Application of unsaturated keto ester compound and herbicide

Abstract

The invention discloses herbicidal activity application of unsaturated keto ester compounds, and belongs to the technical field of organic pesticides. The alkylamino-containing unsaturated keto ester compound can be used as an effective component for preparing a herbicide, and the prepared herbicide has a relatively good weed growth inhibition effect, is safe to commercial crops such as tomatoes, radishes and lettuce, and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of pharmaceutical intermediates and organic pesticides, and particularly to the herbicidal activity of an unsaturated ketoester compound. Background Technology

[0002] Weeds are a key biological factor threatening the scale and efficiency of crop cultivation. Statistics show that weed damage causes crop yield reductions of over 30% annually, resulting in significant losses for agricultural production and posing a challenge to food security. Herbicides are an important means of weed control in modern agriculture, playing a crucial role in ensuring crop yield and quality while reducing labor costs. Although herbicide use is an effective way to address this problem, factors such as pesticide overuse and excessive pesticide residues have led to many new challenges, including weed resistance. Therefore, developing novel, efficient, herbicide-resistant, and environmentally friendly herbicides is of great importance. Summary of the Invention

[0003] The purpose of this invention is to address the shortcomings of existing technologies by providing a bioactive unsaturated keto ester structure, its synthesis method, and its applications. The unsaturated keto ester skeleton provided by this invention will offer novel model molecules for drug development. The synthesis method for the unsaturated keto ester skeleton provided by this invention is green, efficient, and simple to operate.

[0004] The technical solution of this invention is implemented as follows:

[0005] An unsaturated keto ester skeleton, characterized by having the structural formula shown in Formula 1:

[0006]

[0007] In Formula 1, R is any one of methyl, ethyl, propyl, butyl, benzyl, or cyclic alkyl; R 1 It is any one of methyl, trifluoromethyl, cyano, fluorine, chlorine, and bromine; wherein, R and R 1 Whether they are the same or different, each represents a substituent independently.

[0008] The compounds involved in this invention can exist in one or more stereoisomers. These isomers include tautomers, geometric isomers, enantiomers, diastereomers, etc. All such isomers and mixtures thereof are within the scope of this invention.

[0009] Based on the same inventive concept, this invention also provides a method for synthesizing unsaturated keto ester skeletons, and the synthetic process route of this invention is as follows: Figure 1 As shown, it includes the following steps:

[0010] o-aminobenzaldehyde and ethyl pyruvate were mixed evenly in a solvent and reacted under alkaline conditions at 25°C to prepare unsaturated keto ester compounds.

[0011] The structural formula of the above-mentioned o-aminobenzaldehyde is shown in Formula 2:

[0012]

[0013] In Formula 2, R is any one of methyl, ethyl, propyl, butyl, benzyl, or cyclic alkyl; R 1 It is any one of methyl, trifluoromethyl, cyano, fluorine, chlorine, and bromine;

[0014] The structural formula of the above-mentioned ethyl pyruvate is shown in Formula 3:

[0015]

[0016] The above reaction can be detected by thin-layer chromatography. After the reaction is complete, the product is purified to obtain the purified product of the unsaturated keto ester compound.

[0017] Preferably, the synthesis method described above involves reacting at 25°C.

[0018] In the synthesis method described above, the molar ratio of o-aminobenzaldehyde to ethyl pyruvate is 1:(1-2), preferably, the molar ratio of o-aminobenzaldehyde to ethyl pyruvate is 1:1.2.

[0019] In the synthesis method described above, the solvent is ethanol, acetonitrile, N,N-dimethylformamide, or dichloromethane.

[0020] In the synthesis method described above, the amount of solvent used is 10-25 L per mole of o-aminobenzaldehyde and ethyl pyruvate. Preferably, the amount of solvent used is 10 L per mole of o-aminobenzaldehyde and ethyl pyruvate.

[0021] In the synthesis method described above, the basic catalyst is added before the reaction. Preferably, the catalyst is any one of morpholine, piperidine, and tetrahydropyrrole.

[0022] In the synthesis method described above, the amount of the alkaline catalyst is 50–200 mol%. Preferably, the amount of the catalyst is 80 mol%.

[0023] Based on the same inventive concept, this invention also provides a pharmaceutical composition comprising the unsaturated keto ester skeleton as described above, and pharmaceutically acceptable salts, solvates, hydrates, polycrystalline materials, cocrystals, tautomers, geometric isomers, enantiomers, diastereomers, or mixtures thereof, or prodrugs, and pharmaceutically acceptable carriers, diluents, excipients, or combinations thereof. This invention does not specifically limit the carriers, diluents, or excipients, and may use carriers, diluents, or excipients well known to those skilled in the art suitable for pharmaceutical compositions.

