogen atom, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted C3-C6 cycloalkyl group;

[0009] X1 and X2 are each independently selected from any one of a hydrogen atom, a fluorine atom, a cyano group, and a nitro group, and X1 and X2 are not simultaneously hydrogen atoms;

[0010] Y1 and Y5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group;

[0011] Y2 and Y4 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a C1-C6 alkyl group;

[0012] Y3 is a C2-C6 haloalkyl group;

[0013] W is an oxygen atom or a sulfur atom.

[0014] In the embodiments of the present application, when R1 is a substituted C2-C8 epoxyalkyl group, a substituted C3-C9 cycloalkyl group, a substituted phenyl group, a substituted heterocyclic group, a substituted alkenyloxycarbonyl group, a substituted alkynyloxycarbonyl group, a substituted C1-C6 alkylthio group, a substituted C2-C6 alkenyl group, or a substituted C2-C6 alkynyl group, the substituents are selected from one or more of a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a mercapto group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinylamino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted -Si(C1-C6 alkyl)3;

[0015] When L1 or L2 is a substituted group, the substituting groups are each independently selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a mercapto group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinamino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a substituted or unsubstituted -Si(C1-C6 alkyl)3, or one or more of the foregoing;

[0016] When R2 is a substituted C1-C6 alkyl group, a substituted C2-C6 alkenyl group, a substituted C2-C6 alkynyl group, or a substituted C3-C6 cycloalkyl group, the substituting groups are selected from a halogen atom, a cyano group, a substituted or unsubstituted C1-C6 alkoxy group, or a substituted or unsubstituted C3-C6 cycloalkyl group, or one or more of the foregoing.

[0017] In an embodiment of the present application, when Q is a substituted phenyl group, a substituted naphthyl group, or a substituted heterocyclic group, the substituting groups are selected from a halogen atom, a carbamoyl group, a sulfamoyl group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a pentafluorothio group, a substituted or unsubstituted amino group, a substituted or unsubstituted thio group, a substituted or unsubstituted sulfinyl group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C8 epoxyalkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a substituted or unsubstituted C1-C6 carbonyloxy group, a substituted or unsubstituted C1-C6 sulfinyloxy group, a substituted or unsubstituted C1-C6 sulfonyloxy group, or one or more of the foregoing.

[0018] In the embodiments of the present application, R1 is any one of a substituted or unsubstituted C2-C8 epoxyalkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl group, a substituted or unsubstituted C3-C5 cycloalkyl C1-C3 alkyl group, a cyano-substituted C1-C6 alkyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a hydrogen atom, a cyano group, an amino group, a hydroxyl group, and a mercapto group; wherein, the substituents in the substituted C2-C8 epoxyalkyl group, the substituted C3-C9 cycloalkyl group, the substituted C3-C5 cycloalkyl C1-C3 alkyl group, the substituted furyl group, the substituted C1-C6 alkylthio group, the substituted C2-C6 alkenyl group, and the substituted C2-C6 alkynyl group are one or more of a C1-C3 alkyl group, a hydrogen atom, a halogen atom, a cyano group, or a furyl group;

[0019] or is a group represented by -L1-M-L2, wherein L1 is selected from any one of a substituted or unsubstituted C1-C3 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, a substituted or unsubstituted C1-C3 alkoxy group, a substituted or unsubstituted C1-C3 alkylamino group, and a substituted or unsubstituted C1-C3 alkoxycarbonyl group, wherein the substituents in the substituted C1-C3 alkylene group, the substituted C2-C6 alkenylene group, the substituted C1-C3 alkoxy group, the substituted C1-C3 alkylamino group, and the substituted C1-C3 alkoxycarbonyl group are one or more of a hydrogen atom, a halogen atom, a cyano group, or a C1-C3 alkoxy group; M is selected from an oxygen atom, a sulfur atom, or an imino group; L2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, and a substituted or unsubstituted C1-C3 alkoxy group, wherein the substituents in the substituted C1-C3 alkyl group, the substituted C2-C5 alkenyl group, and the substituted C1-C3 alkoxy group are one or more of a hydrogen atom, a halogen atom, a cyano group, a C1-C3 alkoxy group, and a C1-C3 alkylthio group.

[0020] In the embodiments of the present application, R1 is any one of a substituted or unsubstituted C3-C5 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl C1-C3 alkyl group, a cyano-substituted C1-C6 alkyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted C1-C3 alkylthio group, a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a hydrogen atom, and a cyano group; wherein, the substitution groups in the substituted C3-C5 cycloalkyl group, the substituted C1-C3 alkyl C3-C5 cycloalkyl group, the substituted C1-C3 alkyl C3-C5 cycloalkyl C1-C3 alkyl group, the substituted C1-C3 alkoxy group, the substituted C1-C3 alkylthio C1-C3 alkylamino group, the substituted furyl group, the substituted C1-C3 alkoxycarbonyl group, the substituted C1-C3 alkyl group, and the substituted C2-C5 alkenyl group are one or more of a halogen atom, a cyano group, a nitro group, and a furyl group;

[0021] or a group represented by -L1-M-L2, where L1 is selected from any one of a substituted or unsubstituted C1-C3 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, and a substituted or unsubstituted C1-C3 alkyleneoxy group, wherein the substitution groups in the substituted C1-C3 alkylene group, the substituted C2-C6 alkenylene group, and the substituted C1-C3 alkyleneoxy group are one or more of a halogen atom, a cyano group, and a C1-C3 alkoxy group; M is selected from an oxygen atom; L2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C3 alkyl group, and a substituted or unsubstituted C2-C5 alkenyl group, wherein the substitution groups in the substituted C1-C3 alkyl group and the substituted C2-C5 alkenyl group are one or more of a hydrogen atom, a halogen atom, a cyano group, a C1-C3 alkylthio group, and a C1-C3 alkoxy group;

[0022] R2 is a hydrogen atom, a C1-C3 alkyl group, a C2-C5 alkenyl group, a C2-C5 alkynyl group, a C3-C5 cycloalkyl group, or a C1-C3 alkyl C1-C3 alkoxy group.

[0023] In the embodiments of the present application, Q is selected from any one of a substituted or unsubstituted: phenyl group, naphthyl group, pyrimidinyl group, pyridyl group, N-oxidopyridyl group, pyrazinyl group, pyridazinyl group, furyl group, thienyl group, oxazolyl group, isoxazolyl group, oxadiazolyl group, thiazolyl group, isothiazolyl group, thiadiazolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, or tetrazolyl group, quinolinyl group, isoquinolinyl group; wherein the substitution groups are selected from one or more of a halogen atom, a cyano group, a nitro group, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, and a C1-C3 haloalkoxy group.

[0024] In the embodiments of the present application, Q is selected from any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrimidinyl group, and a substituted or unsubstituted pyrazinyl group; wherein, the substitution groups in the substituted phenyl group, substituted pyridyl group, substituted thiophenyl group, substituted pyrimidinyl group, and substituted pyrazinyl group are selected from one or more of a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a methoxy group, and a trifluoromethoxy group.

[0025] In the embodiments of the present application, X1 and X2 are each independently selected from a hydrogen atom or a fluorine atom, and X1 and X2 are not both hydrogen atoms; Y1 and Y5 are each independently a halogen atom, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, or a C1-C3 haloalkoxy group; Y2 and Y4 are each independently a hydrogen atom or a halogen atom; Y3 is a C2-C6 fluoroalkyl group; and W is an oxygen atom.

[0026] In the embodiments of the present application, X1 is a fluorine atom and X2 is a hydrogen atom; Y1 and Y5 are each independently a bromine atom, an iodine atom, a methyl group, a methoxy group, an ethoxy group, a trifluoromethyl group, a pentafluoroethyl group, a trifluoromethoxy group, or a pentafluoroethoxy group; Y2 and Y4 are hydrogen atoms; Y3 is a pentafluoroethyl group, a heptafluoroisopropyl group, or a nonafluoro-2-butyl group; and W is an oxygen atom.

[0027] In the second aspect of the present application, there is also provided a preparation method of the m-diamide compound provided in the first aspect, including the following steps:

[0028] Providing a compound represented by formula (VII) and a compound represented by formula (VI);

[0029] Reacting the compound represented by formula (VII) with the compound represented by formula (VI) to obtain a compound represented by formula (V-1);

[0030] Subjecting the compound represented by formula (V-1) to a bromination reaction to obtain a compound represented by formula (IV-1);

[0031] Subjecting the compound represented by formula (IV-1) to a reduction reaction to obtain a compound represented by formula (III-1);

[0032] Reacting the compound represented by formula (III-1) with an acyl chloride of Q to obtain a compound represented by formula (II-1);

[0033] Reacting the compound represented by formula (II-1) with an acyl chloride of R1 to obtain the m-diamide compound represented by formula (I-1);

[0034] Reacting the compound represented by formula (I-1) with a halogenated hydrocarbon of R2 to obtain the m-diamide compound represented by formula (I);

[0035]

[0036] or include the following steps:

[0037] Provide a compound represented by formula (VII) and a compound represented by formula (VI);

[0038] React the compound represented by formula (VII) and the compound represented by formula (VI) to obtain a compound represented by formula (V-2);

[0039] Subject the compound represented by formula (V-2) to a bromination reaction to obtain a compound represented by formula (IV-2);

[0040] React the compound represented by formula (IV-2) with an acyl chloride of R1 to obtain a compound represented by formula (III-2);

[0041] Subject the compound represented by formula (III-2) to a reduction reaction to obtain a compound represented by formula (II-2);

[0042] React the compound represented by formula (II-2) with an acyl chloride of Q to obtain a m-diamide compound represented by formula (I-2);

[0043] React the compound represented by formula (I-2) with a halohydrocarbon of R2 to obtain a m-diamide compound represented by formula (I);

[0044]

[0045] In formula (I), Q is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group; R1 is any one of a substituted or unsubstituted C2-C8 epoxyalkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a substituted C1-C6 alkyl group, a hydrogen atom, a cyano group, an amino group, a hydroxyl group, and a mercapto group; wherein, when R1 is a substituted C1-C6 alkyl group, the substituents are selected from a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a sulfide group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinamoyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted -Si(C1-C6 alkyl)3, one or more of them;

[0046] or a group represented by -L1-M-L2, wherein, L1 is selected from a substituted or unsubstituted phenylene group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted imino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C3-C9 cycloalkylene group, a substituted or unsubstituted C1-C6 alkyleneoxy group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C8 epoxyalkylene group, a substituted or unsubstituted C2-C6 alkenylene group, a substituted or unsubstituted C2-C6 alkynylene group, a substituted or unsubstituted C2-C6 alkenyloxy group, and a substituted or unsubstituted C2-C6 alkynyloxy group; M is selected from an oxygen atom, a sulfur atom, a carbonyl group, a sulfone group, a sulfoxide group, and an imino group; L2 is selected from a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, and a substituted or unsubstituted C2-C6 alkynyl group;

[0047] R2 is selected from any one of a hydrogen atom, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted C3-C6 cycloalkyl group;

[0048] X1 and X2 are each independently selected from any one of a hydrogen atom, a fluorine atom, a cyano group, and a nitro group, and X1 and X2 are not simultaneously hydrogen atoms;

[0049] Y1 and Y5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 alkyl group, or a substituted or unsubstituted C1-C6 alkoxy group;

[0050] Y2 and Y4 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a C1-C6 alkyl group;

[0051] Y3 is a C2-C6 haloalkyl group;

[0052] W is an oxygen atom or a sulfur atom.

[0053] The third aspect of the present application provides a tautomer, enantiomer, diastereomer, or a pesticidally acceptable salt thereof of the m-diamide compound provided in the first aspect.

[0054] The fourth aspect of the present application provides an application of a tautomer, enantiomer, diastereomer, or a pesticidally acceptable salt thereof of the m-diamide compound provided in the first aspect or the m-diamide compound provided in the third aspect in the preparation of insecticidal drugs in the fields of agriculture, forestry, or hygiene.

[0055] The fifth aspect of the present application further provides an insecticide preparation, and the insecticidal drug includes an active ingredient and an auxiliary; the active ingredient includes the m-diamide compound provided in the first aspect and / or a tautomer, enantiomer, diastereomer, or a pesticidally acceptable salt thereof of the m-diamide compound provided in the third aspect.

[0056] In the embodiments of the present application, the mass percentage content of the active ingredient in the insecticide preparation is 0.1%-99%.

[0057] The sixth aspect of the present application further provides an insecticide composition, and the insecticide composition includes an active ingredient and other active compounds; the active ingredient includes the m-diamide compound provided in the first aspect and / or a tautomer, enantiomer, diastereomer, or a pesticidally acceptable salt thereof of the m-diamide compound provided in the third aspect; the other active compounds include one or more of an insecticide, a bait agent, a disinfectant, an acaricide, a nematicide, a fungicide, a growth regulator, and a herbicide.

