Diene Compounds with Insecticidal Activity, Their Preparation and Use

Abstract

The present invention discloses a diene compound having insecticidal activity, its preparation and use. The diene compound of the present invention has the structure shown in general formula I, and the definitions of each substituent are as described in the specification and claims. The diene compound of the present invention can improve the insecticidal activity of neonicotinoid compounds and / or broaden the insecticidal spectrum, and provide protection for growing and harvested crops from insect attack and infestation.

Description

Technical Field

[0001] The present invention relates to the field of pesticides, and relates to diene compounds having insecticidal activity, their preparation and uses, and more particularly to conjugated diene neonicotinoid insecticides, their preparation and uses. Technical Background

[0002] In the mid-1980s, Bayer developed the first neonicotinoid insecticide, imidacloprid, which became one of the most successful new insecticides. Neonicotinoid insecticides represented by imidacloprid have high insecticidal activity, a broad insecticidal spectrum, low toxicity to mammals and aquatic animals, good systemicity, appropriate field stability and environmental friendliness, and have become an important hot area in the creation of new pesticides. Subsequently, a series of neonicotinoid insecticides such as thiacloprid, clothianidin, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran were developed. Neonicotinoid insecticides have high insecticidal activity, a broad insecticidal spectrum, low toxicity to mammals and aquatic animals, and good systemic properties and appropriate field stability, and have become an important hot area in the creation of pesticides.

[0003] However, due to the relatively serious resistance problems caused by the excessive and frequent use of imidacloprid and the cross-resistance between neonicotinoid insecticides due to structural similarity; in addition, recent studies have shown that neonicotinoid insecticides have certain toxicity to bees; to a certain extent, this limits the application of such compounds and has become an important problem restricting the development of such compounds. At the same time, neonicotinoid insecticides are mainly highly effective against homopteran and coleopteran pests, and their relatively narrow insecticidal spectrum also limits the choice of pesticides in pest control.

[0004] Therefore, structurally modifying nitromethylene compounds with high activity to produce new and more effective insecticides, solving the resistance problems of neonicotinoid insecticides, expanding the insecticidal spectrum, and applying them to insecticides have become the technical problems to be solved by the present invention. Summary of the Invention

[0005] The object of the present invention is to provide a class of compounds for more efficient pest control and their preparation methods. The compounds of the present invention can improve the insecticidal activity of neonicotinoid compounds and / or expand the insecticidal spectrum.

[0006] Another object of the present invention is to provide protection for growing and harvested crops from insect attack and infestation.

[0007] In the first aspect of the present invention, there is provided a compound having the structure shown in General Formula I, or its optical isomers, cis-trans isomers, and agriculturally acceptable salts:

[0008]

[0009] Wherein: R 1is a substituted or unsubstituted five- or six-membered heterocyclic group containing nitrogen, oxygen and / or sulfur, or a substituted or unsubstituted phenyl group, wherein the substitution is with one or more substituents selected from the group consisting of: halogen, C 1-4 haloalkyl or C 1-4 haloalkoxy;

[0010] R 2 、R 3 and R 4 are each independently H, C 1-6 alkyl, allyl, benzyl, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy-carbonyl, phenoxycarbonyl, C 2-6 alkynyl-carbonyl, C 2-3 alkenyl-carbonyl, C 3-6 cycloalkyl-carbonyl, benzoyl, or benzoyl, furancarbonyl or N,N-dimethylcarbonyl substituted with one or more substituents selected from halogen atoms, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy and C 1-4 alkyl-carbonyl;

[0011] or R 2 combines with R 3 、or R 2 combines with R 4 to form -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 - or -CH 2 -XR-CH 2 -, where X is a heteroatom selected from N, O, S, and R is a substituent on the heteroatom, selected from H, C 1-6 alkyl, allyl, benzyl, phenyl, C 1-4 alkoxy-C 1-4 alkyl, C 1-4 alkoxy-carbonyl, phenoxycarbonyl, C 2-3 alkynyl-carbonyl, C 2-3 alkenyl-carbonyl, C 3-6 cycloalkyl-carbonyl, benzoyl, or benzoyl substituted with one or more substituents selected from halogen atoms, C 1-4 haloalkyl, C 1-8 saturated or C 2-8 unsaturated hydrocarbon group or C 1-8Alkoxy and C 1-4 benzoyl, furan carbonyl or N,N-dimethylcarbonyl substituted by a substituent of an alkyl-carbonyl;

[0012] R 5 is a substituted or unsubstituted C 1-8 alkyl, substituted or unsubstituted C 3-8 cycloalkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 1-4 alkylene-C 6-10 aryl, a substituted or unsubstituted five- or six-membered heterocyclic group containing nitrogen, oxygen and / or sulfur, and the substitution means having one or more substituents selected from the group consisting of: C 1-6 alkyl, nitro, fluorine, chlorine, bromine, C 1-6 alkoxy, C 1-6 haloalkyl, hydroxy, amino, methylamino, dimethylamino, or two substituents form a ring with the connected atoms;

[0013] Z is nitro, cyano, ester group, trifluoromethyl, trifluoroacetyl (-COCF 3 ), C 1-6 alkoxycarbonyl, C 1-6 alkyl-formyl, or trifluoromethanesulfonyl (-SO 2 CF 3 )

[0014] In another preferred example, R 1 is a substituted or unsubstituted group selected from the following: phenyl, pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuran, and oxazolyl, wherein the substitution is having one or more substituents selected from the group consisting of: halogen, C 1-4 haloalkyl.

[0015] In another preferred example, R 1 is selected from substituted or unsubstituted groups selected from the following: phenyl, pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuran, and the substitution is having one or more substituents selected from the group consisting of: fluorine, chlorine, bromine, C 1-4 fluoroalkyl (such as -CF 3 )

[0016] In another preferred example, R 2 , R 3 , R 4 are each independently hydrogen, C 1-4 alkyl, C 2-4 alkoxyalkyl, C 1-3 alkoxycarbonyl, or phenoxycarbonyl.

[0017] In another preferred example, R 2 and R 3 , or R2 Combined with R 4 to form -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 - or -CH 2 -XR-CH 2 -, where X is a heteroatom selected from N, O, S, and R is a C 1-4 alkyl group.

[0018] In another preferred example, R 4 is hydrogen.

[0019] In another preferred example, R 5 is a substituted or unsubstituted C 3-6 cycloalkyl group, a substituted or unsubstituted C 6-10 aryl group, a substituted or unsubstituted C 1-4 alkylene-C 6-10 aryl group, a substituted or unsubstituted five- or six-membered heterocyclic group containing nitrogen, oxygen, and / or sulfur, and the five- or six-membered heterocyclic group containing nitrogen, oxygen, and / or sulfur is a pyridyl group, a thiazolyl group, a pyrimidinyl group, tetrahydrofuran, or an oxazolyl group; the substitution means having one or more substituents selected from the following group: C 1-6 alkyl group, nitro group, fluorine, chlorine, bromine, C 1-6 alkoxy group, C 1-6 haloalkyl group, or two substituents form a ring with the connected atom.

[0020] In another preferred example, R 5 is a substituted or unsubstituted group: phenyl group, benzyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, thienyl group, thiazolyl group, triazolyl group, pyrrolyl group, pyridyl group, naphthyl group, furyl group, or quinoline, and the substitution means having 1, 2, or 3 substituents selected from the following group: C 1-6 alkyl group, nitro group, fluorine, chlorine, bromine, C 1-4 alkoxy group, C 1-4 haloalkyl group (such as -CF 3 , -CF(CF 3 )) 2 ), or two substituents form a ring with the connected atom.

[0021] In another preferred example, Z is a nitro group, a cyano group, a trifluoromethyl group, a trifluoroacetyl group, or a trifluoromethanesulfonyl group.

[0022] In another preferred example, Z is a nitro group.

[0023] In another preferred example, the compound has the structure shown in formula (II):

[0024]

[0025] In the formula, R 1 and R 5 are as defined above.

[0026] In another preferred example, R 1 is

[0027] In another preferred example, R 5 is a group listed in the table of the specification, such as (For the following groups without wavy lines, the horizontal line indicates the connection point) etc.

[0028] In another preferred example, the compound is any one of the compounds listed in the examples.

[0029] In the second aspect of the present invention, there is provided an agricultural composition, which comprises:

[0030] (a) The compound described in the first aspect or a pesticidally acceptable salt thereof; and

[0031] (b) A pesticidally acceptable carrier and / or excipient.

[0032] In another preferred example, the agricultural composition comprises 0.001 - 99.99% by weight of the compound described in the first aspect or a pesticidally acceptable salt thereof.

[0033] In another preferred example, the concentration of the compound having the structure shown in General Formula I or a pesticidally acceptable salt thereof is 10 - 800 ppm, preferably 100 - 500 ppm.

[0034] In another preferred example, the dosage form of the pesticidal composition is various conventional pesticidal dosage forms, such as bait.

[0035] In the third aspect of the present invention, there is provided the use of the compound described in the first aspect or the agricultural composition described in the second aspect for killing or preventing agricultural pests, sanitary pests and pests harmful to animal health; or as an insecticidal composition for killing or preventing agricultural pests, sanitary pests and pests harmful to animal health.

[0036] On the other hand, the present invention relates to the use of the above-mentioned compound or a pesticidally acceptable salt thereof, or a combination thereof in the preparation of an insecticidal composition.

[0037] In a fourth aspect of the present invention, there is provided a method for killing and / or preventing pests, which method comprises applying the compound described in the first aspect or a pesticidally acceptable salt thereof, or the insecticide composition described in the second aspect, to a plant body, an animal body, the soil or the environment around them that is suffering from or likely to suffer from pest damage.

[0038] The present invention also provides a method for controlling pests, which comprises applying an insecticidally effective amount (such as 10 - 800 ppm, more preferably 100 - 500 ppm) of the compound having the structure shown in General Formula I of the present invention to plant seeds, plant leaves and / or plant fruits that need to be applied, or to the place where the plants are growing or expected to grow.