[0024] Based on the same inventive concept, the present invention also provides the application of unsaturated ketoester skeletons in the preparation of herbicides.

[0025] The beneficial effects of this invention are:

[0026] 1. This invention efficiently synthesizes unsaturated keto ester skeletons under green and mild conditions.

[0027] 2. This invention provides experimental evidence for the efficient construction of unsaturated keto ester skeletons with good biological activity, and has great practical significance and application value. Attached Figure Description

[0028] Figure 1 This is a flowchart of the synthesis process of the present invention. Detailed Implementation

[0029] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used in this specification includes any and all combinations of one or more of the associated listed items.

[0031] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; unless otherwise specified, the reagents, materials, instruments, etc. used in the following examples are commercially available; the reaction vessels used in the following examples are 25mL thick-walled pressure-resistant tubes.

[0032] Example 1

[0033] 1. This embodiment provides a method for synthesizing an unsaturated keto ester skeleton, which includes the following steps:

[0034] 0.1 mmol of o-aminobenzaldehyde was added to a reaction flask, followed by 1 mL of solvent, 0.08 mmol of catalyst, and finally 0.12 mmol of ethyl pyruvate. The reaction temperature was controlled, and the mixture was continuously stirred. The reaction was monitored by spotting the sample onto a thin-layer chromatography plate until the reactants had completely reacted. After the reaction was complete, the product was purified using a silica gel column chromatography method. The purified product was then rotary evaporated to obtain the target product.

[0035] The reaction formula is as follows:

[0036]

[0037] 2. Following the above method, nine parallel experimental groups were established, each using different alkaline catalysts, solvents, reaction temperatures, and catalyst dosages. The catalysts were piperidine, morpholine, and tetrahydropyrrole; the solvents were ethanol, acetonitrile, and dichloromethane. The specific alkaline catalysts, solvents, reaction temperatures, catalyst dosages, and corresponding yields used in each experimental group are shown in Table 1.

[0038] Table 1. Yields under different alkaline catalysts, solvents, and temperatures.

[0039]

[0040]

[0041] Note: Ethyl pyruvate (0.12 mmol), solvent (1 mL), o-aminobenzaldehyde (0.1 mmol), amount of basic catalyst (0.08 mmol); the above yields are separation yields.

[0042] Based on the analysis of the parallel experimental results above, it can be seen that the synthesis reaction of the present invention yields the highest product yield when using ethanol (1 mL) as solvent, ethyl pyruvate (0.12 mmol), o-aminobenzaldehyde (0.1 mmol), tetrahydropyrrole catalyst (0.08 mmol), and at 25 °C.

[0043] In Examples 2-11 below, the reaction was carried out according to the operating procedure of Example 1. 0.1 mmol of o-aminobenzaldehyde was placed in a reaction flask, followed by the addition of 1 mL of ethanol, 0.08 mmol of tetrahydropyrrole catalyst, and finally 0.12 mmol of ethyl pyruvate. The reaction temperature was controlled at 25°C, and the mixture was continuously stirred. The reaction was monitored by spotting the sample onto a thin-layer chromatography plate until the reactants had completely reacted. After the reaction was complete, the product was purified using a silica gel column chromatography method, and the purified product was obtained by rotary evaporation.

[0044] Example 2

[0045] raw material:

[0046] Product 2: Chemical formula: C 15 H 16 N2O3

[0047] Structural formula:

[0048] Yield: 55%

[0049] 1 H NMR (500MHz, CDCl3) δ8.10(d,J=16.3Hz,1H),7.65(d,J=7.9Hz,1H),7.32(d,J=16.2Hz ,1H),7.27(d,J=7.8Hz,2H),4.41(q,J=7.1Hz,2H),2.83(s,6H),1.42(t,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.1,162.1,154.4,144.7,131.3,129.4,124.7,122.1,121.7,118.6,114.7,62.6,44.7,14.1.HRMS(ESI)m / z:[M+H] + Calcd for C 15 H 17 N2O3 + 273.1234; found: 273.1232.

