A nitro bicyclodecene derivative, its preparation method and application

Abstract

The present invention discloses a nitro bicyclodecene derivative, a preparation method thereof and an application thereof, belonging to the technical field of pesticide preparation. The nitro bicyclodecene derivative of the present invention has the following structural formula: The nitro bicyclodecene derivative of the present invention has a completely novel molecular structure and has high activities against agricultural and forestry pests such as aphids and rice planthoppers.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticide preparation, and particularly relates to a nitro bicyclodecene derivative, a preparation method thereof, and an application thereof. Background Art

[0002] Neonicotinoid pesticides act on insect nicotinic acetylcholine receptors (nAChRs), and have the characteristics of high efficiency, low toxicity, broad spectrum, high selectivity, low residue, and safety for mammals and various aquatic organisms. Therefore, they are widely used. However, in recent years, the resistance and bee toxicity of neonicotinoid pesticides have been reported in many countries and regions, which has attracted wide attention. Therefore, it is urgent to develop novel-structured neonicotinoid pesticides targeting resistance and bee toxicity. Summary of the Invention

[0003] The purpose of the present invention is to provide a nitro bicyclodecene derivative, a preparation method thereof, and an application thereof, so as to solve the problems existing in the above-mentioned prior art.

[0004] To achieve the above purpose, the present invention provides the following solutions:

[0005] One of the technical solutions of the present invention: A nitro bicyclodecene derivative, the structural formula of which is shown in formula (1):

[0006]

[0007] Among them, R1 is selected from pyridyl, thiazolyl, pyrimidinyl, oxazolyl, halogenated pyridyl, halogenated thiazolyl, halogenated pyrimidinyl, halogenated oxazolyl, pyridin-3-yl substituted by fluorine at the 6-position, pyridin-3-yl substituted by chlorine at the 6-position, pyridin-3-yl substituted by bromine at the 6-position, pyridin-3-yl substituted by trifluoromethyl at the 6-position, or 1,3-thiazol-5-yl substituted by chlorine at any 2-positions;

[0008] R2 is selected from H, C 1-6 alkyl, C 3-4 cycloalkyl or halogenated C 1-6 alkyl.

[0009] Another technical solution of the present invention: A preparation method of the above-mentioned nitro bicyclodecene derivative. When R2 is H, the preparation method includes the following steps:

[0010] Compound A, 2-cyclohepten-1-one, and a catalyst are sequentially added into a solvent, and the mixture is heated under reflux for reaction to obtain the nitro bicyclodecene derivative;

[0011] The chemical reaction equation is as follows:

[0012]

[0013] When R2 is not H, the preparation method includes the following steps:

[0014] Compound A, 2-cyclohepten-1-one and a catalyst are successively added to compound B, and the mixture is heated under reflux to obtain the nitro bicyclo decene derivative;

[0015] The structural formula of compound A is shown in formula (2):

[0016]

[0017] The structural formula of compound B is shown in formula (3):

[0018] R2OH

[0019] Formula (3).

[0020] The chemical reaction equation is as follows:

[0021]

[0022] Furthermore, the molar ratio of compound A to 2-cyclohepten-1-one is 7.8:11.7; the catalyst includes aluminum chloride.

[0023] Furthermore, the time of the heating under reflux reaction is 1 - 3 h.

[0024] The third technical solution of the present invention: An application of the above-mentioned nitro bicyclo decene derivative in the preparation of a medicament for controlling pests.

[0025] Furthermore, the medicament for controlling pests includes a medicament for killing or preventing pests.

[0026] Furthermore, the pests include Coleoptera, Hemiptera, Orthoptera, Homoptera, Isoptera, Diptera insects.

[0027] Furthermore, it includes pests that endanger animal health.

[0028] Furthermore, the coleopteran insects include: 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.

[0029] The orthopteran insects include: Blattella germanica, Periplaneta americana, Gryllotalpa africana, or Locusta migratoria.

[0030] The homopteran insects include: Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossypii, Aphis medicaginis, Lipaphis erysimi pseudobrassicae, Stephanitis nashi, or Bemisia tabaci.

[0031] The isopteran insects include: Solenopsis invicta, or Coptotermes formosanus.

[0032] The Diptera insects include: Musca domestica, Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis.

[0033] The pests harmful to animal health include: Hyalomma anatolicum, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia benedeni, Ostertagia spp., protozoa Trypanosoma evansi, Babesia bigemina, etc.