[0058] In the embodiments of the present application, the mass percentage content of the active ingredient in the pesticide composition is 1%-99%. Detailed implementation manners

[0059] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present application without creative efforts shall fall within the protection scope of the present application.

[0060] The present application provides a m - dicarboxamide compound represented by formula (I):

[0061]

[0062] In formula (I), Q is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group; R1 is any one of a substituted or unsubstituted C2 - C8 epoxyalkyl group, a substituted or unsubstituted C3 - C9 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1 - C6 alkylthio group, a substituted or unsubstituted C2 - C6 alkenyl group, a substituted or unsubstituted C2 - C6 alkynyl group, a substituted C1 - C6 alkyl group, a hydrogen atom, a cyano group, an amino group, a hydroxyl group, and a mercapto group; wherein, when R1 is a substituted C1 - C6 alkyl group, the substituent groups are selected from a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a sulfide group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinylamino group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1 - C6 alkyl group, a substituted or unsubstituted C3 - C6 cycloalkyl group, a substituted or unsubstituted C1 - C6 alkoxy group, a substituted or unsubstituted C2 - C6 alkenyl group, a substituted or unsubstituted C2 - C6 alkynyl group, and a substituted or unsubstituted -Si(C1 - C6 alkyl)3, one or more of them;

[0063] or a group represented by -L1-M-L2, where L1 is selected from any one of substituted or unsubstituted phenylene, substituted or unsubstituted heterocyclic group, substituted or unsubstituted imino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted alkenyloxycarbonyl, substituted or unsubstituted alkynyloxycarbonyl, substituted or unsubstituted C1-C6 alkylene, substituted or unsubstituted C3-C9 cycloalkylene, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C1-C6 alkylthio, substituted or unsubstituted C2-C8 epoxyalkylene, substituted or unsubstituted C2-C6 alkenylene, substituted or unsubstituted C2-C6 alkynylene, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy; M is selected from any one of an oxygen atom, a sulfur atom, a carbonyl group, a sulfone group, a sulfoxide group, an imino group; L2 is selected from a hydrogen atom, substituted or unsubstituted phenyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted alkenyloxycarbonyl, substituted or unsubstituted alkynyloxycarbonyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C9 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl;

[0064] R2 is selected from any one of a hydrogen atom, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C3-C6 cycloalkyl;

[0065] X1 and X2 are each independently selected from any one of a hydrogen atom, a fluorine atom, a cyano group or a nitro group, and X1 and X2 are not simultaneously hydrogen atoms;

[0066] Y1 and Y5 are each independently any one of a hydrogen atom, a halogen atom, a cyano group, a nitro group, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy;

[0067] Y2 and Y4 are each independently any one of a hydrogen atom, a halogen atom, a cyano group, a nitro group or C1-C6 alkyl;

[0068] Y3 is C2-C6 haloalkyl;

[0069] W is an oxygen atom or a sulfur atom.

[0070] In the embodiments of the present application, when Q is a substituted phenyl group, a substituted naphthyl group, or a substituted heterocyclic group, the substituents are selected from a halogen atom, a carbamoyl group, a sulfamoyl group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a pentafluorothio group, a substituted or unsubstituted amino group, a substituted or unsubstituted thio group, a substituted or unsubstituted sulfinyl group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C8 epoxyalkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a substituted or unsubstituted C1-C6 carbonyloxy group, a substituted or unsubstituted C1-C6 sulfinyloxy group, and a substituted or unsubstituted C1-C6 sulfonyloxy group, one or more of which. When there are two or more substituents, the substituents may be the same or different. In the embodiments of the present application, the above substituents may further have substituents where possible.

[0071] In some specific embodiments of the present application, when Q is a substituted phenyl group, a substituted naphthyl group, or a substituted heterocyclic group, the substitution groups may be, for example, a halogen atom, an amino group, a carbamoyl group, a sulfamoyl group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a sulfhydryl group, a sulfinyl group, a sulfonyl group, a pentafluorothioalkyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C9 cycloalkyl group, a C3-C9 halocycloalkyl group, a C2-C8 epoxyalkyl group, a C2-C8 haloepoxyalkyl group, a C2-C6 alkenyl group, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group, a C2-C6 haloalkynyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkylthio group, a C1-C6 haloalkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 haloalkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylsulfonyl group, a C1-C6 alkylcarbonyl group, a C1-C6 haloalkylcarbonyl group, a C1-C6 alkylcarbonyloxy group, a C1-C6 haloalkylcarbonyloxy group, a C1-C6 alkylsulfinyloxy group, a C1-C6 haloalkylsulfinyloxy group, a C1-C6 alkylsulfonyloxy group, a C1-C6 haloalkylsulfonyloxy group, a C1-C6 alkoxycarbonyl group, a C1-C6 haloalkoxycarbonyl group, a C1-C6 alkylcarbonylamino group, a C1-C6 haloalkylcarbonylamino group, a C1-C6 alkoxycarbonylamino group, a C1-C6 haloalkoxycarbonylamino group, a C1-C6 alkylamino group, a C1-C6 haloalkylamino group, an amino-substituted C1-C6 alkyl group, an amino-substituted C1-C6 haloalkyl group, a hydroxyl-substituted C1-C6 alkyl group, a hydroxyl-substituted C1-C6 haloalkyl group, a cyano-substituted C1-C6 alkyl group, a cyano-substituted C1-C6 haloalkyl group, a nitro-substituted C1-C6 alkyl group, a nitro-substituted C1-C6 haloalkyl group, a benzyloxy group having a halogen substituent, a benzoyl group having a halogen substituent, a phenylcarbamoyl group having a halogen substituent, a phenylamino group having a halogen substituent, a heterocyclic group having a halogen substituent, a phenylcarbamoyl group having a halogen substituent, and a phenylamino group having a halogen substituent, or one or more of them.

[0072] In some embodiments of the present application, Q is selected from substituted or unsubstituted: phenyl, naphthyl, pyrimidinyl, pyridyl, N-oxidopyridyl, pyrazinyl, pyridazinyl, furyl, thienyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, imidazolyl, pyrazolyl or tetrazolyl, quinolinyl, isoquinolinyl; wherein, the substitution groups are selected from a halogen atom, a cyano group, a nitro group, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkoxy group, or one or more of them.

[0073] In some embodiments of the present application, Q is selected from any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrimidinyl group, and a substituted or unsubstituted pyrazinyl group; wherein, the substituent groups in the substituted phenyl group, substituted pyridyl group, substituted thienyl group, substituted pyrimidinyl group, and substituted pyrazinyl group are selected from one or more of a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a methoxy group, and a trifluoromethoxy group. In some specific embodiments of the present application, Q can be, for example, a phenyl group, a fluorophenyl group, a cyanophenyl group, a trifluoromethylphenyl group, a difluorophenyl group, a trifluorophenyl group, a pyridyl group, a chloropyridyl group, a fluoropyridyl group, a dichlorofluorophenyl group, a thienyl group, a pyrimidinyl group, or a pyrazinyl group.

[0074] In the embodiments of the present application, when R1 is a substituted C1-C6 alkyl group, the substituent groups are selected from one or more of a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a sulfhydryl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinamoyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted -Si(C1-C6 alkyl)3. In the embodiments of the present application, C1-C6 alkyl refers to a C1-C6 chain alkyl group, including a C1-C6 straight-chain alkyl group and a C1-C6 branched-chain alkyl group. In some embodiments of the present application, the number of carbon atoms in the C1-C6 alkyl group can be, for example, 1, 2, 3, 4, 5, or 6.

[0075] In the embodiments of the present application, when R1 is a substituted C2-C8 epoxyalkyl group, a substituted C3-C9 cycloalkyl group, a substituted phenyl group, a substituted heterocyclic group, a substituted alkenyloxycarbonyl group, a substituted alkynyloxycarbonyl group, a substituted C1-C6 alkylthio group, a substituted C2-C6 alkenyl group, or a substituted C2-C6 alkynyl group, the substituent groups are selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a mercapto group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinamoyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted -Si(C1-C6 alkyl)3;

[0076] When L1 or L2 is a substituted group, the substituting groups are each independently selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a mercapto group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinamoyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted -Si(C1-C6 alkyl)3, one or more of them.

[0077] In the embodiments of the present application, when R2 is a substituted C1-C6 alkyl group, a substituted C2-C6 alkenyl group, a substituted C2-C6 alkynyl group, or a substituted C3-C6 cycloalkyl group, the substituting groups are selected from a halogen atom, a cyano group, a substituted or unsubstituted C1-C6 alkoxy group, and a substituted or unsubstituted C3-C6 cycloalkyl group, one or more of them.

[0078] In the embodiments of the present application, when there are two or more substituting groups, the substituting groups may be the same or different. In the embodiments of the present application, the above substituting groups may further have substituting groups where possible.

[0079] In the embodiments of the present application, the number of carbon atoms of the C2-C8 epoxyalkyl group may be, for example, 2, 3, 4, 5, 6, 7, 8; the number of carbon atoms of the C3-C9 cycloalkyl group may be, for example, 3, 4, 5, 6, 7, 8, 9; the number of carbon atoms of the C1-C6 alkylthio group may be, for example, 1, 2, 3, 4, 5, 6; the number of carbon atoms of the C2-C6 alkenyl group may be, for example, 2, 3, 4, 5, 6; the number of carbon atoms of the C2-C6 alkynyl group may be, for example, 2, 3, 4, 5, 6. In the embodiments of the present application, the number of carbon atoms of the substituted or unsubstituted C1-C6 alkyl group may be, for example, 1, 2, 3, 4, 5, 6; the number of carbon atoms of the substituted or unsubstituted C3-C6 cycloalkyl group may be, for example, 3, 4, 5, 6; the number of carbon atoms of the substituted or unsubstituted C1-C6 alkoxy group may be, for example, 1, 2, 3, 4, 5, 6; the number of carbon atoms of the substituted or unsubstituted C2-C6 alkenyl group may be, for example, 2, 3, 4, 5, 6; the number of carbon atoms of the substituted or unsubstituted C2-C6 alkynyl group may be, for example, 2, 3, 4, 5, 6; the number of carbon atoms of the substituted or unsubstituted C1-C6 alkylthio group may be, for example, 1, 2, 3, 4, 5, 6.

[0080] In some embodiments of the present application, R1 is any one of a substituted or unsubstituted C2-C8 epoxyalkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl group, a substituted or unsubstituted C3-C5 cycloalkyl C1-C3 alkyl group, a cyano-substituted C1-C6 alkyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a hydrogen atom, a cyano group, an amino group, a hydroxyl group, and a mercapto group; wherein, the substituents in the substituted C2-C8 epoxyalkyl group, the substituted C3-C9 cycloalkyl group, the substituted C3-C5 cycloalkyl C1-C3 alkyl group, the substituted furyl group, the substituted C1-C6 alkylthio group, the substituted C2-C6 alkenyl group, and the substituted C2-C6 alkynyl group are one or more of a C1-C3 alkyl group, a hydrogen atom, a halogen atom, a cyano group, or a furyl group;

[0081] or is a group represented by -L1-M-L2, wherein L1 is selected from any one of a substituted or unsubstituted C1-C3 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, a substituted or unsubstituted C1-C3 alkoxy group, a substituted or unsubstituted C1-C3 alkylamino group, and a substituted or unsubstituted C1-C3 alkoxycarbonyl group, wherein the substituents in the substituted C1-C3 alkylene group, the substituted C2-C6 alkenylene group, the substituted C1-C3 alkoxy group, the substituted C1-C3 alkylamino group, and the substituted C1-C3 alkoxycarbonyl group are one or more of a hydrogen atom, a halogen atom, a cyano group, or a C1-C3 alkoxy group; M is selected from an oxygen atom, a sulfur atom, or an imino group; L2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C3 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, and a substituted or unsubstituted C1-C3 alkoxy group, wherein the substituents in the substituted C1-C3 alkyl group, the substituted C2-C5 alkenyl group, and the substituted C1-C3 alkoxy group are one or more of a hydrogen atom, a halogen atom, a cyano group, a C1-C3 alkoxy group, and a C1-C3 alkylthio group.

