CN107098894B - N- (2-thienyl) methylene-2-cyano-3-heterocyclic acryloyl hydrazine derivative and application thereof - Google Patents

Abstract

The invention relates to a heterocyclic Schiff base compound and application thereof, in particular to an N- (2-thienyl) methylene-2-cyano-3-heterocyclic acryloyl hydrazine derivative and application thereof. The technical problem to be solved by the invention is to provide a heterocyclic Schiff base compound which can be used as an antioxidant and an agricultural insecticide and has a structural formula shown in a formula I. According to the invention, a principle of splicing bioactive groups is adopted, and a heterocyclic compound is introduced into a Schiff base compound, so that active compounds or active lead compounds with novel structures and excellent activity are found, and a better foundation is laid for the creation of novel antioxidants and insecticides.

Description

N-(2-thienyl)methylene-2-cyano-3-heterocyclylacrylohydrazide derivatives and its application

technical field

The present invention relates to heterocyclic Schiff base compounds and uses thereof, in particular to N-(2-thienyl)methylene-2-cyano-3-heterocyclic acrylohydrazide derivatives and applications thereof.

Background technique

Antioxidants can effectively delay or inhibit the oxidative deterioration of many substances, especially sugars, lipids, proteins, nucleic acids and other biological macromolecules, and are widely used in many fields: (1) In food processing, antioxidants can inhibit Oil is oxidized to prevent its rancidity, and is often used as an antioxidant additive in food; (2) In the fields of life science and medicine, antioxidants can scavenge free radicals in the body, slow down the formation of the body's peroxidative state, and prevent and treat various diseases caused by free radicals. , to improve the body's immunity, thereby protecting human health; (3) in the chemical industry, antioxidants are used as stability additives for chemical products to improve the antioxidant properties of products, thereby extending their service life. Because antioxidants play an irreplaceable role in industrial and agricultural production and daily life, the research and development of efficient, economical, and low-toxic antioxidants is of great significance.

On the other hand, the long-term and large-scale use of pesticides, especially pesticides, not only pollutes the environment and destroys the ecological balance, but also leads to serious "3Rs" (residues, resistance, and rampant pests) and "three causes" (carcinogenic, teratogenicity and mutagenicity). These problems have aroused extensive attention of human beings, and how to effectively solve these problems is a long-term and arduous task facing human beings. In this way, under the circumstance that pesticides are facing huge challenges, and human beings cannot do without pesticides, it is necessary to look for "high-efficiency pests, non-target biosafety, easy degradation in the environment, and degradation products that are safe for human health and the ecological environment." "Environmentally Harmonious Pesticide" or "Green Pesticide" has become the hotspot and frontier of pesticide research.

Schiff bases refer to a class of organic compounds containing >C=N- structures generated by the condensation reaction of primary amines with aldehydes or ketones, which can be obtained either from natural products or by synthetic methods. A large number of studies have shown that Schiff base compounds have a very important role in the fields of medicine, catalysis, analytical chemistry, corrosion and photochromism. At the same time, Schiff base compounds also have good biological activities, such as insecticidal, antifungal, antibacterial, anticancer, antiparasitic, herbicidal and so on. Therefore, in recent decades, people have shown great interest in its research and development, especially in the fields of biology, medicine, pesticides, etc. Unique, environmentally friendly varieties are introduced.

In recent years, heterocyclic compounds have shown an increasingly important role in the research and development of biologically active compounds. Because of its good selectivity, high activity, low dosage, low toxicity and specificity in the physiological and biochemical reactions of harmful organisms, it has become the main body of research. Among them, furan, thiophene, pyridine, pyrimidine, pyrazole, imidazole, thiazole, triazole and other compounds have attracted people's attention due to the emergence of some epoch-making novel agents, and have also become the hotspot and frontier of bioactive compound research .

So far, there are no reports on the use of heterocyclic Schiff bases as antioxidants and agricultural pesticides.

SUMMARY OF THE INVENTION

The technical problem solved by the present invention is to provide a heterocyclic Schiff base compound that can be used as antioxidants and agricultural pesticides.

The N-(2-thienyl)methylene-2-cyano-3-heterocyclylacrylohydrazide derivatives of the present invention have the structural formula shown in formula I:

where _R1 is

R ₂ is hydrogen or halogen;

R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S.