[0034] Furthermore, the nitro bicyclodecene derivative has a high control effect on piercing-sucking and rasping-sucking mouthpart pests (such as agricultural and forestry pests such as whiteflies, aphids, leafhoppers, planthoppers, thrips, etc.).

[0035] Technical solution four of the present invention: An insecticide composition, by weight percentage, the components include 0.0000001-100% of the above-mentioned nitro bicyclodecene derivative, and the balance is a pesticidally acceptable carrier and / or excipient.

[0036] Technical solution five of the present invention: An application of the above insecticide composition in pest control.

[0037] Furthermore, the method of the application specifically includes: applying the insecticide composition to the plant body suffering from or likely to suffer from pest damage, the soil or environment around it.

[0038] The present invention discloses the following technical effects:

[0039] (1) The nitro bicyclodecene derivative of the present invention has a completely novel molecular structure and has high activity against agricultural and forestry pests such as aphids and rice planthoppers.

[0040] (2) The present invention uses 6-Cl-PMNI (such as ) Michael addition reaction, nucleophilic addition reaction, and etherification reaction were carried out with cycloheptenone compounds to synthesize new neonicotinoid compounds of bicyclic cis-nitroene. The nitro group was fixed in the cis form by the large-ring steric hindrance, and at the same time, the pharmacophore structure of "nitro-bicyclodecene" was introduced. The molecular structure is novel and has complete innovation. The compounds of the present invention not only have high activity against pests such as aphids and rice planthoppers, but also can solve the resistance problem existing in the existing neonicotinoid insecticides.

[0041] (3) During the growth and harvesting of plants, the compounds prepared by the present invention can be used to avoid the attack and infestation of plants by insects. Detailed implementation manners

[0042] The various exemplary implementation manners of the present invention will be described in detail below. This detailed description should not be regarded as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation manners of the present invention.

[0043] It should be understood that the terms described in the present invention are only for describing specific implementation manners and are not used to limit the present invention. In addition, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0044] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0045] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific implementation manners of the present invention specification, which are obvious to those skilled in the art. Other implementation manners obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of this application are only exemplary.

[0046] Regarding "comprising", "including", "having", "containing", etc. used herein, they are all open-ended terms, meaning including but not limited to.

[0047] All "parts" mentioned in the following examples are "parts by weight".

[0048] In the first aspect of the present invention, a nitro-bicyclodecene derivative is provided, and its structural formula is shown as formula (1):

[0049]

[0050] Wherein, R1 is selected from pyridyl, thiazolyl, pyrimidinyl, oxazolyl, halogenated derivatives of pyridyl, halogenated derivatives of thiazolyl, halogenated derivatives of pyrimidinyl, halogenated derivatives of oxazolyl, pyridin-3-yl substituted by fluorine at the 6-position, pyridin-3-yl substituted by chlorine at the 6-position, pyridin-3-yl substituted by bromine at the 6-position, pyridin-3-yl substituted by trifluoromethyl at the 6-position, or 1,3-thiazol-5-yl substituted by chlorine at any 2-position;

[0051] R2 is selected from H, C 1-6 alkyl, C 3-4 cycloalkyl or halogenated C 1-6 alkyl.

[0052] The nitro-bicyclodecene derivative with the above structure in the present invention has the effect of preventing and controlling Coleoptera, Hemiptera, Orthoptera, Homoptera, Isoptera, Diptera insects and pests harmful to animal health. When the use concentration is 100 mg / L, the prevention and control effects of a1 (Example 1) and a3 (Example 3) can both reach more than 90%.

[0053] In the second aspect of the present invention, a preparation method of a nitro-bicyclodecene derivative is provided, and the preparation method is selected from any one of the following:

[0054] Method 1: When R2 is H, the preparation method includes the following steps:

[0055] Compound A, 2-cyclohepten-1-one and a catalyst are successively added into a solvent, and the mixture is heated under reflux for reaction to obtain a nitro-bicyclodecene derivative;

[0056] The chemical reaction equation is as follows:

[0057]

[0058] Method 2: When R2 is not H, the preparation method includes the following steps:

[0059] Compound A, 2-cyclohepten-1-one and a catalyst are successively added into Compound B, and the mixture is heated under reflux for reaction to obtain a nitro-bicyclodecene derivative;

[0060] The structural formula of Compound A is shown as formula (2):

[0061]

[0062] The structural formula of Compound B is shown as formula (3):

[0063] R2OH

[0064] Formula (3).

