Preparation method of ferulic acid derivative, bacteriostatic action of composition and application of composition in promoting plant growth

Abstract

The invention discloses a ferulic acid derivative, which is characterized in that the structural formula of the ferulic acid derivative is as follows: # imgabs0 #, and R is benzyl, substituted benzyl or heterocyclic radical. According to the derivative disclosed by the invention, a biological activity determination result shows that the ferulic acid compound containing the amide structure has medium to excellent inhibitory activity on rice bacterial streak pathogen and kiwi fruit bacterial canker pathogen, and the activity in 3d is the best; the inhibitory activities of the compound on rice bacterial leaf streak germs and kiwi fruit bacterial canker germs are 76.8% and 68.1% respectively, which are higher than those of control medicaments thiediazole copper and zinc thiazole.

Description

Technical Field

[0001] The invention relates to the technical field of chemistry, in particular to a ferulic acid derivative plant growth regulator, a preparation method of the compound and use of the composition thereof on rice bacterial leaf streak pathogen, citrus canker pathogen and kiwi fruit bacterial canker pathogen. Background Art

[0002] Plant diseases are one of the important factors that restrict the high yield and good quality of crops. Among them, plant bacterial diseases directly cause crop yield loss and quality decline. The characteristics of epidemic, explosiveness, and destructiveness are common in many plant fungal diseases, making this type of disease extremely destructive and difficult to prevent and control, which seriously affects the sustainable development of agriculture. The prevention and treatment methods mainly rely on fungicides prepared by chemical methods, such as carbendazim and pyrimidine. However, the difficulty of preventing and controlling plant bacterial diseases has been further aggravated due to large-dose, high-frequency application of pesticides and the selective evolution of pests.

[0003] Plant growth regulators are those that are applied directly to the plant from the outside and used in trace amounts to achieve significant regulatory effects. They are divided into different categories. Some are plant growth retardants that can inhibit vigorous plant growth and can be used in urban greening and other aspects. Some are plant growth inhibitors that can inhibit plant growth. Some are plant growth promoters that can promote plant growth, flowering, and maturity. This means that people may be able to regulate and control plant growth according to their own wishes and transform it in the direction they expect. This method of regulating plant metabolic processes or growth and development processes by adding plant growth regulators is called chemical regulation of plants.

[0004] Ethyl garlic is a broad-spectrum fungicide with the advantages of low dosage, high activity, fast effect, easy absorption and degradation by crops, and low resistance of pathogens. Ethyl garlic has good inhibitory effects on a variety of fungi and bacteria. This compound can be used to prevent and control cherry stem rot, peanut leaf spot, etc. Spraying a small amount of seeds will make them germinate faster and the seedlings grow stronger. Ethyl garlic can also be used to prevent and control a variety of diseases on rice, and can also increase the fruit set rate and thousand-grain weight of rice, and improve rice yield. Ethyl garlic is a homologue of allicin. Studies have reported that its fungicidal mechanism of action is (-SS(=O) in its molecular structure 2 ) groups react with substances containing -SH groups in pathogenic bacteria, thereby inhibiting the normal metabolism of the bacteria and achieving the purpose of preventing and controlling diseases.

[0005] Ferulic acid has strong antioxidant activity and is widely used in medicine. Its antioxidant effect has been verified in several acute and chronic pathologies, such as intestinal ischemia, cancer, cardiovascular, skin diseases and diabetes. It also has anti-inflammatory and anticancer activities and the ability to act as a free radical scavenger and an inhibitor or depolymerizer of amyloid structure. Ferulic acid has a significant inhibitory effect on cold viruses, respiratory syncytial virus and human immunodeficiency virus (HIV). With ferulic acid as the lead, a series of leads with potential pharmaceutical activity have been discovered. In recent years, although there have been many reports on ferulic acid in medical research, there are also many reports on the agricultural biological activity of ferulic acid and its derivatives. Structure-activity relationship studies have shown that ferulic acid has a unique skeleton, and its α, β-unsaturated carboxylic acid fragment plays an important role in antiviral activity and exhibits good antiviral activity. Some phenolic plant extracts containing ferulic acid have good antibacterial activity. In recent years, this type of structure has also shown good potential in the innovative research of green pesticides.

[0006] In summary, the ferulic acid derivatives show high pesticide activity, providing a reference for the creation of new and efficient antibacterial and fungicides. Based on the previous work, the present invention designs and synthesizes a series of ferulic acid derivatives containing amide structures, and compounding these compounds with ethoxylated acetoin to form a compound composition. While testing its antibacterial activity, it will also be studied on its plant growth regulator activity, hoping to screen out highly active antibacterial plant growth regulators. Summary of the invention

[0007] The present invention aims to provide a method for preparing a ferulic acid derivative biological plant growth regulator having bactericidal activity and a composition thereof.

[0008] Another object of the present invention is to provide a novel compound having an inhibitory effect on kiwi fruit bacterial canker, rice bacterial leaf streak pathogen and citrus canker pathogen.

[0009] The technical solution of the present invention is: a ferulic acid derivative compound, the derivative has the general formula of the following formula (I):

[0010]

[0011] Wherein, R is benzyl, substituted benzyl, or heterocyclic group. The substituent of the substituted benzyl is a mono- or di-substituted benzyl group, methyl group, methoxy group, halogen group, or cyano group on the benzene ring, and the heterocyclic group is naphthalene or pyridine.

[0012] Wherein: R is benzyl, 2-methylbenzyl, 3-methylbenzyl, p-methylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-cyanobenzyl, 1-naphthyl, 2-benzylopyridine, 3,4-dimethoxybenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl, 2,5-dichlorobenzyl, 2-chloro-4-fluorobenzyl, diphenylmethyl, R-2-methylbenzyl or a disubstituted group of any combination of the above substituents.