Preferably, R ₁ is R ₂ is hydrogen; R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S.

More preferably, R ₁ is R ₂ is hydrogen.

Preferably, R ₁ is R ₂ is halogen; R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S.

More preferably, R ₁ is R ₂ is bromine; R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S.

Further preferably, R ₁ is R ₂ is bromine.

The present invention also provides the use of the compounds of the present invention in the preparation of antioxidants.

The compounds of the present invention have excellent antioxidant properties and can be used as antioxidants.

The present invention also provides the use of the compounds of the present invention in controlling agricultural pests.

The compounds of the present invention can also be used as insecticides, and have good poisoning activity against agricultural pests such as armyworm, corn borer, Tetranychus cinnabarinus, and Culex pipiens pallens. Therefore, it is preferred that the agricultural pest is armyworm, corn borer, Tetranychus cinnabarinus or Culex pipiens pipiens.

The invention adopts the principle of bioactive group splicing, introduces heterocyclic compounds into Schiff base compounds, and discovers some active compounds or active leading compounds with novel structures and excellent activities, thereby laying a solid foundation for the creation of new antioxidants and pesticides. better foundation.

Detailed ways

The present invention provides a compound whose structural formula is shown in formula I:

where _R1 is

R ₂ is hydrogen or halogen;

R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S.

Preferably, R ₁ is R ₂ is hydrogen; R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S. More preferably, R ₁ is R ₂ is hydrogen. Further preferably, R ₁ is R ₂ is hydrogen.

Another preferred, R ₁ is R ₂ is halogen; R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S. More preferably, R ₁ is R ₂ is bromine; R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S. Further preferably, R ₁ is R ₂ is bromine. More preferably, R ₁ is R ₂ is bromine.

The following are the preferred structural formulas of the present invention.

The compounds of the present invention can be obtained by conventional preparation methods.

The compounds of the present invention have excellent antioxidant properties and can be used as antioxidants.

The compounds of the present invention can also be used as insecticides, and have good poisoning activity against agricultural pests such as armyworm, corn borer, Tetranychus cinnabarinus, and Culex pipiens pallens.

The specific embodiments of the present invention will be further described below with reference to the examples, but the present invention is not limited to the scope of the described examples.

Example 1 Synthesis of Compounds 1 to 9

Synthesis principle:

1. Synthesis of compound 1

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01mol of thiophene-2-carbaldehyde and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5h, and detect the end point with a thin-layer silica gel plate (TLC). The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of furfural and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-neck flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Yellow powder; IR(KBr)ν _max (cm- ¹ ): 3423, 2207, 1685, 1612, 1557, 937; ¹ H NMR (300MHz, DMSO-d ₆ )δ(ppm): 11.77(1H,s), 8.66(1H,s), 8.16(1H,s), 8.07(1H,s), 7.68(1H,s), 7.48(1H,s), 7.45(1H,d,J=2.4Hz), 7.14(1H , s), 6.84 (1H, d, J=1.5 Hz); ¹³ C NMR (75 MHz, DMSO-d ₆ ) δ (ppm): 158.28 (1C), 149.40 (1C), 148.79 (1C), 144.69 (1C ), 139.00(1C), 136.98(1C), 131.98(1C), 129.84(1C), 128.28(1C), 122.70(1C), 116.15(1C), 114.37(1C), 100.00(1C); HRMS(ESI) )m/z:Calcd for C ₁₃ H ₁₀ N ₃ O ₂ S[M+H] ⁺ :272.0488,Found:272.0488.

2. Synthesis of compound 2

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01mol of thiophene-2-carbaldehyde and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5h, and detect the end point with a thin-layer silica gel plate (TLC). The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of 5-methylfurfural and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Yellow powder; IR(KBr)ν _max (cm- ¹ ): 3441, 2208, 1672, 1604, 1543, 941; ¹ H NMR (400MHz, DMSO-d ₆ )δ(ppm): 11.67(1H,s), 8.66(1H,s), 7.97(1H,s), 7.70(1H,d,J=4.4Hz), 7.48(1H,d,J=3.2Hz), 7.39(1H,d,J=3.2Hz), 7.15 (1H, t, J=4.0 Hz), 6.53 (1H, d, J=3.6 Hz), 2.44 (3H, s); ¹³ C NMR (100 MHz, DMSO-d ₆ ) δ (ppm): 159.89 (1 C ), 158.66(1C), 147.75(1C), 144.56(1C), 139.19(1C), 136.70(1C), 131.97(1C), 129.86(1C), 128.37(1C), 124.86(1C), 116.49(1C) ), 111.60(1C), 97.81(1C), 14.35(1C); HRMS(ESI) m/z: Calcd for C ₁₄ H ₁₂ N ₃ O ₂ S[M+H] ⁺ : 286.0645, Found: 286.0641.

