Branched chain conjugated diene compound with insecticidal activity as well as preparation method and application thereof

Abstract

The invention provides a branched-chain conjugated diene compound with insecticidal activity as well as a preparation method and application of the branched-chain conjugated diene compound. Specifically, provided are compounds of formula (I), optical isomers, cis-trans-isomers, or pharmaceutically acceptable salts thereof, the compounds have excellent and broad-spectrum insecticidal activity, and are very suitable for the development of low-toxicity, efficient, and environmentally friendly novel pesticides. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of pesticides, and in particular relates to branched conjugated diene neonicotinoid compounds with insecticidal activity, and their preparation and use. Background Art

[0002] Food safety is closely linked to the stable development of society and the economy. Furthermore, the impact of pesticides on environmental organisms is increasingly being recognized and recognized. Therefore, the development of new pesticides that are highly effective, low-toxic, economical, and have different modes of action is urgently needed.

[0003] In the mid-1980s, neonicotinoid insecticides, represented by imidacloprid, developed by Bayer, became a significant class of insecticides due to their high activity against pests and low activity against aquatic animals and mammals. Subsequently, a series of neonicotinoid insecticides were developed, including acetamiprid, nitenpyram, clothianidin, thiamethoxam, and dinotefuran.

[0004] With the frequent use of neonicotinoid insecticides, their resistance and bee toxicity issues have gradually been exposed, which has greatly restricted their use. At the same time, neonicotinoid insecticides mainly target homoptera and coleoptera pests, and their limited insecticide spectrum also limits their use.

[0005] Therefore, there is an urgent need in the art to provide more environmentally friendly neonicotinoid insecticides and solve their resistance problem. Summary of the Invention

[0006] The object of the present invention is to provide a new nicotinoid compound containing a branched conjugated diene having excellent insecticidal activity.

[0007] The first aspect of the present invention provides a compound of formula (I), its optical isomers, cis-trans isomers, or pesticide-acceptable salts thereof:

[0008]

[0009] in:

[0010] R 1 is a substituted or unsubstituted five-membered or six-membered heteroaryl group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, or a substituted or unsubstituted phenyl group, a substituted or unsubstituted five-membered or six-membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, wherein the substitution means that one or more H atoms on the group are independently replaced by a substituent selected from the group consisting of halogen, CN, C 1-8 Alkyl, C 1-8 Halogenated alkyl, C 1-8 Alkoxy or C 1-8 haloalkoxy;

[0011] R 2 、R 3 and R 4 are each independently H, substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy, substituted or unsubstituted C 1-8 Alkoxy C 1-4 Alkyl, substituted or unsubstituted C 1-8 Alkoxy-carbonyl, allyl, benzyl, phenoxycarbonyl, substituted or unsubstituted C 2-8 Alkenyl-carbonyl, substituted or unsubstituted C 2-8 Alkynyl-carbonyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 3-8 Cycloalkyl-carbonyl, substituted or unsubstituted five-membered or six-membered heterocyclyl containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted five-membered or six-membered heterocyclyl-carbonyl containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted benzoyl, substituted or unsubstituted furancarbonyl, substituted or unsubstituted N,N-dimethylcarbonyl; wherein the substitution means that one or more H atoms on the group are independently substituted by substituents selected from the group consisting of halogen, halogenated or unsubstituted C 1-4 Alkyl, halogenated or unsubstituted C 2-4 Alkenyl, halogenated or unsubstituted C 2-4 Alkynyl, halogenated or unsubstituted C 1-4 Alkoxy and halogenated or unsubstituted C 1-4 alkyl-carbonyl;

[0012] or R 2 With R 3 , or R 2 With R 4 Together they constitute substituted or unsubstituted -CH2-CH2-, substituted or unsubstituted -CH2-CH2-CH2-, substituted or unsubstituted -CH2-CH2-CH2-CH2- or substituted or unsubstituted -CH2-X-CH2-, wherein X is selected from NH, O and S; wherein the substitution refers to that one or more H atoms on the group are independently substituted by a substituent selected from the group consisting of H, halogen, substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy, substituted or unsubstituted C 1-8 Alkoxy-C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy-carbonyl, substituted or unsubstituted allyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenoxycarbonyl, substituted or unsubstituted C 2-8 Alkenyl-carbonyl, substituted or unsubstituted C2-8 Alkynyl-carbonyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 3-8 Cycloalkyl-carbonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted furancarbonyl or substituted or unsubstituted N,N-dimethylcarbonyl, and the substitution means that one or more H atoms on the group are further independently substituted by a substituent selected from the group consisting of halogen, halogenated or unsubstituted C 1-4 Alkyl, halogenated or unsubstituted C 2-4 Alkenyl, halogenated or unsubstituted C 2-4 Alkynyl, halogenated or unsubstituted C 1-4 Alkoxy and halogenated or unsubstituted C 1-4 alkyl-carbonyl;

[0013] R 5 is substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted 4-8 membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 6-10 Aryl (including benzo C 3-6 cycloalkyl or benzo 4-6 membered heterocyclic group), substituted or unsubstituted 5-10 heteroaryl groups (including benzo 5-6 membered heteroaryl groups) containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 1-4 Alkylene-Ra, wherein Ra is selected from the group consisting of substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted 4-8 membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 6-10 Aryl (including benzo C 3-6 cycloalkyl or benzo 4-6 membered heterocyclic group), substituted or unsubstituted 5-10 heteroaryl groups (including benzo 5-6 membered heteroaryl groups) containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur; wherein the substitution means that one or more H atoms on the group are independently substituted by a substituent selected from the following group: C 1-8 Alkyl, nitro, fluorine, chlorine, bromine, C 1-4 Alkoxy, C 1-4 Halogenated alkyl, C 1-4 Haloalkoxy, hydroxy, amino, -NH-C 1-4 Alkyl (such as methylamino, ethylamino), -N-(C 1-4 alkyl)2 (such as dimethylamino, diethylamino); and

[0014] Z is nitro, cyano, C 2-6 Ester, trifluoromethyl, trifluoroacetyl, C 1-4 Alkoxyacyl, C 1-4 Alkyl-formyl or trifluoromethanesulfonyl.

[0015] In another preferred embodiment, R 1 is a substituted or unsubstituted group consisting of phenyl, pyridyl, thiazolyl, pyrimidinyl, oxazolyl or tetrahydrofuranyl, wherein the substitution refers to one or more H atoms on the group being independently substituted by a substituent selected from the group consisting of halogen and C 1-4 Halogenated alkyl.

[0016] In another preferred embodiment, R 2 、R 3 and R 4 Each independently is H, C 1-8 Alkyl, C 1-8 Alkoxy C 1-4 Alkyl, C 1-8 Alkoxy-carbonyl or phenoxycarbonyl.

[0017] In another preferred embodiment, R 2 With R 3 or R 2 With R 4 Together they constitute -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2- or -CH2-X-CH2-, wherein X is selected from NH, O and S, and the H atoms in -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2- or -CH2-X-CH2- are optionally replaced by halogen, C 1-4 Alkyl or halogenated C 1-4 Alkyl substitution.

[0018] In another preferred embodiment, R 2 With R 3 or R 2 With R 4 Together they constitute -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, or -CH2-X-CH2-, wherein X is selected from NH, O, and S, and the H atom in NH is optionally replaced by C 1-8 Alkyl substitution.

[0019] In another preferred embodiment, R 4 A hydrogen atom.

[0020] In another preferred embodiment, R 5 is substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted 4-8 membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 6-10aryl, substituted or unsubstituted 5-10 heteroaryl containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, or substituted or unsubstituted C 1-4 Alkylene-C 6-10 Aryl, wherein the substitution means that one or more H atoms on the group are independently substituted by a substituent selected from the group consisting of: C 1-4 Alkyl, nitro, fluorine, chlorine, bromine, C 1-4 Alkoxy, C 1-4 Haloalkyl, hydroxy, amino, methylamino, dimethylamino.

[0021] In another preferred embodiment, R 5 is halogenated or unsubstituted C 1-8 Alkyl; preferably R 5 is halogenated or unsubstituted C 1-6 Alkyl; preferably R 5 is halogenated or unsubstituted C 1-4 Alkyl; optimal R 5 For unsubstituted C 1-4 alkyl.

[0022] In another preferred embodiment, Z is nitro, cyano, C 2-4 ester group, trifluoromethyl group, trifluoroacetyl group or trifluoromethanesulfonyl group.

[0023] In another preferred embodiment, Z is nitro.

[0024] In another preferred embodiment, the compound has a structure represented by general formula (II):

[0025]

[0026] Where R 1 and R 5 As defined above.

[0027] In another preferred embodiment, the compound is any one of the compounds listed in the examples (such as the compounds in Table 1).

[0028] In another preferred embodiment, the R 1 、R 2 、R 3 、R 4 、R 5 and Z are independently and optionally the corresponding groups in the example compounds.

[0029] In another preferred embodiment, the compound is selected from the following group:

[0030]

[0031]

[0032]

[0033]

[0034] The second aspect of the present invention provides an agricultural composition comprising:

[0035] The compound according to the first aspect of the present invention, its optical isomers, cis-trans isomers or pesticide-acceptable salts thereof; and

[0036] Agrochemically acceptable carrier and / or excipient.

[0037] In another preferred embodiment, the agricultural composition comprises 0.001-99.999% by mass of the above-mentioned compound, its optical isomers, cis-trans isomers or its pesticide-acceptable salts.

[0038] In another preferred embodiment, the concentration of the compound, its optical isomers, cis-trans isomers or their pesticide-acceptable salts is 10-1000 mg / L, more preferably 100-500 mg / L.

[0039] In another preferred embodiment, the pesticide composition is in the form of various conventional pesticide formulations, such as emulsifiable concentrates, suspensions, powders, granules, aqueous solutions, and baits.

[0040] The third aspect of the present invention provides the use of the compound described in the first aspect, its optical isomers, cis-trans isomers or their pesticide-acceptable salts and the agricultural composition described in the second aspect in the preparation of pesticides for killing or preventing agricultural pests, sanitary pests and pests that endanger animal health.

[0041] The fourth aspect of the present invention provides an insecticide and / or insect control method, which comprises applying the compound described in the first aspect, its optical isomers, cis-trans isomers or their pesticide-acceptable salts, or the agricultural composition described in the second aspect of the present invention to plants or animals that are or may be affected by insect pests, or to the soil or environment around them.

[0042] The present invention also provides a method for controlling pests, comprising applying an effective insecticidal dose (10-1000 mg / L, preferably 100-500 mg / L) of the compound described in the first aspect of the present invention, its optical isomers, cis-trans isomers or their pesticide-acceptable salts, or the agricultural composition described in the second aspect of the present invention to plant seeds and / or plant leaves and / or plant fruits or the location where the plant is growing or expected to grow.

[0043] In another preferred embodiment, the method is in vitro and non-therapeutic.