[0013] Preferably, R is benzyl, 2-methylbenzyl, 3-methylbenzyl, p-methylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-cyanobenzyl, 1-naphthyl, 2-benzylopyridine, 3,4-dimethoxybenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl, 2,5-dichlorobenzyl, 2-chloro-4-fluorobenzyl, diphenylmethyl, R-2-methylbenzyl or a disubstituted group of any combination of the above substituents.

[0014] A ferulic acid derivative, the specific compound is as follows:

[0015] Compound 3a: (E)-4-(3-(benzylamino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate; Compound 3b: (E)-2-methoxy-4-(3-((2-methylbenzyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate;

[0016] Compound 3c: (E)-2-methoxy-4-(3-(3-methylbenzyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate;

[0017] Compound 3d: (E)-2-methoxy-4-(3-(4-methylbenzyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate;

[0018] Compound 3e: (E)-2-methoxy-4-(3-((2-methoxybenzyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate;

[0019] Compound 3f: (E)-2-methoxy-4-(3-(3-methoxybenzyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate;

[0020] Compound 3g: (E)-2-methoxy-4-(3-((4-methoxybenzyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate;

[0021] Compound 3h: (E)-4-(3-((2-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0022] Compound 3i: (E)-4-(3-((3-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0023] Compound 3j: (E)-4-(3-((4-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0024] Compound 3k: (E)-4-(3-((2-chlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0025] Compound 31: (E)-4-(3-((3-chlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0026] Compound 3m: (E)-4-(3-((4-chlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0027] Compound 3n: (E)-4-(3-((2-bromobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0028] Compound 3o: (E)-4-(3-((3-bromobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0029] Compound 3p: (E)-4-(3-((4-cyanobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0030] Compound 3q: (E)-2-methoxy-4-(3-(naphthalen-1-ylmethyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate;

[0031] Compound 3r: (E)-2-methoxy-4-(3-oxo-3-(pyridin-2-ylmethyl)amino)prop-1-en-1-yl)phenyl isobutyrate;

[0032] Compound 3s: (E)-4-(3-(3,4-dimethoxybenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0033] Compound 3t: (E)-4-(3-(2,4-dichlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate;

[0034] Compound 3u: (E)-4-(3-(3,4-dichlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate.

[0035] Compound 3v: (E)-4-(3-(2,5-dichlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate.

[0036] Compound 3w: (E)-4-(3-((2-chloro-4-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate.

[0037] Compound 3x: (E)-4-(3-(diphenylmethylamino)-3-oxoprop-1-en-1-yl)-2-methoxyphenyl isobutyrate.

[0038] Compound 3y: (R,E)-2-methoxy-4-(3-oxo-3-((1-phenylethyl)amino)prop-1-en-1-yl)phenyl isobutyrate.

[0039] A method for preparing a ferulic acid derivative comprises the following steps:

[0040] (1) reacting ferulic acid and isobutyric anhydride in a sodium hydroxide solution, and then adding dilute sulfuric acid to the mixture to adjust the pH (4-5) to obtain O-isobutylferulic acid 1;

[0041]

[0042] (2) O-isobutylferulic acid 1: 3 mL of dichlorothionyl and 15 mL of dichloromethane were refluxed for 4 h. After the reaction was completed, the system was distilled under reduced pressure to remove excess solvent and dichlorothionyl to obtain the corresponding acid chloride 2.

[0043]

[0044] (3) Add intermediate 2: substituted benzylamine: triethylamine = 1:1 to 1.2:4, 20 mL of dichloromethane, and stir at room temperature for 6 hours. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify it by column chromatography (petroleum ether: ethyl acetate = 3:1 to 1:1) to obtain the target compound.

[0045]

[0046] The derivative is used in preparing medicines and medicaments for preventing and treating kiwi fruit bacterial canker, rice bacterial leaf streak pathogen and citrus canker pathogen.

[0047] A compound pesticide composition, comprising the ferulic acid derivative and allicin. The mass ratio of the derivative to allicin is 1:2-2:1. The derivative is (E)-2-methoxy-4-(3-(4-methylbenzyl)amino)-3-oxoprop-1-en-1-yl)phenyl isobutyrate.

[0048] The composition is used in the preparation of a drug for preventing and treating plant bacterial diseases. The plant bacterial disease is rice streak disease.

[0049] A novel plant growth regulator is a compound (1S, 4S, 10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, which is a compound of the following formula (II):

[0050]

[0051] Beneficial effects of the present invention: The derivatives of the present application, from the results of biological activity assays, can be seen that the ferulic acid compounds containing an amide structure have moderate to excellent inhibitory activity against rice bacterial leaf streak pathogens and kiwi fruit bacterial canker pathogens, among which 3d has the best activity, with inhibitory activities against rice bacterial leaf streak pathogens and kiwi fruit bacterial canker pathogens of 76.8% and 68.1%, respectively, which are higher than the control agents thiophanate-copper and thiazole zinc.

[0052] In addition, the in vitro growth rate method was used to test the activity of the composition against rice bacterial leaf streak and kiwifruit bacterial canker at a concentration of 100 μg / mL. From the biological activity test results in Table 2, it can be seen that the activity of the composite composition against rice bacterial leaf streak and kiwifruit bacterial canker was improved compared with the compounds before compounding. The inhibitory activity of composition 3 (3d: ethyl allicin wettable powder = 2:1) against rice bacterial leaf streak and kiwifruit bacterial canker reached 88.9% and 80.4%, respectively. Therefore, the composite composition of 3d and ethyl allicin has a synergistic effect on rice bacterial leaf streak and kiwifruit bacterial canker.