[0082] In some specific embodiments of the present application, R1 is any one of a substituted or unsubstituted C3-C5 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl C1-C3 alkyl group, a cyano-substituted C1-C6 alkyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted C1-C3 alkylthio group, a substituted or unsubstituted C2-C5 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a hydrogen atom, and a cyano group; wherein, the substitution groups in the substituted C3-C5 cycloalkyl group, the substituted C1-C3 alkyl C3-C5 cycloalkyl group, the substituted C1-C3 alkyl C3-C5 cycloalkyl C1-C3 alkyl group, the substituted C1-C3 alkoxy group, the substituted C1-C3 alkylthio C1-C3 alkylamino group, the substituted furyl group, the substituted C1-C3 alkoxycarbonyl group, the substituted C1-C3 alkyl group, and the substituted C2-C5 alkenyl group are one or more of a halogen atom, a cyano group, a nitro group, and a furyl group;

[0083] or is a group represented by -L1-M-L2, wherein L1 is selected from any one of a substituted or unsubstituted C1-C3 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, and a substituted or unsubstituted C1-C3 alkyleneoxy group, wherein the substitution groups in the substituted C1-C3 alkylene group, the substituted C2-C6 alkenylene group, and the substituted C1-C3 alkyleneoxy group are one or more of a halogen atom, a cyano group, and a C1-C3 alkoxy group; M is selected from an oxygen atom; L2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C3 alkyl group, and a substituted or unsubstituted C2-C5 alkenyl group, wherein the substitution groups in the substituted C1-C3 alkyl group and the substituted C2-C5 alkenyl group are one or more of a hydrogen atom, a halogen atom, a cyano group, a C1-C3 alkylthio group, and a C1-C3 alkoxy group.

[0084] In some specific embodiments of the present application, R1 can be, for example, cyclopropyl, cyclobutyl, cyclopentyl, ethylcyclopropyl, -ethyl(2-methylcyclopropyl), -methyl(3-methylcyclobutyl), -methyl(3-methylcyclopentyl), -CH2SCH3, -CH2SCH2CH3, -CH2SCH3, -furan-2-yl, -methyl(furan-2-yl), -CH2CN, -C2H4CN, -CH=CH2, -CH2CH=CH2CH3, -C(CH3)=CH2, -C≡CH, -C≡CCH3, -CH2C≡CCH3, -CH2OCH3, -CH2OCH2CH3, -CH2CH2OCH3, -CH2OCH2OCH2Cl, or -CH2OCH2CH2OCH3.

[0085] In some embodiments of the present application, R1 may be, for example, a substituted or unsubstituted C3-C5 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl group, a substituted or unsubstituted C1-C3 alkyl C3-C5 cycloalkyl C1-C3 alkyl group, a substituted or unsubstituted C1-C3 alkoxy group, a substituted or unsubstituted C1-C3 alkylthio group, a substituted or unsubstituted C1-C3 alkylamino group, or a substituted or unsubstituted C1-C3 alkoxycarbonyl group. When the R1 contains a cyclic structure such as a cycloalkyl group or a heteroatom such as O, N, or S, the m-diamide compound has relatively excellent pest control efficacy. In some specific embodiments of the present application, R1 may be, for example, a cyclopropyl group, a methylcyclopropyl group, an isopropoxy group, -CH2OCH3, or -CH2OCH2CH3.

[0086] In some embodiments of the present application, R2 may be a hydrogen atom, a C1-C3 alkyl group, a C2-C5 alkenyl group, a C2-C5 alkynyl group, a C3-C5 cycloalkyl group, or a C1-C3 alkyl C1-C3 alkoxy group. In some specific embodiments of the present application, R2 may be, for example, a hydrogen atom, a methyl group, -CH2CH=CH2, -CH2OCH3, -CH3CN, or -CH2C≡CH.

[0087] In some embodiments of the present application, X1 is a fluorine atom; X2 is a hydrogen atom; Y1 and Y5 are each independently a bromine atom, an iodine atom, a methyl group, a methoxy group, an ethoxy group, a trifluoromethyl group, a pentafluoroethyl group, a trifluoromethoxy group, or a pentafluoroethoxy group; Y2 and Y4 are hydrogen atoms; Y3 is a pentafluoroethyl group, a heptafluoroisopropyl group, or a nonafluoro-2-butyl group; and W is an oxygen atom.

[0088] By appropriately selecting the respective groups of R1 and R2 and the mutual cooperation of the appropriate groups between R1 and R2 in the present application, the lipophilicity of the m-diamide compound can be enhanced. When it is applied to the field of pest control, it is more easily absorbed by pests, thus having better insecticidal activity. Currently, the m-diamide compounds commonly used to kill pests in the market produce efficacy through demethylation reactions in organisms, but pests will develop resistance after long-term use. The m-diamide compound provided in the present application produces efficacy through deacylation reactions in organisms. The m-diamide compound with this structure has not been applied to the field of pest control yet, and there is no problem of easy generation of resistance when this structure of m-diamide compound is applied.

[0089] The m-diamide compound provided in the present application has no cross-resistance with existing insecticides. Compared with the existing insecticides on the market, this compound has the advantages of fast efficacy, low dosage, low toxicity, and environmental friendliness against plant pests, and particularly has excellent control efficacy against rice stem borers, diamondback moths, aphids, etc.

[0090] The present application also provides a preparation method of the m-diamide compound provided above, including the following steps:

[0091] S101. Provide the compound shown in formula (VII) and the compound shown in formula (VI);

[0092] S102. React the compound shown in formula (VII) and the compound shown in formula (VI) to obtain the compound shown in formula (V-1);

[0093] S103. Perform a bromination reaction on the compound shown in formula (V-1) to obtain the compound shown in formula (IV-1);

[0094] S104. Perform a reduction reaction on the compound shown in formula (IV-1) to obtain the compound shown in formula (III-1);

[0095] S105. React the compound shown in formula (III-1) with the acyl chloride of Q to obtain the compound shown in formula (II-1);

[0096] S106. React the compound shown in formula (II-1) with the acyl chloride of R1 to obtain the meta-diamide compound shown in formula (I-1);

[0097] S107. React the compound shown in formula (I-1) with the halogenated hydrocarbon of R2 to obtain the meta-diamide compound shown in formula (I);

[0098]

[0099] Or include the following steps:

[0100] S201. Provide the compound shown in formula (VII) and the compound shown in formula (VI);

[0101] S202. React the compound shown in formula (VII) and the compound shown in formula (VI) to obtain the compound shown in formula (V-2);

[0102] S203. Perform a bromination reaction on the compound shown in formula (V-2) to obtain the compound shown in formula (IV-2);

[0103] S204. React the compound shown in formula (IV-2) with the acyl chloride of R1 to obtain the compound shown in formula (III-2);

[0104] S205. Perform a reduction reaction on the compound shown in formula (III-2) to obtain the compound shown in formula (II-2);

[0105] S206. React the compound shown in formula (II-2) with the acyl chloride of Q to obtain the meta-diamide compound shown in formula (I-2);

[0106] S207. React the compound shown in formula (I-2) with the halogenated hydrocarbon of R2 to obtain the m-diamide compound shown in formula (I);

[0107]

[0108] In formula (I), Q is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted heterocyclic group; R1 is any one of a substituted or unsubstituted C2-C8 epoxyalkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, a substituted C1-C6 alkyl group, a hydrogen atom, a cyano group, an amino group, a hydroxyl group, and a mercapto group; wherein, when the R1 is a substituted C1-C6 alkyl group, the substituent group is selected from a cyano group, a nitro group, a hydroxyl group, a carboxyl group, a sulfhydryl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, a sulfinamoyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkenyloxycarbonyl group, a substituted or unsubstituted alkynyloxycarbonyl group, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted -Si(C1-C6 alkyl)3, one or more of them;

[0109] Or a group represented by -L1-M-L2, wherein L1 is selected from any one of substituted or unsubstituted phenylene, substituted or unsubstituted heterocyclic group, substituted or unsubstituted imino, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted alkenyloxycarbonyl, substituted or unsubstituted alkynyloxycarbonyl, substituted or unsubstituted C1-C6 alkylene, substituted or unsubstituted C3-C9 cycloalkylene, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C1-C6 alkylthio, substituted or unsubstituted C2-C8 epoxyalkylene, substituted or unsubstituted C2-C6 alkenylene, substituted or unsubstituted C2-C6 alkynylene, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy; M is selected from any one of an oxygen atom, a sulfur atom, a carbonyl group, a sulfone group, a sulfoxide group, an imino group; L2 is selected from a hydrogen atom, substituted or unsubstituted phenyl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted alkenyloxycarbonyl, substituted or unsubstituted alkynyloxycarbonyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C9 cycloalkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl;

[0110] R2 is selected from any one of a hydrogen atom, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C3-C6 cycloalkyl;

[0111] X1 and X2 are each independently selected from any one of a hydrogen atom, a fluorine atom, a cyano group or a nitro group, and X1 and X2 are not simultaneously hydrogen atoms;

[0112] Y1 and Y5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C6 alkyl, a substituted or unsubstituted C1-C6 alkoxy;

[0113] Y2 and Y4 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group or a C1-C6 alkyl;

[0114] Y3 is a C2-C6 haloalkyl;

[0115] W is an oxygen atom or a sulfur atom.

[0116] In step S101 and step S201, the compound represented by formula (VII) can be obtained by a halogenation reaction or directly purchased from the market. And the compound represented by formula (VI) can be obtained by reacting with an acylating agent or directly purchased from the market. In the embodiments of the present application, the acylating agent can be, for example, thionyl chloride, oxalyl chloride, phosphorus pentachloride or phosphorus trichloride.

[0117] In steps S102 and S202, the molar ratio of the compound represented by formula (VII) to the compound represented by formula (VI) is 0.5 - 2:1. In some embodiments of the present application, the molar ratio of the compound represented by formula (VII) to the compound represented by formula (VI) can be, for example, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.5:1, 1.8:1 or 2:1.

[0118] In the embodiments of the present application, the reactions in steps S102 and S202 are carried out under basic conditions, and the basic conditions are organic bases and / or inorganic bases. In some embodiments of the present application, the organic base can be, for example, one or more of trimethylamine, triethylamine, diisopropylethylamine, tri-n-butylamine, pyridine, piperidine, 3-methylpyridine, 2,6-dimethylpyridine, N-methylmorpholine, 3-methylimidazole, 4-N,N-dimethylaminopyridine; the inorganic base can be, for example, sodium carbonate, potassium carbonate or sodium bicarbonate.

[0119] In the embodiments of the present application, the solvents for the reactions in steps S102 and S202 include one or more of dichloromethane, chloroform, toluene, ethyl acetate, acetone, acetonitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide.

[0120] In steps S103 and S203, when carrying out the bromination reaction, the selected bromides include one or more of bromide salts of alkali metals, bromide salts of alkaline earth metals, hydrobromic acid, bromine, ammonium bromide or N-bromosuccinimide. In some embodiments of the present application, the bromide is N-bromosuccinimide.

[0121] In the embodiments of the present application, the molar ratio of the compounds represented by formula (V-1) and formula (V-2) to the bromide is 0.5 - 2:1. In some embodiments of the present application, the molar ratio of the compounds represented by formula (V-1) and formula (V-2) to the bromide can be, for example, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.5:1, 1.8:1 or 2:1.

[0122] In the embodiments of the present application, the solvents for the bromination reactions in steps S103 and S203 include one or more of dichloromethane, chloroform, toluene, ethyl acetate, acetone, acetonitrile, tetrahydrofuran, dioxane, N,N-dimethylformamide, concentrated sulfuric acid or sodium hydroxide.

[0123] The reducing agents for the reduction reaction in step S104 include metallic elements or metal compounds. In some embodiments of the present application, the metallic element can be, for example, zinc powder and / or iron powder; the metal compound can be, for example, stannous chloride.

[0124] In the embodiments of the present application, the solvent for the reduction reaction in steps S104 and S205 includes one or more of methanol, ethanol, or ethyl acetate.

[0125] In the embodiments of the present application, the reaction temperatures of the reactions in steps S102, S103, S104 and steps S202, S203, S205 are greater than or equal to -10°C and less than or equal to the boiling point of the reaction solvent. In some embodiments of the present application, the reaction temperatures of the reactions in steps S102, S103, S104 and steps S202, S203, S205 can be, for example, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C or 90°C. In some other embodiments of the present application, the reactions in steps S102, S103 and S104 are carried out at the boiling point of the solvent, i.e., under reflux conditions.

[0126] In the embodiments of the present application, the reaction times of the reactions in steps S102, S103, S104 and steps S202, S203, S205 are 0.5 h - 48 h. In some embodiments of the present application, the reaction times of the reactions in steps S102, S103, S104 and steps S202, S203, S205 can be, for example, 0.5 h, 1 h, 3 h, 5 h, 8 h, 10 h, 12 h, 15 h, 16 h, 18 h, 20 h, 23 h, 24 h, 25 h, 28 h, 30 h, 32 h, 33 h, 35 h, 36 h, 38 h, 40 h, 44 h, 45 h or 48 h.