3. Synthesis of compound 3

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01mol of thiophene-2-carbaldehyde and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5h, and detect the end point with a thin-layer silica gel plate (TLC). The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of thiophene-2-carbaldehyde and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Yellow powder; IR(KBr)ν _max (cm- ¹ ): 3433, 2207, 1682, 1581, 1551, 931; ¹ H NMR (300MHz, DMSO-d ₆ )δ(ppm): 11.79(1H,s), 8.66(1H,s),8.51(1H,s),8.13(1H,d,J=4.2Hz),7.96(1H,s),7.68(1H,s),7.49(1H,s),7.33(1H ,s), 7.14(1H,s); ¹³ C NMR (75MHz, DMSO-d ₆ )δ(ppm): 158.29(1C), 144.92(1C), 144.65(1C), 138.98(1C), 138.84(1C ), 136.25(1C), 135.93(1C), 131.98(1C), 129.85(1C), 129.02(1C), 128.28(1C), 116.60(1C), 100.79(1C); HRMS(ESI) m/z: Calcd for C ₁₃ H ₁₀ N ₃ OS ₂ [M+H] ⁺ :288.0260,Found:288.0255.

4. Synthesis of compound 4

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01mol of thiophene-2-carbaldehyde and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5h, and detect the end point with a thin-layer silica gel plate (TLC). The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of 2-furyl acrolein and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to the three-necked flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). . After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Yellow powder; IR(KBr)ν _max (cm- ¹ ): 3425, 2210, 1678, 1596, 1551, 926; ¹ H NMR (400MHz, DMSO-d ₆ )δ(ppm): 11.78(1H,s), 8.65(1H,s),8.09(1H,d,J=12.0Hz),7.97(1H,s),7.71(1H,d,J=4.4Hz),7.50(1H,s),7.44(1H,d , J=14.8 Hz), 7.16 (1H, s), 7.04-6.94 (2H, m), 6.72 (1H, dd, J ₁ =1.6 Hz, J ₂ =1.6 Hz); ¹³ C NMR (100 MHz, DMSO- d ₆ )δ(ppm): 158.13(1C), 152.46(1C), 151.59(1C), 147.36(1C), 144.58(1C), 139.15(1C), 133.84(1C), 132.07(1C), 129.93( 1C), 128.38(1C), 120.79(1C), 117.54(1C), 115.64(1C), 113.89(1C), 105.55(1C); HRMS(ESI) m/z: Calcd for C ₁₅ H ₁₂ N ₃ O ₂ S[M+H] ⁺ :298.0645,Found:298.0640.

5. Synthesis of compound 5

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01 mol of 5-bromothiophene-2-carbaldehyde and add it to 5 mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5 h, and use a thin-layer silica gel plate (TLC) Endpoint detection. The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of furfural and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-neck flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Yellow powder; IR(KBr)ν _max (cm- ¹ ): 3432, 2215, 1687, 1616, 1554, 931; ¹ H NMR (400MHz, DMSO-d ₆ )δ(ppm): 11.86(1H,s), 8.58(1H,s), 8.19(1H,s), 8.08(1H,s), 7.47(1H,s), 7.36(1H,s), 7.30(1H,d,J=2.8Hz), 6.87(1H , dd, J ₁ =1.6 Hz, J ₂ =1.6 Hz); ¹³ C NMR (100 MHz, DMSO-d ₆ ) δ (ppm): 158.44 (1C), 149.58 (1C), 148.90 (1C), 143.95 (1C ), 141.03(1C), 137.19(1C), 132.58(1C), 131.83(1C), 122.86(1C), 116.19(1C), 115.80(1C), 114.50(1C), 100.06(1C); HRMS(ESI) )m/z:Calcd for C ₁₃ H ₉ BrN ₃ O ₂ S[M+H] ⁺ :349.9593,Found:349.9592.