[0050] Example 3

[0051] raw material:

[0052] Product 3: Chemical formula: C 16 H 21 NO3

[0053] Structural formula:

[0054] Yield: 63%

[0055] 1H NMR (500MHz, CDCl3) δ8.31(d,J=16.3Hz,1H),7.65(dd,J=7.9,1.6Hz,1H),7.38(ddd,J=8.5,7.2,1.7Hz,1H),7.23(d,J=16.3Hz,1H),7.11 (dd,J=8.2,1.2Hz,1H),7.08–7.04(m,1H)ppm,4.40(q,J=7.2Hz,2H),3.08(q,J=7.1Hz,4H),1.42(t,J=7.1Hz,3H),1.02(t,J=7.1Hz,6H); 13 C NMR (126MHz, CDCl3) δ184.0,162.9,152.6,147.1,131.6,130.1,128.3,122.7,122.0,120.1,62.3,48.1,14.1,12.3.HRMS(ESI)m / z:[M+H] + Calcdfor C 16 H 22 NO3 + 276.1594; found: 276.1592.

[0056] Example 4

[0057] raw material:

[0058] Product 4: Chemical formula: C 17 H 20 N2O3

[0059] Structural formula:

[0060] Yield: 59%

[0061] 1 H NMR (500MHz, CDCl3) δ8.14(d,J=16.3Hz,1H),7.70(d,J=8.1Hz,1H),7.31(ddd,J=12.9,8.0,6.4H z,3H),4.41(q,J=7.1Hz,2H),3.12(q,J=7.1Hz,4H),1.42(t,J=7.1Hz,3H),1.06(t,J=7.1Hz,6H); 13C NMR (126MHz, CDCl3) δ183.1,162.2,152.4,144.5,133.9,129.2,125.3,124.8,122.2,118.6,114.3,62.6,47.6,14.1,12.2.HRMS(ESI)m / z:[M+H] + Calcd for C 17 H 21 N2O3 + 301.1547; found: 301.1544.

[0062] Example 5

[0063] raw material:

[0064] Product 5: Chemical formula: C 18 H 25 NO3

[0065] Structural formula:

[0066] Yield: 62%

[0067] 1 H NMR (500MHz, CDCl3) δ8.31(d,J=16.3Hz,1H),7.64(dd,J=7.8,1.5Hz,1H),7.36(ddd,J=8.5,7.2,1.7Hz,1H),7.21(d,J=16.3Hz,1H),7.13(dd,J=8.3 ,1.1Hz,1H),7.04(td,J=7.6,1.1Hz,1H),4.39(q,J=7.1Hz,2H),3.01–2.9 5(m,4H),1.52–1.43(m,4H),1.41(t,J=7.2Hz,3H),0.83(t,J=7.4Hz,6H); 13 C NMR (126MHz, CDCl3) δ184.1,162.9,153.1,147.1,131.7,129.8,128.3,122.7,122.0,120.0,62.2,56.3,20.3,14.1,11.6.HRMS(ESI)m / z:[M+H] + Calcd for C 18 H 26 NO3 + 304.1907; found: 304.1905.

[0068] Example 6

[0069] raw material:

[0070] Product 6: Chemical formula: C 20 H 29 NO3

[0071] Structural formula:

[0072] Yield: 64%

[0073] 1 H NMR (500MHz, CDCl3) δ8.29(d,J=16.3Hz,1H),7.64(d,J=7.7Hz,1H),7.36(t,J=7.7Hz,1H),7.21(d,J=16.3Hz,1H),7.12(d,J=8.1Hz,1H),7. 04(t,J=7.5Hz,1H),4.39(q,J=7.1Hz,2H),3.01(t,J=7.5Hz,4H),1.43(dt,J=14.1,7.4Hz,7H),1.25(q,J=7.4Hz,4H),0.85(t,J=7.4Hz,6H); 13 C NMR (126MHz, CDCl3) δ184.1,162.9,153.1,147.1,131.7,129.7,128.3,122.6,121.9,120.0,62.2,54.2,29.2,20.3,14.1,13.9.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 30 NO3 + 332.2220; found: 332.2216.

[0074] Example 7

[0075] raw material:

[0076] Product 7: Chemical formula: C 26 H 25 NO3

[0077] Structural formula:

[0078] Yield: 54%

[0079] 1H NMR (500MHz, CDCl3) δ8.55 (d, J=16.3Hz, 1H), 7.66 (dd, J=7.8, 1.6Hz, 1H), 7.30 (dd,J=7.7,1.6Hz,1H),7.28(q,J=1.6Hz,1H),7.27(d,J=1.5Hz,2H),7.25(d,J= 1.2Hz,2H),7.23–7.21(m,2H),7.19–7.16(m,4H),7.07(t,J=7.5Hz,1H),6.98(d d,J=8.1,1.0Hz,1H),4.39(q,J=7.2Hz,2H),4.13(s,4H),1.40(t,J=7.2Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.8,162.7,152.2,146.4,137.4,131.8,129.5,128.8,1 28.4,128.3,127.3,123.5,122.9,120.6,62.4,58.0,14.2.HRMS(ESI)m / z:[M+H] + Calcd for C 26 H 26 NO3 + 400.1907; found: 400.1902.