[0044] The fifth aspect of the present invention provides a method for preparing the compound of the first aspect, comprising the steps of:

[0045] (i) in the presence of an acid and a metal catalyst, a compound of formula A and a compound of formula B undergo a substitution reaction to obtain an intermediate of formula C;

[0046] and (ii) in the presence of a base, the intermediate of formula C undergoes double bond isomerization reaction to obtain a compound of formula (I),

[0047] Reaction formula (1):

[0048]

[0049] Reaction formula (2):

[0050]

[0051] Where R 1 、R 2 、R 3 、R 4 、R 5 and Z are as defined above.

[0052] In reaction formula (1), the solvent used is selected from one or more of the following solvents having a water content of less than 10 ppm: acetonitrile, tetrahydrofuran, toluene, 1,2-dichloroethane, dichloromethane, 1,4-dioxane, more preferably dichloromethane.

[0053] In reaction formula (1), the metal catalyst used is 1,5-cyclooctadiene iridium chloride dimer, which is coordinated with one selected from the following phosphoramidite ligands L1 to L11 to catalyze the reaction process, and L11 is more preferred.

[0054]

[0055] In reaction formula (1), the preferred molar ratio of iridium to ligand is 1%:4% or 2%:8% or 4%:16%, more preferably 1%:4%.

[0056] In reaction formula (1), the acid catalyst used is a protonic acid or a Lewis acid, selected from one or more of the following: o-nitrobenzoic acid, m-nitrobenzoic acid, diphenyl phosphate, diphenylsulfonimide, trifluoroacetic acid, trichloroacetic acid, acetic acid, phosphoric acid, boron trifluoride ether complex, iron trifluoromethanesulfonate, scandium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, preferably trifluoroacetic acid, trichloroacetic acid, o-nitrobenzoic acid, more preferably trifluoroacetic acid.

[0057] In reaction formula (1), the reaction is carried out at -20-35°C, more preferably 10-25°C.

[0058] In reaction formula (1), the reaction time is 1-48 hours, more preferably 2-12 hours.

[0059] In reaction formula (2), the solvent used is selected from one or more of the following: acetonitrile, tetrahydrofuran, dichloromethane, methanol, ethanol, acetone or 1,2-dichloroethane, more preferably tetrahydrofuran or acetonitrile.

[0060] In reaction formula (2), the inorganic base or organic base used is selected from one of the following: lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, DBU, TBD, more preferably DBU, potassium tert-butoxide.

[0061] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features described in detail below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be listed here one by one. DETAILED DESCRIPTION

[0062] After extensive and intensive research, screening, and testing, the present inventors have developed novel branched conjugated diene compounds with insecticidal activity, as well as methods for their preparation and use. This invention structurally modifies existing nitromethylene neonicotinoid insecticides, specifically introducing a branched allyl structure. This allows for the synthesis of a series of neonicotinoid compounds, demonstrating excellent insecticidal activity and expanding their spectrum of activity. This holds promise for the development of novel, low-toxic, highly effective, and environmentally friendly pesticides. This work was completed on this basis.

[0063] the term

[0064] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0065] As used herein, the terms "comprising" or "including" may be open, semi-closed, or closed. In other words, the terms also include "consisting essentially of" or "consisting of."

[0066] The prefix "C u-v " indicates that the following groups have u to v carbon atoms, such as "C 1-6 ” can be C1, C2, C3, C4, C5 or C6. For example, “C 1-6 "Alkyl" means that the alkyl group has 1 to 6 carbon atoms.

[0067] The term "plurality" refers to two or more, such as two, three, four, five or six.

[0068] The term "halogen" or "halo" refers to fluorine, chlorine, bromine, or iodine.

[0069] The term "alkyl" refers to a straight or branched chain unsubstituted group having 1 to 8 carbon atoms (i.e., C 1-8 Alkyl), preferably a hydrocarbon group of 1 to 6 carbon atoms (i.e., C 1-6 Alkyl), more preferably hydrocarbon group of 1 to 4 carbon atoms (i.e., C 1-4 Examples of "alkyl" include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, and 3-methylpentyl, and the like.

[0070] The term "alkylene" refers to a saturated divalent hydrocarbon radical having 1 to 8 carbon atoms derived by removing two hydrogen atoms from a straight or branched chain saturated hydrocarbon (i.e., C 1-8 Alkylene), preferably a hydrocarbon group of 1 to 4 carbon atoms (i.e., C 1-4 alkylene), more preferably 1-3 carbon atoms (i.e., C 1-3 Examples of "alkylene" include, but are not limited to, methylene, ethylene, isopropylene, and the like.

[0071] The term "alkenyl" refers to an alkenyl group having 2 to 8 carbon atoms (ie, C 2-8 alkenyl), preferably 2-6 carbon atoms (ie, C 2-6 alkenyl) or 2-4 carbon atoms (ie, C 2-4 The term "alkenyl" refers to a straight or branched hydrocarbon group having 1 to 2 carbon-carbon double bonds and is not limited to vinyl, propenyl, butadienyl (including 1,2-butadienyl and 1,3-butadienyl).

[0072] The term "alkynyl" refers to a group having 2 to 8 carbon atoms (ie, C 2-8 Alkynyl), preferably 2-6 carbon atoms (ie, C 2-6 Alkynyl) or 2-4 carbon atoms (i.e., C 2-4 alkynyl), and a straight or branched hydrocarbon group having 1 to 2 carbon-carbon triple bonds.

[0073] The term "cycloalkyl" refers to a non-aromatic, saturated or partially unsaturated cyclic hydrocarbon group, which may be substituted with one or more substituents as described herein, and which has 3 to 6 carbon atoms to form a monocyclic ring, or 7 to 12 carbon atoms to form a bicyclic ring. As used herein, a cycloalkyl group has 3 to 8 ring carbon atoms (i.e., C 3-8 Cycloalkyl) or 3 to 6 ring carbon atoms (ie C 3-6Examples of monocyclic cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 1-cyclopent-1-enyl, 1-cyclopent-2-enyl, 1-cyclopent-3-enyl, cyclohexyl, 1-cyclohex-1-enyl, cycloheptyl, and cyclooctyl. Exemplary bridged bicyclic cycloalkyls include, but are not limited to, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, and bicyclo[3.2.2]nonane.

[0074] The terms "aromatic ring" and "aryl" refer to aromatic carbocyclic groups having a single ring (e.g., monocyclic) or multiple rings (e.g., bicyclic or tricyclic), including fused systems. As used herein, an aryl group has 6 to 10 ring carbon atoms (i.e., C 6-10 Aryl includes bicyclic groups including an aromatic ring fused to a saturated or partially unsaturated carbocyclic or heterocyclic ring (e.g., benzo[C] 3-6 Typically, aryl groups include, but are not limited to, benzene, naphthalene, anthracene, biphenyl, 1,2-dihydronaphthalene, 1,2,3,4-tetrahydronaphthyl, 2,3-dihydrobenzofuranyl, and the like. The "aryl" group includes structures in which an aryl ring is fused to a cycloalkyl or heterocycloalkyl group.

[0075] The terms "heterocycle", "heterocyclic" and "heterocyclyl" refer to an optionally substituted, fully saturated or partially unsaturated non-aromatic ring group, for example, it can be a 3-7 membered monocyclic ring, a 7-11 membered bicyclic ring or a 10-15 membered tricyclic ring system, which has at least one heteroatom in at least one carbon atom-containing ring. Each ring of the heterocyclyl containing a heteroatom can have 1, 2 or 3 heteroatoms selected from oxygen, nitrogen and sulfur. As used herein, the heterocyclyl group has 3 to 10 ring atoms (i.e., 3-10 membered heterocyclyl), 3 to 8 ring atoms (i.e., 3-8 membered heterocyclyl), 3-8 membered heterocyclyl or 3 to 6 ring atoms (i.e., 3-6 membered heterocyclyl) or 5 to 6 ring atoms (i.e., 5-6 membered heterocyclyl). The "heterocyclyl" may be arbitrarily substituted with one or more substituents described herein. Examples of "heterocyclyl" include, but are not limited to, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, morpholino, thiomorpholino, piperazinyl, homopiperazinyl, glycidyl, imidazolidinyl, 3-azabicyclo[3.1.0]hexanyl, 3-azabicyclo[4.1.0]heptanyl, azabicyclo[2.2.2]hexanyl, N-pyridylurea, pyrimidinone and 1,1-dioxo-thiomorpholinyl.

[0076] The term "heteroaryl" or "heteroaromatic ring" refers to a heteroaromatic system containing one or more heteroatoms selected from oxygen, nitrogen and sulfur, including monocyclic, bicyclic or polycyclic fused systems. The heteroaryl group can be arbitrarily substituted with one or more substituents described herein. As used herein, the heteroaryl group can have 5 to 10 ring atoms (i.e., 5-10 membered heteroaryl), 5 to 8 ring atoms (i.e., 3-8 membered heteroaryl), or 5 to 6 ring atoms (i.e., 5-6 membered heteroaryl). The heteroaryl group can have 1 to 3 ring heteroatoms, 1 to 2 ring heteroatoms or 1 ring heteroatom, wherein the ring heteroatoms are independently selected from oxygen, nitrogen and sulfur. Examples of "heteroaryl" include, but are not limited to, pyrrolyl, pyridinyl, pyrazolyl, imidazolyl, pyrazinyl, imidazopyridinyl, benzofuranyl, pyrimidinyl, triazolyl, tetrazolyl, furanyl, thienyl, thiazolyl, quinolinyl, isoquinolinyl, indolyl, and the like.

[0077] The term "acyl" describes a substituent group containing a carbonyl residue -C(=O)R e . Where R e is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl or heteroaryl; each of which may be optionally substituted as defined herein. Examples of acyl include, but are not limited to, formyl, trifluoroacetyl, acetyl, cyclohexylcarbonyl, cyclohexylmethyl-carbonyl and benzoyl.

[0078] The term "ester group" refers to -OC(O)R f and -C(O)OR f Both. Among them R f is alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroalkyl, or heteroaryl; each of which may be optionally substituted as defined herein.

[0079] "Sulfonyl" refers to the group -S(O)2R r , where R r is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroalkyl or heteroaryl, each of which may be optionally substituted as defined herein. Examples of sulfonyl groups include, but are not limited to, methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, phenylsulfonyl and toluenesulfonyl.

[0080] "Oxy" refers to an -O- group, "acyloxy" refers to a -C(=O)-O- group, "carbonyl" refers to a -C(=O)- group, "nitro" refers to a -NO2 group, "cyano" refers to -CN, "hydroxy" refers to -OH, and "amino" refers to -NH2. The term "oxo" represents a divalent radical =O. The term "sulfonamido" refers to a -SO2NH2 group. "Carboxyl" refers to a -COOH group.