[0039] In another preferred example, the pests are selected from: aphids, armyworms.

[0040] In a fifth aspect of the present invention, there is provided a method for preparing the compound described in the first aspect or a pesticidally acceptable salt thereof, which method comprises the steps of:

[0041] Reacting the compound shown in Formula a and the compound shown in Formula b to obtain a compound having the structure shown in General Formula I,

[0042]

[0043] wherein, R 1 、R 2 、R 3 、R 4 、R 5 and the definition of Z are as described above;

[0044] Y is O or S.

[0045] In another preferred example, in a reaction solvent, reacting the compound shown in Formula a and the compound shown in Formula b under the action of a catalyst to obtain a compound having the structure shown in General Formula I.

[0046] In another preferred example, the solvent is selected from one or more of the following groups: acetonitrile, methanol, tetrahydrofuran, ethanol, water, 1,4 - dioxane, acetone, dichloromethane, or 1,2 - dichloroethane.

[0047] In another preferred example, the catalyst is a protonic acid or a Lewis acid, and is selected from one or more of the following groups: hydrochloric acid, acetic acid, phosphoric acid, p - toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, boron trifluoride, aluminum trichloride, ferric trichloride, boric acid, silicic acid, nitric acid, magnesium chloride, cobalt chloride, strontium chloride, palladium chloride, or nickel chloride (boric acid is preferred).

[0048] In another preferred example, the reaction is carried out at - 20 - 80 °C; preferably, it is carried out at 15 - 55 °C.

[0049] In another preferred embodiment, the reaction time is 2 - 96 hours, preferably 24 - 48 hours.

[0050] In the present invention, an aromatic (hetero) ring and / or an alkane-substituted carbon-carbon double bond are introduced onto the nitro-methylene group of the existing nitro-methylene neonicotinoid insecticides to synthesize a novel conjugated diene neonicotinoid compound. This type of compound has significant insecticidal activity, a broad insecticidal spectrum, and strong stability.

[0051] 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 specifically described hereinafter (such as in the examples) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be elaborated one by one here. Detailed Embodiments

[0052] Through long-term and in-depth research, the inventors of the present invention retained the active pharmacophore nitro-methylene on the basis of the structure of the existing nitro-methylene neonicotinoid insecticides and introduced an aromatic (hetero) ring ethylene structure to synthesize a novel conjugated diene neonicotinoid compound. Insecticidal activity tests show that the compounds provided by the present invention have significant insecticidal activity and an expanded insecticidal spectrum. The preparation method is simple, and it is expected to be developed into a new type of pesticide with low toxicity, high efficiency, and environmental friendliness.

[0053] Group definition

[0054] As used herein, the term "C 1-6 alkyl" refers to a straight-chain or branched-chain alkyl having 1 - 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl or similar groups.

[0055] The term "C 1-4 alkoxy" refers to a straight-chain or branched-chain alkoxy having 1 - 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy or similar groups.

[0056] The term "halogen" refers to fluorine, chlorine, bromine, or iodine. The term "halogenated" refers to a group substituted by one or more of the above-mentioned halogen atoms, which may be the same or different, such as trifluoromethyl, pentafluoroethyl or similar groups.

[0057] The term "five- or six-membered heterocyclic group" refers to a five- or six-membered ring containing one or more heteroatoms selected from nitrogen, oxygen or sulfur, such as pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl or oxazolyl, etc.

[0058] Insecticidal activity of the active substance of the present invention

[0059] The term "active substance of the present invention" or "active compound of the present invention" refers to the compound of the present invention or its agrochemically acceptable salts, which have significant insecticidal activity, a broad insecticidal spectrum and strong stability.

[0060] The term "agrochemically acceptable salts" means that the anions of the salts are known and acceptable when forming pharmaceutically acceptable salts of the insecticide. The salts are preferably water-soluble. Suitable acid addition salts formed by the compounds of formula I include salts formed by inorganic acids, such as hydrochlorides, phosphates, sulfates, nitrates; and salts formed by organic acids, such as acetates, benzoates.

[0061] The active substance of the present invention can be used to control and eliminate a wide range of agricultural and forestry plant pests, pests of stored grains, pests harmful to animal health, and public health pests, etc. In this specification, "pesticide" is a general term for substances having the effect of controlling all the pests mentioned above. Examples of pests include, but are not limited to: Coleoptera insects, such as Sitophilus zeamais, Tribolium castaneum, Henosepilachna vigintioctomaculata, Henosepilachna sparsa, Agriotes fuscicollis, Anomala cupripes, Popillia quadriguttata, Monolepta hieroglyphica, Monochamus alternatus, Echinocnemus squameus, Basiprionota bisignata, Anoplophora chinensis, Apriona germari, Scolytus schevy, or Agriotes fuscicollis;Lepidopteran insects, such as Lymantria dispar, Malacosoma Neustria testacea, Diaphania perspectalis, Clania variegata, Cnidocampa flauescens, Dendrolimus punctatus, Orgyia gonostigma, Paranthrene tabaniformis, Spodoptera litura, Chilo suppressalis, Ostrinia nubilalis, Ephestia cautella, Adoxophyes orana, laspyresia splendana, Agrotis fucosa, Galleria mellonella, Plutella xylostella, Phyllocnistis citrella, or Mythimna separata; Homopteran insects, such as Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossydii, Lipaphis erysimipseudobrassicae, Stephanitis nashi, or Bemisia tabaci; Orthopteran insects, such as Blattella germanica, Periplaneta american, Gryllotalpa africana, or Locus migratoria; Isopteran insects, such as Solenopsis invicta, or Coptotermes formosanus; Dipteran insects, such as Musca domestica, Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis;Pests harmful to animal health, such as Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia blanchard, Ostertagia spp., protozoa (Trypanosoma enansi, Babesia bigemina), rabbit coccidia (Occidiosis), tapeworm, Coccidium, etc.

[0062] The compounds of the present invention are particularly effective against piercing-sucking, rasping-sucking, or chewing mouthpart pests such as aphids, leafhoppers, planthoppers, whiteflies, armyworms and other agricultural and forestry pests.

[0063] Insecticide composition containing the active substance of the present invention

[0064] The active substances of the present invention can be prepared into insecticide compositions by conventional methods. These active compounds can be made into conventional formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules; aerosols, natural and synthetic materials impregnated with the active substance, microcapsules in polymers, coating compounds for seeds, and formulations used together with combustion devices, such as smoking cartridges, smoking cans and smoking trays, as well as ULV cold mist and warm mist formulations.

[0065] These formulations can be produced by known methods. For example, the active compounds are mixed with extenders, which are liquid or liquefied gas or solid diluents or carriers, and surfactants, i.e., emulsifiers and / or dispersants and / or foam formers, can be optionally used. For example, when water is used as the extender, organic solvents can also be used as auxiliaries.

[0066] When a liquid solvent is used as the diluent or carrier, it is basically suitable, such as aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons, such as cyclohexane or paraffin, such as mineral oil fractions; alcohols, such as ethanol or ethylene glycol and their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or less common polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water.

[0067] As for the diluent or carrier of liquefied gas, it refers to a liquid that will become a gas under normal temperature and pressure, such as aerosol propellants, such as halogenated hydrocarbons, butane, propane, nitrogen, and carbon dioxide.

[0068] Solid carriers can be ground natural minerals, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silica, alumina, and silicates. Solid carriers for granules are crushed and graded natural zircon, such as calcite, marble, pumice, sepiolite, and dolomite, as well as granules synthesized from inorganic and organic coarse powders, and granules of organic materials such as sawdust, coconut shells, corn cobs, and tobacco stems, etc.

[0069] Nonionic and anionic emulsifiers can be used as emulsifiers and / or foam formers. For example, polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and albumin hydrolysis products. Dispersants include, for example, lignosulfite waste liquor and methyl cellulose.

[0070] Binders can be used in the formulations, such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules, or emulsions, such as gum arabic, polyvinyl alcohol, and polyvinyl acetate.

[0071] Colorants can be used, such as inorganic dyes, such as iron oxide, cobalt oxide, and Prussian blue; organic dyes, such as organic dyes, such as azo dyes or metal phthalocyanine dyes; and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, aluminum, and zinc, etc.

[0072] These active compounds of the present invention can be present as a mixture with other active compounds in their commercial formulations or in the use forms prepared from these formulations. These other active compounds are insecticides, baits, fungicides, acaricides, nematicides, fungicides, growth regulators, etc. Insecticides include, for example, organophosphates, carbamates, pyrethroids, chlorinated hydrocarbons, insect growth regulators, nereistoxin derivatives, pymetrozine, ryanodine receptor inhibitors, and substances produced by microorganisms, such as avermectin. Fungicides include triazoles, methoxyacrylates, plant disease resistance activators, or antiviral agents.

[0073] In addition, these active compounds of the present invention can also be present as a mixture with synergists in their commercial formulations. In the use forms prepared from these formulations, a synergist is a compound that enhances the action of the active compound. Since the active compound itself has activity, it may not be necessary to add a synergist.

[0074] These preparations generally contain 0.001 - 99.99% by weight, preferably 0.01 - 99.9% by weight, more preferably 0.05 - 90% by weight of the active compound of the present invention in the pesticidal composition. The concentration of the active compound in the use form prepared from the commercial preparation can vary within a wide range. The concentration of the active compound in the use form can range from 0.0000001 - 100% (g / v), preferably between 0.0001 and 1%.

[0075] Preparation method of the compound of the present invention

[0076] The target compounds of the present invention (as shown in general formula I) can be prepared by the following methods. However, the conditions of the method, such as reactants, solvents, catalysts, bases, the amounts of the compounds used, reaction temperature, reaction time required, etc. are not limited to the following explanations. The target compounds of the present invention can also be conveniently prepared by combining various synthesis methods described in this specification or known in the art, and such combinations are very easy for those skilled in the art to carry out.