[0080] Example 8

[0081] raw material:

[0082] Product 8: Chemical formula: C 16 H 18 BrNO3

[0083] Structural formula:

[0084] Yield: 49%

[0085] 1 H NMR (500MHz, CDCl3) δ8.17(d,J=15.9Hz,1H),7.35(d,J=8.4Hz,1H),7.06(d,J=15.9Hz,1H),6.97(d,J=1.9Hz,1H),6.9 2(dd,J=8.4,2.0Hz,1H),4.38(d,J=7.2Hz,2H),3.37–3.33(m,4H),1.96(dd,J=9.8,3.4Hz,4H),1.40(t,J=7.1Hz,3H); 13C NMR (126MHz, CDCl3) δ182.9,162.7,151.6,148.1,130.5,126.5,121.7,121.5,118.5,118.2,62.4,52.8,25.8,14.1.HRMS(ESI)m / z:[M+H] + Calcd for C 16 H 19 BrNO3 + 352.0543; found: 352.0538.

[0086] Example 9

[0087] raw material:

[0088] Product 9: Chemical formula: C 17 H 21 NO3

[0089] Structural formula:

[0090] Yield: 54%

[0091] 1 H NMR (500MHz, CDCl3) δ8.23(d,J=16.3Hz,1H),7.61(dd,J=7.7,1.6Hz,1H),7.38(ddd,J=8.5,7.3,1.6Hz,1H),7.22(d,J=16.3Hz,1 H),7.06–7.02(m,2H),4.40(q,J=7.1Hz,2H),2.93–2.89(m,4H),1.76(p,J=5.8Hz,4H),1.61–1.57(m,2H),1.42(t,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ184.2,162.9,155.1,146.9,132.3,128.4,128.0,122.4,120.3,119.2,62.3,54.7,26.3,24.2,14.1.HRMS(ESI)m / z:[M+H] + Calcd forC 17 H 22 NO3 + 288.1594; found: 288.1593.

[0092] Example 10

[0093] raw material:

[0094] Product 10: Chemical formula: C 18 H 23 NO4

[0095] Structural formula:

[0096] Yield: 56%

[0097] 1 H NMR (500MHz, CDCl3) δ8.23 (d, J=16.4Hz, 1H), 7.63 (dd, J=7.8, 1.6Hz, 1H), 7.41 (ddd, J=8 .0,7.3,1.6Hz,1H),7.22(d,J=16.4Hz,1H),7.10(td,J=7.3,1.0Hz,1H),7.05(dd,J=8.2 ,1.1Hz,1H),4.40(q,J=7.2Hz,2H),3.93(dqd,J=10.0,6.2,2.0Hz,2H),2.97(dt,J=10.8 ,1.7Hz,2H),2.52(dd,J=11.8,10.0Hz,2H),1.42(t,J=7.1Hz,3H),1.21(d,J=6.3Hz,6H); 13 C NMR (126MHz, CDCl3) δ184.1,162.7,153.1,146.3,132.4,128.5,128.0,123.2,120.7,119.2,71.9,62.4,59.0,18.9,14.1.HRMS(ESI)m / z:[M+H] + Calcd forC 18 H 24 NO4 + 318.1700; found: 318.1696.

[0098] Example 11

[0099] raw material:

[0100] Product 11: Chemical formula: C 16 H 18 BrNO4

[0101] Structural formula:

[0102] Yield: 48%

[0103] 1H NMR (500MHz, CDCl3) δ8.13(d,J=16.3Hz,1H),7.49(d,J=8.2Hz,1H),7.27(d,J=6.2Hz,1H),7.23(s,1H),7 .19(d,J=1.8Hz,1H),4.40(q,J=7.2Hz,2H),3.92–3.87(m,4H),2.98–2.94(m,4H),1.42(t,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.5,162.4,154.2,144.8,144.6,129.8,126.9,126.6,12 6.5,122.6,121.0,67.0,66.9,62.5,62.4,53.2,14.1,13.8.HRMS(ESI)m / z:[M+H] + Calcd for C 16 H 18 BrNO4 + 368.0492; found: 368.0487.