[0065] The chemical reaction equation is as follows:

[0066]

[0067] Among them, the molar ratio of compound A to 2-cyclohepten-1-one is 7.8:11.7; the catalyst is aluminum chloride; the heating reflux reaction time is 1-3 h.

[0068] In the third aspect of the present invention, there is provided an application of a nitro dicyclodecene derivative in the preparation of a medicament for preventing and controlling pests.

[0069] Among them, the medicament for preventing and controlling pests includes a medicament for killing or preventing pests. The pests include Coleoptera, Hemiptera, Orthoptera, Homoptera, Isoptera, Diptera insects; the pests also include pests that harm animal health.

[0070] Coleoptera insects include: 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.

[0071] Orthoptera insects include: Blattella germanica, Periplaneta americana, Gryllotalpa africana, or Locusta migratoria.

[0072] Homopteran insects include: Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis gossypii, Aphis medicagini, Lipaphis erysimi pseudobrassicae, Stephanitis nashi, or Bemisia tabaci.

[0073] Isopteran insects include: Solenopsis invicta, or Coptotermes formosanus.

[0074] Dipteran insects include: Musca domestica, Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis.

[0075] Pests harmful to animal health include: Hyalomma anatolicum, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia benedeni, Ostertagia spp., protozoa Trypanosoma evansi, Babesia bigemina, etc.

[0076] The nitro bicyclodecene derivatives of the present invention have a high control effect on piercing-sucking and rasping-sucking mouthpart pests (such as agricultural and forestry pests like whiteflies, aphids, leafhoppers, planthoppers, thrips, etc.).

[0077] In the fourth aspect of the present invention, a pesticide composition is provided. By weight percentage, the components include: 0.0000001 - 100% of nitro bicyclodecene derivatives, and the balance is a pesticidologically acceptable carrier and / or excipient.

[0078] The concentration of the active compound (nitro-bicyclodecene derivative) in the pesticidal composition (formulation) can vary within a wide range. The concentration of the active compound (nitro-bicyclodecene derivative) in the formulation can be maintained within the range of 0.0000001 to 100% by weight, preferably 0.001 to 99.99% by weight, more preferably 0.01 to 99.9% by weight, and even more preferably 0.05 to 1% by weight.

[0079] In a fifth aspect of the present invention, there is provided an application of the above pesticidal composition in pest control.

[0080] The method for the application of the pesticidal composition of the present invention specifically includes: applying the pesticidal composition to the plant body suffering from or likely to suffer from pest damage, the soil or the environment around it.

[0081] The active compound (nitro-bicyclodecene derivative) of the present invention can be prepared into a pesticidal composition by conventional methods.

[0082] The active compound (nitro-bicyclodecene derivative) of the present invention can be made into conventional preparations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols.

[0083] Among them, the preparation method of the aerosol includes: impregnating the nitro-bicyclodecene derivative (active substance) in a natural or synthetic material and wrapping it with a polymer (coating compound for seeds) to make microcapsules; the aerosol is a preparation used together with a combustion device, such as a fumigation cartridge, a fumigation can, and a fumigation tray, as well as ULV cold mist and warm mist preparations.

[0084] The above preparations can be produced by known methods. For example, the active compound (nitro-bicyclodecene derivative) is mixed with an extender to make a preparation, and a surfactant (emulsifier, dispersant, foam former, etc.) can also be added. When the extender is water, an organic solvent can be used as an auxiliary agent.

[0085] Mixing the active compound (nitro-bicyclodecene derivative) with an extender, a surfactant, etc. to make different preparations can achieve stable synergistic effects.

[0086] The extender is a diluent or a carrier; the diluent or carrier is liquid, liquefied gas or solid.

[0087] (1) Diluents or carriers for liquids include: aromatic hydrocarbons (xylene, toluene, alkylnaphthalene); chlorinated aromatic or chlorinated aliphatic hydrocarbons (chlorobenzene, vinyl chloride, dichloromethane); aliphatic hydrocarbons (cyclohexane, paraffin, mineral oil fractions); alcohols (ethanol or ethylene glycol and their ethers and esters); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone); or less common polar solvents (dimethylformamide, dimethyl sulfoxide, water).

[0088] (2) Diluents or carriers for liquefied gases refer to liquids that become gases under normal temperature and pressure, such as aerosol propellants (halogenated hydrocarbons, butane, propane, nitrogen, carbon dioxide).