[0077] The preparation method of the target compound of the present invention is: the target compound is obtained by reacting the compounds shown in formula a and formula b under the action of a catalyst.

[0078]

[0079] The catalyst is a protonic acid or a Lewis acid, selected from one or more of the following groups: hydrochloric acid, acetic acid, phosphoric acid, p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, boron trifluoride, aluminum trichloride, iron trichloride, boric acid, silicic acid, nitric acid, magnesium chloride, cobalt chloride, strontium chloride, palladium chloride, or nickel chloride (preferably boric acid).

[0080] The reaction solvents include but are not limited to acetonitrile, methanol, tetrahydrofuran, ethanol, water, 1,4-dioxane, acetone, dichloromethane, or 1,2-dichloroethane (preferably acetonitrile).

[0081] The reaction is carried out at -20 - 80 °C (preferably 15 - 55 °C).

[0082] The reaction time is 2 - 96 hours (preferably 24 - 48 hours).

[0083] The main advantages of the present invention include:

[0084] (1) The present invention provides a class of compounds with novel structures, and these compounds have significant pesticidal activities;

[0085] (2) The compounds provided by the present invention have a simple and easily accessible synthesis method.

[0086] (3) The compounds of the present invention have an expanded insecticidal spectrum and show significant insecticidal activity against Myzus persicae and Mythimna separata in particular.

[0087] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. The experimental methods without specific conditions noted in the following embodiments are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are calculated by weight.

[0088] Example 1 Synthesis of 2-chloro-5-(((E)-2-((E)-1-nitro-3-phenylallylidene)imidazolidin-1-yl)methyl)pyridine

[0089]

[0090] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.600 g (5 mmol) of phenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a pale yellow powder was obtained by column chromatography separation with a yield of 90%. mp = 141.1 - 141.8 °C; 1 HNMR (400 MHz, DMSO) δ 9.82 (s, 1H), 8.38 (d, J = 2.4 Hz, 1H), 7.83 (dd, J = 8.2, 2.4 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.34–7.20 (m, 4H), 7.14 (d, J = 16.4 Hz, 1H), 7.11–7.07 (m, 1H), 6.39 (d, J = 16.4 Hz, 1H), 4.53 (s, 2H), 3.96–3.73 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 162.85, 149.67, 149.18, 139.39, 138.10, 130.32, 128.58, 126.12, 125.15, 124.15, 121.02, 119.74, 105.41, 48.55, 47.88, 42.41. HRMS (ESI) C 18 H 17 N 4 O 2 Na 35 Cl (M+Na) + , calculated value: 379.0938, measured value: 379.0937; C 18 H 17 N 4 O 2 Na37 Cl(M + Na) + , Calculated value: 381.0908, Measured value: 381.0905.

[0091] Example 2 2-Chloro-5-(((E)-2-((E)-1-nitro-3-(o-tolyl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0092]

[0093] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.670 g (5 mmol) of 2-methylphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product was obtained as a pale yellow powder by column chromatography with a yield of 85%. mp = 148.6 - 149.2 °C; 1 H NMR (400 MHz, DMSO) δ 9.77 (s, 1H), 8.38 (d, J = 2.4 Hz, 1H), 7.82 (dd, J = 8.2, 2.4 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.29 (d, J = 7.6 Hz, 1H), 7.13–7.00 (m, 3H), 6.97 (d, J = 16.2 Hz, 1H), 6.56 (d, J = 16.2 Hz, 1H), 4.55 (s, 2H), 3.96–3.75 (m, 4H), 2.24 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 163.37, 149.60, 149.21, 139.26, 137.19, 133.98, 130.74, 130.11, 125.97, 125.75, 124.10, 123.62, 122.42, 116.80, 105.68, 48.72, 48.31, 42.45, 19.53. HRMS (ESI) C 19 H 19 N 4 O 2 Na 35 Cl(M + Na) + , Calculated value: 393.1094, Measured value: 393.1095; C 19 H 19 N 4 O 2 Na 37 Cl(M + Na) + , Calculated value: 395.1065, Measured value: 395.1069.

[0094] Example 3 2-Chloro-5-(((E)-2-((E)-1-nitro-3-(m-tolyl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0095]

[0096] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.670 g (5 mmol) of 3-methylbenzaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product was obtained as a pale yellow powder by column chromatography with a yield of 88%. mp = 135.2 - 135.7 °C; 1 H NMR (400 MHz, DMSO) δ 9.79 (s, 1H), 8.38 (d, J = 2.4 Hz, 1H), 7.83 (dd, J = 8.2, 2.4 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.14–7.01 (m, 4H), 6.91 (d, J = 7.2 Hz, 1H), 6.37 (d, J = 16.4 Hz, 1H), 4.53 (s, 2H), 3.92–3.76 (m, 4H), 2.25 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 167.80, 163.23, 149.63, 149.20, 139.30, 138.36, 137.48, 133.79, 133.52, 133.21, 132.63, 128.41, 124.15, 121.12, 105.27, 48.61, 45.14, 42.50, 20.96. HRMS (ESI) C 19 H 19 N 4 O 2 Na 35 Cl (M+Na) + , calculated value: 393.1094, measured value: 393.1093; C 19 H 19 N 4 O 2 Na 37 Cl (M+Na) + , calculated value: 395.1065, measured value: 395.1062.

[0097] Example 4 2-Chloro-5-(((E)-2-((E)-1-nitro-3-(p-tolyl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0098]

[0099] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.670 g (5 mmol) of 4-methylphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and a pure product in the form of a pale yellow powder was obtained by column chromatography with a yield of 91%. mp = 145.4 - 145.8 °C; 1 H NMR (400 MHz, DMSO) δ 9.78 (s, 1H), 8.37 (d, J = 2.0 Hz, 1H), 7.82 (dd, J = 8.2, 2.4 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.19–7.03 (m, 5H), 6.36 (d, J = 16.4 Hz, 1H), 4.52 (s, 2H), 3.95–3.72 (m, 4H), 2.27 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 163.27, 149.62, 149.26, 139.33, 135.69, 134.98, 130.67, 129.13, 125.00, 124.12, 120.56, 119.28, 105.21, 48.60, 48.25, 42.45, 20.68. HRMS (ESI) C 19 H 19 N 4 O 2 Na 35 Cl (M+Na) + , calculated value: 393.1094, measured value: 393.1093; C 19 H 19 N 4 O 2 Na 37 Cl (M+Na) + , calculated value: 395.1065, measured value: 395.1066.

[0100] Example 5 2-Chloro-5-(((E)-2-((E)-3-(3-methoxyphenyl)-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0101]

[0102] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.750 g (5 mmol) of 3-methoxyphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and the pure product was obtained as a pale yellow powder by column chromatography with a yield of 80%. mp = 132.4 - 132.9 °C; 1 H NMR (400 MHz, DMSO) δ 9.79 (s, 1H), 8.35 (d, J = 2.2 Hz, 1H), 7.83 (dd, J = 8.2, 2.4 Hz, 1H), 7.46 (d, J = 8.2 Hz, 1H), 7.30–7.27 (m, 1H), 7.11–7.03 (m, 2H), 6.88 (d, J = 8.2 Hz, 1H), 6.81 (t, J = 7.4 Hz, 1H), 6.60 (d, J = 16.4 Hz, 1H), 4.50 (s, 2H), 3.86–3.69 (m, 4H), 3.67 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 163.28, 155.64, 149.60, 149.19, 139.23, 130.33, 127.21, 126.63, 125.01, 124.23, 121.51, 120.48, 114.79, 111.10, 105.93, 55.29, 48.61, 48.11, 42.58. HRMS (ESI) C 19 H 19 N 4 O 3 Na 35 Cl (M+Na) + , calculated value: 409.1043, measured value: 409.1042; C 19 H 19 N 4 O 3 Na 37 Cl (M+Na) + , calculated value: 411.1014, measured value: 411.1018.

[0103] Example 6 2-chloro-5-(((E)-2-((E)-3-(2,6-dimethylphenyl)-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0104]

[0105] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.810 g (5 mmol) of 2,4,6-trimethylphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a pale yellow powder was obtained by column chromatography with a yield of 91%. mp = 155.1 - 155.7 °C; 1 H NMR (400 MHz, DMSO) δ 9.59 (s, 1H), 8.32 (d, J = 2.4 Hz, 1H), 7.81 (dd, J = 8.2, 2.4 Hz, 1H), 7.40 (d, J = 8.2 Hz, 1H), 7.31 (d, J = 7.4 Hz, 1H), 7.16–7.01 (m, 1H), 6.90 (d, J = 16.4 Hz, 1H), 6.52 (d, J = 16.4 Hz, 1H), 4.53 (s, 2H), 3.91–3.72 (m, 4H), 2.38 (s, 3H), 2.20 (s, 3H), 2.03 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 163.67, 149.62, 149.31, 139.27, 137.23, 133.97, 130.12, 125.95, 125.71, 124.13, 123.68, 122.44, 116.90, 105.66, 48.73, 48.31, 42.42, 20.91, 19.55, 18.92. HRMS (ESI) C 21 H 23 N 4 O 2 Na 35 Cl (M+Na) + , calculated value: 421.1407, measured value: 421.1408; C 21 H 23 N 4 O 2 Na 37 Cl (M+Na) + , calculated value: 423.1378, measured value: 423.1379.