[0081] The term "substituted" means that one or more hydrogen atoms in a specific group are replaced by any substituent mentioned in the present specification, provided that the normal valence of the specified group or atom is not exceeded and the compound produced by the substitution is stable, that is, a compound that can be isolated, characterized and tested for biological activity. Unless otherwise specified, the "substituted" means that one or more (such as 2, 3 or 4) hydrogen atoms on the group are independently replaced by a group selected from the following groups: H, substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy, substituted or unsubstituted C 1-8 Alkoxy-C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy-carbonyl, substituted or unsubstituted allyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenoxycarbonyl, substituted or unsubstituted C 2-8 Alkenyl-carbonyl, substituted or unsubstituted C 2-8 Alkynyl-carbonyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 3-8 Cycloalkyl-carbonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted furancarbonyl or substituted or unsubstituted N,N-dimethylcarbonyl, and the substitution means that one or more H atoms on the group are independently substituted by a substituent selected from the group consisting of halogen, halogenated or unsubstituted C 1-4 Alkyl, halogenated or unsubstituted C 2-4 Alkenyl, halogenated or unsubstituted C 2-4 Alkynyl, halogenated or unsubstituted C 1-4 Alkoxy and halogenated or unsubstituted C 1-4 Alkyl-carbonyl.

[0082] Active ingredient

[0083] The present invention provides a compound of formula (I), its optical isomers, cis-trans isomers, or pesticide-acceptable salts thereof:

[0084]

[0085] Among them, R 1 、R 2 、R 3 、R 4 、R 5 and Z are as defined above.

[0086] In another preferred embodiment, the compound has a structure represented by general formula (II):

[0087]

[0088] Where R 1 and R5 As defined above.

[0089] In another preferred embodiment, the compound is any one of the compounds in the examples.

[0090] The present invention is intended to include salts of the compounds. A "pesticide-acceptable salt" may have more than one charged atom, and multiple charged atoms may have multiple counterions. In an exemplary embodiment, a salt form of the compound is produced that can convert an otherwise oily or viscous compound into a more easily handled solid material. In another exemplary embodiment, converting the free base of the compound of the invention into the corresponding salt can increase the solubility of the compound in aqueous media and can affect biological properties such as bioavailability, pharmacokinetics, and pharmacodynamics. Therefore, any salt form, such as a pharmaceutically acceptable salt of the compound of the invention, including salts of inorganic acids or salts of organic acids is within the scope of the present invention. Also, various crystalline forms of the pharmaceutically acceptable salts of the compound of the invention are within the scope of the present invention. Any prodrug of the compound of the invention is also within the scope of the present invention. For example, R and R t It may be any group that is cleavable in vivo to produce an amine (eg, a primary or secondary amine).

[0091] As used herein, the term "pesticide-acceptable salt" refers to salts that are suitable for use in contact with the tissues of humans and lower animals without excessive toxicity, irritation, allergic reactions, etc., and commensurate with a reasonable benefit / risk ratio, within the scope of reasonable medical judgment. Pharmaceutically acceptable salts are well known in the art. Pharmaceutically acceptable salts of the compounds of the present invention include those derived from suitable inorganic and organic acids and bases. Examples of pesticide-acceptable non-toxic acid addition salts are salts formed by amino groups with inorganic acids (such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, and perchloric acid) or with organic acids (such as acetic acid, oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, or malonic acid) or by using other methods used in the art (such as ion exchange). Other pharmaceutically acceptable salts include, but are not limited to, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bisulfate, borate, butyrate, camphorate, camphorsulfonate, citrate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptonate, glycerophosphate, gluconate, hemisulfate, heptanoate, hexanoate, hydroiodide, 2-hydroxy-ethanesulfonate, lactobionate, lactate, laurate, lauryl sulfate, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, pivalate, propionate, stearate, succinate, sulfate, tartrate, thiocyanate, p-toluenesulfonate, undecanoate, valerate, and the like.

[0092] Solvates refer to the combination or complex of one or more solvent molecules with the compounds of the present invention. Examples of solvents that form solvates include, but are not limited to, water, isopropanol, ethanol, methanol, dimethyl sulfoxide, ethyl acetate, acetic acid, and ethanolamine. The compounds of the present invention may exist in unsolvated form or in solvated form with pharmaceutically acceptable solvents such as water, ethanol, etc., and the present invention encompasses both solvated and unsolvated forms.

[0093] Some compounds exist as tautomers. Tautomers are in equilibrium with each other. For example, amide-containing compounds can exist in equilibrium with imidic acid tautomers. Regardless of which tautomer is shown, and regardless of the equilibrium properties between the tautomers, it is understood by those of ordinary skill in the art that compounds comprise all or each tautomer of the compound. Therefore, amide-containing compounds are understood to comprise their imidic acid tautomers. Similarly, imidic acid-containing compounds are understood to comprise their amide tautomers.

[0094] The compounds of the present invention may contain asymmetric centers or chiral centers and therefore exist in different stereoisomeric forms. The compounds may be chiral, racemic or may exist as compositions comprising one or more stereoisomers. The present invention includes enantiomers, diastereomers, racemic mixtures, enantiomerically enriched mixtures and diastereomerically enriched mixtures. All stereoisomeric forms of the compounds of the present invention, including but not limited to diastereomers, enantiomers and hindered isomers, and mixtures thereof such as racemic mixtures, will form part of the present invention. In addition, asymmetric carbon atoms may be present in substituents such as alkyl groups. All of these isomers and mixtures thereof are intended to be included in the present invention. If a specific enantiomer of the compounds of the present invention is desired, it can be prepared by asymmetric synthesis or by derivatization with a chiral auxiliary, wherein the resulting diastereomeric mixture is separated and the auxiliary group is split to provide the pure desired enantiomer. Alternatively, when the molecule contains a basic functional group such as an amino group, or an acidic functional group such as a carboxyl group, diastereomeric salts can be formed with an appropriate optically active acid or base, followed by resolution of the diastereomers thus formed by fractional crystallization or chromatography methods known in the art, and subsequent recovery of the pure enantiomers. In addition, separation of enantiomers and diastereomers can be achieved using chromatography on chiral stationary phases.

[0095] In this article, when the stereochemistry of any particular chiral atom is not determined, all stereoisomers are considered. In addition, the present invention relates to all geometric and positional isomers. The compounds of this invention can exist in different tautomeric forms, and all of these forms are included within the scope of the present invention. All stereoisomers of the compounds of this invention are expected to include mixtures or pure or substantially pure forms.

[0096] Herein, unless otherwise indicated, structures depicted herein are also intended to include compounds that differ only in the presence of one or more isotopically enriched atoms. In addition to therapeutic uses, such compounds are useful, for example, as analytical tools or probes in biological assays. Any formula or structure given herein is also intended to represent unlabeled forms as well as isotopically labeled forms of the compound. An isotopically labeled compound has a structure described by the formula given herein, except that one or more atoms are replaced by an atom having a selected atomic mass or mass number. Examples of isotopes that can be incorporated into the compounds of the present disclosure include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, fluorine, and chlorine, such as, but not limited to, 2 H (deuterium, D), 3 H (tritium), 11 C. 13 C. 14 C. 15 N. 18 F. 31 P. 32 P. 35 S.36 Cl and 125 I. Various isotopically labeled compounds of the present disclosure, for example, incorporating radioactive isotopes such as 3 H and 14 C, which can be used in metabolism studies, reaction kinetic studies, detection or imaging techniques such as positron emission tomography (PET) or single photon emission computed tomography (SPECT), including drug or substrate tissue distribution analysis or radiotherapy of patients.

[0097] Insecticidal activity of the substances of the present invention

[0098] The term "active substance of the present invention" or "active compound of the present invention" refers to the compound of the present invention, its optical isomers, cis-trans isomers or pesticide-acceptable salts, which have significant insecticidal activity, a broad insecticidal spectrum, and strong stability.

[0099] The compound provided by the present invention has significant insecticidal activity and can be used to control and eliminate a wide range of agricultural and forestry pests, stored grain pests, animal health pests or public health pests, etc. In the present specification, the pests that can be killed or controlled include but are not limited to the following pests: Coleoptera insects, such as corn weevil (Sitophilus zeamais), red flour beetle (Tribolium castaneum), potato beetle (Henosepilachna vigintioctomaculata), twenty-eight-spotted ladybird (Henosepilachna sparsa), slender-breasted click beetle (Agriotes fuscicollis), red-legged green beetle (Anomala cupripes), four-striped beetle (Popillia quadriguttata), potato leaf beetle (Monoleptahieroglyphica), pine beetle (Monochamus alternatus), rice root beetle (Echinocnemus squameus), paulownia leaf beetle (Basiprionota bisignata), star beetle (Anoplophora chinensis), mulberry beetle (Apriponagermari), umbilical bellied flag beetle (Scolytus schevy), Agriotes fuscicollis; Lepidoptera, such as Lymantria dispar, Malacosoma Neustria testacea, Diaphania perspectalis, Clania variegata, Cnidocampaflauescens, Dendrolimus punctatus, Orgyia gonostigma, Paranthrene tabaniformis, Spodoptera litura, Chilosuppressalis, Ostrinia nubilalis, Ephestia cautella, Adoxophyes orana, Laspyresia truncatula splendana), cutworm (Agrotis fucosa), wax moth (Galleria mellonella), diamondback moth (Plutella xylostella), citrus leafminer (Phyllocnistis citrella), or Oriental armyworm (Mythimnaseparata);Homoptera, such as Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossydii, Lipaphis erysimi pseudobrassicae, Stephanitis nashi, or Bemisia tabaci; Orthoptera, such as Blattella germanica, Periplaneta americana, Gryllotalpa africana, or Locus migratoria; Isoptera, such as Solenopsis invicta, or Coptotermes formosanus. formosanus; Diptera, such as the housefly (Musca domestica), Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis; pests that endanger animal health, such as the cattle tick (Boophilus microplus), Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia blanchard, Ostertagia spp., protozoa (Trypanosoma enansi, Babesia bigemina), Occidiosis, tapeworms, and Coccidium.

[0100] The compound designed by the present invention has special effects on pests with piercing-sucking, rubbing-sucking or chewing mouthparts, such as aphids, leafhoppers, armyworms, plant hoppers and whiteflies.

[0101] Composition

[0102] The active substances of the present invention can be prepared into insecticide compositions in conventional manner, such as solutions, emulsions, foams, powders, pastes, and granules. Aerosols are microcapsules of natural or synthetic materials impregnated with the active substance, encapsulated in polymers. These include seed coating compounds, formulations for use with combustion devices such as fumigation cartridges, trays, and canisters, and ULV cold and hot mist formulations.

[0103] These preparations can be produced by known methods, such as mixing the active compound with an extender, which is a liquid, liquefied gas or solid diluent or carrier, and which may be mixed with any surfactant. In addition, when water is used as the extender, an organic solvent may be used as a cosolvent.