[0127] The reactions in steps S105, S106 and steps S204, S206 are carried out under basic conditions, and the basic conditions are organic bases and / or inorganic bases. In some embodiments of the present application, the organic base can be, for example, one or more of trimethylamine, triethylamine, diisopropylethylamine, tri-n-butylamine, pyridine, piperidine, 3-methylpyridine, 2,6-dimethylpyridine, N-methylmorpholine, 3-methylimidazole, 4-N,N-dimethylaminopyridine; the inorganic base can be, for example, sodium carbonate, potassium carbonate or sodium bicarbonate.

[0128] The reactions in steps S107 and S207 can be carried out in solutions of sodium hydride, potassium hydride, etc. such as N,N-dimethylformamide, tetrahydrofuran.

[0129] In the embodiments of the present application, the reaction temperatures of the reactions in steps S107 and S207 are greater than or equal to -10°C and less than or equal to 45°C. In some embodiments of the present application, the reaction temperatures of the reactions in steps S107 and S207 can be, for example, -10°C, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 35°C, 40°C, 45°C.

[0130] In the embodiments of the present application, the reaction time of the reactions in steps S107 and S207 is 0.5 h - 8 h. In some embodiments of the present application, the reaction time of the reactions in steps S107 and S207 can be, for example, 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h.

[0131] The preparation method described in the second aspect of the present application obtains the m - diamide compounds through an acyl chloride reaction. The acyl chloride reaction has high activity and lower requirements for reaction conditions such as reaction temperature and reaction time. This preparation method is simple, convenient, and has low costs, and can be applied to industrial production. The m - diamide compounds prepared by the preparation method provided by the present invention have no cross - resistance with existing insecticides. Compared with the existing insecticides on the market, this compound has the advantages of fast drug effect, low dosage, low toxicity, and environmental friendliness for plant pests, and particularly has excellent control effects on rice stem borers, diamondback moths, aphids, etc.

[0132] The embodiments of the present application provide a tautomer, enantiomer, diastereomer, or a pharmaceutically acceptable salt thereof of the m - diamide compound provided above.

[0133] The embodiments of the present application further provide an application of the m - diamide compound provided above, or a tautomer, enantiomer, diastereomer, or a pharmaceutically acceptable salt thereof of the m - diamide compound provided above in the preparation of insecticide drugs in the fields of agriculture, forestry, or hygiene.

[0134] In the embodiment of the present application, the pests that the pesticide is used to control include but are not limited to beetles (Coleoptera), such as green bean weevils, corn weevils, red flour beetles, potato beetles, fine-breasted beetles, multi-colored scarab beetles, potato leaf beetles, leaf beetles, pine beetles, rice root weevils, brown powder borers; Lepidoptera pests, such as gypsy moths, yellow-brown tent caterpillars, Pieris rapae Japanese subspecies, Spodoptera litura, cabbage armyworm, striped stem borer, corn borer, dried fruit borer, apple moth, yellow cutworm, greater wax moth, cabbage moth, tobacco budworm, citrus leafminer; Hemiptera pests, for example, black-tailed leafhopper, brown planthopper, mealybug, arrow-pointed shield scale, peach aphid, apple aphid, cotton aphid, radish aphid, pear crown lace bug, green toon, greenhouse whitefly; Thysanoptera pests, for example, palm thrips, western flower thrips; Orthoptera pests, for example, African mole cricket, African migratory locust; Blattodea pests, for example, German cockroach, American cockroach, yellow-breasted termite, house termite; Diptera pests, for example, one or more of housefly, Aedes aegypti, gray ground fly, Culex pipiens pallens, Anopheles sinensis, Culex tritaeniorhynchus, and clover leafminer. In some embodiments of the present application, the insecticide drug may also refer to acaricide drugs, and the pests used for prevention and control include but are not limited to spiders (Arachnids), such as mites (Acarina), for example, soft ticks, hard ticks and sarcoptes, such as the long star tick, tropical flower tick, Persian sharp-edged tick, cattle tick, microscopic cattle tick, ricinus tick, gallinae mite, sheep scabies, human scabies; Acarus spp., such as apple rust mite; Tenuiphagus spp., such as Polyphagous tarsonemus; Tenuipalpids spp., such as purple-red short-palped mite; Tetranychus spp., such as cinnabarinus spider mite, Kanzawa spider mite, Pacific spider mite, cotton spider mite and two-spotted spider mite; one or more of apple spider mite and citrus spider mite.

[0135] The embodiment of the present application also provides an insecticide preparation, which includes an active component, and the active component includes the diamide compound provided above and / or the tautomer, enantiomer, diastereomer or its pesticide acceptable salt of the diamide compound provided above; the insecticide preparation also includes one or more excipients.

[0136] In the embodiments of the present application, the pesticide preparation includes, but is not limited to, solutions, emulsions, wettable powders, granular wettable powders, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural agents impregnated with active compounds, synthetic agents impregnated with active compounds, microcapsules, seed coatings, preparations equipped with combustion devices (the combustion devices may be chimneys and fog cylinders, cans and coils, etc.), cold fog agents, hot fog agents, etc. These pesticide preparations or animal parasite control agents may be prepared by known methods, for example, by mixing the active ingredient with a filler (such as a liquid diluent or carrier, a liquefied gas diluent or carrier, a solid diluent or carrier), and optionally with a surfactant (i.e., an emulsifier and / or a dispersant and / or a foaming agent).

[0137] In the embodiments of the present application, the mass percentage content of the active ingredient in the insecticide preparation is 0.1%-99%. In some embodiments of the present application, the mass percentage content of the active ingredient in the insecticide preparation can be, for example, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99%. In some specific embodiments of the present application, the mass percentage content of the active ingredient in the insecticide preparation can be 0.5%-90%.

[0138] The embodiments of the present application further provide an insecticide composition, which includes an active ingredient and other active compounds; the active ingredient includes the meta-diamide compounds provided above in the present application and / or the tautomers, enantiomers, diastereomers or pharmaceutically acceptable salts of the meta-diamide compounds provided above in the present application; the other active compounds include one or more of insecticides, bait agents, disinfectants, acaricides, nematicides, fungicides, growth regulators and herbicides.

[0139] In the embodiments of the present application, the mass percentage content of the active ingredient in the insecticide composition is 1%-99%. In some specific embodiments of the present application, the mass percentage content of the active ingredient in the insecticide composition can be, for example, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99%. In some embodiments of the present application, the mass percentage content of the active ingredient in the insecticide composition is 20%-70%.

[0140] The insecticide drug, insecticide preparation and insecticide composition provided by the present application have no cross-resistance with existing insecticides. Compared with the existing insecticides on the market, this compound has the advantages of fast drug effect, low dosage, low toxicity and environmental friendliness for plant pests, and particularly has excellent control effects on resistant Chilo suppressalis, Plutella xylostella, aphids, etc.

[0141] The embodiments of the present invention will be further described below with multiple examples.

[0142] Specifically, the meta-diamide compounds described in the present application are shown in formula (VIII), X1 is a fluorine atom, X2 is a hydrogen atom, and some of the meta-diamide compounds are shown in Table 1, but the meta-diamide compounds described in the present invention are not limited to all the compounds in Table 1.

[0143]

[0144] Table 1: Meta-diamide compounds having the chemical structural formula shown in formula (VIII):

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171] Example 1

[0172] Preparation method of Compound No. 11 in Table 1:

[0173] (1) Synthesis of 2-fluoro-N-(2-methyl-4-(2,2,2-trifluoro-1,1-dimethylethyl)phenyl)-3-nitrobenzamide

[0174]

[0175] Add 2-fluoro-3-nitrobenzoic acid (3.00 g, 16.21 mmol) and thionyl chloride (10 ml) to a reaction flask, stir and react under reflux for 2 h, concentrate under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. Add 2-fluoro-3-nitrobenzoyl chloride and pyridine (1.76 g, 22.39 mmol) to a dichloromethane (20 ml) solution of 4-(2,2,2-trifluoro-1,1-dimethylethyl)-2-methylaniline (2.94 g, 10.69 mmol), stop the reaction after reacting at room temperature for 5 hours. Wash with dilute hydrochloric acid (2 mol / L), saturated potassium carbonate solution, and saturated sodium chloride solution, dry over anhydrous sodium sulfate and rotary evaporate to obtain the product as a pale yellow solid (4.50 g, yield 95.23%).

[0176] 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.36 (s, 1H), 8.33 (t, J = 7.1 Hz, 1H), 8.12 (t, J = 6.1 Hz, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.63 - 7.54 (m, 3H), 2.40 (s, 3H).

[0177] ESI-MS (m / z): [M - H - ] theoretical value: 441.0490, measured value: 441.0491.

[0178] (2) Synthesis of N-(2-bromo-6-methyl-4-(2,2,2-trifluoro-1,1-dimethylethyl)phenyl)-2-fluoro-3-nitrobenzamide

[0179]

[0180] Under the condition of 0 °C, dissolve 2-fluoro-N-(2-methyl-4-(2,2,2-trifluoro-1,1-dimethylethyl)phenyl)-3-nitrobenzamide (1.80 g, 4.07 mmol) in concentrated sulfuric acid (10 ml), slowly add N-bromosuccinimide (0.85 g, 4.79 mmol), heat up to 65 °C and react for 2 h. Cool the reaction solution to room temperature, pour the reaction solution into ice water, filter, and wash the obtained solid with ice water, saturated sodium sulfite, and saturated sodium bicarbonate solution to obtain a yellow solid (2.00 g, yield 94.31%).

[0181] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.69 (s, 1H), 8.36–8.32 (m, 1H), 8.12–8.08 (m, 1H), 7.81 (s, 1H), 7.70 (s, 1H), 7.61 (t, J = 6.6 Hz, 1H), 2.42 (s, 3H). ESI-MS (m / z): [M-H-] theoretical value: 518.9596, measured value: 518.9592

[0182] (3) Synthesis of 3-amino-N-(2-bromo-6-methyl-4-(2,2,2-trifluoropropyl)phenyl)-2-fluorobenzamide

[0183]

[0184] Dissolve N-(2-bromo-6-methyl-4-(2,2,2-trifluoropropyl)phenyl)-2-fluoro-3-nitrobenzamide (2.17 g, 4.16 mmol) in ethanol (20 ml), and add stannous chloride dihydrate (3.67 g, 16.31 mmol) in batches. Heat the reaction mixture to 60 °C and react for 4 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with ethyl acetate solution, wash it with 10% aqueous sodium hydroxide solution, filter off the solid, wash the organic layer with saturated brine and dry it over anhydrous sodium sulfate, then rotate it to dryness under reduced pressure to obtain a yellowish-brown solid (1.43 g, yield 70.01%).

[0185] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.14 (s, 1H), 7.79 (s, 1H), 7.68 (s, 1H), 7.00 (t, J = 7.3 Hz, 1H), 6.93 (t, J = 8.1 Hz, 1H), 6.82 (t, J = 6.0 Hz, 1H), 5.41 (s, 2H), 2.39 (s, 3H).

[0186] ESI-MS (m / z): [M-H-] theoretical value: 488.9854, measured value: 488.9849.

[0187] (4) Synthesis of 3-benzamido-N-(2-bromo-6-methyl-4-(2,2,2-trifluoropropyl)phenyl)-2-fluorobenzamide

[0188]

[0189] Dissolve 3-amino-N-(2-bromo-6-methyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)-2-fluorobenzamide (1.40 g, 2.85 mmol) in dichloromethane (10 ml), add pyridine (0.47 g, 6.00 mmol), stir at room temperature for 10 min, dropwise add benzoyl chloride (0.48 g, 3.41 mmol), and react at room temperature for 5 h. After the reaction solution is washed with saturated sodium carbonate and saturated brine and dried over anhydrous sodium sulfate, it is concentrated under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a pale yellow solid (1.52 g, yield 89.95%).

[0190] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.39 (s, 1H), 10.29 (s, 1H), 8.04 - 8.00 (m, 2H), 7.83 (q, J = 6.8 Hz, 2H), 7.70 (s, 1H), 7.64 - 7.54 (m, 4H), 7.43 - 7.35 (m, 1H), 2.42 (s, 3H).

[0191] ESI-MS (m / z): [M-H-] theoretical value: 593.0116, measured value: 593.0116.