[0106] Example 7 2-chloro-5-(((E)-2-((E)-1-nitro-3-(thiophen-2-yl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0107]

[0108] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiophene-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and the pure product was obtained as a yellowish-green powder by column chromatography with a yield of 84%. mp = 141.2 - 141.6 °C; 1 H NMR (400 MHz, DMSO) δ 9.79 (s, 1H), 8.39 (d, J = 2.4 Hz, 1H), 7.84 (dd, J = 8.2, 2.4 Hz, 1H), 7.52 (d, J = 8.2 Hz, 1H), 7.24 (d, J = 5.0 Hz, 1H), 6.96–6.92 (m, 1H), 6.91–6.83 (m, 2H), 6.65 (d, J = 16.0 Hz, 1H), 4.52 (s, 2H), 3.90–3.73 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.08, 149.65, 149.30, 144.31, 139.38, 130.55, 127.76, 124.13, 123.43, 122.70, 121.09, 112.84, 104.77, 48.58, 48.25, 42.46. HRMS (ESI) C 16 H 15 N 4 O 2 NaS 35 Cl (M+Na) + , calculated value: 385.0502, measured value: 385.0504; C 16 H 15 N 4 O 2 NaS 37 Cl (M+Na) + , calculated value: 387.0472, measured value: 387.0473.

[0109] Example 8 2-chloro-5-(((E)-2-((E)-3-(5-methylthiophen-2-yl)-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0110]

[0111] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.700 g (5 mmol) of 5-methylthiophene-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow-green powder was obtained by column chromatography with a yield of 87%. mp = 147.3 - 147.8 °C; 1 H NMR (400 MHz, DMSO) δ 9.71 (s, 1H), 8.33 (d, J = 2.4 Hz, 1H), 7.82 (dd, J = 8.2, 2.4 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.25 (d, J = 5.0 Hz, 1H), 6.93–6.88 (m, 1H), 6.91–6.83 (m, 1H), 6.63 (d, J = 16.0 Hz, 1H), 4.50 (s, 2H), 3.91–3.72 (m, 4H), 2.18 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 163.15, 149.66, 149.39, 144.38, 139.32, 130.45, 124.16, 123.41, 122.77, 121.06, 112.83, 105.27, 48.48, 48.23, 42.41, 20.15. HRMS (ESI) C 17 H 17 N 4 O 2 NaS 35 Cl (M+Na) + , calculated value: 399.0658, measured value: 399.0659; C 17 H 17 N 4 O 2 NaS 37 Cl (M+Na) + , calculated value: 401.0629, measured value: 401.0631.

[0112] Example 9 2-chloro-5-(((E)-2-((E)-3-(furan-2-yl)-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0113]

[0114] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.550 g (5 mmol) of furan-2-carbaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and the pure product in the form of a pale yellow powder was obtained by column chromatography with a yield of 90%. mp = 142.4 - 142.9 °C; 1 H NMR (400 MHz, DMSO) δ 9.80 (s, 1H), 8.41 (d, J = 2.2 Hz, 1H), 7.82 (dd, J = 8.2, 2.2 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.26 (d, J = 4.8 Hz, 1H), 6.98–6.93 (m, 1H), 6.90–6.82 (m, 2H), 6.60 (d, J = 16.2 Hz, 1H), 4.49 (s, 2H), 3.95–3.74 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.09, 149.66, 149.32, 144.32, 139.40, 130.52, 127.75, 124.03, 123.23, 122.58, 121.01, 112.80, 105.27, 48.48, 48.24, 42.43. HRMS (ESI) C 16 H 15 N 4 O 3 Na 35 Cl (M+Na) + , calculated value: 369.0730, measured value: 369.0731; C 16 H 15 N 4 O 3 Na 37 Cl (M+Na) + , calculated value: 371.0701, measured value: 371.0703.

[0115] Example 10 2-Chloro-5-(((E)-2-((E)-1-nitro-3-(1H-pyrrol-2-yl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0116]

[0117] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.545 g (5 mmol) of pyrrole-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and pure product in the form of a pale yellow powder was obtained by column chromatography separation, with a yield of 85%. mp = 149.8 - 150.7 °C; 1 H NMR (400 MHz, DMSO) δ 10.93 (s, 1H), 9.76 (s, 1H), 8.42 (d, J = 2.4 Hz, 1H), 7.84 (dd, J = 8.4, 2.4 Hz, 1H), 7.52 (d, J = 8.4 Hz, 1H), 7.25 (d, J = 4.8 Hz, 1H), 6.96–6.91 (m, 1H), 6.88–6.83 (m, 2H), 6.65 (d, J = 16.4 Hz, 1H), 4.56 (s, 2H), 3.99–3.78 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.19, 149.62, 149.36, 144.35, 139.41, 130.51, 127.69, 124.07, 123.23, 122.59, 121.02, 112.81, 104.99, 48.45, 48.22, 42.42. HRMS (ESI) C 16 H 16 N 5 O 2 Na 35 Cl (M+Na) + , calculated value: 368.0890, measured value: 368.0891; C 16 H 16 N 5 O 2 Na 37 Cl (M+Na) + , calculated value: 370.0861, measured value: 370.0862.

[0118] Example 11 2-Chloro-5-(((E)-2-((E)-1-nitro-3-(thiophen-3-yl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0119]

[0120] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiophene-3-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow-green powder was obtained by column chromatography separation, with a yield of 93%. mp = 146.2 - 146.6 °C; 1 H NMR (400 MHz, DMSO) δ 9.75 (s, 1H), 8.37 (d, J = 2.4 Hz, 1H), 7.83 (dd, J = 8.2, 2.4 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.44 (dd, J = 5.0, 3.0 Hz, 1H), 7.22–7.12 (m, 2H), 6.95 (d, J = 16.4 Hz, 1H), 6.46 (d, J = 16.4 Hz, 1H), 4.52 (s, 2H), 3.92–3.72 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.17, 149.63, 149.29, 141.09, 139.37, 130.62, 126.43, 124.53, 124.15, 121.40, 119.46, 114.69, 104.81, 48.54, 48.19, 42.44. HRMS (ESI) C 16 H 15 N 4 O 2 NaS 35 Cl (M+Na) + , calculated value: 385.0502, measured value: 385.0501; C 16 H 15 N 4 O 2 NaS 37 Cl (M+Na) + , calculated value: 387.0472, measured value: 387.0474.

[0121] Example 12 4-((1E,3E)-3-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ylidene)-3-nitro-1-yl)thiazole

[0122]

[0123] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.635 g (5 mmol) of thiazole-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and pure product in the form of a pale yellow powder was obtained by column chromatography separation, with a yield of 78%. mp = 161.2 - 161.8 °C; 1 H NMR (400 MHz, DMSO) δ 9.79 (s, 1H), 8.36 (d, J = 2.4 Hz, 1H), 7.85 (dd, J = 8.2, 2.4 Hz, 1H), 7.53 (d, J = 8.2 Hz, 1H), 7.48 (dd, J = 5.0, 3.0 Hz, 1H), 7.24–7.13 (m, 1H), 6.99 (d, J = 16.2 Hz, 1H), 6.47 (d, J = 16.2 Hz, 1H), 4.51 (s, 2H), 3.96–3.71 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.09, 149.62, 149.27, 141.19, 139.39, 130.61, 126.44, 124.18, 121.41, 119.56, 114.73, 104.85, 48.50, 48.22, 42.34. HRMS (ESI) C 15 H 14 N 5 O 2 NaS 35 Cl (M+Na) + , calculated value: 386.0454, measured value: 386.0455; C 15 H 14 N 5 O 2 NaS 37 Cl (M+Na) + , calculated value: 388.0425, measured value: 388.0426.

[0124] Example 13 2-chloro-5-(((E)-2-((E)-1-nitro-3-(4H-1,2,4-triazol-3-yl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0125]

[0126] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.555 g (5 mmol) of 4H-1,2,4-triazole-3-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and pure product in the form of a pale yellow powder was obtained by column chromatography separation, with a yield of 84%. mp = 159.8 - 160.7 °C; 1 H NMR (400 MHz, DMSO) δ 10.79 (s, 1H), 9.77 (s, 1H), 8.34 (d, J = 2.4 Hz, 1H), 7.86 (dd, J = 8.2, 2.4 Hz, 1H), 7.53 (d, J = 8.2 Hz, 1H), 7.27–7.14 (m, 1H), 6.98 (d, J = 16.2 Hz, 1H), 6.37 (d, J = 16.2 Hz, 1H), 4.50 (s, 2H), 3.97–3.72 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.11, 149.66, 149.19, 141.15, 139.43, 126.40, 124.19, 121.47, 119.53, 114.71, 104.77, 48.51, 48.24, 42.36. HRMS (ESI) C 14 H 14 N 7 O 2 Na 35 Cl (M+Na) + , calculated value: 370.0795, measured value: 370.0796; C 14 H 14 N 7 O 2 Na 37 Cl (M+Na) + , calculated value: 372.0766, measured value: 372.0767.

[0127] Example 14 2-chloro-5-(((E)-2-((E)-1-nitro-3-(pyridin-2-yl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0128]

[0129] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred until dissolved at room temperature. After 10 minutes, 0.605 g (5 mmol) of pyridine-2-carbaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and the pure product was obtained as a yellow powder by column chromatography with a yield of 81%. mp = 156.3 - 156.9 °C; 1 HNMR (400 MHz, DMSO) δ 9.85 (s, 1H), 8.40 (d, J = 2.4 Hz, 1H), 7.85 (dd, J = 8.2, 2.4 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.35–7.21 (m, 2H), 7.18 (d, J = 16.2 Hz, 1H), 7.14–7.09 (m, 2H), 6.34 (d, J = 16.2 Hz, 1H), 4.51 (s, 2H), 3.96–3.74 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.25, 149.77, 149.17, 139.36, 138.11, 136.40, 130.36, 128.58, 126.13, 125.19, 124.14, 121.03, 119.77, 105.42, 48.54, 47.82, 42.44. HRMS (ESI) C 17 H 16 N 5 O 2 Na 35 Cl (M+Na) + , calculated value: 380.0890, measured value: 380.0892; C 17 H 16 N 5 O 2 Na 37 Cl (M+Na) + , calculated value: 382.0861, measured value: 382.0862.