[0104] When a liquid is used as a diluent or carrier, it is basically suitable, such as aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffin; alcohols, such as ethanol or ethylene glycol and their ethers or polymers; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; other polar solvents, such as N,N-dimethylformamide, dimethyl sulfoxide or water.

[0105] Liquefied gas diluents or carriers refer to liquids that will become gases at normal temperature and pressure, such as aerosol propellants, such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide.

[0106] Solid carriers include ground natural minerals such as clay, quartz, talc, montmorillonite, attapulgite, kaolin or diatomaceous earth, and ground synthetic minerals such as dispersed silicic acid, silicates and alumina. Solid carriers for granules are aged and graded natural zircons such as calcite, pumice, marble, sepiolite and dolomite, as well as inorganic and organic coarse powders and synthetic particles. Organic materials include sawdust, coconut shells, corn cobs and tobacco stems and crushed particles thereof.

[0107] Nonionic and anionic emulsifiers can be used as emulsifiers and / or foam formers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, alkylaryl polyethylene glycols, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and albumin hydrolysates. Dispersants include lignin sulfite waste liquor and methylcellulose.

[0108] Binders such as carboxymethylcellulose and natural or synthetic polymers in the form of powders, granules or emulsions, such as gum arabic, polyethylene and polyvinyl acetate, may be used in the formulation.

[0109] Colorants that may be used include inorganic dyes such as iron oxide, cobalt oxide, and Prussian blue; organic dyes such as azo dyes or metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, zinc, boron, copper, cobalt, and aluminum.

[0110] The active compound of the present invention can be used in a mixture with other active compounds, including insecticides, baits, fungicides, acaricides, nematicides and / or growth regulators.

[0111] The active compounds of the present invention can be used in a mixture with synergists to enhance the activity of the compounds of the present invention.

[0112] These formulations usually contain 0.001-99.999% by weight, preferably 0.1-99.9% by weight, more preferably 0.5-90% by weight of the active compound of the invention. The content of the active compound in the use formulations prepared from commercial formulations can vary within wide ranges.

[0113] Preparation method

[0114] The target compound of the present invention can be obtained from the compounds of formula A and formula B through reaction formula (1) and reaction formula (2), comprising the steps of:

[0115] (i) in the presence of an acid and a metal catalyst, a compound of formula A and a compound of formula B undergo a substitution reaction to obtain an intermediate of formula C;

[0116] and (ii) in the presence of a base, the intermediate of formula C undergoes double bond isomerization reaction to obtain a compound of formula (I),

[0117] Reaction formula (1):

[0118]

[0119] Reaction formula (2):

[0120]

[0121] Where R 1 、R 2 、R 3 、R 4 、R 5 and Z are as defined above.

[0122] In reaction formula (1), the solvent used is selected from one or more of the following solvents having a water content of less than 10 ppm: acetonitrile, tetrahydrofuran, toluene, 1,2-dichloroethane, dichloromethane, 1,4-dioxane, more preferably dichloromethane.

[0123] In reaction formula (1), the metal catalyst used is 1,5-cyclooctadiene iridium chloride dimer, which is coordinated with one selected from the following phosphoramidite ligands L1 to L11 to catalyze the reaction process, and L11 is more preferred.

[0124]

[0125] In reaction formula (1), the preferred molar ratio of iridium to ligand is 1%:4% or 2%:8% or 4%:16%, more preferably 1%:4%.

[0126] In reaction formula (1), the acid catalyst used is a protonic acid or a Lewis acid, selected from one or more of the following: o-nitrobenzoic acid, m-nitrobenzoic acid, diphenyl phosphate, diphenylsulfonimide, trifluoroacetic acid, trichloroacetic acid, acetic acid, phosphoric acid, boron trifluoride ether complex, iron trifluoromethanesulfonate, scandium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, preferably trifluoroacetic acid, trichloroacetic acid, o-nitrobenzoic acid, more preferably trifluoroacetic acid.

[0127] In reaction formula (1), the reaction is carried out at -20-35°C, more preferably 10-25°C.

[0128] In reaction formula (1), the reaction time is 1-48 hours, more preferably 2-12 hours.

[0129] In reaction formula (2), the solvent used is selected from one or more of the following: acetonitrile, tetrahydrofuran, dichloromethane, methanol, ethanol, acetone or 1,2-dichloroethane, more preferably tetrahydrofuran or acetonitrile.

[0130] In reaction formula (2), the inorganic base or organic base used is selected from one of the following: lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, DBU, TBD, more preferably DBU, potassium tert-butoxide.

[0131] The conditions of the method, such as raw materials, solvent, temperature, catalyst, acid, base, ratio, and reaction time, can be selected as needed, such as (but not limited to) the conditions of the following examples.

[0132] The main advantages of the present invention include:

[0133] 1. The present invention provides a class of novel branched conjugated diene neonicotinoid compounds with excellent insecticidal activity.

[0134] 2. The compounds of the present invention can control insect pests that are resistant to existing neonicotinoid insecticides.

[0135] 3. The compounds of the present invention have excellent, broad-spectrum insecticidal activity and can expand the insecticidal spectrum of neonicotinoid compounds, and are expected to develop new low-toxic, high-efficiency, and environmentally friendly pesticides.

[0136] The present invention will be further described below in conjunction with specific implementation. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the present invention. The experimental methods in the following examples, for which specific conditions are not specified, are generally based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are calculated by weight.

[0137] Example 1 Synthesis of 2-chloro-5-(((E)-2-((Z)-1-nitro-2-phenylbut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0138]

[0139] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol) and Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-phenylpropyl-2-ene-1-ol (2.0mmol) was then added, and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The mixture was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60°C overnight. After removing the solvent, the mixture was separated by column chromatography to obtain a yellow solid. The light yellow solid was slurried with isopropyl ether to obtain a light yellow solid with a yield of 53%. mp: 144-146°C; 1 H NMR (400MHz, CDCl3) δ10.10(brs,1H),7.94(d,J=2.4Hz,1H),7.31–7.19(m,5H),7.15(d,J=8.0Hz,1H),6.96(dd,J=8.0,2.4Hz,1H),6 .42(q,J=6.9Hz,1H),4.55(d,J=16.0Hz,1H),4.36(d,J=16.0Hz,1H),3.79(t,J=9.2Hz,2H),3.59–3.28(m,2H),1.76(d,J=6.8Hz,3H); 13C NMR (100MHz, CDCl3) δ160.8,151.1,148.4,139.4,137.5,132.6,131.6,130.4,129.0(2 C),127.7,125.5(2C),124.4,106.6,50.3,48.9,41.7,16.1; HRMS(ESI-TOF)m / z:[M+H] + calcd for C 19 H 20 ClN4O2:371.1269; found:371.1270.

[0140] Example 2 2-Chloro-5-(((E)-2-((Z)-2-(4-chlorophenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0141]

[0142] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried over a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and the mixture was stirred at room temperature for 15 minutes, during which time the solution turned red. Racemic 1-(4-chlorophenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60°C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 55%. mp: 157–159°C; 1H NMR (400MHz, CDCl3) δ10.05(brs,1H),8.02(d,J=2.5Hz,1H),7.23-7.19(m,5H),7.05(dd,J=8.4,2.4Hz,1 H),6.39(q,J=6.9Hz,1H),4.42(s,2H),3.82(t,J=9.4Hz,2H),3.61-3.41(m,2H).,1.75(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.8,151.4,148.3,138.1,137.3,133.4,132.0,131.7,130.3 ,129.1(2C),126.8(2C),124.5,106.2,50.4,49.0,41.8,16.2; HRMS(EI-TOF)m / z:[M] + calcd for C 19 H 18 Cl2N4O2:404.0801; found:404.0806.

[0143] Example 3 2-Chloro-5-(((E)-2-((Z)-1-nitro-2-(p-tolyl)but-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0144]

[0145] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-methylphenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 26%. mp: 142–144 ° C; 1 H NMR (400MHz, CDCl3) δ10.12(brs,1H),7.98(d,J=2.5Hz,1H),7.20-7.14(m,3H),7.08-7.02(m,2H),6.99(dd,J=8.4,2.4H z,1H),6.37(q,J=6.9Hz,1H),4.47(s,2H),3.80(t,J=9.2Hz,2H),3.59-3.37(m,2H),2.31(s,3H),1.75(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.8,151.1,148.4,137.5(4),137.4(9),136.6,132.4,130.6,130.5 ,129.7(2C),125.5(2C),124.4,106.8,50.3,48.9,41.7,21.2,16.1; HRMS(EI-TOF)m / z:[M] + calcd for C 20 H 21 ClN4O2:384.1348; found:384.1352.

[0146] Example 4 2-Chloro-5-(((E)-2-((Z)-2-(4-methoxyphenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0147]

[0148] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-methoxyphenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 26%. mp: 116–118 ° C; 1 H NMR (400MHz, CDCl3) δ10.10(brs,1H),7.97(s,1H),7.22–7.13(m,3H),7.02(d,J=8.4Hz,1H),6.77(d,J=8.4Hz,2H),6.28(q ,J=6.9Hz,1H),4.53(d,J=16.0Hz,1H),4.40(d,J=16.8Hz,1H),3.84–3.75(m,5H),3.58–3.39(m,2H),1.73(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.8,159.3,151.0,148.3,137.4,132.0,131.9,130.5,129.4,12 6.7(2C),124.4,114.3(2C),106.7,55.4,50.3,48.9,41.7,16.0; HRMS(EI-TOF)m / z:[M]+ calcdfor C 20 H 21 ClN4O3:400.1297; found:400.1307.

[0149] Example 5 2-chloro-5-(((E)-2-((Z)-2-(naphthalen-2-yl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0150]

[0151] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(naphthalene-2-yl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The mixture was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the yellow solid was separated by column chromatography, and the light yellow solid was obtained by slurrying with isopropyl ether with a yield of 65%. mp: 101–103 ° C; 1 H NMR (400MHz, CDCl3) δ10.12(brs,1H),7.94(d,J=2.4Hz,1H),7.78–7.74(m,1H),7.72–7.67(m,2H),7.62(s,1H),7.49–7.40(m,3H),6.94(d,J =8.4Hz,1H),6.88(dd,J=8.4,2.4Hz,1H),6.52(q,J=6.9Hz,1H),4.42(s,2H),3.77(t,J=9.2Hz,2H),3.56–3.32(m,2H),1.79(d,J=6.8Hz,3H); 13C NMR (100MHz, CDCl3) δ160.9,151.0,148.0,137.1,136.7,133.7,132.9,132.6,132.0,130.4,128.7,1 28.2,127.6,126.5,126.1,124.6,124.2,123.5,106.6,50.4,48.9,41.7,16.2; HRMS(EI-TOF)m / z:[M] + calcd for C 23 H 21 ClN4O2:420.1348; found:420.1357.