[0192] (5) Synthesis of 3-benzamido-N-(2-bromo-6-methyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)-N-(cyclopropanecarbonyl)-2-fluorobenzamide

[0193]

[0194] Dissolve 3-benzamido-N-(2-bromo-6-methyl-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)-2-fluorobenzamide (1.00 g, 1.68 mmol) in dichloromethane (10 ml), stir at room temperature for 10 min, dropwise add cyclopropanecarbonyl chloride (0.18 g, 1.72 mmol), and react at room temperature overnight. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is concentrated under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.40 g, yield 36.01%).

[0195] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.26 (s, 1H), 8.00 (d, J = 7.1 Hz, 2H), 7.97 (s, 1H), 7.86 (s, 1H), 7.82 - 7.78 (m, 1H), 7.63 (t, J = 7.4 Hz, 1H), 7.55 (t, J = 7.5 Hz, 2H), 7.47 (t, J = 6.2 Hz, 1H), 7.34 (dd, J = 10.1, 5.6 Hz, 1H), 2.44 (s, 3H), 1.40 (ddd, J = 12.1, 7.8, 4.4 Hz, 1H), 0.99 - 0.92 (m, 2H), 0.91 – 0.84 (m, 2H).

[0196] ESI-MS (m / z): [M - H - ] theoretical value: 661.0378, measured value: 661.0379.

[0197] Example 2

[0198] Preparation method of compound No. 146 in Table 1:

[0199] (1) Preparation of 4-(perfluoropropan-2-yl)-2-(trifluoromethyl)aniline:

[0200] To a mixed solution of 150 ml of ethyl acetate and 150 ml of water, add 2-(trifluoromethyl)aniline (100 g, 0.608 mol), 85% sodium sulfite (131 g, 0.639 mol) and tetrabutylammonium sulfate (20.9 g, 0.0608 mol), then add sodium bicarbonate (53.9 g, 0.639 mol). At room temperature, add perfluoroisopropyl iodide (198 g, 0.669 mol) dropwise and react at room temperature for 6 h. After liquid separation, evaporate the organic phase solvent under reduced pressure, add 500 ml of ethyl acetate, dropwise add 4M hydrochloric acid / ethyl acetate solution (160 g, 0.608 mol), stir at room temperature for 30 minutes, and then continue to stir at 5 °C for 1 h. After filtration, wash the clear liquid successively with water and saturated sodium bicarbonate aqueous solution, dry over anhydrous sodium sulfate, and distill off the solvent under reduced pressure. Purify by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a yellow solution (60.0 g, yield 30%).

[0201] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 7.51 (d, J = 9.0 Hz, 1H), 7.43 (s, 1H), 7.02 (d, J = 8.9 Hz, 1H), 6.37 (s, 2H).

[0202] ESI-MS (m / z): [M-H-] Theoretical value: 328.0189, Measured value: 328.0190.

[0203] (2) Synthesis of 2-Fluoro-3-nitro-N-(4-(perfluoropropan-2-yl)-2-(trifluoromethyl)phenyl)benzamide

[0204]

[0205] Add 2-fluoro-3-nitrobenzoic acid (1.66 g, 8.97 mmol) and thionyl chloride (10 ml) to the reaction flask, stir and react under reflux conditions for 2 h, concentrate under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. Add 2-fluoro-3-nitrobenzoyl chloride to a solution of 4-(perfluoropropan-2-yl)-2-(trifluoromethyl)aniline (2.36 g, 7.17 mmol) in acetonitrile (20 ml), heat to 80 °C and react for 8 h. Wash with dilute hydrochloric acid (2 mol / L), saturated sodium carbonate solution, and saturated sodium chloride solution, dry over anhydrous sodium sulfate and then rotary evaporate to obtain the product as a white solid (3.20 g, yield 90.16%).

[0206] The 1H NMR data of the compound (400 MHz, DMSO-d6) are as follows (δ [ppm]): δ 10.74 (s, 1H), 8.37 - 8.32 (m, 1H), 8.15 - 8.03 (m, 3H), 7.94 (s, 1H), 7.61 (t, J = 7.9 Hz, 1H).

[0207] ESI-MS (m / z): [M-H-] Theoretical value: 495.0208, Measured value: 495.0203.

[0208] (3) Synthesis of N-(2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-nitrobenzamide

[0209]

[0210] Add 2-fluoro-3-nitro-N-(4-(perfluoropropan-2-yl)-2-(trifluoromethyl)phenyl)benzamide (2.00 g, 4.03 mmol), sodium hydroxide (0.30 g, 7.50 mmol) and acetonitrile (10 ml) to the reaction flask, add N-bromosuccinimide (0.92 g, 5.17 mmol) in portions, stop the reaction after reacting at room temperature for 7 h. Rotary evaporate the reaction solution under reduced pressure, dissolve it with ethyl acetate solution, wash with saturated sodium sulfite, saturated sodium bicarbonate solution, and saturated sodium chloride solution, dry over anhydrous sodium sulfate and then rotary evaporate to obtain the product as a white solid (1.76 g, yield 76.35%).

[0211] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 11.13 (s, 1H), 8.45 (d, J = 1.1 Hz, 1H), 8.41 - 8.35 (m, 1H), 8.06 (ddd, J = 7.5, 5.9, 1.6 Hz, 1H), 7.98 (s, 1H), 7.65 (t, J = 8.0 Hz, 1H).

[0212] ESI-MS (m / z): [M-H-] Theoretical value: 572.9313, Measured value: 572.9318.

[0213] (4) Synthesis of 3-amino-N-(2-bromo-4-(2,2,2-trifluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide

[0214]

[0215] Dissolve N-(2-bromo-4-(2,2,2-trifluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-nitrobenzamide (1.76 g, 3.07 mmol) in ethanol (20 ml), add stannous chloride dihydrate (2.76 g, 12.26 mmol) in batches, and heat to 60 °C for reaction for 4 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with ethyl acetate solution, wash it with 10% aqueous sodium hydroxide solution, filter off the solid, wash the organic layer with saturated brine and dry it over anhydrous sodium sulfate, then rotate it to dryness under reduced pressure to obtain a yellow solid (1.20 g, yield 71.99%).

[0216] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.74 (s, 1H), 8.37 - 8.32 (m, 1H), 8.15 - 8.03 (m, 4H), 7.94 (s, 1H), 7.61 (t, J = 7.9 Hz, 1H).

[0217] ESI-MS (m / z): [M-H-] Theoretical value: 542.9571, Measured value: 542.9574.

[0218] (5) Synthesis of 3-benzamido-N-(2-bromo-4-(2,2,2-trifluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide

[0219]

[0220] Dissolve 3-amino-N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.20 g, 2.21 mmol) in acetonitrile (10 ml), heat to 80 °C, dropwise add benzoyl chloride (0.20 g, 1.42 mmol), and react for 2 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with ethyl acetate solution, wash it with saturated sodium carbonate and saturated brine, dry it over anhydrous sodium sulfate, then rotate it to dryness under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a pale yellow solid (1.32 g, yield 92.31%).

[0221] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.80 (s, 1H), 10.32 (s, 1H), 8.43 (s, 1H), 8.04 (d, J = 7.2 Hz, 2H), 7.98 (s, 1H), 7.86 (t, J = 6.9 Hz, 1H), 7.66 - 7.54 (m, 4H), 7.41 (t, J = 7.8 Hz, 1H). ESI-MS (m / z): [M - H - Theoretical value: 646.9833, measured value: 646.9833.

[0222] (6) Synthesis of N-acryloyl-3-benzamido-N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide:

[0223]

[0224] Add 3-benzamido-N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.00 g, 1.54 mmol) to 10 ml of dichloromethane, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add acryloyl chloride (0.18 g, 1.98 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is rotated to dryness under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.80 g, yield 74.03%).

[0225] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.31 (s, 1H), 8.59 (s, 1H), 8.11 (s, 1H), 8.05 - 7.99 (m, 2H), 7.92 - 7.84 (m, 1H), 7.63 (dd, J = 8.4, 6.2 Hz, 1H), 7.55 (t, J = 7.4 Hz, 2H), 7.47 - 7.35 (m, 2H), 6.42 (dd, J = 16.4, 1.2 Hz, 1H), 6.13 (dd, J = 16.4, 10.3 Hz, 1H), 5.90 (dd, J = 10.4, 1.2 Hz, 1H).

[0226] ESI-MS (m / z): [M - H - ] Theoretical value: 700.9939, Measured value: 700.9943.

[0227] Example 3

[0228] Preparation method of compound No. 152 in Table 1:

[0229]

[0230] Dissolve 3-benzamido-N-(2-bromo-4-(2,2,2-trifluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.00 g, 1.54 mmol) in dichloromethane (10 ml), add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add cyclopropanecarbonyl chloride (0.18 g, 1.72 mmol), and react overnight at room temperature. The reaction solution is washed with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.53 g, 48.13%).

[0231] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.28 (s, 1H), 8.61 (s, 1H), 8.11 (s, 1H), 8.03 - 7.99 (m, 2H), 7.83 (td, J = 7.5, 1.7 Hz, 1H), 7.67 - 7.62 (m, 1H), 7.58 - 7.53 (m, 2H), 7.48 - 7.40 (m, 1H), 7.40 - 7.34 (m, 1H), 1.42 (ddd, J = 12.1, 7.8, 4.4 Hz, 1H), 0.99 - 0.92 (m, 2H), 0.91 - 0.84 (m, 2H).

[0232] ESI-MS (m / z): [M-H-] Theoretical value: 715.0095, Measured value: 715.0097.

[0233] Example 4

[0234] Preparation method of compound No. 154 in Table 1:

[0235]

[0236] Add 3-benzamido-N-(2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.00 g, 1.54 mmol) to 10 ml of dichloromethane, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add 2-methylcyclopropanecarbonyl chloride (0.24 g, 2.02 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is concentrated under reduced pressure, and the residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.65 g, 57.79%).

[0237] 1H-NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.32 (s, 1H), 8.61 (t, J = 7.9 Hz, 1H), 8.09 (dt, J = 10.2, 4.6 Hz, 3H), 7.87 - 7.78 (m, 1H), 7.46 - 7.35 (m, 4H), 1.37 - 1.00 (m, 3H), 0.90 - 0.74 (m, 4H).

[0238] ESI-MS (m / z): [M-H-] Theoretical value: 731.0232, Measured value: 731.0234.

[0239] Example 5

[0240] Preparation method of compound No. 157 in Table 1:

[0241]

[0242] To 10 mL of dichloromethane was added 3-benzamido-N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.00 g, 1.54 mmol). Triethylamine (0.23 g, 2.31 mmol) was added, and the mixture was stirred at room temperature for 10 min. Then cyclopropylacetyl chloride (0.24 g, 2.02 mmol) was added dropwise, and the reaction was carried out overnight at room temperature. The reaction mixture was washed with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.84 g, 74.68%).

[0243] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.30 (s, 1H), 8.57 (s, 1H), 8.07 (s, 1H), 8.05 - 7.98 (m, 2H), 7.82 (td, J = 7.3, 2.5 Hz, 1H), 7.63 (t, J = 7.3 Hz, 1H), 7.55 (t, J = 7.4 Hz, 2H), 7.43 - 7.33 (m, 2H), 2.18 (qd, J = 18.0, 6.7 Hz, 2H), 0.88 (dd, J = 11.0, 6.0 Hz, 1H), 0.46 - 0.36 (m, 2H), 0.06 - 0.00 (m, 2H).

[0244] ESI-MS (m / z): [M-H-] theoretical value: 729.0252, measured value: 729.0260.

[0245] Example 6

[0246] Preparation method of compound No. 166 in Table 1:

[0247]

[0248] To 10 mL of dichloromethane was added 3-benzamido-N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.00 g, 1.54 mmol). Triethylamine (0.23 g, 2.31 mmol) was added, and the mixture was stirred at room temperature for 10 min. Then methoxyacetyl chloride (0.30 g, 2.76 mmol) was added dropwise, and the reaction was carried out overnight at room temperature. The reaction mixture was washed with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.84 g, 75.32%).

[0249] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.40 - 10.22 (m, 1H), 8.57 (s, 1H), 8.07 (s, 1H), 8.04 - 7.99 (m, 2H), 7.84 (t, J = 6.7 Hz, 1H), 7.66 - 7.60 (m, 1H), 7.55 (dd, J = 10.2, 4.6 Hz, 2H), 7.43 (t, J = 6.1 Hz, 1H), 7.37 (t, J = 7.8 Hz, 1H), 4.16–3.88 (m, 2H), 3.19 (s, 3H).

[0250] ESI-MS (m / z): [M-H-] Theoretical value: 719.0045, Measured value: 719.0058.