[0053] Finally, plant growth regulating activity: The plant growth activity test results of the target compounds showed that the target compounds had certain plant growth regulating activity, among which compounds 3a, 3b and 3h had good auxin activity, which was higher than indoleacetic acid. Compound 3f had good cytokinin activity, and the activity was higher at high concentration. DETAILED DESCRIPTION

[0054] Overall embodiment

[0055]

[0056] Ferulic acid (2.0 g, 0.010 mol) was added to 10 ml of NaOH (1.1 g, 0.027 mol) aqueous solution. The mixture was stirred and cooled to 10 °C. Subsequently, isobutyric anhydride (2.0 g, 0.013 mol) was added to the cold solution, and the reaction mixture was stirred at 20 °C for 10 minutes. The reaction was continued to stir at room temperature for 30 minutes and the reaction was stopped. Then 2.5 M dilute sulfuric acid was added to the reaction system to promote the formation of a white precipitate, while the pH value was maintained in the range of 4 to 5. Finally, the obtained white precipitate was filtered and washed with distilled water several times to obtain a white solid with a total yield of 80%. The obtained intermediate 1 was dissolved in 15 ml of dichloromethane and SOCl was added. 2 (3 mL), 2-3 drops of DMF were added, and the reaction was stopped after stirring and refluxing for 4 h. The solvent was removed to isolate the key intermediate 2.

[0057] Preparation of target compounds 3a-3y:

[0058] Various substituted benzylamines (2.4 mmol) and Et3N (1.4 mL, 10.0 mmol) were mixed in 20 mL of DCM solution and stirred at 25 °C for 0.5 h. Then, the appropriate intermediate 2 (2.0 mmol) was added to the above solution and stirred at room temperature for 6 h. The reaction mixture was washed with saturated brine and heated in anhydrous Na 2 SO 4 The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (1 / 1, v / v) as eluent to obtain the target compounds 3a-3y in yields of 52-68%.

[0059] 2. Spectral data of target compounds 3a-3y

[0060]

[0061] (E)-4-(3-(benzylamino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3a)white solid, mp 129–130℃, yield: 54.0%. 1 H NMR (400 MHz, DMSO-d 6,ppm)δ:8.60(t,J=6.0Hz,1H),7.47(d,J=15.8Hz,1H),7.36–7.23(m,6H),7.17(dd,J=8.2,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.70(d,J=15.8Hz,1H),4.41(d,J=5.9Hz,2H),3.80(s,3H),2.81(hept,J=6.9Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.37,164.90,151.09,140.33,139.38,138.37,133.85,128.33,127.37,126.85,123.16,122.35,120.08,111.58,55.87,42.34,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcdfor C 21 H 23 NO 4 Na:376.1519,found:376.1518.

[0062]

[0063] (E)-2-methoxy-4-(3-((2-methylbenzyl)amino)-3-oxoprop-1-en-1-yl)phenylisobutyrate(3b)

[0064] white solid,mp 133–134℃,yield:52.3%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.44(t,J=5.7Hz,1H),7.47(d,J=15.8Hz,1H),7.32(d,J=1.9Hz,1H),7.26–7.23(m,1H),7.18–7.15(m,4H),7.11(d,J=8.1Hz,1H),6.73(d,J=15.8Hz,1H),4.38(d,J=5.6Hz,2H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),2.30(s,3H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6,ppm)δ:174.37,164.78,151.08,140.31,138.27,136.86,135.77,133.88,129.97,127.86,127.00,125.79,123.16,122.34,120.07,111.53,55.85,40.57,39.52,33.16,18.77,18.64.HRMS(ESI)m / z:[M+Na] + calcd for C 22 H 25 NO 4 Na:390.1676,found:390.1671.

[0065]

[0066] (E)-2-methoxy-4-(3-((3-methylbenzyl)amino)-3-oxoprop-1-en-1-yl)phenylisobutyrate(3c)

[0067] white solid,mp 139–140℃,yield:55.9%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.56(t,J=6.0Hz,1H),7.47(d,J=15.8Hz,1H),7.33(d,J=1.9Hz,1H),7.24–7.16(m,2H),7.12–7.05(m,4H),6.70(d,J=15.8Hz,1H),4.37(d,J=5.9Hz,2H),3.80(s,3H),2.81(hept,J=6.9Hz,1H),2.29(s,3H),1.23(d,J=7.0Hz,6H); 13 CNMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,164.83,151.08,140.33,139.25,138.32,137.39,133.85,128.24,127.97,127.47,124.50,123.15,122.38,120.08,111.57,55.86,42.30,33.15,21.01,18.76.HRMS(ESI)m / z:[M+Na] + calcd forC 22 H 25 NO 4Na:390.1676,found:390.1672.

[0068]

[0069] (E)-2-methoxy-4-(3-((4-methylbenzyl)amino)-3-oxoprop-1-en-1-yl)phenylisobutyrate(3d)

[0070] white solid,mp 142–143℃,yield:58.2%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.54(t,J=6.0Hz,1H),7.47(d,J=15.8Hz,1H),7.32(d,J=1.9Hz,1H),7.20–7.09(m,6H),6.69(d,J=15.8Hz,1H),4.36(d,J=5.9Hz,2H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),2.28(s,3H),1.23(d,J=6.9Hz,6H); 13 C NMR(100MHz,DMSO-d6 , ppm)δ:174.35,164.82,151.08,140.32,138.27,136.31,135.88,133.86,128.84,127.35,123.14,122.41,120.05,111.57,55.86,42.07,33.15,20.65,18.75.HRMS(ESI)m / z:[M+Na] + calcd for C 22 H 25 NO 4 Na:390.1676,found:390.1670.

[0071]

[0072] (E)-2-methoxy-4-(3-((2-methoxybenzyl)amino)-3-oxoprop-1-en-1-yl)phenylisobutyrate(3e)

[0073] white solid,mp 136–137℃,yield:54.1%. 1H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.38(t,J=5.9Hz,1H),7.46(d,J=15.8Hz,1H),7.33(d,J=1.8Hz,1H),7.28–7.16(m,3H),7.11(d,J=8.1Hz,1H),7.00(dd,J=8.3,1.1Hz,1H),6.92(td,J=7.4,1.1Hz,1H),6.75(d,J=15.8Hz,1H),4.37(d,J=5.8Hz,2H),3.82(s,3H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,164.95,156.73,151.08,140.31,138.18,133.91,128.18,127.99,126.59,123.14,122.46,120.13,120.06,111.55,110.51,55.86,55.32,37.50,33.16,18.76.HRMS(ESI)m / z:[M+Na] + calcd for C 22 H 25 NO 5 Na:406.1625,found:406.1629.