[0130] Example 15 2-chloro-5-(((E)-2-((E)-3-(5-chloropyridin-2-yl)-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0131] Take

[0132] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.775 g (5 mmol) of 5-chloro-2-pyridineacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 80%. mp = 163.5 - 164.6 °C; 1 H NMR (400 MHz, DMSO) δ 9.91 (s, 1H), 8.45 (d, J = 2.2 Hz, 1H), 7.84 (dd, J = 8.2, 2.2 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.35–7.22 (m, 2H), 7.17 (d, J = 16.4 Hz, 1H), 7.13–7.08 (m, 1H), 6.39 (d, J = 16.4 Hz, 1H), 4.52 (s, 2H), 3.95–3.73 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.15, 149.76, 149.18, 139.37, 138.11, 136.45, 130.33, 128.68, 126.16, 125.49, 125.14, 121.05, 119.78, 105.32, 48.64, 47.88, 42.45. HRMS (ESI) C 17 H 15 N 5 O 2 Na 35 Cl 2 (M+Na) + , calculated value: 414.0500, measured value: 414.0501; C 17 H 15 N 5 O 2 Na 35 Cl 37 Cl(M+Na) + , calculated value: 416.0471, measured value: 416.0472; C 17 H 15 N 5 O 2 Na 37 Cl 2 (M+Na) + , calculated value: 418.0508, measured value: 418.0507.

[0133] Example 16 2-chloro-5-(((E)-2-((E)-3-cyclohexyl-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0134]

[0135] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of cyclohexaneacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 88%. mp = 153.2 - 153.9 °C; 1 HNMR(400 MHz, DMSO) δ 9.54 (s, 1H), 8.34 (d, J = 2.4 Hz, 1H), 7.77 (dd, J = 8.2, 2.4 Hz, 1H), 7.52 (d, J = 8.2 Hz, 1H), 6.17 (dd, J = 16.2, 1.0 Hz, 1H), 5.41 (dd, J = 16.2, 6.8 Hz, 1H), 4.52 (s, 2H), 3.83–3.63 (m, 4H), 1.87–1.76 (m, 1H), 1.64–1.53 (m, 4H), 1.29–0.98 (m, 4H), 0.96–0.84 (m, 2H). 13 C NMR(101 MHz, DMSO) δ 163.02, 149.47, 148.92, 138.94, 131.11, 130.54, 124.10, 119.76, 104.80, 48.95, 48.71, 42.36, 40.52, 32.58, 25.63, 25.51. HRMS(ESI) C 18 H 23 N 4 O 2 Na 35 Cl (M+Na) + , calculated value: 385.1407, measured value: 385.1408; C 18 H 23 N 4 O 2 Na 37 Cl (M+Na) + , calculated value: 387.1378, measured value: 387.1378.

[0136] Example 17 2-chloro-5-(((E)-2-((E)-3-cyclopentyl-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0137]

[0138] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred until dissolved at room temperature. After 10 minutes, 0.560 g (5 mmol) of cyclopentaneacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 84%. mp = 139.9 - 140.6 °C; 1 HNMR (400 MHz, DMSO) δ 9.59 (s, 1H), 8.44 (d, J = 2.4 Hz, 1H), 7.78 (dd, J = 8.2, 2.4 Hz, 1H), 7.55 (d, J = 8.2 Hz, 1H), 6.18 (d, J = 16.4 Hz, 1H), 5.81 (d, J = 16.4 Hz, 1H), 4.51 (s, 2H), 3.93–3.75 (m, 4H), 1.88–1.76 (m, 1H), 1.63–1.52 (m, 4H), 1.27–0.96 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.32, 149.48, 148.91, 138.92, 131.14, 130.56, 124.10, 119.79, 104.88, 48.85, 48.72, 42.46, 40.42, 32.68, 25.66. HRMS (ESI) C 17 H 21 N 4 O 2 Na 35 Cl (M+Na) + , calculated value: 371.1251, measured value: 371.1252; C 17 H 21 N 4 O 2 Na 37 Cl (M+Na) + , calculated value: 373.1221, measured value: 373.1222.

[0139] Example 18 2-chloro-5-(((E)-2-((E)-3-(3-methoxyphenyl)-1-nitroallylidene)imidazolidin-1-yl)methyl)thiazole

[0140]

[0141] 0.520 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was added to 20 ml of acetonitrile and stirred until dissolved at room temperature. After 10 minutes, 0.750 g (5 mmol) of 3-methoxyphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 82%. mp = 127.6 - 128.1 °C; 1 H NMR (400 MHz, DMSO) δ 9.64 (s, 1H), 7.67 (s, 1H), 7.40 (dd, J = 7.6, 1.2 Hz, 1H), 7.18–7.07 (m, 2H), 6.95 (d, J = 8.0 Hz, 1H), 6.88 (t, J = 7.4 Hz, 1H), 6.75 (d, J = 16.6 Hz, 1H), 4.66 (s, 2H), 3.86–3.79 (m, 4H), 3.79 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 162.66, 155.67, 151.61, 141.74, 134.75, 127.16, 127.02, 124.98, 121.75, 120.58, 115.34, 111.15, 106.05, 55.34, 48.19, 44.33, 42.28. HRMS (ESI) C 17 H 18 N 4 O 3 S 35 Cl (M + H) + , calculated value: 393.0788, measured value: 393.0787; C 17 H 18 N 4 O 3 S 37 Cl (M + H) + , calculated value: 395.0759, measured value: 395.0756.

[0142] Example 19 2-Chloro-5-(((E)-2-((E)-3-cyclohexyl-1-nitroallylidene)imidazolidin-1-yl)methyl)thiazole

[0143]

[0144] 0.520 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of cyclohexaneacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 87%. mp = 128.3 - 128.7 °C; 1 HNMR(400MHz,DMSO)δ9.39(s,1H),7.66(s,1H),6.25(dd,J=16.2,0.8Hz,1H),5.54(dd,J=16.2,6.8Hz,1H),4.64(s,2H),3.79–3.64(m,4H),2.01–1.90(m,1H),1.70–1.62(m,4H),1.27–0.99(m,6H). 13 C NMR(101MHz,DMSO)δ162.34,151.20,141.30,135.20,131.30,119.67,105.07,48.39,44.52,42.20,40.72,32.66,25.66,25.52.HRMS(ESI)C 16 H 21 N 4 O 2 NaS 35 Cl(M+Na) + , calculated value: 391.0971, measured value: 391.0972; C 16 H 21 N 4 O 2 NaS 37 Cl(M+Na) + , calculated value: 393.0942, measured value: 393.0947.

[0145] Example 20 2-chloro-5-(((E)-2-((E)-1-nitro-3-(thiophen-2-yl)allylidene)imidazolidin-1-yl)methyl)thiazole

[0146]

[0147] 0.520 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiazole-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a dark green powder was obtained by column chromatography with a yield of 80%. mp = 133.3 - 133.9 °C;1 1H NMR (400 MHz, DMSO) δ 9.68 (s, 1H), 7.70 (s, 1H), 7.27 (d, J = 5.0 Hz, 1H), 6.99–6.94 (m, 1H), 6.94–6.86 (m, 2H), 6.76 (d, J = 16.0 Hz, 1H), 4.64 (s, 2H), 3.88–3.72 (m, 4H). 13 13C NMR (101 MHz, DMSO) δ 162.43, 151.69, 144.30, 141.82, 134.66, 127.81, 123.61, 122.88, 121.07, 113.72, 105.02, 48.19, 44.32, 42.30. HRMS (ESI) C 14 H 13 N 4 O 2 NaS 2 35 Cl (M + Na) + , calculated: 391.0066, found: 391.0067; C 14 H 13 N 4 O 2 NaS 2 37 Cl (M + Na) + , calculated: 393.0037, found: 393.0040.

[0148] Example 21 2-Chloro-5-(((E)-2-((E)-3-(5-methylthiophen-2-yl)-1-nitroallylidene)imidazolidin-1-yl)methyl)thiazole

[0149]

[0150] 0.520 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.710 g (5 mmol) of 4-methylthiazole-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 85%. mp = 137.7 - 138.3 °C; 1 1H NMR (400 MHz, DMSO) δ 9.70 (s, 1H), 7.71 (s, 1H), 6.99–6.94 (m, 1H), 6.94–6.86 (m, 2H), 6.78 (d, J = 16.0 Hz, 1H), 4.66 (s, 2H), 3.89–3.71 (m, 4H), 1.86 (s, 3H).13 C NMR (101 MHz, DMSO) δ 162.49, 152.19, 144.50, 141.92, 134.65, 127.82, 123.65, 122.93, 121.01, 113.81, 105.13, 48.30, 44.22, 42.31, 15.32. HRMS (ESI) C 15 H 15 N 4 O 2 NaS 2 35 Cl (M+Na) + , calculated value: 405.0223, measured value: 405.0224; C 15 H 15 N 4 O 2 NaS 2 37 Cl (M+Na) + , calculated value: 407.0193, measured value: 407.0194.

[0151] Example 22 2-Chloro-5-(((E)-2-((E)-3-(furan-2-yl)-1-nitroallylidene)imidazolidin-1-yl)methyl)thiazole

[0152]

[0153] 0.520 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)thiazole was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.550 g (5 mmol) of furan-2-carboxaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 82%. mp = 140.3 - 140.9 °C; 1 HNMR (400 MHz, DMSO) δ 9.65 (s, 1H), 7.71 (s, 1H), 7.26 (d, J = 5.2 Hz, 1H), 6.98–6.92 (m, 1H), 6.91–6.82 (m, 2H), 6.74 (d, J = 16.0 Hz, 1H), 4.60 (s, 2H), 3.87–3.73 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 162.44, 151.79, 144.35, 141.85, 134.64, 127.80, 123.63, 122.88, 121.12, 113.76, 105.01, 48.22, 44.35, 42.28. HRMS (ESI) C 14H 13 N 4 O 3 NaS 35 Cl(M + Na) + , Calculated value: 375.0295, Measured value: 375.0296; C 14 H 13 N 4 O 3 NaS 37 Cl(M + Na) + , Calculated value: 377.0265, Measured value: 377.0267.