[0089] (3) Solid carriers can be natural minerals on the ground, such as kaolin, clay, talc, quartz, activated clay, montmorillonite, diatomaceous earth, synthetic minerals on the ground;

[0090] Solid carriers also include: highly dispersed silica, alumina, silicates. Solid carriers for granules include crushed and classified natural zircon, such as calcite, marble, pumice, sepiolite, dolomite, and granules synthesized from inorganic and organic coarse powders, organic materials (sawdust, coconut shells, corn cobs, tobacco stalk granules, etc.).

[0091] Emulsifiers include non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, and albumin hydrolysis products. Dispersants include: lignosulfite waste liquor, methyl cellulose, etc.

[0092] Example 1

[0093] A preparation method of a nitro bicyclodecene derivative (a1):

[0094] Add CH2Cl2 (20.0 mL) to a 100 mL three-necked flask, then successively add 2-chloro-5-((2-(nitromethylene)-1-imidazolidinyl)methyl)-pyridine (1.99 g, 7.8 mmol), 2-cyclohepten-1-one (1.3 mL, 11.7 mmol), and add anhydrous aluminum chloride (0.52 g, 3.9 mmol). Heat under reflux for 1 h, monitor the reaction by TLC. After the raw material spot (the raw material spot of 2-chloro-5-((2-(nitromethylene)-1-imidazolidinyl)methyl)-pyridine) disappears, stop heating, cool to room temperature, add distilled water to remove the unreacted anhydrous aluminum chloride, add an appropriate amount of sodium bicarbonate, dry with anhydrous magnesium sulfate, filter by suction, and concentrate and distill under reduced pressure. Perform column chromatography separation to obtain the nitro bicyclodecene derivative (a1), a light beige-white powder, with a weight of 1.97 g and a yield of 69.2%.

[0095] mp = 67.8 - 68.5 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.53 (d, J = 2.4 Hz, 1H, Py - H), 7.61 (dd, J = 8.1, 2.5 Hz, 1H, Py - H), 7.28 (d, J = 8.1 Hz, 1H, Py - H), 5.28 (s, 1H, -OH), 4.96 (d, J = 15.5 Hz, 1H, Py - CH2 - N), 4.59 (d, J = 15.5 Hz, 1H, Py - CH2 - N), 4.11 - 3.52 (m, 4H, N - CH2 - CH2 - N), 3.42 - 3.34 (m, 1H, -CH-), 2.30 - 1.19 (m, 10H, -CH2 -). 13 13C NMR (101 MHz, CDCl3) δ 158.05, 151.29, 149.23, 139.43, 131.19, 124.56, 110.98, 89.93, 52.16, 48.94, 41.36, 36.87, 33.62, 31.45, 31.33, 23.90, 23.32. HRMS (ESI+): calcd for C 17 H 22 ClN4O3 (M + H) + 365.1375; found, 365.1374.

[0096] The structural formula of a1 is as follows:

[0097]

[0098] Example 2

[0099] A preparation method of a nitro - bicyclodecene derivative (a2):

[0100] Add anhydrous methanol (15.0 mL) to a 100 mL three - necked flask, and then successively add 2 - chloro - 5 - ((2 - (nitromethylene) - 1 - imidazolidinyl)methyl) - pyridine (1.99 g, 7.8 mmol), 2 - cyclohepten - 1 - one (1.3 mL, 11.7 mmol), and add anhydrous aluminum chloride (0.52 g, 3.9 mmol). Heat under reflux for 1 h, and monitor the reaction by TLC. After the raw material spot (the raw material spot of 2 - chloro - 5 - ((2 - (nitromethylene) - 1 - imidazolidinyl)methyl) - pyridine) disappears, stop heating, cool to room temperature, add distilled water to remove the unreacted anhydrous aluminum chloride, add an appropriate amount of sodium bicarbonate, dry with anhydrous magnesium sulfate, filter by suction, and concentrate and distill under reduced pressure. Perform column chromatography separation to obtain the nitro - bicyclodecene derivative (a2), a pale yellow powder, with a weight of 1.19 g and a yield of 40.3%.