[0074]

[0075] (E)-2-methoxy-4-(3-((3-methoxybenzyl)amino)-3-oxoprop-1-en-1-yl)phenylisobutyrate(3f)

[0076] white solid,mp 139–141℃,yield:56.7%. 1 H NMR(400MHz,DMSO-d 6,ppm)δ:8.58(t,J=6.0Hz,1H),7.48(d,J=15.8Hz,1H),7.33(d,J=1.9Hz,1H),7.25(t,J=8.1Hz,1H),7.17(dd,J=8.3,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.88–6.87(m,2H),6.82(dd,J=7.7,2.1Hz,1H),6.71(d,J=15.8Hz,1H),4.38(d,J=5.9Hz,2H),3.80(s,3H),3.74(s,3H),2.81(hept,J=6.9Hz,1H),1.23(d,J=7.0Hz,6H); 13 CNMR(100MHz,DMSO-d 6 ,ppm)δ:174.35,164.89,159.33,151.09,140.95,140.34,138.37,133.85,129.39,123.15,122.33,120.09,119.51,113.06,112.19,111.59,55.87,54.98,42.29,33.16,18.76.HRMS(ESI)m / z:[M+Na] + calcd forC 22 H 25 NO 5 Na:406.1625,found:406.1621.

[0077]

[0078] (E)-2-methoxy-4-(3-((4-methoxybenzyl)amino)-3-oxoprop-1-en-1-yl)phenylisobutyrate(3g)

[0079] white solid,mp 168–170℃,yield:60.5%. 1 H NMR(400MHz,DMSO-d 6,ppm)δ:8.51(t,J=5.9Hz,1H),7.46(d,J=15.8Hz,1H),7.32(d,J=1.9Hz,1H),7.24–7.21(m,2H),7.16(dd,J=8.3,1.8Hz,1H),7.10(d,J=8.1Hz,1H),6.91–6.88(m,2H),6.68(d,J=15.8Hz,1H),4.33(d,J=5.9Hz,2H),3.80(s,3H),3.73(s,3H),2.81(hept,J=6.9Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,164.75,158.27,151.08,140.31,138.23,133.87,131.29,128.73,123.14,122.45,120.04,113.73,111.57,55.86,55.06,41.80,39.52,33.15,18.76.HRMS(ESI)m / z:[M+Na] + calcd for C 22 H 25 NO 5 Na:406.1625,found:406.1631.

[0080]

[0081] (E)-4-(3-((2-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3h)

[0082] white solid,mp 138–140℃,yield:57.8%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.59(t,J=5.9Hz,1H),7.47(d,J=15.8Hz,1H),7.39–7.30(m,3H),7.21–7.16(m,3H),7.11(d,J=8.1Hz,1H),6.71(d,J=15.8Hz,1H),4.44(d,J=5.8Hz,2H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.35,164.98,160.13(d, 1 J C-F =243.0Hz),151.08,140.37,138.51,133.80,129.77(d, 3 J C-F =5.0Hz),129.01(d, 3 J C-F =8.0Hz),125.90(d, 2 J C-F =14.0Hz),124.35(d, 4 J C-F =3.0Hz),123.15,122.13,120.12,115.11(d, 2 J C-F =21.0Hz),111.57,55.86,36.21(d, 3 J C-F =4.0Hz),33.15,18.75.HRMS(ESI)m / z:[M+Na] + calcd for C 21 H 22 FNO 4 Na:394.1425,found:394.1428.

[0083]

[0084] (E)-4-(3-((3-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3i)

[0085] white solid,mp 136–137℃,yield:59.8%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.66(t,J=6.0Hz,1H),7.48(d,J=15.7Hz,1H),7.41–7.34(m,2H),7.19–7.05(m,5H),6.70(d,J=15.8Hz,1H),4.42(d,J=6.0Hz,2H),3.80(s,3H),2.81(hept,J=6.9Hz,1H),1.23(d,J=7.0Hz,6H); 13C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.35,165.04,162.23(d, 1 J C-F =241.0Hz),151.09,142.46(d, 3 J C-F =7.0Hz),140.38,138.57,133.79,130.27(d, 3 J C-F =8.0Hz),123.29(d, 4 J C-F =3.0Hz),123.15,122.16,120.16,113.93(d, 2 J C-F =21.0Hz),113.56(d, 2 J C-F =21.0Hz),111.60,55.87,41.83,33.15,18.76.HRMS(ESI)m / z:[M+Na] + calcd forC 21 H 22 FNO 4 Na:394.1425,found:394.1420.

[0086]

[0087] (E)-4-(3-((4-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3j)

[0088] white solid,mp 150–151℃,yield:64.6%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.61(t,J=6.0Hz,1H),7.47(d,J=15.8Hz,1H),7.36–7.31(m,3H),7.19–7.09(m,4H),6.69(d,J=15.8Hz,1H),4.39(d,J=5.9Hz,2H),3.80(s,3H),2.81(hept,J=6.9Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6,ppm)δ:174.35,164.91,161.20(d, 1 J C-F =240.0Hz),151.09,140.36,138.44,135.61(d, 4 J C-F =3.0Hz),133.82,129.33(d, 3 J C-F =8.0Hz),123.15,122.27,120.11,115.03(d, 2 J C-F =21.0Hz),111.58,55.87,41.61,33.15,18.75.HRMS(ESI)m / z:[M+Na] + calcd forC 21 H 22 FNO 4 Na:394.1425,found:394.1424.