[0154] Example 23 2 - Chloro - 5 - (((E)-2 - ((E)-3 - 2,4,6 - trimethylphenyl - 1 - nitroallylidene)imidazolidin - 1 - yl)methyl)thiazole

[0155]

[0156] Dissolve 0.520 g (2 mmol) of 2 - chloro - 5 - ((2 - (nitromethylene)imidazolidin - 1 - yl)methyl)thiazole in 20 ml of acetonitrile and stir to dissolve at room temperature. After 10 minutes, slowly add dropwise 0.810 g (5 mmol) of 2,4,6 - trimethylphenylacetaldehyde. After reacting for 24 hours, remove the solvent and separate by column chromatography to obtain a pure yellow powder with a yield of 89%. mp = 147.0 - 147.6 °C; 1 H NMR(400 MHz, DMSO) δ 9.66(s, 1H), 7.74(s, 1H), 7.26(d, J = 5.0 Hz, 1H), 7.18–7.02(m, 2H), 6.75(d, J = 16.0 Hz, 1H), 4.59(s, 2H), 3.88–3.72(m, 4H), 2.60(s, 9H). 13 C NMR(101 MHz, DMSO) δ 163.04, 151.89, 144.32, 141.83, 134.67, 133.10, 132.88, 127.80, 123.63, 122.88, 121.12, 113.76, 105.11, 48.24, 44.34, 42.26, 22.11, 21.28, 20.11. HRMS(ESI) C 19 H 21 N 4 O 2 NaS 35 Cl(M + Na) + , Calculated value: 427.0971, Measured value: 427.0972; C 19 H 21 N4 O 2 NaS 37 Cl(M+Na) + , Calculated value: 429.0942, Measured value: 429.0944.

[0157] Example 24 (E)-2-((E)-1-Nitro-3-(thiophen-2-yl)allylidene)-1-((tetrahydrofuran-3-yl)methyl)imidazolidine

[0158]

[0159] 0.426 g (2 mmol) of (2-(nitromethylene)-1-((tetrahydrofuran-3-yl)methyl)imidazolidine) was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiazole-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography separation with a yield of 80%. mp = 131.1 - 131.9 °C; 1 HNMR(400 MHz, DMSO) δ 9.58 (s, 1H), 7.26 (d, J = 5.0 Hz, 1H), 7.18–7.02 (m, 3H), 6.76 (d, J = 16.0 Hz, 1H), 4.59 (s, 2H), 4.26–4.05 (m, 4H), 3.88–3.72 (m, 4H), 2.31 (m, 1H), 1.63 (m, 2H). 13 C NMR(101 MHz, DMSO) δ 151.69, 144.31, 141.86, 134.68, 132.84, 127.85, 113.73, 105.21, 80.16, 78.55, 48.24, 44.32, 42.26, 33.11, 20.28. HRMS(ESI) C 15 H 19 N 3 O 3 NaS(M+Na) + , Calculated value: 344.1045, Measured value: 344.1046.

[0160] Example 25 (E)-2-((E)-1-Nitro-3-(m-tolyl)allylidene)-1-((tetrahydrofuran-3-yl)methyl)imidazolidine

[0161]

[0162] 0.426 g (2 mmol) of (2-(nitromethylene)-1-(tetrahydrofuran-3-yl)methyl)imidazolidine was added to 20 ml of acetonitrile and stirred until dissolved at room temperature. After 10 minutes, 0.670 g (5 mmol) of 3-methylphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 92%. mp = 134.4 - 135.3 °C; 1 HNMR(400 MHz, DMSO) δ 9.61 (s, 1H), 7.35 (d, J = 5.0 Hz, 1H), 7.22 (d, J = 4.8 Hz, 1H), 7.19–7.01 (m, 3H), 6.68 (d, J = 16.0 Hz, 1H), 4.53 (s, 2H), 4.21–4.02 (m, 4H), 3.86–3.71 (m, 4H), 2.31 (m, 1H), 2.11 (s, 3H), 1.62 (m, 2H). 13 CNMR(101 MHz, DMSO) δ 152.65, 144.30, 141.76, 134.63, 134.26, 133.66, 132.84, 127.82, 113.71, 105.11, 80.12, 78.59, 48.34, 44.36, 42.29, 33.18, 20.33, 15.81. HRMS(ESI)C 18 H 23 N 3 O 3 Na(M + Na) + , calculated value: 352.1637, measured value: 352.1638.

[0163] Example 26 5-(((E)-2-((E)-1-nitro-3-(thiophen-2-yl)allylidene)imidazolidin-1-yl)methyl)-2-(trifluoromethyl)pyridine

[0164]

[0165] 0.576 g (2 mmol) of 2-(trifluoromethyl)-5-((2-(nitromethylene)imidazolin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred until dissolved at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiazole-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 82%. mp = 145.2 - 145.8 °C; 11H NMR (400 MHz, DMSO) δ 9.61 (s, 1H), 7.88 (m, 2H), 7.25 (d, J = 5.0 Hz, 1H), 7.19–7.02 (m, 4H), 6.72 (d, J = 16.0 Hz, 1H), 4.49 (s, 2H), 3.86–3.68 (m, 4H). 13 13C NMR (101 MHz, DMSO) δ 160.25, 151.69, 144.31, 143.28, 143.01, 141.86, 134.68, 134.54, 134.21, 132.84, 127.85, 113.73, 105.21, 80.16, 48.24, 44.32, 42.26. HRMS (ESI) C 17 H 15 N 4 O 2 NaSF 3 (M + Na) + , calculated: 419.0766, found: 419.0767.

[0166] Example 27 5 - (((E)-2 - ((E)-1 - nitro - 3 - (m - methylphenyl)allylidene)imidazolidin - 1 - yl)methyl)-2 - (trifluoromethyl)pyridine

[0167] 0.576 g (2 mmol) of 2 - (trifluoromethyl)-5 - ((2 - (nitromethylene)imidazolin - 1 - yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.670 g (5 mmol) of 3 - methylbenzaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 85%. mp = 149.1 - 150.1 °C; 1 1H NMR (400 MHz, DMSO) δ 9.67 (s, 1H), 7.79 (m, 2H), 7.26 (d, J = 5.0 Hz, 1H), 7.19–7.02 (m, 5H), 6.74 (d, J = 16.0 Hz, 1H), 4.51 (s, 2H), 3.91–3.78 (m, 4H), 2.79 (s, 3H). 13 13C NMR (101 MHz, DMSO) δ 160.25, 151.72, 144.33, 143.27, 143.01, 141.86, 134.68, 134.54, 134.21, 133.95, 133.64, 132.84, 127.85, 113.73, 105.21, 80.16, 48.24, 44.32, 42.26, 20.15. HRMS (ESI) C20 H 19 N 4 O 2 NaF 3 (M + Na) + , Calculated value: 427.1358, Measured value: 427.1359.

[0168] Example 28 (E)-1-((6-chloropyridin-3-yl)methyl)-2-((E)-1-nitro-3-(m-tolyl)allylidene)hexahydropyrimidine

[0169]

[0170] 0.536 g (2 mmol) of 1-(6-chloro-3-picolyl)-2-nitromethylenehexahydropyrimidine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.670 g (5 mmol) of 3-methylphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 86%. mp = 144.2 - 144.9 °C; 1 HNMR(400 MHz, DMSO) δ 9.77 (s, 1H), 8.36 (d, J = 2.2 Hz, 1H), 7.86 (dd, J = 8.2, 2.2 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.16–7.05 (m, 4H), 6.91 (d, J = 7.2 Hz, 1H), 6.44 (d, J = 16.4 Hz, 1H), 4.52 (s, 2H), 3.91–3.78 (m, 4H), 2.35 (s, 3H), 1.99–1.89 (m, 2H). 13 C NMR(101 MHz, DMSO) δ 167.80, 163.23, 149.63, 149.20, 139.30, 138.36, 137.48, 133.79, 133.52, 133.21, 132.63, 128.41, 124.15, 121.12, 105.27, 48.61, 45.45, 45.14, 42.50, 20.96. HRMS(ESI) C 20 H 21 N 4 O 2 Na 35 Cl (M + Na) + , Calculated value: 407.1251, Measured value: 407.1252; C 20 H 21 N 4 O 2 Na 37 Cl (M + Na)+ , Calculated value: 409.1221, measured value: 409.1222.

[0171] Example 29 (E)-1-((6-chloropyridin-3-yl)methyl)-2-((E)-1-nitro-3-(thiophen-2-yl)allylidene)hexahydropyrimidine

[0172]

[0173] 0.536 g (2 mmol) of 1-(6-chloro-3-methylpyridinyl)-2-nitromethylenehexahydropyrimidine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiophene-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellowish-green powder was obtained by column chromatography with a yield of 90%. mp = 132.2 - 133.1 °C; 1 HNMR (400 MHz, DMSO) δ 9.76 (s, 1H), 8.39 (d, J = 2.4 Hz, 1H), 7.84 (dd, J = 8.2, 2.4 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.45 (dd, J = 5.0, 3.0 Hz, 1H), 7.22–7.12 (m, 2H), 6.85 (d, J = 16.4 Hz, 1H), 6.46 (d, J = 16.4 Hz, 1H), 4.50 (s, 2H), 3.92–3.72 (m, 4H), 1.97–1.87 (m, 2H). 13 C NMR (101 MHz, DMSO) δ 163.17, 149.63, 149.29, 141.09, 139.37, 130.62, 126.43, 124.53, 124.15, 121.40, 119.46, 114.69, 104.81, 48.54, 48.19, 48.01, 42.44. HRMS (ESI) C 17 H 17 N 4 O 2 NaS 35 Cl (M+Na) + , Calculated value: 399.0658, measured value: 399.0659; C 17 H 17 N 4 O 2 NaS 37 Cl (M+Na) + , Calculated value: 401.0629, measured value: 401.0630.