[0104] Example 12

[0105] raw material:

[0106] Product 12: Chemical formula: C 14 H 16 ClNO3

[0107] Structural formula:

[0108] Yield: 57%

[0109] 1 H NMR (500MHz, CDCl3) δ8.10(d,J=16.6Hz,1H),7.64(d,J=16.6Hz,1H),7.22(t,J=8.1Hz,1H ),7.15(t,J=8.0Hz,2H),7.10(d,J=12.5Hz,2H),7.06(ddd,J=8.1,3.7,1.1Hz,3H),6.97( dd,J=8.2,1.1Hz,1H),6.88(dd,J=8.1,1.1Hz,2H),6.51(d,J=12.5Hz,2H),4.40(q,J=7.2 Hz,2H),4.06(q,J=7.2Hz,4H),2.75(s,6H),1.42(t,J=7.1Hz,3H),1.18(t,J=7.2Hz,6H); 13C NMR (125MHz, CDCl3) δ184.7,181.5,162.7,160.9,155.9,153.1,143.9,136.8,135.9,134.1,131.1,129.8,127 .71,125.7,125.1,124.9,123.7,123.7,116.9,116.9,62.4,61.9,44.5,43.2,14.1,13.8.HRMS(ESI)m / z:[M+H] + Calcd forC 14 H 17 ClNO3 + 282.0891; found: 282.0889.

[0110] Example 13

[0111] raw material:

[0112] Product 13: Chemical formula: C 14 H 16 ClNO3

[0113] Structural formula:

[0114] Yield: 56%

[0115] 1 H NMR(500MHz, CDCl3) δ8.29(d,J=16.4Hz,1H),7.56(dd,J=7.9,1.5Hz,1H),7.40(dd,J=7.9,1.5Hz,1H),7 .23(d,J=16.4Hz,1H),7.10(t,J=7.9Hz,1H),4.40(q,J=7.2Hz,2H),2.90(s,6H),1.42(t,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.5,162.5,145.0,146.2,135.24,134.5,133.7,126.3,125.8,122.0,62.4,43.3,14.1.HRMS(ESI)m / z:[M+H] + Calcd for C 14 H 17 ClNO3 + 282.0891; found: 282.0889.

[0116] Example 14

[0117] raw material:

[0118] Product 14: Chemical formula: C 14 H 16 BrNO3

[0119] Structural formula:

[0120] Yield: 51%

[0121] 1 H NMR (500MHz, CDCl3) δ8.09(d,J=16.2Hz,1H),7.44(d,J=8.3Hz,1H),7.23(d,J=16.3H z,1H),7.17–7.11(m,2H),4.40(q,J=7.2Hz,2H),2.79(s,6H),1.41(t,J=7.2Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.4,162.5,155.6,145.8,129.9,126.4,126.0,125.0,121.9,120.0,62.4,44.9,14.1.HRMS(ESI)m / z:[M+H] + Calcd for C 14 H 17 BrNO3 + 326.0386; found: 326.0382.

[0122] Example 15

[0123] raw material:

[0124] Product 15: Chemical formula: C 14 H 16 BrNO3

[0125] Structural formula:

[0126] Yield: 57%

[0127] 1 H NMR (500MHz, CDCl3) δ8.10(d,J=16.2Hz,1H),7.70(d,J=2.4Hz,1H),7.44(dd,J=8.7,2.4Hz,1H) ,7.25(s,1H),6.92(d,J=8.7Hz,1H),4.40(q,J=7.1Hz,2H),2.76(s,6H),1.42(t,J=7.2Hz,3H); 13C NMR (126MHz, CDCl3)δ

[0128] 183.3,162.4,153.7,145.2,134.5,131.0,129.1,120.6,120.2,114.6,62.5,45.0,14.1.HRMS(ESI)m / z:[M+H] + Calcd for C 14 H 17 BrNO3 + 326.0386; found: 326.0382.

