4-(cyanomethylene)-3, 4-dihydropyridone compound as well as synthesis method and application thereof

Abstract

The invention discloses a 4-(cyanomethylene)-3, 4-dihydropyridone compound and a synthesis method and application thereof.The synthesis method comprises the steps that a 1-enoyl cyclopropanamide compound and a cyanomethyl phosphodiester compound serve as raw materials, organic alkali serves as a catalyst, the raw materials are dissolved in an organic solvent, and the raw materials are reacted at the temperature of 50-60 DEG C to obtain the 4-(cyanomethylene)-3, 4-dihydropyridone compound. The preparation method comprises the following steps: carrying out intramolecular N-nucleophilic addition, intermolecular condensation and phosphodiesters removal reaction by heating to obtain the 4-(cyanomethylene)-3, 4-dihydropyridone compound. According to the synthesis method, the used raw materials are wide in source, simple and easy to obtain, the reaction condition is mild, the product stability is high, the yield is good, and the obtained 4-(cyanomethylene)-3, 4-dihydropyridone compound has excellent insecticidal activity and has good application prospects in the field of insecticidal drugs.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and in particular relates to a 4-(cyanomethylene)-3,4-dihydropyridinone compound, a synthesis method thereof, and an application thereof. Background Art

[0002] In the 1970s, based on computational chemistry and structure design methods, scholars obtained a very effective nicotine insecticide ingredient - nitrothiazine. However, due to its defect of being easily decomposed by light, later researchers successively developed different generations of neonicotinoid insecticides on its basis: imidacloprid 1, imidacloprid 2, thiamethoxam 3, nitenpyram 4. The evolution of nicotine insecticides and the structural formulas of neonicotinoid insecticides are shown as follows.

[0003]

[0004] Analyzing from the evolution of nicotine insecticides and the structures of neonicotinoid insecticides, it is found that most compounds contain X structures and Y structures of C=C-NO2 or C=N-NO2(CN), and the Y structure is a heterocyclic structure or a chain structure.

[0005] Neonicotinoid insecticides are currently the most widely used insecticides in the fields of agriculture and forestry. Their core mechanism of action is to interfere with the nicotinic acetylcholine receptors (nAChRs) in the insect nervous system, resulting in blocked nerve conduction in insects and ultimately causing paralysis and death. Neonicotinoid insecticides have biochemical characteristics such as high insecticidal efficiency, broad insecticidal spectrum, low toxicity to non-target organisms, no cross-resistance with traditional insecticides (such as carbamates, organophosphates, cyclodienes, pyrethroids), good plant systemicity, novel mechanism of action, and high environmental compatibility. In particular, they have very good control effects on piercing-sucking mouthpart pests (such as aphids and leafhoppers). Therefore, this type of insecticide has been widely used worldwide. However, with the large-scale use of the above-mentioned neonicotinoid insecticides, two major problems have gradually emerged: First, it causes a certain degree of damage to the environment; second, the resistance of pests to this type of neonicotinoid insecticides is continuously increasing, resulting in a significant weakening of the insecticidal effect. Therefore, there is an urgent need for a low-toxic and highly effective alternative product in the market. Summary of the Invention

[0006] To solve the above problems, the object of the present invention is to provide a 4-(cyanomethylene)-3,4-dihydropyridinone compound, which is highly similar in structure to neonicotinoid insecticides and has a C=C-CN group similar to the X structure in most neonicotinoid insecticides in Formula 1 above and a heterocyclic skeleton (pyridinone) in the Y structure; a synthesis method of the above 4-(cyanomethylene)-3,4-dihydropyridinone compound is also provided; at the same time, the application of the above 4-(cyanomethylene)-3,4-dihydropyridinone compound is provided. The target of neonicotinoid insecticides is the nicotinic acetylcholine receptor. According to the principle that similar structures are likely to act on the same target, the synthesis of the 4-(cyanomethylene)-3,4-dihydropyridinone compound provides an innovative direction and alternative varieties for specific insecticides targeting this target.