[0101] mp = 150.4 - 151.2 °C. 1 H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 2.4 Hz, 1H, Py - H), 7.77 (dd, J = 8.2, 2.5 Hz, 1H, Py - H), 7.30 (d, J = 8.3 Hz, 1H, Py - H), 4.78 (d, J = 15.2 Hz, 1H, Py - CH2 - N), 4.72 (d, J = 15.2 Hz, 1H, Py - CH2 - N), 3.78 - 3.49 (m, 4H, N - CH2 - CH2 - N), 3.48 - 3.43 (m, 1H, - CH -), 3.09 (s, 3H, - CH3), 2.31 - 1.16 (m, 10H, - CH2 -). 13 C NMR (101 MHz, CDCl3) δ 158.50, 150.89, 149.81, 138.97, 131.11, 124.16, 111.03, 86.00, 53.56, 51.95, 48.44, 41.27, 39.38, 36.87, 34.29, 32.20, 24.48, 23.73. HRMS (ESI+): calcd for C 18 H 24 ClN4O3 (M + H) + 379.1531; found, 379.1536.

[0102] Example 3

[0103] A method for preparing a nitro - bicyclodecene derivative (a3):

[0104] Add anhydrous ethanol (15.0 mL) to a 100 mL three - necked flask, then successively add 2 - chloro - 5 - ((2 - (nitromethylene) - 1 - imidazolidinyl)methyl) - pyridine (1.99 g, 7.8 mmol), 2 - cyclohepten - 1 - one (1.3 mL, 11.7 mmol), and add anhydrous aluminum chloride (0.52 g, 3.9 mmol). Heat under reflux for 2 h and monitor the reaction by TLC. After the raw material spot (the raw material spot of 2 - chloro - 5 - ((2 - (nitromethylene) - 1 - imidazolidinyl)methyl) - pyridine) disappears, stop heating, cool to room temperature, add distilled water to remove the unreacted anhydrous aluminum chloride, add an appropriate amount of sodium bicarbonate, dry with anhydrous magnesium sulfate, filter by suction, and concentrate and distill under reduced pressure. Perform column chromatography separation to obtain the nitro - bicyclodecene derivative (a3), a pale yellow solid, with a weight of 1.42 g and a yield of 46.3%.

[0105] mp = 140.1 - 140.8 °C. 11H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 2.5 Hz, 1H, Py-H), 7.77 (dd, J = 8.2, 2.5 Hz, 1H, Py-H), 7.30 (d, J = 8.2 Hz, 1H, Py-H), 4.77 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.72 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.75 - 3.40 (m, 6H, N-CH2-CH2-N and O-CH2-), 3.18 - 3.10 (m, 1H, -CH-), 2.32 - 1.31 (m, 10H, -CH2-), 1.15 (t, J = 7.0 Hz, 3H, -CH3). 13 13C NMR (101 MHz, CDCl3) δ 158.05, 151.29, 149.23, 139.47, 131.20, 124.58, 111.02, 89.83, 56.89, 52.15, 48.91, 41.43, 37.23, 33.58, 32.33, 31.58, 23.96, 23.34, 15.51. HRMS (ESI+): calcd for C 19 H 26 ClN4O3 (M + H) + 393.1688; found, 393.1700.

[0106] Example 4

[0107] A method for preparing a nitro - bicyclodecene derivative (a4):

[0108] Add dried n - propanol (15.0 mL) to a 100 mL three - necked flask, then successively add 2 - chloro - 5 - ((2 - (nitromethylene) - 1 - imidazolidinyl)methyl) - pyridine (1.99 g, 7.8 mmol), 2 - cyclohepten - 1 - one (1.3 mL, 11.7 mmol), and anhydrous aluminum chloride (0.52 g, 3.9 mmol). Heat under reflux for 3 h and monitor the reaction by TLC. After the raw material spot (the raw material spot of 2 - chloro - 5 - ((2 - (nitromethylene) - 1 - imidazolidinyl)methyl) - pyridine) disappears, stop heating, cool to room temperature, add distilled water to remove the unreacted anhydrous aluminum chloride, add an appropriate amount of sodium bicarbonate, dry with anhydrous magnesium sulfate, filter by suction, and concentrate and distill under reduced pressure. Perform column chromatography separation to obtain the nitro - bicyclodecene derivative (a4), a pale yellow powder, with a weight of 1.87 g and a yield of 58.9%.