[0174] Example 30 (1E,3E)-N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N'-methyl-2-nitro-4-(thiophen-2-yl)buta-1,3-diene-1,1-diamine

[0175]

[0176] 0.540 g (2 mmol) of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N-methyl-2-nitroethene-1,1-diamine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiophene-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed, and the pure product in the form of a yellow-green powder was obtained by column chromatography separation, with a yield of 78%. mp = 121.2 - 121.9 °C; 1 H NMR (400 MHz, DMSO) δ 9.78 (s, 1H), 8.32 (d, J = 2.4 Hz, 1H), 7.80 (dd, J = 8.2, 2.4 Hz, 1H), 7.54 (d, J = 8.2 Hz, 1H), 7.24 (d, J = 5.0 Hz, 1H), 6.96–6.92 (m, 1H), 6.91–6.83 (m, 2H), 6.62 (d, J = 16.0 Hz, 1H), 4.53 (s, 2H), 3.24 (m, 2H), 2.10 (m, 3H), 1.45 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 163.18, 149.67, 149.32, 144.30, 139.35, 130.56, 127.76, 124.15, 123.44, 122.71, 121.04, 112.82, 104.97, 48.48, 28.25, 24.46, 15.26. HRMS (ESI) C 17 H 19 N 4 O 2 NaS 35 Cl (M+Na) + , calculated value: 401.0815, measured value: 401.0816; C 17 H 19 N 4 O 2 NaS 37 Cl (M+Na) + , calculated value: 403.0785, measured value: 403.0786.

[0177] Example 31 (1E,3E)-N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N'-methyl-2-nitro-4-(m-tolyl)buta-1,3-diene-1,1-diamine

[0178]

[0179] 0.540 g (2 mmol) of N-((6-chloropyridin-3-yl)methyl)-N-ethyl-N-methyl-2-nitroethene-1,1-diamine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.670 g (5 mmol) of 3-methylphenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product was obtained as a yellow powder by column chromatography with a yield of 81%. mp = 124.2 - 124.9 °C; 1 H NMR (400 MHz, DMSO) δ 9.74 (s, 1H), 8.38 (d, J = 2.4 Hz, 1H), 7.86 (dd, J = 8.2, 2.4 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.14–7.02 (m, 4H), 6.88 (d, J = 7.2 Hz, 1H), 6.49 (d, J = 16.4 Hz, 1H), 4.53 (s, 2H), 3.25 (m, 2H), 2.14 (m, 3H), 2.35 (s, 3H), 1.46 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 167.83, 163.26, 149.64, 149.21, 139.34, 138.37, 137.48, 133.79, 133.53, 133.21, 132.63, 128.41, 124.15, 121.12, 105.19, 48.61, 25.45, 22.14, 20.50, 15.96. HRMS (ESI) C 20 H 23 N 4 O 2 Na 35 Cl (M+Na) + , calculated value: 409.1407, measured value: 409.1408; C 20 H 23 N 4 O 2 Na 37 Cl (M+Na) + , calculated value: 411.1378, measured value: 411.1379.

[0180] Example 32 2-Chloro-5-(((E)-2-((E)-1-nitro-3-(4-nitrophenyl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0181]

[0182] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.825 g (5 mmol) of 4-nitrobenzaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a pale yellow powder was obtained by column chromatography with a yield of 82%. mp = 139.8 - 140.6 °C; 1 H NMR (400 MHz, DMSO) δ 9.77 (s, 1H), 8.35 (d, J = 2.0 Hz, 1H), 7.81 (dd, J = 8.2, 2.4 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.18–7.01 (m, 5H), 6.35 (d, J = 16.4 Hz, 1H), 4.50 (s, 2H), 3.94–3.73 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.29, 149.58, 149.25, 139.34, 135.66, 134.88, 130.61, 129.17, 125.04, 124.22, 120.46, 119.23, 105.20, 48.61, 48.35, 42.49. HRMS (ESI) C 18 H 16 N 5 O 4 Na 35 Cl (M+Na) + , calculated value: 424.0789, measured value: 424.0790; C 18 H 16 N 5 O 4 Na 37 Cl (M+Na) + , calculated value: 426.0759, measured value: 426.0761.

[0183] Example 33 2-Chloro-5-(((E)-2-((E)-3-(4-fluorophenyl)-1-nitroallylidene)imidazolidin-1-yl)methyl)pyridine

[0184]

[0185] 0.508 g (2 mmol) of 2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.690 g (5 mmol) of 4-fluorophenylacetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow powder was obtained by column chromatography with a yield of 88%. mp = 122.5 - 123.2 °C; 1 HNMR (400 MHz, DMSO) δ 9.75 (s, 1H), 8.32 (d, J = 2.2 Hz, 1H), 7.82 (dd, J = 8.4, 2.2 Hz, 1H), 7.52 (d, J = 8.4 Hz, 1H), 7.17–7.01 (m, 5H), 6.32 (d, J = 16.4 Hz, 1H), 4.51 (s, 2H), 3.97–3.75 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.31, 149.54, 149.29, 139.35, 135.68, 134.85, 130.61, 129.14, 125.14, 124.18, 120.44, 119.33, 105.21, 48.62, 48.32, 42.44. HRMS (ESI) C 18 H 16 N 4 O 2 Na 35 ClF (M+Na) + , calculated value: 397.0844, measured value: 397.0845; C 18 H 16 N 4 O 2 Na 37 ClF (M+Na) + , calculated value: 399.0814, measured value: 399.0815.

[0186] Example 34 (2E,3E)-2-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ylidene)-4-(thiophen-2-yl)vinyl-3-acetonitrile

[0187]

[0188] 0.468 g (2 mmol) of (E)-2-(1-((6-chloropyridin-3-yl)methyl)imidazolin-2-ylidene)acetonitrile was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiophene-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product was obtained as a yellowish-green powder by column chromatography with a yield of 85%. mp = 137.2 - 137.9 °C; 1 H NMR (400 MHz, DMSO) δ 9.81 (s, 1H), 8.38 (d, J = 2.2 Hz, 1H), 7.85 (dd, J = 8.2, 2.2 Hz, 1H), 7.50 (d, J = 8.2 Hz, 1H), 7.22 (d, J = 5.0 Hz, 1H), 6.97–6.93 (m, 1H), 6.90–6.83 (m, 2H), 6.64 (d, J = 16.0 Hz, 1H), 4.51 (s, 2H), 3.89–3.72 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.18, 149.64, 149.31, 144.32, 139.35, 130.45, 128.55, 127.76, 124.14, 123.42, 122.71, 121.03, 112.80, 104.75, 48.49, 48.20, 42.41. HRMS (ESI) C 17 H 15 N 4 NaS 35 Cl (M+Na) + , calculated value: 365.0604, measured value: 365.0605; C 17 H 15 N 4 NaS 37 Cl (M+Na) + , calculated value: 367.0574, measured value: 367.0575.

[0189] Example 35 (3E,4E)-3-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ylidene)-1,1,1-trifluoro-5-(thiophen-2-yl)pent-4-E-2-one

[0190]

[0191] 0.610 g (2 mmol) of (E)-3-(1-((6-pyridin-3-yl)methyl)imidazolin-2-ylidene)vinyl)-1,1,1-trifluoropropan-2-one was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiophene-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product was obtained as a light yellow powder by column chromatography with a yield of 90%. mp = 144.9 - 145.5 °C; 1 H NMR (400 MHz, DMSO) δ 9.80 (s, 1H), 8.36 (d, J = 2.2 Hz, 1H), 7.84 (dd, J = 8.2, 2.2 Hz, 1H), 7.51 (d, J = 8.2 Hz, 1H), 7.21 (d, J = 5.0 Hz, 1H), 6.98–6.92 (m, 1H), 6.88–6.83 (m, 2H), 6.62 (d, J = 16.0 Hz, 1H), 4.50 (s, 2H), 3.88–3.73 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.28, 149.61, 149.32, 144.30, 139.33, 130.44, 128.56, 127.66, 125.75, 124.16, 123.41, 122.73, 121.13, 112.76, 104.73, 48.44, 48.16, 42.39. HRMS (ESI) C 18 H 15 N 3 OF 3 NaS 35 Cl (M+Na) + , calculated value: 436.0474, measured value: 436.0475; C 18 H 15 N 3 OF 3 NaS 37 Cl (M+Na) + , calculated value: 438.0445, measured value: 438.0446.

[0192] Example 36 2-Chloro-5-(((E)-2-((E)-3-(thiophen-2-yl)-1-((trifluoromethyl)sulfonyl)allylidene)imidazolidin-1-yl)methyl)pyridine

[0193]

[0194] 0.682 g (2 mmol) of (E)-2-chloro-5-((2-(((trifluoromethyl)sulfonyl)methylene)imidazolin-1-yl)methyl)pyridine was added to 20 ml of acetonitrile and stirred to dissolve at room temperature. After 10 minutes, 0.630 g (5 mmol) of thiophene-2-acetaldehyde was slowly added dropwise. After reacting for 24 hours, the solvent was removed and the pure product in the form of a yellow-green powder was obtained by column chromatography separation, with a yield of 88%. mp = 142.6 - 143.3 °C; 1 H NMR (400 MHz, DMSO) δ 9.83 (s, 1H), 8.37 (d, J = 2.4 Hz, 1H), 7.84 (dd, J = 8.2, 2.4 Hz, 1H), 7.49 (d, J = 8.2 Hz, 1H), 7.20 (d, J = 5.0 Hz, 1H), 6.96–6.92 (m, 1H), 6.88–6.83 (m, 2H), 6.64 (d, J = 16.0 Hz, 1H), 4.50 (s, 2H), 3.89–3.71 (m, 4H). 13 C NMR (101 MHz, DMSO) δ 163.28, 149.65, 149.30, 144.31, 139.34, 130.46, 128.53, 127.74, 124.15, 123.41, 122.72, 121.04, 112.79, 104.78, 48.46, 48.21, 42.42. HRMS (ESI) C 17 H 15 N 3 O 2 F 3 NaS 2 35 Cl (M+Na) + , calculated value: 472.0144, measured value: 472.0145; C 17 H 15 N 3 O 2 F 3 NaS 2 37 Cl (M+Na) + , calculated value: 474.0114, measured value: 474.0115.