6. Synthesis of compound 6

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01 mol of 5-bromothiophene-2-carbaldehyde and add it to 5 mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5 h, and use a thin-layer silica gel plate (TLC) Endpoint detection. The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of 5-methylfurfural and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Orange crystal; IR(KBr)ν _max (cm- ¹ ): 3445, 2206, 1672, 1603, 1541, 971; ¹ H NMR (400MHz, DMSO-d ₆ )δ(ppm): 11.75(1H,s), 8.57(1H,s),7.97(1H,s),7.39(1H,s),7.34(1H,d,J=3.6Hz),7.28(1H,d,J=3.2Hz),6.54(1H,d , J=3.2Hz), 2.44 (3H, s); ¹³ C NMR (100MHz, DMSO-d ₆ )δ(ppm): 159.95(1C), 158.70(1C), 147.73(1C), 143.65(1C), 141.10(1C), 136.78(1C), 132.43(1C), 131.76(1C), 124.94(1C), 116.42(1C), 115.71(1C), 111.62(1C), 97.67(1C), 14.36(1C); HRMS(ESI)m/z:Calcd for C ₁₄ H ₁₁ BrN ₃ O ₂ S[M+H] ⁺ :363.9750,Found:363.9750.

7. Synthesis of compound 7

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01 mol of 5-bromothiophene-2-carbaldehyde and add it to 5 mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5 h, and use a thin-layer silica gel plate (TLC) Endpoint detection. The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of thiophene-2-carbaldehyde and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Orange powder; IR(KBr)ν _max (cm- ¹ ): 3433, 2209, 1687, 1584, 1557, 971; ¹ H NMR (400MHz, DMSO-d ₆ )δ(ppm): 11.88(1H,s), 8.57(1H,s), 8.51(1H,s), 8.17(1H,d,J=4.8Hz), 7.98(1H,s), 7.37-7.31(3H,m); ¹³ C NMR (100MHz, DMSO- d ₆ )δ(ppm): 158.48(1C), 145.12(1C), 143.89(1C), 141.01(1C), 139.01(1C), 136.34(1C), 136.14(1C), 132.58(1C), 131.83( 1C), 129.15(1C), 116.66(1C), 115.80(1C), 100.84(1C); HRMS(ESI) m/z: Calcd for C ₁₃ H ₉ BrN ₃ OS ₂ [M+H] ⁺ :365.9365, Found: 365.9365.

8. Synthesis of compound 8

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01 mol of 5-bromothiophene-2-carbaldehyde and add it to 5 mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5 h, and use a thin-layer silica gel plate (TLC) Endpoint detection. The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of 3-pyridinecarboxaldehyde and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Yellow powder; IR(KBr)ν _max (cm- ¹ ): 3445, 2230, 1663, 1614, 1551, 967; ¹ H NMR (400MHz, DMSO-d ₆ )δ(ppm): 12.07(1H,s), 9.05(1H,s),8.77(1H,d,J=4.4Hz),8.59(1H,s),8.45(1H,d,J=8.0Hz),8.34(1H,s),7.67(1H,dd , J ₁ =4.8Hz, J ₂ =5.2Hz), 7.41(1H,d,J=3.6Hz),7.32(1H,d,J=3.6Hz); ¹³ C NMR (100MHz, DMSO-d ₆ )δ (ppm): 158.09(1C), 153.13(1C), 151.86(1C), 149.24(1C), 144.38(1C), 140.81(1C), 136.52(1C), 132.99(1C), 131.93(1C), 128.51 (1C), 124.68(1C), 116.11(1C), 116.06(1C), 107.97(1C); HRMS(ESI) m/z: Calcd for C ₁₄ H ₁₀ BrN ₄ OS[M+H] ⁺ : 360.9753, Found :360.9756.