[0251] Example 7

[0252] Preparation method of compound No. 167 in Table 1:

[0253]

[0254] Add 3-benzamido-N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.00 g, 1.54 mmol) to 10 ml of dichloromethane, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add ethoxyacetyl chloride (0.30 g, 2.45 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1), a white solid (0.85 g, 75.32%) is obtained.

[0255] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.32 (s, 1H), 8.56 (s, 1H), 8.07 (s, 1H), 8.04 - 7.97 (m, 2H), 7.88 - 7.80 (m, 1H), 7.67 - 7.60 (m, 1H), 7.55 (t, J = 7.4 Hz, 2H), 7.40 (dt, J = 15.6, 7.1 Hz, 2H), 4.06 (dd, J = 38.6, 17.3 Hz, 2H), 3.38 - 3.31 (m, 2H), 1.00 (t, J = 7.0 Hz, 3H).

[0256] ESI-MS (m / z): [M-H-] Theoretical value: 735.0181, Measured value: 735.0188.

[0257] Example 8

[0258] Preparation method of Compound No. 337 in Table 1: (1) Preparation of N-(-bromo-6-methyl-4-(perfluoropropan-2-yl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide

[0259]

[0260] Add 3-amino-N-(2-bromo-6-methyl-4-(perfluoropropan-2-yl)phenyl)-2-fluorobenzamide (1.70 g, 3.48 mmol) to 10 ml of dichloromethane, add pyridine (0.55 g, 6.90 mmol), stir at room temperature for 10 min, dropwise add p-fluorobenzoyl chloride (0.54 g, 3.40 mmol), and react at room temperature for 5 h. After the reaction solution is washed with saturated sodium carbonate and saturated brine and dried over anhydrous sodium sulfate, it is rotary evaporated under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a pale yellow solid (1.80 g, yield 84.65%).

[0261] 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.39 (s, 1H), 10.33 (s, 1H), 8.12 - 8.07 (m, 2H), 7.81 (t, J = 6.8 Hz, 2H), 7.70 (s, 1H), 7.61 (t, J = 6.1 Hz, 1H), 7.43 - 7.37 (m, 3H), 2.41 (s, 1H).

[0262] ESI-MS (m / z): [M-H-] theoretical value: 611.0022, measured value: 611.0022.

[0263] (2) Synthesis of N-(2-bromo-6-methyl-4-(perfluoropropan-2-yl)phenyl)-N-(cyclopropanecarbonyl)-2-fluoro-3-(4-fluorobenzamido)benzamide

[0264]

[0265] Dissolve N-(-bromo-6-methyl-4-(perfluoropropan-2-yl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide (1.00 g, 1.63 mmol) in dichloromethane (10 ml), dropwise add cyclopropanecarbonyl chloride (0.18 g, 1.72 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is rotary evaporated under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.43 g, yield 38.73%).

[0266] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.29 (s, 1H), 8.08 (dd, J = 8.8, 5.5 Hz, 2H), 7.97 (s, 1H), 7.86 (s, 1H), 7.83 - 7.77 (m, 1H), 7.47 (t, J = 6.8 Hz, 1H), 7.42 - 7.32 (m, 3H), 2.44 (s, 3H), 1.42 (ddd, J = 12.1, 7.8, 4.4 Hz, 1H), 0.99 - 0.92 (m, 2H), 0.91 - 0.84 (m, 2H).

[0267] ESI-MS (m / z): [M - H - ] theoretical value: 681.0263, measured value: 681.0270.

[0268] Example 9

[0269] Preparation method of compound No. 474 in Table 1:

[0270] (1) Synthesis of N-(2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide

[0271]

[0272] To 10 ml of acetonitrile was added 3-amino-N-(2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.20 g, 2.21 mmol). The temperature was raised to 80 °C, and p-fluorobenzoyl chloride (0.34 g, 2.14 mmol) was added dropwise. The reaction was carried out for 2 h. The reaction solution was concentrated to dryness under reduced pressure, dissolved in ethyl acetate solution, washed with saturated sodium carbonate and saturated brine, dried over anhydrous sodium sulfate, and then concentrated to dryness under reduced pressure. The residue was purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (1.40 g, yield 95.27%).

[0273] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.78 (s, 1H), 10.34 (s, 1H), 8.44 (s, 1H), 8.13 - 8.07 (m, 2H), 7.98 (s, 1H), 7.84 (t, J = 7.5 Hz, 1H), 7.62 - 7.57 (m, 1H), 7.44 - 7.36 (m, 3H).

[0274] ESI-MS (m / z): [M - H - ] theoretical value: 664.9739, measured value: 664.9747.

[0275] (2) Synthesis of N - acryloyl - N - (2 - bromo - 4 - (2,2,3,3,3 - pentafluoropropyl) - 6 - (trifluoromethyl)phenyl) - 2 - fluoro - 3 - (4 - fluorobenzamido)benzamide

[0276]

[0277] To 10 ml of dichloromethane, add N - (2 - bromo - 4 - (2,2,3,3,3 - pentafluoropropyl) - 6 - (trifluoromethyl)phenyl) - 2 - fluoro - 3 - (4 - fluorobenzamido)benzamide (1.00 g, 1.50 mmol), add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add acryloyl chloride (0.18 g, 1.98 mmol), and react overnight at room temperature. After the reaction solution is washed with dilute hydrochloric acid (2N), saturated brine, and dried over anhydrous sodium sulfate, it is rotary - evaporated under reduced pressure. The residue is purified by column chromatography (eluent: n - hexane:ethyl acetate = 10:1) to obtain a white solid (0.54 g, 50.07%).

[0278] The 1H - NMR (400 MHz, DMSO - d6) data of the compound are as follows (δ [ppm]): δ 10.34 (s, 1H), 8.60 (s, 1H), 8.13 - 8.06 (m, 3H), 7.90 - 7.84 (m, 1H), 7.47 - 7.35 (m, 4H), 6.42 (dd, J = 16.4, 1.3 Hz, 1H), 6.13 (dd, J = 16.4, 10.3 Hz, 1H), 5.90 (dd, J = 10.4, 1.3 Hz, 1H).

[0279] ESI - MS (m / z): [M - H - ] theoretical value: 718.9845, measured value: 718.9846.

[0280] Example 10

[0281] Preparation method of compound No. 478 in Table 1:

[0282]

[0283] N-(2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide (1.00 g, 1.50 mmol) was added to 10 ml of dichloromethane. Triethylamine (0.23 g, 2.31 mmol) and 4-dimethylaminopyridine (0.07 g, 0.50 mmol) were added. The mixture was stirred at room temperature for 10 min, and 2-butynoyl chloride (0.17 g, 1.66 mmol) was added dropwise. The reaction was carried out overnight at room temperature. After the reaction solution was washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it was concentrated under reduced pressure. The residue was purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.40 g, 36.48%).

[0284] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.40 (s, 1H), 8.63 (s, 1H), 8.13 - 8.08 (m, 3H), 7.87 (td, J = 7.5, 1.7 Hz, 1H), 7.53 - 7.36 (m, 4H), 1.76 (s, 3H).

[0285] ESI-MS (m / z): [M - H - ] theoretical value: 730.9845, measured value: 730.9859.

[0286] Example 11

[0287] Preparation method of compound No. 480 in Table 1:

[0288]

[0289] N-(2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide (1.00 g, 1.50 mmol) was dissolved in dichloromethane (10 ml). Triethylamine (0.23 g, 2.31 mmol) was added. The mixture was stirred at room temperature for 10 min, and cyclopropanecarbonyl chloride (0.18 g, 1.72 mmol) was added dropwise. The reaction was carried out overnight at room temperature. After the reaction solution was washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it was concentrated under reduced pressure. The residue was purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.49 g, 44.57%).

[0290] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.31 (s, 1H), 8.61 (s, 1H), 8.09 (dd, J = 7.7, 4.2 Hz, 3H), 7.83 (t, J = 6.7 Hz, 1H), 7.45 - 7.33 (m, 4H), 1.42 (ddd, J = 12.1, 7.8, 4.4 Hz, 1H), 0.99 - 0.92 (m, 2H), 0.91 - 0.84 (m, 2H).

[0291] ESI-MS (m / z): [M-H-] Theoretical value: 733.0002, Measured value: 733.0012.

[0292] Example 12

[0293] Preparation method of compound No. 480 in Table 1: (1) Synthesis of N-(2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-N-(cyclopropanecarbonyl)-2-fluoro-3-nitrobenzamide

[0294]

[0295] Add N-(2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-nitrobenzamide (1.40 g, 2.43 mmol) to 10 ml of acetonitrile, heat to 60 °C, add triethylamine (0.32 g, 3.16 mmol), and then dropwise add cyclopropylcarbonyl chloride (0.38 g, 3.65 mmol). Keep the temperature and react for about 1 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with dichloromethane solution, wash it with dilute hydrochloric acid (2N), saturated sodium carbonate solution, saturated brine, and dry it over anhydrous sodium sulfate. Then rotate it to dryness under reduced pressure to obtain an off-white solid (1.40 g, 89.71%).

[0296] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 8.64 (d, J = 1.3 Hz, 1H), 8.39–8.27 (m, 1H), 8.13 (s, 1H), 7.89 (t, J = 6.0 Hz, 1H), 7.59 (t, J = 8.0 Hz, 1H), 1.49–1.39 (m, 1H), 0.91 (dd, J = 19.1, 8.7 Hz, 4H).

[0297] (2) Synthesis of 3-amino-N-(2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-N-(cyclopropanecarbonyl)-2-fluorobenzamide

[0298]

[0299] Dissolve N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-N-(cyclopropanecarbonyl)-2-fluoro-3-nitrobenzamide (1.2 g, 1.87 mmol) in ethanol (20 ml), add stannous chloride dihydrate (1.68 g, 7.45 mmol) in batches, and heat the reaction mixture to 60 °C for 3 - 4 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with ethyl acetate solution, add an excessive amount of saturated sodium carbonate solution, centrifuge, take the organic phase, dry it with anhydrous sodium sulfate, and rotate it to dryness under reduced pressure to obtain a brown solid (0.93 g, 81.28%).

[0300] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 8.56 (d, J = 6.5 Hz, 1H), 8.06 (s, 1H), 7.01–6.89 (m, 2H), 6.72–6.61 (m, 1H), 5.36 (d, J = 35.7 Hz, 2H), 1.46–1.37 (m, 1H), 1.01–0.78 (m, 4H).

[0301] (3) Synthesis of N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-N-(cyclopropanecarbonyl)-2-fluoro-3-(4-fluorobenzamido)benzamide:

[0302]

[0303] Dissolve 3-amino-N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-N-(cyclopropanecarbonyl)-2-fluorobenzamide (0.9 g, 1.47 mmol) in acetonitrile (10 ml), heat it to 80 °C, and dropwise add 4-fluorobenzoyl chloride (0.26 g, 1.61 mmol). React for 2 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with dichloromethane, wash it with saturated sodium carbonate and saturated brine, dry it with anhydrous sodium sulfate, and then rotate it to dryness under reduced pressure. The residue is purified by column chromatography (the eluent is n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.73 g, 67.52%).

[0304] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.31 (s, 1H), 8.61 (s, 1H), 8.09 (dd, J = 7.7, 4.2 Hz, 3H), 7.83 (t, J = 6.7 Hz, 1H), 7.45 - 7.33 (m, 4H), 1.42 (ddd, J = 12.1, 7.8, 4.4 Hz, 1H), 0.99 - 0.92 (m, 2H), 0.91 - 0.84 (m, 2H).

[0305] ESI-MS (m / z): [M-H-] Theoretical value: 733.0002, Measured value: 733.0004.

[0306] Example 13

[0307] Preparation method of compound No. 482 in Table 1:

[0308]

[0309] Dissolve N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide (1.00 g, 1.50 mmol) in dichloromethane (10 ml), add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add 2-methylcyclopropanecarbonyl chloride (0.24 g, 2.02 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is concentrated under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.65 g, 58.00%).

[0310] 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.29 (s, 1H), 8.61 (t, J = 8.3 Hz, 1H), 8.11 (d, J = 7.8 Hz, 1H), 8.01 (t, J = 6.1 Hz, 2H), 7.83 (dd, J = 14.5, 7.0 Hz, 1H), 7.63 (t, J = 7.2 Hz, 1H), 7.56 (t, J = 7.5 Hz, 2H), 7.47 - 7.33 (m, 2H), 1.39 - 1.02 (m, 3H), 0.89 - 0.74 (m, 4H).

[0311] ESI-MS (m / z): [M-H-] Theoretical value: 749.0138, Measured value: 749.0137.