[0195] Other compounds shown in Table 1 were obtained by referring to the preparation method of the above examples.

[0196] Example 37: Insecticidal activity test of the compounds of the present invention

[0197] (1) Insecticidal activity against aphids

[0198] Aphids belong to the pests of Homoptera and have piercing-sucking mouthparts. They are common crop pests. Taking Aphis craccivora as the test object, the dipping method was used for the test.

[0199] Operation process: Weigh various samples accurately, add them to N, N-dimethylformamide respectively to prepare a 10 g / L mother liquor. During the experiment, dilute it to a concentration of 100 mg / L with an aqueous solution containing 0.2 mL / L Triton X-100. After the wingless adult aphids stably fed on the mung bean sprouts, immerse them together with the mung bean sprouts into the medicinal liquid with a concentration of 100 mg / L. Take them out after 5 s, blot the excess medicinal liquid with blotting paper, transfer them into a clean container and raise them at a constant temperature of 23 °C. Set 3 replicates for each concentration, and the control group is the aqueous solution containing 0.2 mL / L Triton X-100. After 24 hours of treatment, count the number of dead test aphids and calculate the mortality rate (%): Mortality rate (%) = (number of live insects in the control group - number of live insects in the treatment group) / number of live insects in the control group × 100%. The results are shown in the following table.

[0200] (2) Insecticidal activity against Nilaparvata lugens

[0201] Nilaparvata lugens belongs to the pests of Homoptera and has piercing-sucking mouthparts. It is a common crop pest. Taking Nilaparvata lugens as the test object, the spraying method was used for the test.

[0202] Operation process: Accurately prepare a 100 mg / L solution of the compound to be tested with acetone as the solvent, and use an acetone aqueous solution treatment as the blank control. Repeat each treatment 3 cups (i.e., repeat 3 times). Spray 2 mL evenly into each cup with a small manual sprayer. 10 Nilaparvata lugens were introduced into each pot 6 hours before applying the medicine. A total of 3 batches of experiments were carried out successively. After 24 hours of treatment, count the number of dead test insects and calculate the mortality rate (%):

[0203] Mortality rate (%) = (number of live insects in the control group - number of live insects in the treatment group) / number of live insects in the control group × 100%.

[0204] The results are shown in Table 1 below.

[0205]

[0206] Table 1 Activity of the compound shown by general formula I

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217] Example 38

[0218] (a) Oily suspension

[0219] Prepare the following components in proportion: 25% (weight percentage, the same below) of any one of Compounds 1-187; 5% of polyoxyethylene sorbitol hexaoleate; 70% of higher aliphatic hydrocarbon oil. Grind the components together in a sand mill until the solid particles are reduced to less than about 5 microns. The resulting viscous suspension can be used directly or after emulsification in water.

[0220] (b) Aqueous suspension

[0221] Prepare the following components in proportion: 25% of any one of Compounds 1-187; 3% of hydrated attapulgite; 10% of calcium lignosulfonate; 0.5% of sodium dihydrogen phosphate; 61.5% of water. Grind the components together in a ball mill until the solid particles are reduced to less than about 10 microns. This aqueous suspension can be used directly.

[0222] (c) Bait

[0223] Prepare the following components in proportion: 0.1-10% of any one of Compounds 1-187; 80% of wheat flour; 19.9-10% of molasses. Mix these components thoroughly and form a bait shape as needed. The edible bait can be dispersed in places infested by sanitary pests, such as homes or industrial sites, such as kitchens, hospitals or stores, or outdoor areas, to control pests by oral ingestion.

[0224] All documents mentioned in this invention are incorporated herein by reference as if each document was individually incorporated by reference. In addition, it should be understood that after reading the above content of this invention, those skilled in the art can make various changes or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

Claims

1. A compound having the structure shown in General Formula I, or a pesticidally acceptable salt thereof: In the formula: R 1 is a substituted or unsubstituted five- or six-membered heterocyclic group containing nitrogen, oxygen and / or sulfur, or a substituted or unsubstituted phenyl group, Wherein, The substitution is with one or more substituents selected from the group consisting of: halogen, C 1-4 haloalkyl; R 2 、R 3 each independently represents C 1-6 alkyl, C 1-4 alkoxy-C 1-4 alkyl, phenoxycarbonyl; or R 2 combined with R 3 to form -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -; R 4 is H; R 5 is a substituted or unsubstituted C 3-8 cycloalkyl, a substituted or unsubstituted C 6-10 aryl, a substituted or unsubstituted C 1-4 alkylene-C 6-10 aryl, a substituted or unsubstituted five- or six-membered heterocyclic group containing nitrogen, oxygen and / or sulfur, wherein the substitution means having one or more substituents selected from the group consisting of: C 1-6 alkyl, nitro, fluorine, chlorine, bromine, C 1-6 alkoxy, C 1-6 haloalkyl, or two substituents form a ring with the connected atoms; Z is nitro, cyano, ester group, trifluoromethyl, trifluoroacetyl (-COCF 3 ), C 1-6 alkyl-formyl, or trifluoromethanesulfonyl (-SO 2 CF 3 ).

2. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, R 1 is a substituted or unsubstituted group selected from the following: phenyl, pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, and oxazolyl, wherein the substitution is with one or more substituents selected from the group consisting of halogen, C 1-4 haloalkyl.

3. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, R 1 selected from the following substituted or unsubstituted groups: phenyl, pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl, said substitution being with one or more substituents selected from the group consisting of: fluorine, chlorine, bromine, C 1-4 fluoroalkyl.

4. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, R 2 、R 3 are each independently C 1-4 alkyl, C 2-4 alkoxy-C 1-4 alkyl, or phenoxycarbonyl.

5. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, R 2 Combined with R 3 to form -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -.

6. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, R 5 is a substituted or unsubstituted C 3-6 cycloalkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 1-4 alkylene-C 6-10 aryl, a five- or six-membered heterocyclic group containing nitrogen, oxygen and / or sulfur, which is substituted or unsubstituted, and the five- or six-membered heterocyclic group containing nitrogen, oxygen and / or sulfur is pyridyl, thiazolyl, pyrimidinyl, tetrahydrofuranyl or oxazolyl; the substitution means having one or more substituents selected from the group consisting of: C 1-6 alkyl, nitro, fluorine, chlorine, bromine, C 1-6 alkoxy, C 1-6 haloalkyl, or two substituents form a ring with the connected atoms.

7. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, R 5 is a substituted or unsubstituted group selected from the following: phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, thienyl, thiazolyl, triazolyl, pyrrolyl, pyridyl, naphthyl, furyl, wherein the substitution means having 1, 2 or 3 substituents selected from the group consisting of: C 1-6 alkyl, nitro, fluorine, chlorine, bromine, C 1-4 alkoxy, C 1-4 haloalkyl, or two substituents form a ring with the connecting atoms.

8. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, Z is nitro.

9. The compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, has the structure shown in Formula (II): wherein, R 1 and R 5 are as defined in claim 1.

10. The compound according to claim 9 or a pesticidally acceptable salt thereof, characterized in that, R 1 For 11. The compound according to claim 10 or a pesticidally acceptable salt thereof, characterized in that, R 5 Selected from:

12. An agricultural composition, which comprises: (a) The compound according to any one of claims 1 - 11 or a pesticidally acceptable salt thereof; and (b) A pesticidally acceptable carrier and / or excipient.

13. The use of the compound according to any one of claims 1 - 11 or the agricultural composition according to claim 12, characterized in that, for preparing an insecticidal composition for killing or preventing agricultural pests, sanitary pests and pests harmful to animal health.

14. The use according to claim 13, characterized in that, the pests are selected from: aphids, armyworms.

15. A method for killing and / or preventing pests, the method comprising applying the compound according to any one of claims 1 - 11 or a pesticidally acceptable salt thereof or the agricultural composition according to claim 12 to a plant body suffering from or likely to suffer from pest damage, the soil or the environment around it.

16. The method according to claim 15, characterized in that, the pests are selected from: aphids, armyworms.

17. A method for controlling pests, applying an insecticidally effective amount of the compound according to any one of claims 1 - 11 or the agricultural composition according to claim 12 to plant seeds or plant leaves and / or plant fruits or places where plants are growing or expected to grow.

18. The method according to claim 17, characterized in that, the pests are selected from: aphids, armyworms.

19. The preparation method of the compound according to claim 1 or a pesticidally acceptable salt thereof, characterized in that, the method comprises the step: reacting the compound shown in Formula a and the compound shown in Formula b to obtain a compound having the structure shown in General Formula I, In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and Z are defined as described in claim 1; Y is O or S.

20. The preparation method according to claim 19, characterized in that, in a reaction solvent, reacting the compound shown in Formula a and the compound shown in Formula b under the action of a catalyst to obtain a compound having the structure shown in General Formula I; Among them, the solvent is selected from one or more of the following groups: acetonitrile, methanol, tetrahydrofuran, ethanol, water, 1,4-dioxane, acetone, dichloromethane, or 1,2-dichloroethane; The catalyst is a protonic acid or a Lewis acid, and is selected from one or more of the following groups: hydrochloric acid, acetic acid, phosphoric acid, p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, boron trifluoride, aluminum trichloride, iron trichloride, boric acid, silicic acid, nitric acid, magnesium chloride, cobalt chloride, strontium chloride, palladium chloride, or nickel chloride.

21. The preparation method according to claim 20, characterized in that, the reaction is carried out at 15-55 °C for 2-96 hours.

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