[0152] Example 6 5-((1E,2E)-1-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ylidene)-1-nitrobut-2-en-2-yl)-4-methylthiazole

[0153]

[0154] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-methylthiazol-5-yl)propyl-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5 ((2- (nitromethylene) imidazolidin-1-yl) methyl) pyridine was complete (monitored by TLC), and saturated sodium bicarbonate solution was added for extraction, and the mixture was extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, and then the organic phase was dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was used to separate a light yellow solid. The intermediate was directly put into the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, column chromatography was used to separate a yellow solid, which was slurried with isopropyl ether to obtain a light yellow solid with a yield of 35%.

[0155] mp:169–171°C; 1 H NMR (400MHz, CDCl3) δ9.94 (brs, 1H), 8.50 (s, 1H), 8.08 (d, J=

[0156] 2.8Hz,1H),7.27(d,J=8.4Hz,1H),7.13(dd,J=8.4,2.4Hz,1H),6.23(q,J=6.9Hz,1H),4.5 4(s,2H),3.82(t,J=9.2Hz,2H),3.52(t,J=9.2Hz,2H),2.35(s,3H),1.78(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.4,151.5,149.5,148.4,148.3,137.2,135.5,133.9,130. 1,124.6(9),124.6(6),107.4,50.1,48.9,41.8,16.8,16.1; HRMS(EI-TOF)m / z:[M] + calcd for C 17 H 18 ClN5O2S:391.0864; found:391.0868.

[0157] Example 7 Methyl 4-((1E,2Z)-1-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ylidene)-1-nitrobut-2-en-2-yl)benzoate

[0158]

[0159] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol) and Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried over a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and the mixture was stirred at room temperature for 15 minutes, while the solution turned red. Racemic 4-(1-hydroxyallyl) methyl benzoate (2.0mmol) was then added and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 55%. mp: 124–126 ° C; 1 H NMR (400MHz, CDCl3) δ10.04(brs,1H),8.00(d,J=2.4Hz,1H),7.92(d,J=8.4Hz,2H),7.35(d,J=8.4Hz,2H),7.18(d,J=8.4Hz,1H),7.06( dd,J=8.4,2.4Hz,1H),6.53(q,J=6.9Hz,1H),4.40(s,2H),3.91(s,3H),3.83(t,J=9.2Hz,2H),3.64–3.40(m,2H),1.78(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ166.8,160.9,151.3,148.2,144.0,137.2,134.0,132.2,130.3(2C),130.2,12 9.2,128.8,125.6,125.4(2C),124.5,106.0,52.2,50.4,49.0,41.8,16.3; HRMS(ESI-TOF)m / z:[M+H] + calcd for C 21 H 21 ClN4O4:429.1324; found:429.1326.

[0160] Example 8 2-chloro-5-(((E)-2-((Z)-1-nitro-2-(thien-3-yl)but-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0161]

[0162] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a heat gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and stirred at room temperature for 15 minutes, during which time the solution turned red. Racemic 1-(thiophen-3-yl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 43%. mp: 159–161 ° C; 1 H NMR (400MHz, CDCl3) δ10.04(brs,1H),7.97(s,1H),7.28–7.17(m,2H),7.10–6.98(m,3H),6.32(q,J=6.4Hz,1H), 4.57(d,J=16.0Hz,1H),4.36(d,J=16.0Hz,1H),3.81(t,J=9.2Hz,2H),3.61-3.41(m,2H),1.71(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.6,151.1,148.3,142.0,137.4,130.7,130.5,128.3,1 26.8,124.9,124.4,120.7,106.7,50.5,48.9,41.7,15.6; HRMS(EI-TOF)m / z:[M]+ calcd for C 17 H 17 ClN4O2S:376.0755; found:376.0760.

[0163] Example 9 2-chloro-5-(((E)-2-((Z)-1-nitro-2-(4-(trifluoromethyl)phenyl)but-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0164]

[0165] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-(trifluoromethyl))prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60°C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 52%. mp: 151–153°C; 1 H NMR (400MHz, CDCl3) δ10.04(brs,1H),8.03(d,J=2.4Hz,1H),7.50(d,J=8.4Hz,2H),7.39(d,J=8.0Hz,2H),7.17(d,J=8.0Hz,1H),7.01 (dd,J=8.4,2.4Hz,1H),6.51(q,J=6.9Hz,1H),4.41(d,J=6.0Hz,2H),3.84(t,J=9.2Hz,2H),3.67–3.40(m,2H),1.79(d,J=6.8Hz,3H); 13C NMR (100MHz, CDCl3) δ160.8,151.4,148.2,143.1,137.1,133.9,131.9,130.1,129.5(q,J C-F =32.2Hz),125.9(q,J C-F =3.9Hz)(2C),125.8(2C),124.5,123.9(q,J C-F =269.9Hz),105.9,50.4,49.0,41.8,16.3.

[0166] 19 F NMR(376MHz, CDCl3)δ-62.41(s); HRMS(EI-TOF)m / z:[M] + calcd for C 20 H 18 ClF3N4O2:438.1065; found:438.1073.

[0167] Example 10 2-Chloro-5-(((E)-2-((Z)-2-(4-fluorophenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0168]

[0169] Under nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol), Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-fluorophenyl)prop-2-ene-1-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60°C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 53%. mp: 155–157°C; 1 H NMR(400MHz, CDCl3) δ10.06(brs,1H),8.01(d,J=2.4Hz,1H),7.28–7.19(m,3H),7.06(dd,J=8.4,2.4Hz,1H),6.98–6. 91(m,2H),6.34(q,J=6.9Hz,1H),4.50–4.38(m,2H),3.82(t,J=9.2Hz,2H),3.60–3.41(m,2H),1.75(d,J=6.8Hz,3H); 13 C NMR(100MHz,CDCl3)δ162.4(d,J C-F =247.5Hz),160.8,151.3,148.4,137.3,135.7,131.7,131.3,130.3,127.1(d,J C-F =8.0Hz)(2C),124.5,115.9(d,J C-F =21.5Hz)(2C),106.4,50.3,49.0,41.8,16.1; 19 F NMR(376MHz, CDCl3)δ-114.68–-114.81(m); HRMS(EI-TOF)m / z:[M] +calcd for C 19 H 18 ClFN4O2:388.1097; found:388.1105.

[0170] Example 11 2-Chloro-5-(((E)-2-((Z)-2-(2-fluorophenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0171]

[0172] Under nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol), Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(2-fluorophenyl)prop-2-ene-1-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 29%. mp: 144–146 ° C; 1 H NMR (400MHz, CDCl3) δ10.11(brs,1H),7.98(d,J=2.4Hz,1H),7.24–7.11(m,3H),7.10–7.02(m,2H),6.92–6.84( m,1H),6.53(q,J=6.9Hz,1H),4.61(s,2H),3.79(t,J=9.2Hz,2H),3.47(t,J=9.2Hz,2H),1.80(d,J=6.8Hz,3H); 13 C NMR(100MHz,CDCl3)δ160.5,160.0(d,J C-F =247.8Hz),151.1,148.4,137.5(d,JC-F =7.9Hz),137.4,130.4,129.6(d,J C-F =3.2Hz),128.8(d,J C-F =8.8Hz),127.6(d,J C-F =9.9Hz),127.1(d,J C-F =2.8Hz),124.7(d,J C-F =3.5Hz),124.4,116.4(d,J C-F =23.5Hz),107.6,50.1,48.7,41.6,16.4; 19 FNMR(376MHz, CDCl3)δ-117.77--117.91(m); HRMS(EI-TOF)m / z:[M] + calcd for C 19 H 18 ClFN4O2:388.1097; found:388.1098.

[0173] Example 12 2-chloro-5-(((E)-2-((Z)-2-(3-methoxyphenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0174]

[0175] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(3-methoxyphenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 59%. mp: 146–148 ° C; 1 H NMR (400MHz, CDCl3) δ10.08 (brs, 1H), 7.96 (d, J = 2.4Hz, 1H), 7.20-7.14 (m, 2H), 7. 03(dd,J=8.4,2.4Hz,1H),6.88(d,J=7.6Hz,1H),6.80(d,J=2.4Hz,1H),6.76(dd,J =8.0,2.4Hz,1H),6.40(q,J=6.9Hz,1H),4.54(d,J=16.0Hz,1H),4.38(d,J=16.0Hz ,1H).3.79(t,J=9.2Hz,2H),3.74(s,3H),3.58–3.39(m,2H),1.75(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.8,160.2,151.1,148.3,141.1,137.5,132.5,131.9,130.5,130. 0,124.4,118.1,112.6,111.8,106.6,55.4,50.3,48.9,41.7,16.1; HRMS(EI-TOF)m / z:[M] + calcd for C 20 H 21ClN4O3:400.1297; found:400.1301.

[0176] Example 13 5-(((E)-2-((Z)-2-(4-bromophenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)-2-chloropyridine

[0177]

[0178] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-bromophenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 73%. mp: 147–149 ° C; 1 H NMR (400MHz, CDCl3) δ10.04(brs,1H),8.02(d,J=2.4Hz,1H),7.37(d,J=8.8Hz,2H),7.21(d,J=8.4Hz,1H),7.15(d,J=8.4Hz,2H), 7.05(dd,J=8.4,2.4Hz,1H),6.40(q,J=6.9Hz,1H),4.41(s,2H),3.83(t,J=9.2Hz,2H),3.63–3.41(m,2H),1.74(d,J=6.8Hz,3H); 13C NMR (100MHz, CDCl3) δ160.8,151.3,148.2,138.5,137.2,132.1,132.0(2C),131.8,1 30.2,127.1(2C),124.5,121.5,106.0,50.4,49.0,41.8,16.2; HRMS(EI-TOF)m / z:[M] + calcd for C 19 H 18 Cl 79 BrN4O2:448.0302; found:448.0305; calcd for C 19 H 18 Cl 81 BrN4O2:450.0281; found:450.0280.

[0179] Example 14 2-chloro-5-(((E)-2-((Z)-2-(6-methoxypyridin-3-yl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0180]

[0181] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a heat gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(6-methoxypyridin-3-yl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 76%. mp: 165–167 ° C; 1H NMR (400MHz, CDCl3) δ10.04(brs,1H),8.05(d,J=2.4Hz,1H),8.02(d,J=2.4H z,1H),7.52(dd,J=8.8,2.4Hz,1H),7.22(d,J=8.0Hz,1H),7.14(dd,J=8.0,2. 4Hz,1H),6.65(d,J=7.6Hz,1H),6.31(q,J=6.9Hz,1H),4.47(d,J=2.4Hz,2H), 3.91(s,3H),3.83(t,J=9.2Hz,2H),3.62–3.43(m,2H),1.75(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ163.7,160.8,151.3,148.3,144.0,137.2,135.9,130.5,130.3,1 29.6,128.6,124.5,111.1,105.8,53.7,50.4,49.0,41.8,16.1; HRMS(EI-TOF)m / z:[M] + calcd for C 19 H 20 ClN5O3:401.1255; found:401.1254.