[0312] Example 14

[0313] Preparation method of compound No. 484 in Table 1:

[0314]

[0315] Dissolve N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide (1.00 g, 1.50 mmol) in dichloromethane (10 ml), add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add cyclopropylacetyl chloride (0.24 g, 2.02 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1), a white solid (0.99 g, 88.00%) is obtained.

[0316] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.33 (s, 1H), 8.56 (s, 1H), 8.08 (dd, J = 8.8, 5.5 Hz, 3H), 7.85 - 7.76 (m, 1H), 7.43 - 7.32 (m, 4H), 2.17 (qd, J = 17.8, 6.7 Hz, 2H), 0.87 (dd, J = 10.2, 5.2 Hz, 1H), 0.46 - 0.35 (m, 2H), 0.06 - 0.07 (m, 2H).

[0317] ESI-MS (m / z): [M - H - ] theoretical value: 747.0158, measured value: 747.0170.

[0318] Example 15

[0319] Preparation method of compound No. 494 in Table 1:

[0320]

[0321] Charge N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide (1.00 g, 1.50 mmol) into 5 ml of acetonitrile, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add methylacetyl chloride (0.24 g, 2.21 mmol), and react at room temperature for 2 h. Concentrate the reaction solution under reduced pressure, dissolve it with dichloromethane solution, wash it with dilute hydrochloric acid (2N) and saturated brine, dry it over anhydrous sodium sulfate, concentrate under reduced pressure, and the residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1), a white solid (0.80 g, 72.37%) is obtained.

[0322] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.36 (s, 1H), 8.57 (s, 1H), 8.12 - 8.06 (m, 3H), 7.83 (t, J = 6.8 Hz, 1H), 7.44 - 7.35 (m, 4H), 4.03 (dd, J = 38.9, 16.5 Hz, 2H), 3.19 (s, 3H).

[0323] ESI-MS (m / z): [M - H - ] Theoretical value: 736.9950, Measured value: 736.9943.

[0324] Example 16

[0325] Preparation method of compound No. 495 in Table 1:

[0326]

[0327] Add N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluoro-3-(4-fluorobenzamido)benzamide (1.00 g, 1.50 mmol) to 10 ml of acetonitrile, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add ethoxyacetyl chloride (0.31 g, 2.53 mmol), and react at room temperature for 2 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with dichloromethane, wash it with dilute hydrochloric acid (2N), saturated brine, dry it over anhydrous sodium sulfate, then rotate it to dryness under reduced pressure, and purify the residue by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a pale yellow solid (0.80 g, 70.83%).

[0328] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.35 (s, 1H), 8.56 (s, 1H), 8.11 - 8.05 (m, 3H), 7.83 (t, J = 6.7 Hz, 1H), 7.46 - 7.34 (m, 4H), 4.05 (dd, J = 38.2, 16.3 Hz, 2H), 3.34 (dd, J = 13.8, 6.8 Hz, 2H), 0.99 (t, J = 7.0 Hz, 3H).

[0329] ESI-MS (m / z): [M - H - ] Theoretical value: 753.0086, Measured value: 753.0096.

[0330] Example 17

[0331] Preparation method of Compound No. 661 in Table 1: (1) Synthesis of N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide

[0332]

[0333] Add 3-amino-N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (2.50 g, 4.59 mmol) to 10 ml of acetonitrile, heat to 80 °C, add 4-cyanobenzoyl chloride (0.76 g, 4.59 mmol), and react for 2 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with ethyl acetate solution, wash it with saturated sodium carbonate and saturated brine, dry it over anhydrous sodium sulfate, then rotate it to dryness under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a light yellow solid (2.85 g, yield 92.16%).

[0334] 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.81 (s, 1H), 10.60 (s, 1H), 8.44 (s, 1H), 8.17 (d, J = 8.5 Hz, 2H), 8.07 (t, J = 6.8 Hz, 2H), 7.99 (d, J = 8.5 Hz, 1H), 7.87 (t, J = 6.8 Hz, 1H), 7.62 (dd, J = 10.0, 3.8 Hz, 1H), 7.43 (t, J = 7.9 Hz, 1H). ESI-MS (m / z): [M-H-] theoretical value: 671.9786, measured value: 671.9783

[0335] (2) Synthesis of N-acryloyl-N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide

[0336]

[0337] Add N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide (1.00 g, 1.48 mmol) to 10 ml of dichloromethane, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add acryloyl chloride (0.40 g, 4.42 mmol), and react overnight at room temperature. Wash the reaction solution with saturated sodium bicarbonate and saturated brine, dry it over anhydrous sodium sulfate, then rotate it to dryness under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.86 g, 79.73%).

[0338] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.58 (s, 1H), 8.59 (s, 1H), 8.15 (d, J = 8.1 Hz, 2H), 8.10 (s, 1H), 8.04 (d, J = 8.2 Hz, 2H), 7.88 (d, J = 6.7 Hz, 1H), 7.42 (dt, J = 15.6, 7.4 Hz, 2H), 6.42 (dd, J = 16.5, 6.5 Hz, 1H), 6.12 (dd, J = 16.5, 10.3 Hz, 1H), 5.91 (t, J = 8.2 Hz, 1H).

[0339] ESI-MS (m / z): [M-H-] Theoretical value: 725.9892, Measured value: 725.9893.

[0340] Example 18

[0341] Preparation method of compound No. 667 in Table 1:

[0342]

[0343] N-(2-Bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide (1.00 g, 1.48 mmol) was added to 10 ml of dichloromethane, triethylamine (0.23 g, 2.31 mmol) was added, and the mixture was stirred at room temperature for 10 min. Then cyclopropylcarbonyl chloride (0.50 g, 4.78 mmol) was added dropwise, and the reaction was carried out overnight at room temperature. The reaction mixture was washed with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.90 g, 81.76%).

[0344] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.56 (d, J = 13.8 Hz, 1H), 8.60 (s, 1H), 8.17 - 8.12 (m, 2H), 8.10 (s, 1H), 8.05 (t, J = 6.4 Hz, 2H), 7.89 - 7.82 (m, 1H), 7.45 - 7.39 (m, 1H), 7.37 (t, J = 7.8 Hz, 1H), 1.45 - 1.37 (m, 1H), 0.98 - 0.91 (m, 2H), 0.88 (dd, J = 11.0, 6.2 Hz, 2H).

[0345] ESI-MS (m / z): [M-H-] Theoretical value: 740.0048, Measured value: 740.0052.

[0346] Example 19

[0347] Preparation method of compound No. 669 in Table 1:

[0348]

[0349] Add N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide (1.00 g, 1.48 mmol) to 10 ml of dichloromethane, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add 2-methylcyclopropanecarbonyl chloride (0.50 g, 4.22 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is concentrated under reduced pressure, and the residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.78 g, 69.59%).

[0350] 1H-NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.56 (s, 1H), 8.61 (t, J = 7.8 Hz, 1H), 8.12 (dt, J = 12.5, 6.7 Hz, 3H), 8.05 (d, J = 8.5 Hz, 2H), 7.90 - 7.82 (m, 1H), 7.49 - 7.35 (m, 2H), 1.36 - 1.01 (m, 3H), 0.90 - 0.74 (m, 4H).

[0351] ESI-MS (m / z): [M-H-] Theoretical value: 756.0184, Measured value: 756.0183.

[0352] Example 20

[0353] Preparation method of compound No. 671 in Table 1:

[0354]

[0355] To 10 mL of dichloromethane, add N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide (1.00 g, 1.48 mmol), add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add cyclopropylacetyl chloride (0.50 g, 4.22 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is rotary evaporated under reduced pressure. The residue is purified by column chromatography (the eluent is n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.82 g, 72.97%).

[0356] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.58 (s, 1H), 8.57 (s, 1H), 8.19 - 8.12 (m, 2H), 8.09 - 8.02 (m, 3H), 7.84 (s, 1H), 7.38 (dd, J = 15.3, 6.5 Hz, 2H), 2.16 (dd, J = 20.2, 12.6 Hz, 2H), 0.88 (s, 1H), 0.41 (d, J = 8.1 Hz, 2H), 0.03– -0.01 (m, 2H).

[0357] ESI-MS (m / z): [M-H-] theoretical value: 754.0205, measured value: 754.0201.

[0358] Example 21

[0359] Preparation method of compound No. 681 in Table 1:

[0360]

[0361] To 10 mL of dichloromethane, add N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide (1.00 g, 1.48 mmol), add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add methoxyacetyl chloride (0.50 g, 4.61 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is rotary evaporated under reduced pressure. The residue is purified by column chromatography (the eluent is n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.83 g, yield 75.00%).

[0362] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.61 (d, J = 13.2 Hz, 1H), 8.57 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.06 (t, J = 7.6 Hz, 3H), 7.86 (t, J = 6.8 Hz, 1H), 7.42 (dt, J = 15.7, 7.1 Hz, 2H), 4.02 (dd, J = 41.2, 17.6 Hz, 2H), 3.39 - 3.29 (m, 3H).

[0363] ESI-MS (m / z): [M-H-] Theoretical value: 745.9977, Measured value: 745.9978.

[0364] Example 22

[0365] Preparation method of compound No. 682 in Table 1:

[0366]

[0367] Add N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(4-cyanobenzamido)-2-fluorobenzamide (1.00 g, 1.48 mmol) to 10 ml of dichloromethane, add triethylamine (0.23 g, 2.31 mmol), stir at room temperature for 10 min, dropwise add ethoxyacetyl chloride (0.50 g, 4.08 mmol), and react overnight at room temperature. After the reaction solution is washed with saturated sodium bicarbonate and saturated brine and dried over anhydrous sodium sulfate, it is concentrated under reduced pressure, and the residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.84 g, yield 74.32%).

[0368] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.60 (s, 1H), 8.56 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.06 (t, J = 6.4 Hz, 3H), 7.87 (t, J = 6.8 Hz, 1H), 7.42 (dt, J = 15.7, 7.1 Hz, 2H), 4.15 - 3.96 (m, 2H), 3.34 (dd, J = 14.9, 8.1 Hz, 2H), 1.03–0.96 (m, 3H).

[0369] ESI-MS (m / z): [M-H-] Theoretical value: 758.0154, Measured value: 758.0170.

[0370] Example 23

[0371] Preparation method of compound No. 959 in Table 1:

[0372] (1) Synthesis of N-(3-((2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)-2-chloronicotinamide

[0373]

[0374] Add 3-amino-N-(2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-2-fluorobenzamide (1.20 g, 2.20 mmol) to 5 ml of acetonitrile, heat up to 80 °C, add 2-chloronicotinoyl chloride (0.39 g, 2.21 mmol), and react for 2 h. Rotate the reaction solution to dryness under reduced pressure, dissolve it with ethyl acetate solution, wash it with saturated potassium carbonate and saturated brine, dry it over anhydrous sodium sulfate, then rotate it to dryness under reduced pressure. The residue is purified by column chromatography (the eluent is n-hexane:ethyl acetate = 10:1) to obtain a pale yellow solid (1.20 g, yield 79.75%).

[0375] 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.81 (s, 1H), 10.75 (s, 1H), 8.55 (dd, J = 4.8, 1.8 Hz, 1H), 8.44 (s, 1H), 8.17 (q, J = 7.3 Hz, 1H), 8.10 (dd, J = 7.5, 1.8 Hz, 1H), 7.98 (s, 2H), 7.61 - 7.52 (m, 2H), 7.43 (t, J = 7.9 Hz, 1H).

[0376] ESI-MS (m / z): [M-H-] theoretical value: 683.9376, measured value: 683.9371.

[0377] (2) Synthesis of N-(3-((2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-6-(trifluoromethyl)phenyl)(cyclopropanecarbonyl)carbamoyl)-2-fluorophenyl)-2-chloronicotinamide

[0378]

[0379] Dissolve N-(3-((2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)-2-chloronicotinamide (1.04 g, 1.52 mmol) in dichloromethane (10 ml). Dropwise add cyclopropanecarbonyl chloride (0.22 g, 2.10 mmol) thereto under an ice bath, and react for 3 h. After the reaction solution is washed with saturated sodium bicarbonate, dilute hydrochloric acid (2 N), saturated brine and dried over anhydrous sodium sulfate, it is concentrated under reduced pressure. The residue is purified by column chromatography (eluent: n-hexane:ethyl acetate = 10:1) to obtain a white solid (0.63 g, yield 55.12%).

[0380] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 10.72 (s, 1H), 8.62 (s, 1H), 8.55 (dd, J = 4.8, 1.9 Hz, 1H), 8.18 (dd, J = 10.1, 6.7 Hz, 1H), 8.10 (dd, J = 7.4, 1.7 Hz, 2H), 7.57 (dd, J = 7.5, 4.8 Hz, 1H), 7.40 - 7.36 (m, 2H), 1.43 (ddd, J = 12.2, 7.6, 4.5 Hz, 1H), 0.98–0.92 (m, 2H), 0.91 - 0.86 (m, 2H).