9. Synthesis of compound 9

(1) Synthesis of intermediates

Place 0.01 mol of cyanoacetazide in a three-necked flask, add 15 mL of dichloromethane as a solvent, 3 mL of acetic acid as a catalyst, and stir at room temperature. Take 0.01 mol of 5-bromothiophene-2-carbaldehyde and add it to 5 mL of dichloromethane. After fully dissolving, add it dropwise to a three-necked flask with a constant pressure dropping funnel, react for 5 h, and use a thin-layer silica gel plate (TLC) Endpoint detection. The reaction solution was placed in a beaker and washed repeatedly with distilled water until neutral. Separation and distillation under reduced pressure, drying after suction filtration to obtain an intermediate.

(2) Synthesis of target compounds

Take 0.01 mol of the intermediate and put it in a three-necked flask, add 15 mL of anhydrous ethanol as a solvent, 3 mL of triethylamine as a catalyst, and stir at 50°C. Take 0.01mol of 2-furyl acrolein and add it to 5mL of dichloromethane. After fully dissolving, add it dropwise to the three-necked flask with a constant pressure dropping funnel, react for 1h, and detect the end point with a thin-layer silica gel plate (TLC). . After the reaction was completed, the reaction solution was poured into a 500 mL beaker, 300 mL of petroleum ether was added and stirred, and solid matter was precipitated. After suction filtration and drying, the crude product was recrystallized with a mixed solution of acetonitrile: anhydrous ethanol=1:10 to obtain the target product.

Yellow powder; IR(KBr)ν _max (cm ^-1 ): 3446, 2213, 1688, 1624, 1557, 929; ¹ H NMR (400MHz, DMSO-d ₆ )δ(ppm): 11.85(1H,s), 8.56(1H,s),8.09(1H,d,J=11.6Hz),7.97(1H,d,J=1.2Hz),7.44(1H,d,J=14.8Hz),7.36(1H,s), 7.30 (1H, d, J=3.2 Hz), 7.04-6.93 (2H, m), 6.72 (1H, dd, J ₁ =1.6 Hz, J ₂ =1.6 Hz); ¹³ C NMR (100 MHz, DMSO-d ₆ )δ(ppm): 152.59(1C), 151.59(1C), 147.46(1C), 143.69(1C), 141.04(1C), 134.01(1C), 132.61(1C), 131.84(1C), 120.74(1C) , 117.66(1C), 115.81(1C), 115.60(1C), 113.94(1C), 105.42(1C), 99.99(1C); HRMS(ESI) m/z: Calcd for C ₁₅ H ₁₁ BrN ₃ O ₂ S [M+H] ⁺ :375.9750,Found:375.9753.

Test Example 1 Determination of the insecticidal activity of the compounds of the present invention

1. Test pests

The 3rd instar larvae of armyworm, the 3rd instar larvae of corn borer, the adult mites of Tetranychus cinnabarinus, and the 3rd instar larvae of Culex pipiens pipiens are all sensitive strains raised indoors for many generations.

2. Determination of armyworms

The sample to be tested was dissolved in dimethyl sulfoxide and diluted with 0.1% Tween-80 aqueous solution to a certain concentration, and the corresponding solution without the sample to be tested was used as a negative control. Cut the corn leaves into 2 × 4cm pieces, soak them in the solution to be tested for 5s, remove them, drain them and put them in a petri dish (6cm) with filter paper at the bottom, insert 15 3rd instar larvae, and then put them into Placed in a laboratory with a temperature of 22-24°C, a relative humidity of 60%, and a light time of 14:10h, the animals were continuously raised, and the mortality was recorded after 24h. Each experiment was repeated 3 times, and the following formula was used to calculate the corrected mortality rate:

3. Determination method of corn borer

The sample to be tested was dissolved in dimethyl sulfoxide and diluted with 0.1% Tween-80 aqueous solution to a certain concentration, and the corresponding solution without the sample to be tested was used as a negative control. Cut the tender ears and tender husks of corn into small pieces, soak them in the solution to be tested for 10s, remove them, drain and put them into a glass petri dish with a diameter of 6cm and a height of 9cm, and insert 15 neat and healthy corns. The third instar larvae of the borer were placed in a laboratory with a temperature of 22-24°C, a relative humidity of 60%, and a light time of 14:10h, and the death was recorded after 24h. The following formula calculates the adjusted mortality rate:

4. Determination method of Tetranychus cinnabarinus

The sample to be tested was dissolved in dimethyl sulfoxide and diluted with 0.1% Tween-80 aqueous solution to a certain concentration, and the corresponding solution without the sample to be tested was used as a negative control. Collect kidney bean leaves with a high density of insect populations, carefully select healthy adult mites (30-50) to stay on the leaf surface, immerse the leaf with insects in the solution to be tested for 5s, remove it, drain it and place it on the bottom. In a petri dish (6cm) of filter paper, placed in a laboratory with a temperature of 22-24°C, a relative humidity of 60%, and a light time of 14:10h to continue feeding, and the death situation was recorded after 24h, and each experiment was repeated 3 times. Adjusted mortality was calculated using the following formula:

5. Determination of Culex pipiens pallens

Using the method recommended by the World Health Organization, the sample to be tested was dissolved in dimethyl sulfoxide and diluted to a certain concentration with 0.1% Tween-80 aqueous solution, and the corresponding solution without the sample to be tested was used as a negative control. Take 1mL of each solution and add it to 118mL wax paper cups containing 99mL distilled water and 20 3rd instar larvae of Culex pipiens pallens respectively. Place these paper cups at a temperature of 22-24°C, a relative humidity of 60%, and a light time of At 14:10h, the animals were kept in the laboratory, and the mortality was recorded after 24h. Each experiment was repeated three times, and the corrected mortality rate was calculated using the following formula:

6. Test results

The insecticidal results of the compounds of the present invention are shown in Table 1.

Table 1

^a : Average of three replicates.

It can be seen from Table 1 above that the compounds of the present invention have good poisoning activity against these pests.

Test Example 2 Determination of Antioxidative Properties of Compounds of the Invention

1. Instruments and Reagents

Model 721B spectrophotometer, 1,1-diphenyl-2-picrylhydrazine (DPPH), 95% ethanol.

2. Measurement steps

(1) Preparation of DPPH and sample solution

Accurately weigh 0.0130 g of DPPH with an analytical balance, and dilute to a 500 mL volumetric flask with 95% ethanol to obtain a solution with a concentration of 26 mg/L; accurately weigh 0.0100 g of the sample to be tested, and dilute to a 100 mL volumetric flask with 95% ethanol , a sample solution with a concentration of 100 mg/L was obtained.

(2) Add 4 mL of DPPH solution and 1 mL of 95% ethanol solution to the 10 mL conical flask in turn. After the mixing reaction is stable, take 95% ethanol as the reference solution, and measure its absorbance value at λmax=518 nm, denoted as A ₀ .

(3) Add 4 mL of DPPH solution and 1 mL of the solution to be tested in turn in a 10 mL conical flask, shake well, and stabilize the reaction at room temperature for 40 min. Using 95% ethanol as the reference solution, measure its absorbance at wavelength λmax=518 nm value, denoted as A _S . Each experiment was repeated three times, and the free radical scavenging rate Y (%) of antioxidants was calculated with the following formula:

3. Determination results of antioxidant properties

Table 2 When the concentration is 100mg/L, the scavenging rate of compounds to DPPH free radicals

^a : Average of three replicates.

It can be seen from the above Table 2 that the scavenging rate of the compounds of the present invention to DPPH free radicals is all above 82%, that is, they all have good antioxidant properties.

Claims (10)

1. The compound whose structural formula is shown in formula I: where _R1 is R ₂ is hydrogen or halogen; R ₃ is hydrogen, C1-C4 alkyl or halogen; R ₄ is hydrogen, C1-C4 alkyl or halogen; X is O or S. 2. The compound of claim 1, wherein R ₂ is hydrogen. 3. compound according to claim 2, is characterized in that: R ₁ is 4. The compound of claim 1, wherein R ₂ is halogen. 5. The compound of claim 4, wherein R ₂ is bromine. 6. compound according to claim 5 is characterized in that: R ₁ is 7. compound according to claim 1, is characterized in that, its structural formula is as follows: 8. Use of the compound of any one of claims 1 to 7 in the preparation of antioxidants. 9. Use of the compound of any one of claims 1 to 7 in the preparation of pesticides for controlling agricultural pests. 10. The application of the compound according to claim 9 in the preparation of pesticides for controlling agricultural pests, wherein the agricultural pests are armyworm, corn borer, Tetranychus cinnabarinus or Culex pipiens pipiens.