[0182] Example 15 2-chloro-5-(((E)-2-(((E)-2-methyl-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0183]

[0184] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol) and Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 3-butene-2-ol (2.0mmol) was then added, and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and saturated sodium bicarbonate solution was added for extraction. The mixture was extracted three times with CH2Cl2, and the organic phases were combined and washed once with saturated brine. The organic phase was then dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of tetrahydrofuran and potassium tert-butoxide (1.0 mmol) was added until the intermediate was completely reacted. After quenching with water, the mixture was extracted three times with ethyl acetate. The organic phases were combined and washed once with saturated brine. The organic phase was then dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed to obtain a yellow solid. The light yellow solid was obtained by slurrying with isopropyl ether with a yield of 51%. mp: 165–167°C; 1 H NMR (400MHz, CDCl3) δ9.81(brs,1H),8.24(d,J=2.4Hz,1H),7.50(dd,J=8.4,2.4Hz,1H),7.36(d,J=8.4Hz,1H),5.53( qd,J=6.8,2.0Hz,1H),4.47(s,2H),3.81(t,J=9.2Hz,2H),3.56(t,J=9.2Hz,2H),1.88(s,3H),1.45(d,J=6.8Hz,3H); 13 CNMR(100MHz, CDCl3)δ160.9,151.4,148.2,137.1,130.6,130.4,128.1,124.7,113.0,50.4,49.5,42.0,16.7,13.7; HRMS(EI-TOF)m / z:[M] + calcd for C 14 H 17 ClN4O2:308.1035; found:308.1042.

[0185] Example 16 2-chloro-5-(((E)-2-(((E)-2-ethyl-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)pyridine

[0186]

[0187] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol) and Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-pentene-3-ol (2.0mmol) was then added, and the reaction mixture immediately turned light yellow. 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC), and extracted with saturated sodium bicarbonate solution, extracted three times with CH2Cl2, and the organic phases were combined and washed once with saturated brine. The organic phase was then dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of tetrahydrofuran and potassium tert-butoxide (1.0 mmol) was added until the intermediate reacted completely. After quenching with water, the mixture was extracted three times with ethyl acetate. The organic phases were combined and washed once with saturated brine. The organic phase was then dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was performed to obtain a yellow solid. The yield of the light yellow solid was 52% after slurrying with isopropyl ether. mp: 153–155°C; 1 H NMR (400MHz, CDCl3) δ9.97(brs,1H),8.24(d,J=2.4Hz,1H),7.50(dd,J=8.4,2.4Hz,1H),7.36(d,J=8.4Hz,1H),5.53(q,J=6.9Hz,1 H),4.55(s,2H),3.80(t,J=9.2Hz,2H),3.54(t,J=9.2Hz,2H),2.38(q,J=7.6Hz,2H),1.48(d,J=6.8Hz,3H),1.02(t,J=7.6Hz,3H); 13C NMR (100MHz, CDCl3) δ160.9,151.4,148.3,137.2,133.4,130.5,130.0,124.7,111.7,50.2,49.4,41.8,23.6,13.7,12.0; HRMS (EI-TOF) m / z: [M] + calcd for C 15 H 19 ClN4O2:322.1191; found:322.1195.

[0188] Example 17 2-chloro-5-(((E)-2-(((E)-2-ethylidene-1-nitrosopentyl)imidazolidin-1-yl)methyl)pyridine

[0189]

[0190] Under nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol), Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-heptene-3-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC). Saturated sodium bicarbonate solution was added for extraction, and the mixture was extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate. The solvent was removed and separated by column chromatography to obtain a light yellow solid. The intermediate was dissolved in 10 mL of tetrahydrofuran and potassium tert-butoxide (1.0 mmol) was added until the intermediate reacted completely. After quenching with water, the mixture was extracted three times with ethyl acetate. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate. The solvent was removed and separated by column chromatography to obtain a yellow solid. The light yellow solid was slurried with isopropyl ether in a yield of 51%. mp: 148–150°C; 1H NMR (400MHz, CDCl3) δ9.98(brs,1H),8.24(d,J=2.4Hz,1H),7.50(dd,J=8.4,2.4Hz,1H),7.37(d,J=8.4Hz,1H),5.54(q,J=6.9Hz,1H),4.57( s,2H),3.79(t,J=9.2Hz,2H),3.55(t,J=9.2Hz,2H),2.28(t,J=8.6Hz,2H),1.50(d,J=7.2Hz,3H),1.48–1.39(m,2H),0.93(t,J=7.2Hz,3H); 13 CNMR(100MHz, CDCl3)δ160.6,151.4,148.3,137.2,132.4,130.6,130.5,124.7,112.1,50.2,49.3,41.7,33.4,21.2,14.8,13.9; HRMS(EI-TOF)m / z:[M] + calcd for C 16 H 21 ClN4O2:336.1348; found:336.1357.

[0191] Example 18 2-chloro-5-(((E)-2-(((E)-2-ethylidene-1-nitrosohexyl)imidazolidin-1-yl)methyl)pyridine

[0192]

[0193] Under nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol), Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-hexene-3-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was complete (monitored by TLC). Saturated sodium bicarbonate solution was added for extraction, and the mixture was extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate. The solvent was removed and separated by column chromatography to obtain a light yellow solid. The intermediate was dissolved in 10 mL of tetrahydrofuran and potassium tert-butoxide (1.0 mmol) was added until the reaction was complete. After quenching with water, the mixture was extracted three times with ethyl acetate. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate. The solvent was removed and separated by column chromatography to obtain a yellow solid. The light yellow solid was slurried with isopropyl ether in a yield of 51%. mp: 155–157°C; 1 H NMR (400MHz, CDCl3) δ9.99(brs,1H),8.25(s,1H),7.51(d,J=8.4Hz,1H),7.37(d,J=8.4Hz,1H),5.54(q,J=6.9Hz,1H),4.57(s,2H) ,3.79(t,J=9.2Hz,2H),3.54(t,J=9.0Hz,2H),2.35–2.26(m,2H),1.50(d,J=6.8Hz,3H),1.45–1.23(m,4H),0.88(t,J=7.2Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.6,151.4,148.3,137.2,132.5,130.5,130.4,124.7 ,112.1,50.2,49.3,41.7,30.9,30.0,23.5,14.1,13.8; HRMS(EI-TOF)m / z:[M] + calcd for C 17 H 23 ClN4O2:350.1504; found:350.1513.

[0194] Example 19 2-Chloro-5-(((E)-2-(((E)-2-methyl-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0195]

[0196] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol) and Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and the mixture was stirred at room temperature for 15 minutes, while the solution turned red. Racemic 3-butene-2-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC). Saturated sodium bicarbonate solution was added for extraction, and the mixture was extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate. The solvent was removed and separated by column chromatography to obtain a light yellow solid. The intermediate was dissolved in 10 mL of tetrahydrofuran and potassium tert-butoxide (1.0 mmol) was added until the reaction was complete. After quenching with water, the mixture was extracted three times with ethyl acetate. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate. The solvent was removed and separated by column chromatography to obtain a yellow solid. The light yellow solid was slurried with isopropyl ether in a yield of 52%. mp: 147–149°C; 1 H NMR (400MHz, CDCl3) δ9.75 (brs, 1H), 7.42 (s, 1H), 5.63 (qd, J = 6.9, 1.4Hz, 1H), 4.58 (s ,2H),3.78(t,J=9.0Hz,2H),3.59(t,J=9.2Hz,2H),1.93(s,3H),1.67(d,J=8.0Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.2, 152.9, 140.2, 135.5, 130.6, 128.5, 113.0, 49.7, 45.4, 41.9, 16.7, 14.1; HRMS (EI-TOF) m / z: [M] + calcd for C 12 H 15 ClN4O2S:314.0599; found:314.0598.

[0197] Example 20 2-Chloro-5-(((E)-2-((Z)-1-nitro-2-phenylbut-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0198]

[0199] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol) and Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-phenylpropyl-2-ene-1-ol (2.0mmol) was then added, and the reaction mixture immediately turned light yellow. (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 43%. mp: 107–109 ° C; 1 H NMR (400MHz, CDCl3) δ10.01(brs,1H),7.40–7.21(m,5H),7.18(s,1H),6.53(q,J=6.9Hz,1H),4.63(d ,J=16.0Hz,1H),4.47(d,J=15.6Hz,1H),3.83–3.69(m,2H),3.64–3.40(m,2H),1.81(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.3,153.1,140.3,140.1,139.2,131.4,129.1(2C),1 27.8,127.6,125.5(2C),106.6,49.7,44.8,41.7,16.2; HRMS(EI-TOF)m / z:[M] + calcd for C17 H 17 ClN4O2S:376.0755; found:376.0759.

[0200] Example 21 2-Chloro-5-(((E)-2-((Z)-2-(4-chlorophenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0201]

[0202] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-chlorophenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 47%. mp: 132–134 ° C; 1 H NMR(400MHz, CDCl3)δ9.94(brs,1H),7.33–7.25(m,4H),7.23(s,1H),6.50(q,J=6.9Hz,1H),4.62(d, J=16.0Hz,1H),4.38(d,J=16.0Hz,1H),3.86–3.74(m,2H),3.68–3.43(m,2H),1.79(d,J=6.8Hz,3H); 13C NMR (100MHz, CDCl3) δ160.3,153.1,140.4,137.8,135.3,133.5,131.9,131.7,129.2(2C),126.8(2C),106.1,49.8,44.9,41.8,16.2.

[0203] Example 22 2-Chloro-5-(((E)-2-((Z)-1-nitro-2-(p-tolyl)but-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0204]

[0205] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-methylphenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 30%. mp: 114–116 ° C; 1 H NMR (400MHz, CDCl3) δ10.01(brs,1H),7.26(d,J=8.8Hz,2H),7.19(s,1H),7.10(d,J=8.0Hz,2H),6.47(q,J=6.9Hz,1H),4 .66(d,J=16.0Hz,1H),4.44(d,J=16.0Hz,1H),3.84–3.73(m,2H),3.65–3.41(m,2H),2.32(s,3H),1.79(d,J=6.8Hz,3H); 13C NMR (100MHz, CDCl3) δ160.3,153.0,140.3,137.7,136.4,135.6,132.6,130.2,12 9.8(2C),125.4(2C),106.6,49.7,44.8,41.7,21.2,16.1; HRMS(EI-TOF)m / z:[M] + calcd for C 18 H 19 ClN4O2S:390.0912; found:390.0913.