[0109] mp = 130.8 - 131.7 °C. 11H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 2.5 Hz, 1H, Py-H), 7.77 (dd, J = 8.2, 2.5 Hz, 1H, Py-H), 7.30 (d, J = 8.2 Hz, 1H, Py-H), 4.78 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.71 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.75 - 3.28 (m, 6H, N-CH2-CH2-N and O-CH2-), 3.06 - 3.00 (m, 1H, -CH-), 2.31 - 1.15 (m, 12H, -CH2-), 0.88 (t, J = 7.4 Hz, 3H, -CH3). 13 13C NMR (101 MHz, CDCl3) δ 158.00, 151.28, 149.23, 139.45, 131.23, 124.56, 111.04, 89.68, 63.03, 52.12, 48.89, 41.46, 37.06, 33.63, 32.31, 31.58, 23.94, 23.36, 23.24, 10.81. HRMS (ESI+): calcd for C 20 H 28 ClN4O3 (M+H) + 407.1844; found, 407.1853.

[0110] Example 5

[0111] A method for preparing a nitro-bicyclodecene derivative (a5):

[0112] Same as Example 4, except that n-propanol was replaced with an equal volume of isopropanol; the nitro-bicyclodecene derivative (a5) was obtained as a pale yellow solid with a weight of 2.01 g and a yield of 63.3%.

[0113] mp = 145.6 - 146.3 °C. 11H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 2.5 Hz, 1H, Py-H), 7.76 (dd, J = 8.2, 2.6 Hz, 1H, Py-H), 7.31 (d, J = 8.3 Hz, 1H, Py-H), 4.82 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.71 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.78 - 3.51 (m, 5H, O-CH- and N-CH2-CH2-N), 3.50 - 3.45 (m, 1H, -CH-), 2.08 - 1.19 (m, 10H, -CH2-), 1.11 (dd, J = 9.2, 6.1 Hz, 6H, -CH3). 13 13C NMR (101 MHz, CDCl3) δ 157.47, 153.09, 149.24, 139.44, 131.66, 124.61, 110.72, 90.35, 64.45, 51.98, 48.69, 42.08, 37.60, 34.08, 33.75, 31.69, 25.17, 24.17, 24.01, 23.49. HRMS (ESI+): calcd for C 20 H 28 ClN4O3 (M + H) + 407.1844; found, 407.1852.

[0114] Example 6

[0115] A preparation method of a nitro - bicyclodecene derivative (a6):

[0116] Same as Example 4, except that n - propanol was replaced with n - butanol of the same volume; the nitro - bicyclodecene derivative (a6) was obtained, a pale yellow solid, with a weight of 1.87 g and a yield of 57.0%.

[0117] mp = 94.6 - 95.4 °C. 11H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 2.4 Hz, 1H, Py-H), 7.77 (dd, J = 8.2, 2.5 Hz, 1H, Py-H), 7.30 (d, J = 8.2 Hz, 1H, Py-H), 4.78 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.71 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.75 - 3.32 (m, 6H, N-CH2-CH2-N and O-CH2-), 3.10 - 3.04 (m, 1H, -CH-), 2.32 - 1.16 (m, 14H, -CH2-), 0.89 (t, J = 7.3 Hz, 3H, -CH3). 13 13C NMR (101 MHz, CDCl3) δ 158.00, 151.30, 149.24, 139.47, 131.24, 124.58, 111.74, 89.70, 61.23, 52.13, 48.90, 41.47, 37.09, 33.62, 32.29, 32.12, 31.59, 23.96, 23.36, 19.56, 14.03. HRMS (ESI+): calcd for C 21 H 30 ClN4O3 (M + H) + 421.2001; found, 421.2012.

[0118] Example 7

[0119] A method for preparing a nitro bicyclodecene derivative (a7):

[0120] Same as Example 4, except that n-propanol was replaced with isobutanol of the same volume; nitro bicyclodecene derivative (a7) was obtained as a pale yellow solid with a weight of 1.85 g and a yield of 56.3%.

[0121] mp = 118.5 - 119.2 °C. 11H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 2.5 Hz, 1H, Py-H), 7.76 (dd, J = 8.2, 2.5 Hz, 1H, Py-H), 7.30 (d, J = 8.3 Hz, 1H, Py-H), 4.80 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.70 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.76 - 3.12 (m, 6H, N-CH2-CH2-N and O-CH2-), 2.86 - 2.81 (m, 1H, -CH-), 2.31 - 1.15 (m, 11H, -CH2- and -CH-), 0.87 (dd, J = 6.7, 0.9 Hz, 6H, -CH3). 13 13C NMR (101 MHz, CDCl3) δ 157.94, 151.27, 149.23, 139.45, 131.26, 124.56, 111.05, 89.55, 67.95, 52.09, 48.86, 41.51, 36.91, 33.67, 32.31, 31.59, 28.80, 23.92, 23.36, 19.64, 19.56. HRMS (ESI+): calcd for C 21 H 30 ClN4O3 (M + H) + 421.2001; found, 421.2007.