[0129] Example 16

[0130] raw material:

[0131] Product 16: Chemical formula: C 14 H 16 FNO3

[0132] Structural formula:

[0133] Yield: 51%

[0134] 1 H NMR (500MHz, CDCl3) δ8.32(dd,J=16.4,1.8Hz,1H),7.44(dt,J=7.1,1.5Hz,1H),7.26(dd,J=16.4,1.7H z,1H),7.14–7.05(m,2H),4.41(qd,J=7.2,1.6Hz,2H),2.86–2.83(m,6H),1.42(td,J=7.1,1.7Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.6,162.5,161.9,159.9,145.4,145.4,145.4,141.2,141.1,133.5,133. 5,125.0,124.9,123.2,123.2,121.7,119.5,119.3,62.4,44.7,44.6,14.1.HRMS(ESI)m / z:[M+H] + Calcd for C 14 H 17 FNO3 + 266.1187; found: 266.1185.

[0135] Example 17

[0136] raw material:

[0137] Product 17: Chemical formula: C 14 H 16 FNO3

[0138] Structural formula:

[0139] Yield: 53%

[0140] 1 H NMR(500MHz, CDCl3)δ7.98(d,J=16.6Hz,1H),7.47(dd,J=16.6,1.4Hz,1H),7.31–7.27(m,1H),6.82(d,J=8.2Hz,1 H),6.75(t,J=8.8Hz,1H),6.70(dd,J=19.7,8.6Hz,1H),4.40(q,J=7.1Hz,2H),2.79(s,6H),1.41(t,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ184.5,163.8,162.7,161.8,156.4,156.4,140.6,135.3,132.1,132.1,130.6,130.5,124.6,124.0, 123.9,115.5,115.4,114.0,114.0,113.4,109.1,109.0,109.0,62.3,62.1,45.0,43.9,14.1,13.8.HRMS(ESI)m / z:[M+H] + Calcd for C 14 H 17 FNO3 + 266.1187; found: 266.1185.

[0141] Example 18

[0142] raw material:

[0143] Product 18: Chemical formula: C 15 H 16 F3NO3

[0144] Structural formula:

[0145] Yield: 56%

[0146] 1H NMR (500MHz, CDCl3) δ8.11(d,J=16.2Hz,1H),7.80(d,J=2.2Hz,1H),7.56(dd,J=8.7,2.2Hz,1H),7.2 9(d,J=16.3Hz,1H),7.07(d,J=8.6Hz,1H),4.41(q,J=7.2Hz,2H),2.87(s,6H),1.42(t,J=7.1Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.2,162.4,156.8,145.7,128.3,128.3,126.3,126.1,126.1,126.1,120.6,118.0,62.5,44.6,14.1.HRMS(ESI)m / z:[M+H] + Calcd for C 15 H 17 F3NO3 + 316.1155; found: 316.1152.

[0147] Example 19

[0148] raw material:

[0149] Product 19: Chemical formula: C 15 H 19 NO3

[0150] Structural formula:

[0151] Yield: 50%

[0152] 1 H NMR (500MHz, CDCl3) δ8.20(d,J=16.2Hz,1H),7.50(d,J=7.9Hz,1H),7.20(d,J=16.2Hz,1H) ,6.87–6.81(m,2H),4.39(q,J=7.1Hz,2H),2.77(s,6H),2.35(s,3H),1.41(t,J=7.2Hz,3H); 13 C NMR (126MHz, CDCl3) δ183.9,163.0,154.9,147.0,143.0,128.7,124.5,123.1,119.2,119.0,62.2,45.2,21.9,14.1.HRMS(ESI)m / z:[M+H] + Calcd forC 15 H 20 NO3+ 262.1438; found: 262.1436.

[0153] Example 20

[0154] raw material:

[0155] Product 20: Chemical formula: C 16 H 20 ClNO3

[0156] Structural formula:

[0157] Yield: 60%

[0158] 1 H NMR (500MHz, CDCl3) δ8.17(d,J=16.3Hz,1H),7.56(d,J=8.4Hz,1H),7.23(d,J=16.3Hz,1H),7.07–7. 01(m,2H),4.39(q,J=7.2Hz,2H),3.08(q,J=7.1Hz,4H),1.41(t,J=7.1Hz,3H),1.04(t,J=7.1Hz,6H); 13 C NMR (126MHz, CDCl3) δ183.5,162.6,153.5,145.7,137.6,129.4,128.2,122.8,122.0,120.0,62.4,47.9,14.1,12.2.HRMS(ESI)m / z:[M+H] + Calcd for C 16 H 20 ClNO3 + 310.1204; found: 310.1201.