[0089]

[0090] (E)-4-(3-((2-chlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3k)

[0091] white solid,mp 143–145℃,yield:56.8%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.61(t,J=5.9Hz,1H),7.50–7.45(m,2H),7.39–7.28(m,4H),7.18(dd,J=8.2,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.75(d,J=15.8Hz,1H),4.47(d,J=5.8Hz,2H),3.81(s,3H),2.82(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6,ppm)δ:174.37,165.10,151.10,140.39,138.62,136.22,133.79,132.18,129.17,129.09,128.74,127.22,123.18,122.07,120.18,111.58,55.87,40.32,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcdfor C 21 H 22 ClNO 4 Na:410.1130,found:410.1124.

[0092]

[0093] (E)-4-(3-((3-chlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3l)

[0094] white solid,mp 150–151℃,yield:62.7%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.66(t,J=6.0Hz,1H),7.48(d,J=15.7Hz,1H),7.39–7.30(m,4H),7.27(dt,J=7.3,1.5Hz,1H),7.18(dd,J=8.3,1.9Hz,1H),7.11(d,J=8.1Hz,1H),6.70(d,J=15.8Hz,1H),4.41(d,J=6.0Hz,2H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),1.23(d,J=6.9Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.34,165.04,151.09,142.06,140.39,138.61,133.77,132.99,130.21,127.08,126.77,126.00,123.14,122.12,120.19,111.59,55.87,41.78,33.15,18.75.HRMS(ESI)m / z:[M+Na] + calcd for C 21 H 22 ClNO4 Na:410.1130,found:410.1125.

[0095]

[0096] (E)-4-(3-((4-chlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3m)

[0097] white solid,mp 169–170℃,yield:65.8%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.67(t,J=6.0Hz,1H),7.48(d,J=15.8Hz,1H),7.40–7.38(m,2H),7.34–7.31(m,3H),7.17(dd,J=8.1,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.70(d,J=15.8Hz,1H),4.40(d,J=6.0Hz,2H),3.80(s,3H),2.81(hept,J=6.9Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,Chloroform-d,ppm)δ:175.22,165.67,151.30,141.17,140.76,136.76,133.53,133.26,129.15,128.77,123.03,120.48,120.42,111.47,55.84,43.01,33.94,18.94.HRMS(ESI)m / z:[M+Na] + calcd forC 21 H 22 ClNO 4 Na:410.1130,found:410.1121.

[0098]

[0099] (E)-4-(3-((2-bromobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3n)

[0100] white solid,mp 134–135℃,yield:56.0%.1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.61(t,J=5.9Hz,1H),7.63(dd,J=7.9,1.2Hz,1H),7.48(d,J=15.8Hz,1H),7.41–7.34(m,3H),7.25–7.17(m,2H),7.12(d,J=8.1Hz,1H),6.76(d,J=15.8Hz,1H),4.44(d,J=5.8Hz,2H),3.81(s,3H),2.82(hept,J=7.0Hz,1H),1.23(d,J=6.9Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,165.10,151.09,140.39,138.65,137.74,133.79,132.42,129.04,129.02,127.79,123.18,122.51,122.05,120.18,111.58,55.88,42.83,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcd forC 21 H 22 BrNO 4 Na:454.0624,found:454.0621.

[0101]

[0102] (E)-4-(3-((3-bromobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3o)

[0103] white solid,mp 164–166℃,yield:60.1%. 1 H NMR(400MHz,DMSO-d 6,ppm)δ:8.66(t,J=6.0Hz,1H),7.50–7.43(m,3H),7.34(d,J=1.9Hz,1H),7.31–7.30(m,2H),7.18(dd,J=8.3,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.69(d,J=15.8Hz,1H),4.41(d,J=6.0Hz,2H),3.80(s,3H),2.81(hept,J=6.9Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,165.03,151.09,142.34,140.39,138.63,133.77,130.54,129.98,129.68,126.42,123.15,122.11,121.64,120.20,111.59,55.88,41.73,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcd forC 21 H 22 BrNO 4 Na:454.0624,found:454.0618.

[0104]

[0105] (E)-4-(3-((4-cyanobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3p)

[0106] white solid,mp 127–128℃,yield:65.8%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.73(t,J=6.1Hz,1H),7.82–7.79(m,2H),7.50–7.46(m,3H),7.34(d,J=1.9Hz,1H),7.18(dd,J=8.3,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.71(d,J=15.7Hz,1H),4.49(d,J=6.0Hz,2H),3.81(s,3H),2.81(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.35,165.18,151.10,145.40,140.43,138.75,133.73,132.30,128.07,123.16,121.98,120.20,118.88,111.62,109.57,55.89,42.06,33.16,18.76.HRMS(ESI)m / z:[M+Na] + calcd for C 22 H 22 N 2 O 4 Na:401.1472,found:454.1481.

[0107]

[0108] (E)-2-methoxy-4-(3-((naphthalen-1-ylmethyl)amino)-3-oxoprop-1-en-1-yl)phenylisobutyrate(3q)

[0109] white solid,mp 122–123℃,yield:68.0%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.62(t,J=5.7Hz,1H),8.12(dd,J=7.8,1.2Hz,1H),7.96(dd,J=7.4,2.3Hz,1H),7.87(dd,J=6.5,2.9Hz,1H),7.60–7.49(m,5H),7.32(d,J=1.9Hz,1H),7.16(dd,J=8.2,1.8Hz,1H),7.10(d,J=8.1Hz,1H),6.73(d,J=15.8Hz,1H),4.88(d,J=5.6Hz,2H),3.79(s,3H),2.81(hept,J=6.9Hz,1H),1.22(d,J=6.9Hz,6H); 13 CNMR(100MHz,DMSO-d 6,ppm)δ:174.35,164.74,151.07,140.34,138.43,134.52,133.85,133.35,130.96,128.52,127.71,126.30,125.86,125.83,125.44,123.58,123.15,122.31,120.09,111.54,55.83,40.47,33.15,18.75.HRMS(ESI)m / z:[M+Na] + calcd for C 25 H 25 NO 4 Na:426.1676,found:426.1664.