[0007] To achieve the above object of the invention, the following technical scheme is adopted:

[0008] A 4-(cyanomethylene)-3,4-dihydropyridinone compound, the structural formula of which is:

[0009]

[0010] Wherein, Ar 1 is selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 4-ClC6H4, 2-MeC6H4, 2,4-Me2C6H3, 2-ClC6H4, Bn;

[0011] Ar 2 is selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 2-MeC6H4, 4-ClC6H4, 2-pyridyl.

[0012] A synthesis method of a 4-(cyanomethylene)-3,4-dihydropyridinone compound, which uses a 1-acylcyclopropanecarboxamide compound A and a cyanomethyl phosphodiester compound B as raw materials, an organic base as a catalyst, is dissolved in an organic solvent, and through heating, an intramolecular N-nucleophilic addition, an intermolecular condensation, and a dephosphodiester reaction are carried out to obtain a 4-(cyanomethylene)-3,4-dihydropyridinone compound C;

[0013] The reaction route is as follows:

[0014]

[0015] Wherein, Ar 1 is selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 4-ClC6H4, 2-MeC6H4, 2,4-Me2C6H3, 2-ClC6H4, Bn;

[0016] Ar2 Selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 2-MeC6H4, 4-ClC6H4, 2-pyridyl;

[0017] R is selected from Et or iPr.

[0018] Furthermore, the molar ratio of the above-mentioned 1-enoylcyclopropanecarboxamide compound A to the cyanomethyl phosphodiester compound B is 1:1 to 1.2, and the dosage ratio of the 1-enoylcyclopropanecarboxamide compound A, the organic solvent, and the organic base is 1 mmol: 6 - 8 mL: 0.5 - 1.0 mmol.

[0019] Furthermore, the above-mentioned organic base is one of 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-dimethylaminopyridine, 1,5-diazabicyclo[4.3.0]-5-nonene.

[0020] Furthermore, the above-mentioned organic solvent is acetonitrile or ethanol.

[0021] Furthermore, the above-mentioned reaction temperature is 60 - 80 °C.

[0022] Furthermore, the above-mentioned reaction time is 10 - 15 h.

[0023] Furthermore, for the synthesis method of the above-mentioned 4-(cyanomethylene)-3,4-dihydropyridinone compounds, the reaction process is monitored by thin-layer chromatography TLC. After the reactant 1-enoylcyclopropanecarboxamide compound A completely disappears, water is added to the reaction system to stop the reaction, and then extraction is carried out with an extractant, and the organic phases are combined; then the organic phase is dried with a desiccant, filtered, concentrated, and column chromatographed to obtain the 4-(cyanomethylene)-3,4-dihydropyridinone compound C.

[0024] Even further, the above-mentioned extractant is dichloromethane, ethyl acetate, or diethyl ether.

[0025] Even further, the above-mentioned organic phase desiccant is anhydrous sodium sulfate, anhydrous calcium chloride, or anhydrous magnesium sulfate.

[0026] Another object of the present invention is to provide an application of a 4-(cyanomethylene)-3,4-dihydropyridinone compound in the preparation of insecticidal drugs.

[0027] Furthermore, the above-mentioned insecticidal drug is a drug for controlling aphids, diamondback moths, and Spodoptera litura.

[0028] A method for testing the insecticidal activity of 4-(cyanomethylene)-3,4-dihydropyridinone compounds. An indoor general screening activity experiment is carried out on agricultural pests, and the feed mixing method is used to test the insecticidal activity of 4-(cyanomethylene)-3,4-dihydropyridinone compounds. At the general screening concentration of 500 μg / mL, compound C has good insecticidal activity. For different pests, such as aphids, diamondback moths, and Spodoptera litura, the mortality rate is between 50% and 95%.