[0381] ESI-MS (m / z): [M-H-] Theoretical value: 751.9638, Measured value: 751.9641.

[0382] Example 24

[0383] Preparation method of compound No. 1101 in Table 1:

[0384]

[0385] Add 0.717 g (1.0 mmol) of 3-benzamido-N-(2-bromo-4-(2,2,2-trifluoropropyl)-6-(trifluoromethyl)phenyl)-N-(cyclopropanecarbonyl)-2-fluorobenzamide to a DMF solution containing 1.3 mmol of sodium hydride. Dropwise add 1.3 mmol of methyl iodide thereto at room temperature, and react for 5 h. Extract with water and ethyl acetate, take the organic layer and concentrate it under reduced pressure. The residue is purified by column chromatography to obtain a white solid (0.23 g, yield 31%).

[0386] The 1H NMR (400 MHz, DMSO-d6) data of the compound are as follows (δ [ppm]): δ 8.58 (d, J = 1.2 Hz, 1H), 8.08 (s, 1H), 7.57 (s, 1H), 7.42 (t, J = 6.3 Hz, 1H), 7.36–7.18 (m, 6H), 3.50 (d, J = 8.8 Hz, 3H), 1.31 (s, 1H), 0.96–0.80 (m, 4H).

[0387] ESI-MS (m / z): [M+Cl-] Theoretical value: 765.0019, Measured value: 765.0033.

[0388] In the embodiments of the present invention, the m-diamide compounds indicated by other compound numbers in Table 1 can be prepared by making corresponding adjustments according to the preparation methods described in the above examples; not too much discussion is made in this embodiment. Equivalent changes made to the claims still fall within the scope covered by the invention.

[0389] Effect Examples

[0390] Some compounds in this application form were tested for activity against a variety of pests.

[0391] (1) Activity determination of Chilo suppressalis:

[0392] Preparation of the compound liquid medicine: Weigh 10 mg of the original drug with a balance, prepare a 1% mother liquor with DMF, and then dilute it with distilled water containing 0.1% Tween-80 to four test concentrations of 5 mg / L, 3.0 mg / L, 1.5 mg / L, and 0.75 mg / L for standby.

[0393] Using the dipping method, after the water bamboo slices are dipped in the medicine for 10 s, they are placed in a plastic box lined with filter paper and dried naturally in the shade. 10 third-instar Chilo suppressalis are placed in each box, and the number of dead insects is observed in an observation room at 26 °C with 16 h of light and 8 h of darkness after 4 days.

[0394] The control compound CK01 chlorantraniliprole is shown in formula (IX), and the control compound CK02 (compound 6-5909 in CN102119143B) is shown in formula (X).

[0395]

[0396] Compounds 11, 142, 146, 152, 154, 157, 166, 167, 337, 474, 478, 480, 482, 484, 494, 495, 661, 665, 667, 669, 671, 681, 682, 959, 1101, 1120, and 1136 in Table 1 had a mortality rate of greater than 90% against Chilo suppressalis after 4 days at a concentration of 5 mg / L. Then, low-concentration activity tests were conducted on 146, 152, 157, 166, 167, 474, 478, 480, 484, 667, and 671, and the results are shown in Table 2.

[0397] Table 2: Results of the activity determination of some compounds in Table 1 against Chilo suppressalis

[0398]

[0399]

[0400] Note: The compound numbers correspond to those in Table 1

[0401] (2) Activity determination of Plutella xylostella:

[0402] Preparation of the compound liquid medicine: Weigh 10 mg of the original drug with a balance, prepare a 1% stock solution with DMF, and then dilute it with distilled water containing 0.1% Tween-80 to four test concentrations of 3 mg / L, 1 mg / L, 0.5 mg / L, and 0.1 mg / L for standby.

[0403] Using the dipping method, after dipping the Chinese cabbage leaves for 10 s, place them in a plastic box lined with filter paper and let them air-dry naturally. Place 10 third-instar Plutella xylostella in each box and observe the number of dead insects after 3 days in an observation room with a 16 h light and 8 h dark cycle at 26°C.

[0404] Among them, compounds 11, 142, 146, 152, 154, 157, 166, 167, 337, 474, 478, 480, 482, 484, 494, 495, 661, 665, 667, 669, 671, 681, 682, 959, 1101, 1120, and 1136 had a mortality rate of greater than 90% against Plutella xylostella after 3 days at a concentration of 3 mg / L. Then, low-concentration activity tests were conducted on 146, 152, 157, 166, 167, 474, 478, 480, 484, 667, and 671, and the results are shown in Table 3.

[0405] Table 3: Results of the activity determination of some compounds in Table 1 against Plutella xylostella

[0406]

[0407]

[0408] Note: The compound numbers correspond to Table 1

[0409] The results show that the m - diamide compounds provided by the present invention have high biological activities against Chilo suppressalis and Plutella xylostella, and there is no cross - resistance between the m - diamide compounds and chlorantraniliprole. Among pesticide organic small - molecule compounds, due to the different types, group volumes, and electronegativities of substituents, the metabolic and conductive properties of the whole molecule in the organism vary greatly, and the differences in biological activities are also significant. Moreover, the metabolic and conductive properties of the molecule and the ability of the molecule to bind to the receptor are unpredictable and require a large amount of creative work to obtain.

[0410] The preferred embodiments have been described in detail above, but the present invention is not limited to the above - mentioned specific embodiments. Under the inspiration of this application, those skilled in the art can also make various specific transformations without departing from the scope of protection of this application, and all of these belong to the scope of protection of the present invention.

Claims

1. A meta-diamide compound represented by formula (Ⅰ): In formula (I), Q is selected from any one of substituted or unsubstituted: phenyl, pyridyl; wherein, The substituent group is selected from one or more of a halogen atom, a cyano group, a nitro group, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, and a C1-C3 haloalkoxy group; R1 is any one of a C3-C9 cycloalkyl group, a C3-C5 cycloalkyl group substituted by a C1-C3 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, and a C1-C3 alkyl group substituted by a C3-C5 cycloalkyl group; Or it is a group represented by -L1-O-L2, wherein L1 is a C1-C6 alkylene group; L2 is a C1-C6 alkyl group; R2 is selected from a hydrogen atom and a C1-C6 alkyl group; X1 and X2 are each independently selected from a hydrogen atom or a fluorine atom, and X1 and X2 are not simultaneously hydrogen atoms; Y1 and Y5 are each independently any one of a halogen atom, a C1-C6 alkyl group, and a C1-C3 haloalkyl group; Y2 and Y4 are hydrogen atoms; Y3 is a C2-C6 haloalkyl group; W is an oxygen atom.

2. The m-diamide compound according to claim 1, wherein The R1 is any one of a C3-C5 cycloalkyl group, a C3-C5 cycloalkyl group substituted by a C1-C3 alkyl group, a C1-C3 alkyl group substituted by a C3-C5 cycloalkyl group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group; Or it is a group represented by -L1-O-L2, wherein L1 is a C1-C3 alkylene group; L2 is a C1-C3 alkyl group.

3. The m-diamide compound according to claim 1, wherein The R1 is one or more of a cyclopropyl group, a cyclopropyl group substituted by a methyl group, a methyl group substituted by a cyclopropyl group, a vinyl group, a propynyl group, -CH2OCH3, and -CH2OCH2CH3; The R2 is a hydrogen atom or a C1-C3 alkyl group.

4. The m-diamide compound according to claim 1, wherein The Q is selected from any one of a substituted or unsubstituted phenyl group and a substituted or unsubstituted pyridyl group; wherein, the substituent group in the substituted phenyl group and the substituted pyridyl group is selected from one or more of a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a methoxy group, and a trifluoromethoxy group.

5. The m-diamide compound according to claim 1, wherein The Y1 and Y5 are each independently a halogen atom and a C1-C3 haloalkyl group; the Y3 is a C2-C6 fluoroalkyl group.

6. The m-diamide compound according to claim 1, wherein The X1 is a fluorine atom, and the X2 is a hydrogen atom; the Y1 and Y5 are each independently a bromine atom, a methyl group, a trifluoromethyl group, and a pentafluoroethyl group; the Y3 is a pentafluoroethyl group, a heptafluoroisopropyl group, or a nonafluoro-2-butyl group.

7. A method for preparing a meta-diamide compound as described in claim 1, characterized in that, It includes the following steps: Providing a compound represented by formula (Ⅶ) and a compound represented by formula (Ⅵ); Reacting the compound represented by formula (Ⅶ) with the compound represented by formula (Ⅵ) to obtain a compound represented by formula (Ⅴ-1); Subjecting the compound represented by formula (Ⅴ-1) to a bromination reaction to obtain a compound represented by formula (Ⅳ-1); Subjecting the compound represented by formula (Ⅳ-1) to a reduction reaction to obtain a compound represented by formula (Ⅲ-1); Reacting the compound represented by formula (Ⅲ-1) with an acyl chloride of Q to obtain a compound represented by formula (Ⅱ-1); Reacting the compound represented by formula (Ⅱ-1) with an acyl chloride of R1 to obtain a meta-diamide compound represented by formula (Ⅰ-1); Reacting the compound represented by formula (I-1) with a halogenated hydrocarbon of R2 to obtain a meta-diamide compound represented by formula (Ⅰ); Or it includes the following steps: Provide a compound represented by formula (Ⅶ) and a compound represented by formula (Ⅵ); React the compound represented by formula (Ⅶ) and the compound represented by formula (Ⅵ) to obtain a compound represented by formula (Ⅴ-2); Subject the compound represented by formula (Ⅴ-2) to a bromination reaction to obtain a compound represented by formula (Ⅳ-2); React the compound represented by formula (Ⅳ-2) with an acyl chloride of R1 to obtain a compound represented by formula (Ⅲ-2); Subject the compound represented by formula (Ⅲ-2) to a reduction reaction to obtain a compound represented by formula (Ⅱ-2); React the compound represented by formula (Ⅱ-2) with an acyl chloride of Q to obtain a meta-diamide compound represented by formula (Ⅰ-2); React the compound represented by formula (I-2) with a halogenated hydrocarbon of R2 to obtain a meta-diamide compound represented by formula (Ⅰ); In formula (Ⅰ), Q is selected from any one of substituted or unsubstituted: phenyl, pyridyl; wherein, the substituent group is selected from one or more of a halogen atom, a cyano group, a nitro group, a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, and a C1-C3 haloalkoxy group; R1 is any one of a C3-C9 cycloalkyl group, a C3-C5 cycloalkyl group substituted by a C1-C3 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, and a C1-C3 alkyl group substituted by a C3-C5 cycloalkyl group; Or is a group represented by -L1-O-L2, wherein, L1 is a C1-C6 alkylene group; L2 is a C1-C6 alkyl group; R2 is selected from a hydrogen atom, a C1-C6 alkyl group; X1 and X2 are each independently selected from a hydrogen atom or a fluorine atom, and X1 and X2 are not simultaneously hydrogen atoms; Y1 and Y5 are each independently any one of a halogen atom, a C1-C6 alkyl group, or a C1-C3 haloalkyl group; Y2 and Y4 are hydrogen atoms; Y3 is a C2-C6 haloalkyl group; W is an oxygen atom.

8. An enantiomer, diastereomer, or a pesticidally acceptable salt thereof of the meta-diamide compound according to any one of claims 1-6.

9. Use of the meta-diamide compound according to any one of claims 1-6 or an enantiomer, diastereomer, or a pesticidally acceptable salt thereof of the meta-diamide compound according to claim 8 in the agricultural, forestry, or health fields for the preparation of insecticidal drugs.

10. An insecticide preparation, characterized in that, The insecticidal preparation comprises an active ingredient and an excipient; the active ingredient comprises the meta-diamide compound according to any one of claims 1-6 and / or an enantiomer, diastereomer, or a pesticidally acceptable salt thereof of the meta-diamide compound according to claim 8; the mass percentage content of the active ingredient in the insecticidal preparation is 0.1%-99%.

11. An insecticide composition, characterized in that, The pesticidal composition comprises an active ingredient and other active compounds; the active ingredient comprises a m-diamide compound as described in any one of claims 1-6 and / or an enantiomer, diastereomer or a pesticidally acceptable salt of the m-diamide compound as described in claim 8; the other active compounds comprise one or more of insecticides, bait agents, disinfectants, acaricides, nematicides, fungicides, growth regulators and herbicides; the mass percentage content of the active ingredient in the pesticidal composition is 1%-99%.

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