[0122] Example 8

[0123] A method for preparing a nitro - bicyclodecene derivative (a8):

[0124] Same as Example 4, except that n - propanol was replaced with n - pentanol of the same volume; nitro - bicyclodecene derivative (a8) was obtained, a light yellow - brown solid, weighing 1.86 g, with a yield of 54.8%.

[0125] mp = 120.6 - 121.4 °C. 11H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 2.5 Hz, 1H, Py-H), 7.76 (dd, J = 8.3, 2.5 Hz, 1H, Py-H), 7.29 (d, J = 8.2 Hz, 1H, Py-H), 4.77 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.71 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.74 - 3.30 (m, 6H, N-CH2-CH2-N and O-CH2-), 3.09 - 3.02 (m, 1H, -CH-), 2.31 - 1.17 (m, 16H, -CH2-), 0.86 (t, J = 6.9 Hz, 3H, -CH3). 13 13C NMR (101 MHz, CDCl3) δ 157.98, 151.24, 149.22, 139.43, 131.22, 124.53, 111.02, 89.67, 61.49, 52.10, 48.89, 41.46, 37.06, 33.59, 32.27, 31.57, 29.69, 28.46, 23.92, 23.33, 22.58, 14.04. HRMS (ESI+): calcd for C 22 H 32 ClN4O3 (M + H) + 435.2157; found, 435.2165.

[0126] Example 9

[0127] A method for preparing a nitro - bicyclodecene derivative (a9):

[0128] Same as Example 4, except that n - propanol was replaced with cyclopropylmethanol of the same volume; the nitro - bicyclodecene derivative (a9) was obtained, which is a light yellow - brown solid with a weight of 2.07 g and a yield of 63.3%.

[0129] mp = 114.7 - 115.4 °C. 11H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 2.5 Hz, 1H, Py-H), 7.76 (dd, J = 8.2, 2.5 Hz, 1H, Py-H), 7.30 (d, J = 8.2 Hz, 1H, Py-H), 4.78 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.71 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.77 - 3.13 (m, 6H, N-CH2-CH2-N and O-CH2-), 3.03 - 2.95 (m, 1H, -CH-), 2.28 - 1.14 (m, 10H, -CH2-), 0.97 - 0.87 (m, 1H, -CH-), 0.56 - 0.49 (m, 2H, -CH2-), 0.21 - 0.10 (m, 2H, -CH2-). 13 13C NMR (101 MHz, CDCl3) δ 156.91, 152.15, 149.22, 139.43, 131.20, 124.56, 114.13, 89.68, 66.28, 52.10, 48.86, 41.45, 37.10, 33.64, 32.33, 31.54, 23.93, 23.34, 10.78, 3.17, 2.78. HRMS (ESI+): calcd for C 21 H 28 ClN4O3 (M + H) + 419.1844; found, 419.1854.

[0130] Example 10

[0131] A method for preparing a nitro - bicyclodecene derivative (a10):

[0132] Same as Example 4, except that n - propanol was replaced with cyclohexanol of the same volume; nitro - bicyclodecene derivative (a10) was obtained, a light yellow - brown solid, with a weight of 1.93 g and a yield of 55.4%.

[0133] mp = 107.6 - 108.3 °C. 11H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 2.4 Hz, 1H, Py-H), 7.76 (dd, J = 8.2, 2.5 Hz, 1H, Py-H), 7.31 (d, J = 8.3 Hz, 1H, Py-H), 4.82 (d, J = 15.2 Hz, 1H, Py-CH2-N), 4.71 (d, J = 15.2 Hz, 1H, Py-CH2-N), 3.77 - 3.43 (m, 5H, N-CH2-CH2-N and O-CH-), 3.43 - 3.35 (m, 1H, -CH-), 2.32 - 1.11 (m, 20H, -CH2-). 13 13C NMR (101 MHz, CDCl3) δ 157.77, 151.33, 149.24, 139.45, 131.33, 124.61, 111.28, 90.30, 70.40, 52.01, 48.74, 42.16, 37.62, 35.66, 35.31, 34.47, 34.19, 33.67, 31.71, 25.57, 24.61, 24.24, 23.38. HRMS (ESI+): calcd for C 23 H 32 ClN4O3 (M + H) + 447.2157; found, 447.2185.