[0029] Due to the adoption of the above-mentioned technical solution, the present invention has the following advantages:

[0030] The 4-(cyanomethylene)-3,4-dihydropyridinone compounds of the present invention are constructed in one step through a tandem reaction process of intramolecular N-nucleophilic addition, intermolecular condensation, and dephosphorylation of dimethyl phosphate to form a series of multi-functionalized 4-(cyanomethylene)-3,4-dihydropyridinone compounds.

[0031] The synthesis method of the 4-(cyanomethylene)-3,4-dihydropyridinone compounds of the present invention uses raw materials with wide sources, which are simple and easy to obtain. The reaction conditions are mild, the structure has diversity, it is easy to operate, the steps are economical, the product has high stability, and the yield is good.

[0032] The 4-(cyanomethylene)-3,4-dihydropyridinone compounds of the present invention have excellent insecticidal activity, have important scientific value and practical application prospects in the field of pesticides, can provide a unique neonicotinoid insecticide for the control of pests in agricultural production, provide a rich screening library and design ideas for specific insecticides targeting nicotinic acetylcholine receptors, and have good application prospects in the field of insecticidal drugs. Description of the Drawings

[0033] Figure 1 is the hydrogen spectrum of the target product C1 in Example 1;

[0034] Figure 2 is the carbon spectrum of the target product C1 in Example 1;

[0035] Figure 3 is the hydrogen spectrum of the target product C2 in Example 2;

[0036] Figure 4 is the carbon spectrum of the target product C2 in Example 2;

[0037] Figure 5 is the hydrogen spectrum of the target product C3 in Example 3;

[0038] Figure 6 is the carbon spectrum of the target product C3 in Example 3;

[0039] Figure 7It is the single crystal structure diagram of the target product C7 in Example 7. Detailed implementation mode

[0040] The present invention can be further described in detail with reference to the following examples; however, the following examples are merely illustrative, and the present invention is not limited to these examples.

[0041] In each of the following examples, for the selection of organic bases, DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene, DMAP is 4-dimethylaminopyridine, and DBN is 1,5-diazabicyclo[4.3.0]-5-nonene.

[0042] Example 1

[0043] Add 1-acryloylcyclopropanecarboxamide compound A1 (291 mg, 1 mmol), diethyl cyanomethylphosphonate B1 (0.16 mL, 1 mmol), and EtOH (6 mL) to a 50 mL pressure-resistant bottle, and then slowly add DBU (0.15 mL, 1 mmol). Stir at 70 °C for 12 h; monitor the reaction by TLC until reactant A1 completely disappears, then pour the reaction solution into ice water, stir vigorously, and extract three times with dichloromethane (3×10 mL). Combine the organic phases; then dry the organic phase with anhydrous sodium sulfate, rotary evaporate to remove the solvent, and purify by column chromatography to obtain 284 mg of white target product C1 with a yield of 91%.

[0044] Specific reaction formula:

[0045]

[0046] Spectral data of compound C1: 1 H NMR (CDCl3, 400 MHz): δ: 1.08 (q, J = 4.0 Hz, 2H), 1.80 (q, J = 4.0 Hz, 2H), 5.61 (s, 1H), 7.07 - 7.11 (m, 1H), 7.23 - 7.31 (m, 2H), 7.35 (s, 1H), 7.37 - 7.41 (m, 5H), 7.54 - 7.56 (m, 2H); 13 C NMR (CDCl3, 100 MHz): δ: 16.4, 29.3, 101.3, 116.2, 120.2, 123.5, 124.8, 128.0, 129.0, 129.1, 130.3, 134.8, 137.3, 139.9, 157.5, 168.8.

[0047] The hydrogen spectrum and carbon spectrum of compound C1 are shown respectively in Figure 1 and Figure 2 .

[0048] Insecticidal activity test of compound C1: Using Spodoptera litura as the test object, the feed mixing method was adopted; 10 mg of compound C1 sample was weighed, then 2 mL of DMSO (dimethyl sulfoxide) solvent was taken with a 5 mL pipette and dissolved, and 18 mL of an aqueous solution containing 0.1% (w / v) Tween-80 was added, and mixed well to obtain a determination solution of 500 μg / mL. The results showed that the mortality rate of Spodoptera litura reached 64% after 48 h.