[0110]

[0111] (E)-2-methoxy-4-(3-oxo-3-((pyridin-2-ylmethyl)amino)prop-1-en-1-yl)phenylisobutyrate(3r)

[0112] white solid,mp 141–142℃,yield:57.6%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.67(t,J=6.0Hz,1H),8.52(ddd,J=4.8,1.9,1.0Hz,1H),7.77(td,J=7.7,1.8Hz,1H),7.48(d,J=15.8Hz,1H),7.35(d,J=1.8Hz,1H),7.32(dt,J=7.8,1.1Hz,1H),7.27(ddd,J=7.5,4.8,1.2Hz,1H),7.18(dd,J=8.3,1.9Hz,1H),7.11(d,J=8.1Hz,1H),6.78(d,J=15.8Hz,1H),4.51(d,J=5.9Hz,2H),3.81(s,3H),2.82(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6,ppm)δ:174.37,165.09,158.42,151.09,148.88,140.37,138.49,136.76,133.84,123.17,122.27,122.17,121.18,120.14,111.61,55.89,44.37,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcd for C 20 H 22 N 2 O 4 Na:377.1472,found:377.1475.

[0113]

[0114] (E)-4-(3-((3,4-dimethoxybenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3s)

[0115] white solid,mp 150–151℃,yield:63.5%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.50(t,J=5.8Hz,1H),7.46(d,J=15.8Hz,1H),7.32(d,J=1.9Hz,1H),7.16(dd,J=8.2,1.9Hz,1H),7.10(d,J=8.1Hz,1H),6.92–6.89(m,2H),6.82(dd,J=8.2,2.0Hz,1H),6.69(d,J=15.8Hz,1H),4.33(d,J=5.8Hz,2H),3.80(s,3H),3.73(d,J=6.0Hz,6H),2.81(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.37,164.76,151.08,148.67,147.85,140.31,138.25,133.88,131.71,123.16,122.44,120.06,119.58,111.77,111.58,111.57,55.87,55.58,55.45,42.20,33.16,18.77.HRMS(ESI)m / z:[M+Na]+ calcd for C 23 H 27 NO 6 Na:436.1731,found:436.1728.

[0116]

[0117] (E)-4-(3-((2,4-dichlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3t)

[0118] white solid,mp 151–152℃,yield:63.0%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.65(t,J=5.9Hz,1H),7.63(d,J=2.1Hz,1H),7.48(d,J=15.8Hz,1H),7.44(dd,J=8.4,2.1Hz,1H),7.38(d,J=8.4Hz,1H),7.34(d,J=1.9Hz,1H),7.18(dd,J=8.3,1.8Hz,1H),7.12(d,J=8.1Hz,1H),6.74(d,J=15.8Hz,1H),4.45(d,J=5.8Hz,2H),3.81(s,3H),2.82(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,165.16,151.10,140.43,138.76,135.51,133.73,133.06,132.31,130.40,128.61,127.36,123.18,121.90,120.21,111.58,55.88,40.15,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcdfor C 21 H 21 Cl 2 NO 4 Na:444.0740,found:444.0733.

[0119]

[0120] (E)-4-(3-((3,4-dichlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3u)

[0121] white solid,mp 129–130℃,yield:64.2%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.68(t,J=6.1Hz,1H),7.60(d,J=8.3Hz,1H),7.54(d,J=2.0Hz,1H),7.48(d,J=15.8Hz,1H),7.34(d,J=1.9Hz,1H),7.29(dd,J=8.3,2.1Hz,1H),7.18(dd,J=8.3,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.69(d,J=15.8Hz,1H),4.40(d,J=6.0Hz,2H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),1.23(d,J=6.9Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,165.11,151.09,140.79,140.42,138.73,133.73,130.89,130.52,129.32,129.25,127.69,123.16,122.00,120.23,111.60,55.89,41.27,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcd forC 21 H 21 Cl 2 NO 4 Na:444.0740,found:444.0735.

[0122]

[0123] (E)-4-(3-((2,6-dichlorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3v)

[0124] white solid,mp 135–136℃,yield:61.0%. 1H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.29(t,J=4.7Hz,1H),7.53–7.50(m,2H),7.45(d,J=15.8Hz,1H),7.39(dd,J=8.7,7.4Hz,1H),7.29(d,J=1.8Hz,1H),7.15–7.08(m,2H),6.67(d,J=15.8Hz,1H),4.63(d,J=4.7Hz,2H),3.79(s,3H),2.81(hept,J=7.0Hz,1H),1.22(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.34,164.63,151.06,140.34,138.33,135.60,133.82,133.31,130.33,128.58,123.15,122.00,120.13,111.37,55.80,38.99,33.14,18.75.HRMS(ESI)m / z:[M+Na] + calcd for C 21 H 21 Cl 2 NO 4 Na:444.0740,found:444.0733.

[0125]

[0126] (E)-4-(3-((2-chloro-4-fluorobenzyl)amino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3w)

[0127] white solid,mp 139–140℃,yield:59.8%. 1 H NMR(400MHz,DMSO-d 6,ppm)δ:8.61(t,J=5.8Hz,1H),7.50–7.40(m,3H),7.33(d,J=1.9Hz,1H),7.23(td,J=8.6,2.7Hz,1H),7.18(dd,J=8.2,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.73(d,J=15.8Hz,1H),4.44(d,J=5.7Hz,2H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),1.23(d,J=6.9Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.35,165.09,161.01(d, 1 J C-F =245.0Hz),151.09,140.41,138.67,133.76,132.87(d, 3 J C-F =10.0Hz),132.66(d, 4 J C-F =3.0Hz),130.64(d, 3 J C-F =9.0Hz),123.16,121.99,120.19,116.44(d, 2 J C-F =25.0Hz),114.29(d, 2 J C-F =21.0Hz),111.57,55.87,39.81,33.15,18.75.HRMS(ESI)m / z:[M+Na] + calcd for C 21 H 21 ClFNO 4 Na:428.1035,found:428.1033.