[0206] Example 23 2-Chloro-5-(((E)-2-((Z)-2-(4-fluorophenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0207]

[0208] Under nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol), Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-fluorophenyl)prop-2-ene-1-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 48%. mp: 107–109 ° C; 1H NMR(400MHz, CDCl3)δ9.99(brs,1H),7.34(dd,J=8.4,5.2Hz,2H),7.24(s,1H),7.04–6.97(m,2H),6.46(q,J=6.9Hz ,1H),4.65(d,J=16.0Hz,1H),4.44(d,J=16.0Hz,1H),3.88–3.75(m,2H),3.68–3.44(m,2H),1.80(d,J=6.8Hz,3H); 13 C NMR(100MHz,CDCl3)δ162.6(d,J C-F =247.3Hz),160.3,153.3,140.4,135.3(4)(d,J C-F =3.2Hz),135.3(0),131.8,131.2,127.1(d,J C-F =8.0Hz)(2C),116.0(d,J C-F =21.6Hz)(2C),106.4,49.8,44.9,41.8,16.2; 19 F NMR(376MHz, CDCl3)δ-114.62–-114.75(m); HRMS(EI-TOF)m / z:[M] + calcdfor C 17 H 16 ClFN4O2S:396.0661; found:396.0664.

[0209] Example 24 2-Chloro-5-(((E)-2-((Z)-1-nitro-2-(4-(trifluoromethyl)phenyl)but-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0210]

[0211] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a heat gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-(trifluoromethyl)phenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and saturated sodium bicarbonate solution was added for extraction. The mixture was extracted three times with CH2Cl2, and the organic phases were combined and washed once with saturated brine. The organic phase was then dried over anhydrous sodium sulfate, the solvent was removed, and column chromatography was used to separate a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, column chromatography was used to separate a yellow solid, which was slurried with isopropyl ether to obtain a light yellow solid with a yield of 43%. mp: 171–173 ° C; 1 H NMR (400MHz, CDCl3) δ9.94(brs,1H),7.56(d,J=8.4Hz,2H),7.48(d,J=8.4Hz,2H),7.24(s,1H),6.61(q,J=6.9Hz, 1H),4.60(d,J=16.0Hz,1H),4.40(d,J=16.0Hz,1H),3.88–3.75(m,2H),3.70–3.45(m,2H),1.83(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.3,153.2,142.8,140.4,135.1,133.6,132.0,129.6(q,J C-F =32.5Hz),126.0(q,J C-F =3.8Hz),124.2(q,J C-F =270.1Hz),125.7,105.8,49.8,45.0,41.8,16.4; 19 FNMR(376MHz, CDCl3)δ-62.42(s); HRMS(EI-TOF)m / z:[M] + calcd for C 18 H16 ClF3N4O2S:44.0629; found:444.0636.

[0212] Example 25 2-chloro-5-(((E)-2-((Z)-2-(4-methoxyphenyl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0213]

[0214] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a hot air gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 1-(4-methoxyphenyl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The mixture was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the yellow solid was separated by column chromatography, and the light yellow solid was obtained by slurrying with isopropyl ether with a yield of 48%. mp: 125–127 ° C; 1 H NMR (400MHz, CDCl3) δ10.01(brs,1H),7.29(d,J=8.8Hz,2H),7.27(s,1H),6.83(d,J=8.8Hz,2H),6.40(q,J=6.9Hz ,1H),4.67(d,J=16.0Hz,1H),4.45(d,J=16.0Hz,1H),3.86–3.73(m,5H),3.65–3.43(m,2H),1.78(d,J=7.2Hz,3H); 13C NMR (100MHz, CDCl3) δ160.3,159.5,153.1,140.3,135.6,132.1,131.8,129.3,12 6.7(2C),114.5(2C),106.7,55.5,49.8,44.8,41.8,16.0.; HRMS(EI-TOF)m / z:[M] + calcd for C 18 H 19 ClN4O3S:406.0861; found:406.0865.

[0215] Example 26 2-chloro-5-(((E)-2-((Z)-2-(6-methoxypyridin-3-yl)-1-nitrobut-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0216]

[0217] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk bottle dried with a heat gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and then stirred at room temperature for 15 minutes, during which time the solution turned red. Racemic 1-(6-methoxypyridin-3-yl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 33%. mp: 129–131 ° C; 1H NMR (400MHz, CDCl3) δ9.95(brs,1H),8.14(d,J=2.8Hz,1H),7.61(dd,J=8.8,2.8Hz,1H),7.25(s,1H),6.71(d,J=8.8Hz,1H) ,6.42(q,J=6.8Hz,1H),4.70(s,1H),4.47(s,1H),3.92(s,3H),3.86–3.74(m,2H),3.67–3.45(m,2H),1.80(d,J=7.2Hz,3H); 13 C NMR (100MHz, CDCl3) δ163.8,160.3,153.1,146.6,144.0,140.3,136.0,135.3,1 30.4,129.8,128.4,111.2,53.7,49.8,44.9,41.8,16.1; HRMS(EI-TOF)m / z:[M] + calcdfor C 17 H 18 ClN5O3S:407.0813; found:407.0816.

[0218] Example 27 2-chloro-5-(((E)-2-((Z)-1-nitro-2-(thien-3-yl)but-2-en-1-yl)imidazolidin-1-yl)methyl)thiazole

[0219]

[0220] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01 mmol) and Carreira ligand (rac)-L11 (0.04 mmol) were added to a 50 mL Schlenk flask dried with a heat gun. After the flask was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0 mL) was added and stirred at room temperature for 15 minutes, during which time the solution turned red. Racemic 1-(thiophen-3-yl)prop-2-en-1-ol (2.0 mmol) was then added, and the reaction mixture immediately turned light yellow. 2-Chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole (1.0 mmol) and trifluoroacetic acid (1.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature until the reaction of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was complete (monitored by TLC), and then extracted with saturated sodium bicarbonate solution and extracted three times with CH2Cl2. The organic phases were combined and washed once with saturated brine, then dried over anhydrous sodium sulfate, and the solvent was removed. The product was separated by column chromatography to obtain a light yellow solid. The intermediate was directly used in the next reaction without detection. The intermediate was dissolved in 10 mL of acetonitrile, DBU (4.0 mmol) was added, and the reaction was stirred at 60 ° C overnight. After removing the solvent, the product was separated by column chromatography to obtain a yellow solid. The product was slurried with isopropyl ether to obtain a light yellow solid with a yield of 66%. mp: 132–134 ° C; 1 H NMR (400MHz, CDCl3) δ9.97(brs,1H),7.31–7.24(m,2H),7.21(s,1H),7.18(dd,J=5.2,1.2Hz,1H),7.06(dd,J=2 .8,1.2Hz,1H),6.45(q,J=6.9Hz,1H),4.58(s,2H),3.85–3.72(m,2H),3.67–3.45(m,2H),1.77(d,J=6.8Hz,3H); 13 C NMR (100MHz, CDCl3) δ160.0,153.1,141.7,140.3,135.6,130.5,128.5,126.9,124.9,120.9,106.6,49.8,44.7,41.7,15.6; HRMS (EI-TOF) m / z: [M] + calcd for C 15 H 15 ClN4O2S2:382.0319; found:382.0329.

[0221] Example 28 (E)-2-((E)-2-methyl-1-nitrobut-2-en-1-yl)-1-(tetrahydrofuran-3-yl)methyl)imidazolidine

[0222]

[0223] Under nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol), Carreira ligand (rac)-L11 (0.04mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and then stirred at room temperature for 15 minutes, while the solution turned red. Racemic 3-butene-2-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. (E)-2-(nitromethylene)-1-(tetrahydrofuran-3-yl)methyl)imidazolidine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was continued to stir at room temperature until the (E)-2-(nitromethylene)-1-(tetrahydrofuran-3-yl)methyl)imidazolidine reaction was complete (monitored by TLC), the solvent was removed, and column chromatography was used to separate and obtain a light yellow solid. The intermediate was dissolved in 10 mL of tetrahydrofuran and potassium tert-butoxide (1.0 mmol) was added until the intermediate reacted completely. After removal of the solvent, column chromatography was performed to obtain a yellow solid. Slurrying with isopropyl ether gave a pale yellow solid in 47% yield. mp: 120–122°C; 1 H NMR(400MHz, CDCl3)δ9.84(brs,1H),5.51(q,J=6.9Hz,1H),3.89–3.62(m,7H),3.48–3.40(m,1H),3.31–3 .20(m,2H),2.52–2.39(m,1H),2.08–1.99(m,1H),1.91(s,3H),1.72(d,J=6.8Hz,3H),1.58–1.48(m,1H); 13 C NMR(100MHz, CDCl3)δ161.1,129.9,128.7,112.9,71.1,67.7,51.3,50.4,41.9,38.4,30.2,16.7,14.0; HRMS(EI-TOF)m / z:[M] + calcd for C 13 H 21 N3O3:267.1577; found:267.1586.

[0224] Example 29 (E)-2-((Z)-1-nitro-2-phenylbut-2-en-1-yl)-1-(tetrahydrofuran-3-yl)methyl)imidazolidine

[0225]

[0226] Under a nitrogen atmosphere, [Ir(cod)Cl]2 (0.01mmol) and Carreira ligand (rac)-L11 (0.004mmol) were added to a 50mL Schlenk bottle dried with a hot air drying gun. After the bottle was evacuated and backfilled with nitrogen, freshly distilled CH2Cl2 (10.0mL) was added and the mixture was stirred at room temperature for 15 minutes, during which time the solution turned red. Racemic 1-phenylpropyl-2-ene-1-ol (2.0mmol) was then added and the reaction mixture immediately turned light yellow. (E)-2-(nitromethylene)-1-(tetrahydrofuran-3-yl)methyl)imidazolidine (1.0mmol) and trifluoroacetic acid (1.0mmol) were added sequentially. The reaction mixture was continued to stir at room temperature until the (E)-2-(nitromethylene)-1-(tetrahydrofuran-3-yl)methyl)imidazolidine reaction was complete (monitored by TLC), the solvent was removed, and column chromatography was used to separate and obtain a light yellow solid. This intermediate was used directly in the next reaction without testing. The intermediate was dissolved in 10 mL of acetonitrile, and DBU (4.0 mmol) was added. The reaction was stirred at 60°C overnight. After removal of the solvent, column chromatography afforded a yellow solid, which was then slurried with isopropyl ether to afford a pale yellow solid in 57% yield. mp: 114–116°C; 1 H NMR (400MHz, CDCl3) δ10.09(brs,1H),7.36(d,J=7.6Hz,2H),7.32–7.27(m,2H),7.21(t,J=7.6Hz,1H),6.57–6.46(m,1H),3.83–3.73(m,2H) ),3.72–3.62(m,3H),3.61–3.49(m,2H),3.46–2.90(m,3H),2.33–2.16(m,1H),1.93–1.81(m,1H),1.78(d,J=6.8Hz,3H),1.38–1.10(m,1H); 13 C NMR (100MHz, CDCl3) δ161.1,139.4,133.2,130.5,128.8(2C),127.5,125.4(2C ),106.4,70.8,67.6,50.5,50.2,41.8,38.4,30.0,15.9; HRMS(EI-TOF)m / z:[M] + calcdfor C 18 H 23 N3O3:329.1734; found:329.1737.