[0049] Example 2

[0050] 1-Alkenoyl cyclopropanecarboxamide compound A2 (321 mg, 1 mmol), diethyl cyanomethylphosphonate B1 (0.16 mL, 1 mmol), and EtOH (6 mL) were added to a 50 mL pressure-resistant bottle, and then DBU (0.15 mL, 1 mmol) was slowly added, and the mixture was stirred at 70 °C for 12 h; the reaction was monitored by TLC until the reactant A2 completely disappeared, then the reaction solution was poured into ice water, stirred vigorously, and extracted three times with ethyl acetate (3×10 mL), and the organic phases were combined; then the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and the product was separated and purified by column chromatography to obtain 301 mg of white target product C2, with a yield of 88%.

[0051] Specific reaction formula:

[0052]

[0053] Spectral data of compound C2: 1 H NMR (CDCl3, 400 MHz): δ: 1.06 (d, J = 4.0 Hz, 2H), 1.77 (d, J = 4.0 Hz, 2H), 3.75 (s, 3H), 5.60 (s, 1H), 6.81 (d, J = 8.0 Hz, 2H), 7.19 (s, 1H), 7.27 - 7.34 (m, 1H), 7.38 - 7.44 (m, 4H), 7.55 (q, J = 8.0 Hz, 2H); 1313C NMR (CDCl3, 100 MHz): δ: 16.3, 29.1, 55.5, 101.2, 114.1, 116.3, 122.3, 123.6, 127.9, 129.0, 130.2, 130.5, 134.9, 139.8, 156.8, 157.6, 168.8.

[0054] The 1H NMR spectrum and 13C NMR spectrum of Compound C2 are shown in Figure 3 and Figure 4 .

[0055] Insecticidal activity test of Compound C2: Using Spodoptera litura as the test object, the feed mixing method was adopted; 10 mg of Compound C2 sample was weighed, then 2 mL of DMSO solvent was taken with a 5 mL pipette and dissolved, and 18 mL of aqueous solution containing 0.1% Tween-80 was added and mixed well to obtain a 500 μg / mL test solution. The results showed that the mortality rate of Spodoptera litura after 48 h reached 56%.

[0056] Example 3

[0057] To a 50 mL pressure-resistant flask, 1-acylcyclopropanecarboxamide Compound A3 (325 mg, 1 mmol), diisopropyl cyanomethylphosphonate B2 (0.2 mL, 1 mmol), and EtOH (8 mL) were added. Then, DBU (0.18 mL, 1 mmol) was slowly added, and the mixture was stirred at 60 °C for 12 h; the reaction was monitored by TLC until Compound A3 completely disappeared. Then, the reaction solution was poured into ice water, stirred vigorously, and extracted three times with dichloromethane (3 × 10 mL). The organic phases were combined; then the organic phase was dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and the product was purified by column chromatography to obtain 280 mg of white target product C3 with a yield of 81%.

[0058] Specific reaction formula:

[0059]

[0060] Spectral data of Compound C3: 11H NMR (CDCl3, 400 MHz): δ: 1.08 (d, J = 4.0 Hz, 2H), 1.78 (d, J = 4.0 Hz, 2H), 5.62 (s, 1H), 7.10 (t, J = 8.0 Hz, 1H), 7.24 - 7.27 (m, 1H), 7.28 - 7.31 (m, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.39 - 7.41 (m, 2H), 7.47 (d, J = 8.0 Hz, 2H); 13 13C NMR (CDCl3, 100 MHz): δ: 16.3, 29.3, 101.7, 116.1, 120.3, 124.0, 124.9, 129.0, 129.1, 129.3, 133.4, 136.1, 137.4, 138.4, 157.2, 168.7.

[0061] The 1H NMR spectrum and 13C NMR spectrum of Compound C3 are shown in Figure 5 and Figure 6 .