[0134] Effect Example 1

[0135] Insecticidal Activity Test

[0136] Spraying method: The spraying method was used to conduct a bioactivity test on 10 target compounds against Bemisia tabaci. Bemisia tabaci belongs to the Hemiptera insects, is a species complex that is morphologically difficult to distinguish, is a vector of many plant viruses, mainly including hundreds of important food and fiber crops, and is a relatively common pest in agricultural production.

[0137] a) Before the experiment, the Potter spraying tower was cleaned first, and its spraying pressure was stabilized at 1.47×10 5 Pa.

[0138] b) The compounds prepared in Examples 1 - 10 were dissolved in DMSO (dimethyl sulfoxide) to prepare a stock solution with a concentration of 1000 mg / L, and then diluted with a 0.1 vol.% Tween - 80 aqueous solution to a medicament solution with a concentration of 100 mg / L.

[0139] c) Select robust and uniform tomato potted plants, keep the three central leaves, put the prepared liquid medicine into a Potter spray tower, select 150 whiteflies with consistent physiological states and place them on tomato leaves, and conduct quantitative spraying, evenly spraying the medicine on both the front and back sides of tomato leaves, with 2 replicates for each treatment.

[0140] d) Raise the whiteflies after treatment with the Potter spray tower.

[0141] e) Observe and record the survival situation of the whiteflies after 48 h of treatment, and calculate the relevant mortality rate.

[0142] Table 1 Insecticidal activities of different compounds

[0143]

[0144]

[0145] Effect Example 2

[0146] Preparation of the insecticide composition

[0147] (a) Oil-based suspension: Prepare the following components in proportion: 25% (weight percentage, the same below) of any one compound among compounds a1 - a10, 5% polyoxyethylene sorbitan hexaoleate, 70% higher aliphatic hydrocarbon oil. Grind each component together in a sand mill until the solid particles are reduced to below about 5 microns. The resulting viscous suspension can be used directly or after emulsification in water.

[0148] (b) Water-based suspension: Prepare the following components in proportion: 25% (weight percentage, the same below) of any one compound among compounds a1 - a10, 3% hydrated attapulgite, 10% calcium lignosulfonate, 0.5% sodium dihydrogen phosphate, 61.5% water. Grind each component together in a ball mill until the solid particles are reduced to below about 10 microns. This water-based suspension can be used directly.

[0149] (c) Bait: Prepare the following components in proportion: 0.1 - 10% (weight percentage, the same below) of any one compound among compounds a1 - a10, 80% wheat flour, 19.9 - 10% molasses. Thoroughly mix these components and form a bait shape as needed. The edible bait can be dispersed in the 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.

[0150] The embodiments described above are only descriptions of the preferred embodiments of the present invention and do not limit the scope of the present invention. Without departing from the spirit of the present invention's design, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. A nitrobicyclodecene derivative for controlling Bemisia tabaci, characterized in that: The structural formula is shown in formula (1): Wherein, R1 is 2-chloropyridine; R2 is selected from H or ethyl.

2. A method for preparing the nitrobicyclodecene derivative according to claim 1, characterized in that: When R2 is H, the preparation method comprises the following steps: Adding compound A, 2-cycloheptene-1-one and a catalyst in a solvent in sequence, heating and refluxing to obtain the nitrobicyclodecene derivative; When R2 is not H, the preparation method comprises the following steps: Adding compound A, 2-cycloheptene-1-one and a catalyst to compound B in sequence, heating and refluxing to obtain the nitrobicyclodecene derivative; The structural formula of the compound A is shown in formula (2): The structural formula of the compound B is shown in formula (3): R2OH Formula (3); The catalyst is aluminum chloride.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the compound A to 2-cyclohepten-1-one is 7.8:11.

7.

4. The preparation method according to claim 2, characterized in that: The heating reflux reaction time is 1 to 3 hours.

5. Use of the nitrobicyclodecene derivative according to claim 1 in the preparation of an agent for controlling pests; The pest is Bemisia tabaci.

6. The use according to claim 5, characterized in that: The pesticides for controlling pests include pesticides for killing or preventing pests.

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