[0128]

[0129] (E)-4-(3-(benzhydrylamino)-3-oxoprop-1-en-1-yl)-2-methoxyphenylisobutyrate(3x)

[0130] white solid,mp 178–179℃,yield:65.3%. 1 H NMR(400MHz,DMSO-d 6,ppm)δ:9.03(d,J=8.7Hz,1H),7.48(d,J=15.8Hz,1H),7.37–7.31(m,9H),7.28–7.24(m,2H),7.17(dd,J=8.2,1.8Hz,1H),7.11(d,J=8.1Hz,1H),6.85(d,J=15.8Hz,1H),6.27(d,J=8.6Hz,1H),3.81(s,3H),2.81(hept,J=7.0Hz,1H),1.23(d,J=7.0Hz,6H); 13 C NMR(100MHz,DMSO-d 6 ,ppm)δ:174.36,164.13,151.09,142.47,140.39,138.68,133.84,128.41,127.29,127.00,123.18,122.29,120.24,111.36,56.11,55.83,33.16,18.77.HRMS(ESI)m / z:[M+Na] + calcd for C 27 H 27 NO 4 Na:452.1832,found:452.1835.

[0131]

[0132] (R,E)-2-methoxy-4-(3-oxo-3-((1-phenylethyl)amino)prop-1-en-1-yl)phenylisobutyrate(3y)

[0133] white solid,mp 142–143℃,yield:62.0%. 1 H NMR(400MHz,DMSO-d 6 ,ppm)δ:8.55(d,J=8.1Hz,1H),7.42(d,J=15.8Hz,1H),7.36–7.31(m,5H),7.25–7.21(m,1H),7.15(dd,J=8.3,1.8Hz,1H),7.10(d,J=8.1Hz,1H),6.70(d,J=15.8Hz,1H),5.09–5.02(m,1H),3.80(s,3H),2.81(hept,J=7.0Hz,1H),1.41(d,J=7.0Hz,3H),1.23(d,J=6.9Hz,6H); 13CNMR (100MHz, DMSO-d 6 ,ppm)δ:174.36,163.94,151.07,144.56,140.30,138.16,133.88,128.27,126.67,126.01, 123.15,122.57,120.13,111.35,55.83,47.99,33.15,22.48,18.76.HRMS(ESI)m / z:[M+Na] + Calculate for C 22 H 25 NO 4 Na:390.1676,found:390.1671.

[0134] 3. Antimicrobial activity data

[0135] The antibacterial activity was determined by turbidity. Pure dimethyl sulfoxide (DMSO) was used as negative control, and fungicides zinc thiazole and thiophanate-methyl were used as positive controls. The inhibitory effect of the target compound on pathogenic bacteria was detected at concentrations of 100 and 50 μg / mL. The materials required for NB culture medium (glucose, peptone, yeast powder, beef paste, weighing 15g, 7.5g, 1.5g, 4.5g respectively) were weighed and dissolved in 1500ml of secondary water, and the pH value was adjusted to 7.0-7.2. 40μL of NB solution containing bacteria Psa, Xoc or Xac was taken with a pipette and mixed with 4ml NB solution and 1ml 0.1% Tween-20 solution (containing the test compound or positive control agent). The above solution was incubated at 28°C and 180rpm for 1 to 3 days. The bacterial growth was monitored by optical density method at 595nm (OD595). When the OD value of the blank control is between 0.6 and 0.8, the OD value of the compound is detected (200 μL of the solution is added to a 96-well plate on an enzyme counter, and the absorbance of the compound at 595 nm is detected).

[0136] I=(C tur –T tur ) / C tur ×100%

[0137] Among them C tur is the turbidity value of the blank control group, T tur is the turbidity value of the drug-treated group, I tur is the inhibition rate.

[0138] Table 1. In vitro antibacterial activity of target compounds against Xanthomonas oryzae, Xanthomonas citri var. citri and Xanthomonas oxysporum

[0139]

[0140]

[0141] From the biological activity test results in Table 1, it can be seen that the ferulic acid compounds containing amide structure have moderate to excellent inhibitory activity against rice bacterial leaf streak fungus and kiwi fruit bacterial canker fungus, among which 3d has the best activity, with inhibitory activities of 76.8% and 68.1% against rice bacterial leaf streak fungus and kiwi fruit bacterial canker fungus, respectively, which are higher than the control agents thiophanate-copper and thiazole zinc.

[0142] 4. Preparation of target compound 3d composition

[0143] The wettable powder of the target compound 3d and ethionin is used to prepare a composite composition. In each composition, the ratio of the target compound 3d and ethionin is calculated according to the mass ratio. The following preparations of the target compound 3d and ethionin are prepared as needed.

[0144] Composition 1: 3d: ethyl allicin wettable powder = 1:1

[0145] Composition 2: 3d: ethyl allicin wettable powder = 1:2

[0146] Composition 3: 3d: ethyl allicin wettable powder = 2:1

[0147] Anti-rice bacterial leaf streak disease and kiwifruit bacterial canker disease activity of the combination of target compound 3d

[0148] The antibacterial activity of the combination of target compound 3d and ethionine was tested against rice bacterial leaf streak pathogen and kiwi fruit bacterial canker pathogen using the turbidity method (the antibacterial activity test method mentioned previously).

[0149] Table 2 Inhibitory activity of drugs against bacterial leaf streak pathogen of rice and bacterial canker pathogen of kiwi fruit

[0150]

[0151] The in vitro growth rate method was used to test the activity of the composition against rice bacterial leaf streak pathogen and kiwi fruit bacterial canker pathogen at a concentration of 100 μg / mL. From the biological activity test results in Table 2, it can be seen that the activity of the composite composition against rice bacterial leaf streak pathogen and kiwi fruit canker pathogen was improved compared with the compounds before compounding. The inhibitory activity of composition 3 (3d: ethyl allicin wettable powder = 2:1) against rice bacterial leaf streak pathogen and kiwi fruit bacterial canker pathogen reached 88.9% and 80.4%, respectively. Therefore, the composite composition of 3d and ethyl allicin has a synergistic effect on rice bacterial leaf streak pathogen and kiwi fruit bacterial canker pathogen.