[0062] Insecticidal activity test of Compound C3: Using Plutella xylostella as the test object, the feed mixing method was adopted; 10 mg of Compound C3 sample was weighed, then 2 mL of DMSO solvent was taken with a 5 mL pipette and dissolved, and 18 mL of aqueous solution containing 0.1% Tween - 80 was added. After thorough mixing, a 500 μg / mL determination solution was obtained. The results showed that the mortality rate of Plutella xylostella after 48 h reached 88%.

[0063] Example 4

[0064] Add 1 - acylcyclopropanecarboxamide Compound A4 (321 mg, 1 mmol) and diethyl cyanomethylphosphonate B1 (0.16 mL, 1 mmol), CH3CN (6 mL) to a 50 mL pressure - resistant flask. Then, slowly add DBU (0.15 mL, 1 mmol), and stir at 80 °C for 15 h; monitor the reaction by TLC until Compound A4 completely disappears. Then, pour the reaction solution into ice water, stir vigorously, and extract three times with dichloromethane (3 × 10 mL). Combine the organic phases; then dry the organic phase with anhydrous calcium chloride, remove the solvent by rotary evaporation, and purify by column chromatography to obtain 287 mg of the white target product C4 with a yield of 84%.

[0065] Specific reaction formula:

[0066]

[0067] Spectral data of Compound C4: 1 1H NMR (CDCl3, 400 MHz): δ: 1.08 (d, J = 4.0 Hz, 2H), 1.78 (d, J = 4.0 Hz, 2H), 3.84 (s, 3H), 5.53 (s, 1H), 6.91 (d, J = 8.0 Hz, 2H), 7.07 - 7.11 (m, 1H), 7.26 - 7.30 (m, 3H), 7.39 (d, J = 8.0 Hz, 2H), 7.50 (d, J = 8.0 Hz, 2H); 13 13C NMR (CDCl3, 100 MHz): δ: 16.4, 29.3, 55.4, 99.7, 114.5, 116.5, 120.2, 121.3, 124.7, 127.6, 129.0, 129.6, 137.4, 139.5, 157.8, 161.4, 169.0.

[0068] Insecticidal activity test of Compound C4: Taking aphids as the test object, the feed - mixing method of medicine was adopted; Weighed 10 mg of Compound C4 sample, then used a 5 - mL pipette to take 2 mL of DMSO solvent to dissolve it, added 18 mL of aqueous solution containing 0.1% Tween - 80, and mixed well to obtain a determination solution of 500 μg / mL. The results showed that the mortality rate of aphids after 48 h reached 66%.

[0069] Example 5

[0070] Add 1 - enoyl - cyclopropanecarboxamide compound A5 (305 mg, 1 mmol) and diethyl cyanomethylphosphonate B1 (0.16 mL, 1 mmol), CH3CN (8 mL) to a 50 - mL pressure - resistant bottle. Then, slowly add DBN (0.11 mL, 1 mmol), and stir at 70 °C for 14 h; Monitor the reaction by TLC. After the reactant A5 completely disappeared, pour the reaction solution into ice water, stir vigorously, and extract three times with ether (3×10 mL). Combine the organic phases; Then dry the organic phase with anhydrous sodium sulfate, remove the solvent by rotary evaporation, and purify by column chromatography to obtain 254 mg of white target product C5, with a yield of 78%.

[0071] Specific reaction formula:

[0072]

[0073] Spectral data of Compound C5: 11H NMR (CDCl3, 400 MHz): δ: 1.11 (d, J = 4.0 Hz, 2H), 1.82 (d, J = 4.0 Hz, 2H), 4.50 (q, J = 16.0 Hz, 2H), 5.64 (s, 1H), 7.02 - 7.06 (m, 1H), 7.23 - 7.27 (m, 2H), 7.32 - 7.43 (m, 8H); 13 13C NMR (CDCl3, 100 MHz): δ: 20.1, 30.7, 51.2, 98.9, 101.3, 119.5, 126.3, 126.9, 127.2, 128.0, 128.5, 128.6, 128.9, 138.1, 138.6, 165.8, 173.0.