[0227] Test Example: Insecticidal Activity Test of the Present Invention

[0228] Test Example 1 Insecticidal activity against aphids

[0229] Aphids, belonging to the order Homoptera, have piercing-sucking mouthparts and are common crop pests. Taking alfalfa aphid (Aphis craccivora) as an example, the immersion method was used for testing.

[0230] Procedure: Accurately weigh the sample, add N,N-dimethylformamide to a 10 g / L stock solution, and dilute to 100 mg / L with 0.2 mL / L Triton X-100 aqueous solution. Select several 7-day-old aphids and starve them in the dark for approximately one hour. Then, allow them to crawl onto broad bean seedlings until their mouthparts pierce the sprouts (2-3 hours). Once the wingless adult aphids have established a stable feeding pattern on the sprouts, immerse them, along with the sprouts, in a 100 mg / L solution. Remove them after 3 seconds. Repeat three times, remove the remaining solution with absorbent paper, transfer the aphids to a clean container, and maintain a constant temperature of 25°C. Three replicates are set up for each concentration. A 0.2 mL / L Triton X-100 aqueous solution is used as a control. After 48 hours of treatment, count the number of dead aphids and calculate the mortality rate (%): mortality (%) = (number of live aphids in the control - number of live aphids in the treatment) / number of live aphids in the control × 100%. The results are shown in the table below.

[0231] Test Example 2 Insecticidal activity against armyworms

[0232] Armyworm (Mythimna separata) belongs to the order Lepidoptera and has chewing mouthparts. It is a common crop pest and was tested using the spray method.

[0233] Cut 2cm wide corn leaves into 5cm long pieces and place the leaves with the back facing upwards on a Petri dish with moistened filter paper. Use a spray gun to evenly spray both sides of the leaves (spraying pressure: 10psi, equivalent to 0.7kg / cm 2 The leaves were air-dried in the dark and then inoculated with third-instar larvae of armyworms. The petri dishes were moved to a standard observation room (23-25°C, 40-60% relative humidity, 13 hours light / 11 hours dark). During the observation period, water was added to maintain leaf freshness. When the treated leaves were consumed by the test insects, fresh, untreated feed was added. Studies were conducted 72 hours after testing.

[0234] Table 1 Activity of compounds represented by general formula I

[0235]

[0236]

[0237]

[0238]

[0239] Test Example 3: Median lethality test on aphids

[0240] This experiment used the leaf dipping method. An aqueous solution of each compound was prepared, to which 0.2 mL / L of Triton X-100 was added as a surfactant and no more than 0.5 parts per million by volume of dimethyl sulfoxide (DMSO) was added as a cosolvent. The mixture was then diluted with 0.1% Triton X-100 (0.1 mg / L) to obtain a series of concentrations of 4, 2, 1, 0.5, 0.25, 0.125, and 0.062 mg / L. Several 7-day-old aphids were selected and starved in the dark for about an hour. They were then allowed to climb onto broad bean seedlings until their mouthparts pierced the bean sprouts (2-3 hours). After the wingless adult aphids had stably sucked on the bean sprouts, they were immersed in the corresponding concentration of the drug solution together with the bean sprouts. After 3 seconds, they were removed and repeated three times. The excess drug solution was absorbed with absorbent paper, and the aphids were transferred to a clean container and kept at a constant temperature of 25°C. Three parallel groups were set up for each concentration. The control was a 0.2 mL / L Triton X-100 aqueous solution. After 48 h of treatment, LC was calculated using SPSS software. 50 value.

[0241] Table 2 LC values ​​of the active compounds against alfalfa aphid 50 value

[0242]

[0243]

[0244] All documents mentioned in this application are incorporated herein by reference, just as if each document were incorporated herein by reference individually. It should also be understood that after reading the above teachings of the present invention, those skilled in the art may make various changes or modifications to the present invention, and that such equivalents also fall within the scope of the claims appended hereto.

Claims

1. A compound of formula (I), its optical isomers, cis-trans isomers, or pesticide-acceptable salts thereof: in: R 1 is a substituted or unsubstituted five-membered or six-membered heteroaryl group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, or a substituted or unsubstituted phenyl group, a substituted or unsubstituted five-membered or six-membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, wherein the substitution means that one or more H atoms on the group are independently replaced by a substituent selected from the group consisting of halogen, CN, C 1-8 Alkyl, C 1-8 Halogenated alkyl, C 1-8 Alkoxy or C 1-8 haloalkoxy; R 2 、R 3 and R 4 are each independently H, substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy, substituted or unsubstituted C 1-8 Alkoxy C 1-4 Alkyl, substituted or unsubstituted C 1-8 Alkoxy-carbonyl, allyl, benzyl, phenoxycarbonyl, substituted or unsubstituted C 2-8 Alkenyl-carbonyl, substituted or unsubstituted C 2-8 Alkynyl-carbonyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 3-8 Cycloalkyl-carbonyl, substituted or unsubstituted five-membered or six-membered heterocyclyl containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted five-membered or six-membered heterocyclyl-carbonyl containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted benzoyl, substituted or unsubstituted furancarbonyl, substituted or unsubstituted N,N-dimethylcarbonyl; wherein the substitution means that one or more H atoms on the group are independently substituted by substituents selected from the group consisting of halogen, halogenated or unsubstituted C 1-4 Alkyl, halogenated or unsubstituted C 2-4 Alkenyl, halogenated or unsubstituted C 2-4 Alkynyl, halogenated or unsubstituted C 1-4 Alkoxy and halogenated or unsubstituted C 1-4 alkyl-carbonyl; or R 2 With R 3 , or R 2 With R 4 Together they constitute substituted or unsubstituted -CH2-CH2-, substituted or unsubstituted -CH2-CH2-CH2-, substituted or unsubstituted -CH2-CH2-CH2-CH2- or substituted or unsubstituted -CH2-X-CH2-, wherein X is selected from NH, O and S; wherein the substitution refers to that one or more H atoms on the group are independently substituted by a substituent selected from the group consisting of H, halogen, substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy, substituted or unsubstituted C 1-8 Alkoxy-C 1-8 Alkyl, substituted or unsubstituted C 1-8 Alkoxy-carbonyl, substituted or unsubstituted allyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenoxycarbonyl, substituted or unsubstituted C 2-8 Alkenyl-carbonyl, substituted or unsubstituted C 2-8 Alkynyl-carbonyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted C 3-8 Cycloalkyl-carbonyl, substituted or unsubstituted benzoyl, substituted or unsubstituted furancarbonyl or substituted or unsubstituted N,N-dimethylcarbonyl, and the substitution means that one or more H atoms on the group are further independently substituted by a substituent selected from the group consisting of halogen, halogenated or unsubstituted C 1-4 Alkyl, halogenated or unsubstituted C 2-4 Alkenyl, halogenated or unsubstituted C 2-4 Alkynyl, halogenated or unsubstituted C 1-4 Alkoxy and halogenated or unsubstituted C 1-4 alkyl-carbonyl; R 5 is substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted 4-8 membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 6-10 Aryl (including benzo C 3-6 cycloalkyl or benzo 4-6 membered heterocyclic group), substituted or unsubstituted 5-10 heteroaryl groups (including benzo 5-6 membered heteroaryl groups) containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 1-4 Alkylene-Ra, wherein Ra is selected from the group consisting of substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted 4-8 membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 6-10 Aryl (including benzo C 3-6 cycloalkyl or benzo 4-6 membered heterocyclic group), substituted or unsubstituted 5-10 heteroaryl groups (including benzo 5-6 membered heteroaryl groups) containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur; wherein the substitution means that one or more H atoms on the group are independently substituted by a substituent selected from the following group: C 1-8 Alkyl, nitro, fluorine, chlorine, bromine, C 1-4 Alkoxy, C 1-4 Halogenated alkyl, C 1-4 Haloalkoxy, hydroxy, amino, -NH-C 1-4 Alkyl (such as methylamino, ethylamino), -N-(C 1-4 alkyl)2 (such as dimethylamino, diethylamino); and Z is nitro, cyano, C 2-6 Ester, trifluoromethyl, trifluoroacetyl, C 1-4 Alkoxyacyl, C 1-4 Alkyl-formyl or trifluoromethanesulfonyl.

2. The compound according to claim 1, wherein R 1 is a substituted or unsubstituted group consisting of phenyl, pyridyl, thiazolyl, pyrimidinyl, oxazolyl or tetrahydrofuranyl, wherein the substitution refers to one or more H atoms on the group being independently substituted by a substituent selected from the group consisting of halogen and C 1-4 Halogenated alkyl.

3. The compound according to claim 1, wherein R 2 With R 3 or R 2 With R 4 Together they constitute -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2- or -CH2-X-CH2-, wherein X is selected from NH, O and S, and the H atoms in -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2- or -CH2-X-CH2- are optionally replaced by halogen, C 1-4 Alkyl or halogenated C 1-4 Alkyl substitution.

4. The compound according to claim 1, wherein R 5 is substituted or unsubstituted C 1-8 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, substituted or unsubstituted 4-8 membered heterocyclic group containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted 5-10 heteroaryl containing 1-3 heteroatoms selected from nitrogen, oxygen and sulfur, or substituted or unsubstituted C 1-4 Alkylene-C 6-10 Aryl, wherein the substitution means that one or more H atoms on the group are independently substituted by a substituent selected from the group consisting of: C 1-4 Alkyl, nitro, fluorine, chlorine, bromine, C 1-4 Alkoxy, C 1-4 Haloalkyl, hydroxy, amino, methylamino, dimethylamino.

5. The compound according to claim 1, wherein The compound has the structure shown in general formula (II): Where R 1 and R 5 As defined above.

6. The compound according to claim 1, wherein The compound is selected from the group consisting of:

7. An agricultural composition comprising: The compound according to the first aspect of the present invention, its optical isomers, cis-trans isomers or pesticide-acceptable salts thereof; as well as Agrochemically acceptable carrier and / or excipient.

8. Use of the compound according to any one of claims 1 to 6, its optical isomers, cis-trans isomers or their pesticide-acceptable salts, and the agricultural composition according to claim 7 in the preparation of an insecticide for killing or preventing agricultural pests, sanitary pests and pests that endanger animal health.

9. A method for killing and / or preventing insects, which comprises applying the compound according to any one of claims 1 to 6, its optical isomers, cis-trans isomers or their pesticide-acceptable salts, or the agricultural composition according to claim 7 to a plant or animal that is or may be infested by an insect, or to the soil or environment surrounding the plant or animal.

10. A method for preparing the compound according to claim 1, comprising the steps of: (i) in the presence of an acid and a metal catalyst, a compound of formula A and a compound of formula B undergo a substitution reaction to obtain an intermediate of formula C; and (ii) in the presence of a base, the intermediate of formula C undergoes double bond isomerization reaction to obtain a compound of formula (I), Reaction formula (1): Reaction formula (2): Where R 1 、R 2 、R 3 、R 4 、R 5 and Z as defined in claim 1.

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