[0152] 5. Plant growth regulating activity test

[0153] (1) Test method

[0154] The wheat sheath cutting test method and the radish cotyledon expansion method were used. The plant growth regulating activity of the target compound was determined. Preparation of buffered nutrient solution: Weigh 1.019g of citric acid, 2.350g of potassium hydrogen phosphate trihydrate, and 20g of sugar, mix and dilute to 1L, and a citric acid-phosphate buffer solution with a pH of -5 is obtained. In the wheat sheath test method, indoleacetic acid (IAA) is used as the standard control, and in the radish cotyledon expansion method, kinetin (KT) is used as the standard control. Preparation of sample solution and standard control solution: Weigh an appropriate amount of the target compound and the control sample, add a few drops of DMF to dissolve, then add - drops of emulsifier (Tween-80), and use the buffer solution to prepare sample solutions with a concentration of 100μg / mL, and then dilute to 50, 10, and 1μg / mL in sequence. Preparation of germination bed: Weigh 2.4g of agar, heat 400mL of water until dissolved, pour into a porcelain plate and cool to form a germination bed.

[0155] (1) Wheat bud sheath cutting test method:

[0156] First, weigh about 50g of wheat seeds, soak them for 4 hours, then rinse them repeatedly with clean water, and after draining the water, evenly place them in the germination bed, seal them with a film, and then place them in an artificial climate box at a temperature of 25±1℃ for cultivation in a dark environment. When the wheat bud sheath grows to 2.5-3cm, select the bud sheaths with the same growth trend, use a blade to cut out their sensitive sections, and only take one section from each bud sheath. After cutting, shade them and rinse them in distilled water for one hour. Then, measure 8mL of each sample solution and place them in a culture dish with a diameter of 9cm. Place two filter paper pieces in each culture dish, then evenly place the cut 10 bud sheath segments in each treated culture dish, and then place them in an artificial climate box at 25±1℃ for dark cultivation again. After 48 hours, measure the total length of the 10 bud sheaths, compare them with the blank buffer solution control group, and compare them with the standard solution control group of the same concentration. The inhibitory or promoting effect is calculated and used as an evaluation index for the function of drug auxin. Calculate according to the following formula:

[0157] Effect = (treatment - blank) / blank × 100%

[0158] If the calculation result is positive, it means there is a promoting effect; if the calculation result is negative, it means there is an inhibitory effect. Finally, the efficacy is evaluated. The evaluation criteria are:

[0159]

[0160] (2) Radish cotyledon expansion test method:

[0161] First weigh about 30g of radish seeds, soak them in warm water until the seeds turn white, then wash them with clean water, drain the water and put them in the germination bed, seal them with a film, and then place them in an artificial climate box at 25±1℃ for dark culture for about 72 hours, and set aside after completion. Measure 8mL of each sample solution and place it in a culture dish with a diameter of 9cm, and put two pieces of paper in each culture dish. Select radish seedlings with uniform growth and cotyledon size, cut off the cotyledons without petioles, place 10 cotyledons for each treatment, and weigh the fresh weight of the cotyledons before treatment in each group and record the data, then cover the culture dish cover and place it in an artificial climate box for dark culture. After 72 hours, take out the cotyledons of each group, use absorbent paper to absorb the moisture on the surface of the cotyledons, weigh the fresh weight of the cotyledons after treatment in each group and record the data, calculate the percentage of fresh weight gain of the cotyledons after culture, and use this as the evaluation index of the function of the drug sample cytokinin. Its calculation method and evaluation criteria are the same as those of the wheat bud sheath cutting test method.

[0162] (3) Biological test results

[0163] Table 3 Plant growth regulator activity of some target compounds

[0164]

[0165]

[0166] The plant growth activity test results of this series of target compounds are shown in Table 3. The preliminary biological activity test results show that the target compounds have certain plant growth activity, among which compounds 3a, 3b and 3h have good auxin activity, which is higher than indoleacetic acid. Compound 3f has good cytokinin activity, and the activity is higher at high concentration.

Claims

1. A ferulic acid derivative, characterized in that: The structural formula of the ferulic acid derivative is as follows: Wherein, R is benzyl, substituted benzyl, or heterocyclic group.

2. A ferulic acid derivative according to claim 1, characterized in that: The substituent of the substituted benzyl group is a mono- or di-substituted benzene ring with methyl, methoxy, halogen or cyano, and the heterocyclic group is naphthalene or pyridine.

3. The method for preparing a ferulic acid derivative according to claim 1, characterized in that: The reaction formula is as follows:

4. The method for preparing a ferulic acid derivative according to claim 3, characterized in that: The method comprises the following steps: first, reacting ferulic acid with isobutyric anhydride in a sodium hydroxide solution, then adding dilute sulfuric acid to the mixture to adjust the pH (4-5) to obtain 80% of O-isobutylferulic acid 1; then converting the O-isobutylferulic acid into the corresponding acyl chloride 2 by reacting with thionyl chloride; finally, preparing the target compound by acid-amine coupling reaction of the intermediate 2 with a substituted benzylamine.

5. Use of a ferulic acid derivative as claimed in claim 1 or 2 in the preparation of drugs and medicaments for preventing and controlling kiwi fruit bacterial canker, rice bacterial leaf streak pathogen and citrus canker pathogen.

6. A compound pesticide composition, characterized in that: The composition comprises the ferulic acid derivative according to claim 1 and ethionine.

7. The composition according to claim 6, characterized in that: The mass ratio of the derivative to ethionine is 1:2-2:

1.

8. Use of the composition according to claim 6 in the preparation of a medicament for preventing and treating bacterial leaf streak of rice and bacterial canker of kiwi fruit.

9. The composition according to claim 6, characterized in that: The derivative is 3d.

10. Application of a ferulic acid derivative as claimed in claim 1 or 2 in the preparation of a plant growth regulator.

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