[0074] Insecticidal activity test of Compound C5: Using Spodoptera litura as the test object, the feed - mixing method of adding medicine was adopted; 10 mg of Compound C5 sample was weighed, then 2 mL of DMSO solvent was taken with a 5 - mL pipette to dissolve it, and 18 mL of aqueous solution containing 0.1% Tween - 80 was added and mixed well to obtain a determination solution of 500 μg / mL. The results showed that the mortality rate of Spodoptera litura after 48 h reached 73%.

[0075] Example 6

[0076] Add 1 - enoyl cyclopropanecarboxamide Compound A6 (292 mg, 1 mmol) and diethyl cyanomethylphosphonate B1 (0.19 mL, 1.2 mmol), CH3CN (8 mL) to a 50 - mL pressure - resistant bottle. Then, slowly add DMAP (98 mg, 0.8 mmol), and stir at 80 °C for 10 h; Monitor the reaction by TLC. After the reactant A6 completely disappeared, pour the reaction solution into ice water, stir vigorously, and extract three times with dichloromethane (3 × 10 mL). Combine the organic phases; Then dry the organic phase with anhydrous magnesium sulfate, evaporate the solvent by rotary evaporation, and separate and purify by column chromatography to obtain 235 mg of the white target product C6 with a yield of 75%.

[0077] Specific reaction formula:

[0078]

[0079] Spectral data of Compound C6: 11H NMR (CDCl3, 400 MHz): δ: 1.06 (d, J = 4.0 Hz, 2H), 1.76 (d, J = 4.0 Hz, 2H), 5.72 (s, 1H), 7.07 - 7.22 (m, 3H), 7.29 - 7.31 (m, 2H), 7.50 - 7.64 (m, 4H), 8.57 - 8.59 (m, 1H); 13 13C NMR (CDCl3, 100 MHz): δ: 16.9, 29.5, 101.4, 116.4, 120.2, 120.3, 122.3, 122.9, 124.2, 128.9, 135.5, 136.3, 138.0, 149.8, 154.8, 162.1, 163.2.

[0080] Insecticidal activity test of Compound C6: Using aphids as the test object, the feed - mixing method of adding drugs was adopted; 10 mg of Compound C6 sample was weighed, then 2 mL of DMSO solvent was taken with a 5 - mL pipette and dissolved, and 18 mL of aqueous solution containing 0.1% Tween - 80 was added. After thorough mixing, a determination solution of 500 μg / mL was obtained. The results showed that the mortality rate of aphids after 48 h was as high as 92%.

[0081] Example 7

[0082] Add 1 - enoyl - cyclopropanecarboxamide Compound A7 (325 mg, 1 mmol), diethyl cyanomethylphosphonate B1 (0.16 mL, 1 mmol), and EtOH (8 mL) to a 50 - mL pressure - resistant bottle. Then, slowly add DBU (0.14 mL, 0.9 mmol), and stir at 70 °C for 12 h; monitor the reaction by TLC until the reactant A1 completely disappears. Then, pour the reaction solution into ice water, stir vigorously, and extract with dichloromethane three times (3×10 mL). Combine the organic phases; then dry the organic phase with anhydrous sodium sulfate; remove the solvent by rotary evaporation, and separate and purify by column chromatography to obtain 284 mg of the white target product C7 with a yield of 82%.

[0083] Specific reaction formula:

[0084]

[0085] Spectral data of Compound C7: 11H NMR (CDCl3, 400 MHz): δ: 1.10 (d, J = 4.0 Hz, 2H), 1.80 (d, J = 4.0 Hz, 2H), 5.61 (s, 1H), 7.22 - 7.28 (m, 2H), 7.32 - 7.35 (m, 2H), 7.36 - 7.41 (m, 4H), 7.54 - 7.56 (m, 2H); 13 13C NMR (CDCl3, 100 MHz): δ: 16.5, 29.3, 101.4, 121.5, 123.4, 127.9, 129.0, 129.1, 129.9, 130.3, 134.8, 135.9, 140.0, 157.2, 157.5, 168.9.