[0159] Example 21

[0160] raw material:

[0161] Product 21: Chemical formula: C 16 H 20 ClNO3

[0162] Structural formula:

[0163] Yield: 55%

[0164] 1H NMR (500MHz, CDCl3) δ8.20(d,J=16.3Hz,1H),7.61(d,J=2.5Hz,1H),7.32(dd,J=8.7,2.6Hz,1H),7.23(d,J=16.3Hz,1 H),7.04(d,J=8.7Hz,1H),4.40(q,J=7.2Hz,2H),3.05(q,J=7.1Hz,4H),1.42(t,J=7.1Hz,3H),1.01(t,J=7.1Hz,6H); 13 C NMR (126MHz, CDCl3) δ183.4,162.5,150.9,145.2,131.6,131.3,128.1,127.8,123.3,120.8,62.5,48.1,14.1,12.2.HRMS(ESI)m / z:[M+H] + Calcd for C 16 H 20 ClNO3 + 310.1204; found: 310.1201.

[0165] Example 22

[0166] raw material:

[0167] Product 22: Chemical formula: C 16 H 20 ClNO3

[0168] Structural formula:

[0169] Yield: 49%

[0170] 1 H NMR (500MHz, CDCl3) δ8.38(d,J=16.5Hz,1H),7.52(dd,J=7.9,1.5Hz,1H),7.35(dd,J=7.9,1.5 Hz,1H),7.09–7.05(m,2H),4.32(d,J=7.1Hz,2H),1.34(t,J=7.1Hz,3H),0.91(t,J=7.2Hz,6H); 13 C NMR (126MHz, CDCl3) δ184.0,162.7,147.6,147.1,137.3,136.0,133.5,126.2,125.7,122.0,62.4,47.8,14.2,14.1.HRMS(ESI)m / z:[M+H] + Calcdfor C16 H 20 ClNO3 + 310.1204; found: 310.1201.

[0171] Example 23

[0172] raw material:

[0173] Product 23: Chemical formula: C 17 H 20 F3NO3

[0174] Structural formula:

[0175] Yield: 52%

[0176] 1 H NMR (500MHz, CDCl3) δ8.07(d,J=16.3Hz,1H),7.76(d,J=2.2Hz,1H),7.49(dd,J=8.6,2.2Hz,1H),7.23(d,J=16.3Hz,1 H),7.05(d,J=8.5Hz,1H),4.33(q,J=7.1Hz,2H),3.09(q,J=7.1Hz,4H),1.35(t,J=7.2Hz,3H),1.01(t,J=7.1Hz,6H); 13 C NMR (126MHz, CDCl3) δ183.2,162.4,155.0,145.5,128.8,127.8,127.8,125.8,125.8,125.2,123.9,123.6,1 23.1,121.8,121.0,120.7,119.6,62.5,62.4,47.6,46.7,29.7,14.1,13.7,12.4,12.3.HRMS(ESI)m / z:[M+H] + Calcd for C 17 H 21 F3NO3 + 344.1468; found: 344.1463.

[0177] Example 24

[0178] raw material:

[0179] Product 24: Chemical formula: C 16 H 20 BrNO3

[0180] Structural formula:

[0181] Yield: 48%

[0182] 1 H NMR(500MHz, CDCl3)δ8.16(d,J=16.3Hz,1H),7.49(d,J=8.3Hz,1H),7.25–7.20(m,2H),7.18(dd,J=8.4 ,1.9Hz,1H),4.39(q,J=7.1Hz,2H),3.07(q,J=7.1Hz,4H),1.41(t,J=7.1Hz,3H),1.04(t,J=7.1Hz,6H); 13 C NMR (126MHz, CDCl3) δ183.5,162.6,153.5,145.7,129.5,128.6,126.1,125.8,125.1,120.2,62.4,47.9,14.1,12.3.HRMS(ESI)m / z:[M+H] + Calcd for C 16 H 21 BrNO3 + 354.0699; found: 354.0695.

[0183] Example 25

[0184] raw material:

[0185] Product 25: Chemical formula: C 16 H 20 BrNO3

[0186] Structural formula:

[0187] Yield: 59%

[0188] 1 H NMR (500MHz, CDCl3) δ8.18(d,J=16.3Hz,1H),7.75(d,J=2.4Hz,1H),7.45(dd,J=8.6,2.4Hz,1H),7.23(d,J=16.3Hz,1 H), 6.98 (d, J = 8.7Hz, 1H), 4.40 (q, J = 7.2Hz, 2H), 3.05 (q, J = 7.1Hz, 4H), 1.42 (t, J = 7.2Hz, 3H), 1.02 (t, J = 7.1Hz, 6H); 13C NMR (126MHz, CDCl3) δ183.4,162.5,151.3,145.1,134.1,131.9,130.8,123.6,120.8,115.5,62.5,48.0,14.1,12.2.HRMS(ESI)m / z:[M+H] + Calcd for C 16 H 21 BrNO3 + 354.0699; found: 354.0695.

[0189] Example 26

[0190] raw material:

[0191] Product 26: Chemical formula: C 16 H 20 FNO3

[0192] Structural formula:

[0193] Yield: 57%

[0194] 1 H NMR (500MHz, CDCl3) δ8.35(d,J=16.5Hz,1H),7.39(dd,J=7.7,1.6Hz,1H),7.12(d,J=16.5Hz,1H),7.08–6. 99(m,2H),4.31(q,J=7.1Hz,2H),3.02(qd,J=7.2,1.7Hz,4H),1.32(t,J=7.1Hz,3H),0.88(t,J=7.2Hz,6H); 13 CNMR (126MHz, CDCl3) δ184.0,163.1,162.7,161.1,146.0,146.0,138.3,138.2,136.1,136.1,125 .9,125.8,122.8,122.8,121.8,119.0,118.8,62.3,48.5,48.4,14.1,13.4.HRMS(ESI)m / z:[M+H] + Calcd forC 16 H 21 FNO3 + 294.1500; found: 294.1497.

[0195] Example 27

[0196] raw material:

[0197] Product 27: Chemical formula: C 16 H 20 FNO3

[0198] Structural formula:

[0199] Yield: 55%

[0200] 1 H NMR (500MHz, CDCl3) δ8.04(d,J=16.7Hz,1H),7.50(dd,J=16.7,1.2Hz,1H),7.29(td,J=8.2,6.2Hz,1H),6.88(d,J=8.2Hz,1H),6.77(dd,J=10.9,8. 2Hz, 1H), 4.40 (q, J=7.2Hz, 2H), 3.74 (q, J=3.0, 2.2Hz, 2H), 3.09 (q, J=7. 1Hz,4H),1.86–1.84(m,2H),1.41(t,J=7.1Hz,3H),1.04(t,J=7.1Hz,6H); 13 CNMR (126MHz, CDCl3) δ184.6,163.9,162.8,161.8,154.3,154.2,140.7,131.6,131.5,124.1,124.0 ,118.1,118.0,117.4,117.4,109.8,109.6,68.0,62.3,47.9,25.6,14.1,12.2.HRMS(ESI)m / z:[M+H] + Calcd forC 16 H 21 FNO3 + 294.1500; found: 294.1497.

[0201] Herbicide test results: The compounds of this invention showed inhibition rates of stem and root inhibition against barnyard grass, respectively.

[0202]

[0203] Note: "++++" indicates an inhibition rate of 90%-100% at a concentration of 50 mg / L; "++++" indicates an inhibition rate of 70%-90% at a concentration of 50 mg / L; "+++" indicates an inhibition rate of 50%-70% at a concentration of 50 mg / L; "++" indicates an inhibition rate of 30%-50% at a concentration of 50 mg / L; and "+" indicates an inhibition rate of 10%-30% at a concentration of 50 mg / L.

[0204] Most of the compounds in this invention exhibit an inhibition rate of over 70% against barnyardgrass roots and stems at a concentration of 50 mg / L. These compounds demonstrate a good inhibitory effect on root and stem growth, thus showing promising application prospects in weed control.

[0205] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Application of alkylamine-containing unsaturated ketoesters in the preparation of herbicides.

2. A ketoester backbone containing an alkylamine group, characterized in that, Its structural formula is shown in Equation 1: In Formula 1, R is any one of methyl, ethyl, propyl, butyl, benzyl, or cyclic alkyl; R 1 It is any one of methyl, trifluoromethyl, cyano, fluorine, chlorine, and bromine; wherein, R and R 1 Whether they are the same or different, each represents a substituent independently.

3. The application of the alkylamine-containing unsaturated ketoester bioactive framework according to claim 1 in the preparation of herbicides, characterized in that, Application of weed control in the cultivation of cash crops such as tomatoes, radishes, and lettuce.

4. A herbicide, characterized in that, Its active ingredient is one or more of the alkylamine-containing unsaturated ketoester compounds described in claim 2.

5. The herbicide according to claim 4, characterized in that, The herbicide also contains pesticide-acceptable adjuvants, additives, stabilizers, flavorings, emulsifiers, or synergists.

6. The herbicide according to claim 4, characterized in that, The effective concentration of the herbicide is 25–100 mg / L.

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