[0086] The single - crystal structure of Compound C7 is as Figure 7 shown.

[0087] Insecticidal activity test of Compound C7: Using Spodoptera litura as the test object, the feed - mixing method of adding medicine was adopted; Weigh 10 mg of Compound C6 sample, then use a 5 - mL pipette to take 2 mL of DMSO solvent to dissolve it, add 18 mL of aqueous solution containing 0.1% Tween - 80, and mix well to obtain a determination solution of 500 μg / mL. The results show that the mortality rate of aphids after 48 h is 82%.

[0088] The above - mentioned are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A 4-(cyanomethylene)-3,4-dihydropyridinone compound, characterized in that: Its structural formula is as follows: Among them, Ar 1 is selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 4-ClC6H4, 2-MeC6H4, 2,4-Me2C6H3, 2-ClC6H4, Bn; Ar 2 Selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 2-MeC6H4, 4-ClC6H4, 2-pyridyl.

2. A method for synthesizing 4-(cyanomethylene)-3,4-dihydropyridinone compounds, characterized in that: Using 1-acyl cyclopropanecarboxamide compound A and cyanomethyl phosphodiester compound B as raw materials, an organic base as a catalyst, dissolved in an organic solvent, through intramolecular N-nucleophilic addition, intermolecular condensation, and dephosphodiester reaction by heating, 4-(cyanomethylene)-3,4-dihydropyridinone compound C is obtained; The reaction route is as follows: Among them, Ar 1 is selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 4-ClC6H4, 2-MeC6H4, 2,4-Me2C6H3, 2-ClC6H4, Bn; Ar 2 selected from one of Ph, 4-MeC6H4, 4-MeOC6H4, 2-MeC6H4, 4-ClC6H4, 2-pyridyl; R is selected from Et or iPr.

3. The synthetic method of 4-(cyanomethylene)-3,4-dihydropyridinone compounds according to claim 2, wherein: The molar ratio of the 1-acyl cyclopropanecarboxamide compound A to the cyanomethyl phosphodiester compound B is 1:1 to 1.2, and the dosage ratio of the 1-acyl cyclopropanecarboxamide compound A, the organic solvent, and the organic base is 1 mmol: 6 - 8 mL: 0.5 - 1.0 mmol.

4. The synthetic method of 4-(cyanomethylene)-3,4-dihydropyridinone compounds according to claim 2, characterized in that: The organic base is one of 1,8-diazabicyclo[5.4.0]undec-7-ene, 4-dimethylaminopyridine, and 1,5-diazabicyclo[4.3.0]-5-nonene.

5. The synthetic method of 4-(cyanomethylene)-3,4-dihydropyridinone compounds according to claim 2, characterized in that: The organic solvent is acetonitrile or ethanol.

6. The synthetic method of 4-(cyanomethylene)-3,4-dihydropyridinone compounds according to claim 2, characterized in that: The reaction temperature is 60 - 80 °C.

7. The synthetic method of the 4-(cyanomethylene)-3,4-dihydropyridinone compound according to claim 2, wherein: The reaction time is 10 - 15 h.

8. The synthetic method of 4-(cyanomethylene)-3,4-dihydropyridinone compounds according to claim 2, characterized in that: Monitor the reaction process by thin-layer chromatography TLC. After the reactant 1-acyl cyclopropanecarboxamide compound A completely disappears, add water to the reaction system to stop the reaction, and then extract with an extractant and combine the organic phases; then dry the organic phase with a desiccant, filter, concentrate, and perform column chromatography to obtain 4-(cyanomethylene)-3,4-dihydropyridinone compound C.

9. Use of the 4-(cyanomethylene)-3,4-dihydropyridinone compound according to claim 1 in the preparation of an insecticidal drug.

10. The application according to claim 9, characterized in that: The insecticidal drug is a drug for controlling aphids, diamondback moths, and Spodoptera litura.

Images