A cinnamic acid oxime ester compound, preparation method and application

Abstract

The present invention belongs to the technical field of pathogen control, and particularly relates to a cinnamic acid oxime ester compound, a preparation method and an application thereof. The cinnamic acid oxime ester compound has a structural formula as shown in Formula I: The preparation method of the compound of the present invention is simple in operation and easy to obtain raw materials. The compound has broad-spectrum bactericidal activity, and particularly has obvious inhibitory effects on Botrytis cinerea of tomato, Valsa mali of apple tree and Gaeumannomyces graminis of wheat, and can be used as a bactericide for the prevention and control of the above plant diseases.

Description

Technical Field

[0001] The invention belongs to the technical field of pathogen control, and particularly relates to a cinnamic acid oxime ester compound, a preparation method and an application thereof. Background Art

[0002] Oxime esters possess excellent biological activity, with their medicinal applications widely reported and a strong research foundation for their agricultural applications. In 2017, Xia Lijuan et al. reported heterocyclic 1,4-pentadien-3-one oxime esters with strong inhibitory activity against wheat fusarium head blight and apple rot pathogens (Applied Chemistry, 2017, 34, 316). Jiang Lin et al. synthesized a series of new 3,3-dimethyl-1-(pyridin-3-yl)-butan-2-one oxime esters, demonstrating strong fungicidal activity against eggplant sclerotinia sclerotiorum and tomato gray mold (Organic Chemistry, 2017, 37, 2767).

[0003] Cinnamic acid is widely found in various plants, especially in the medicinal plant cinnamon, which is one of the main active ingredients. Cinnamic acid and its derivatives have various excellent biological activities, such as anti-cancer, anti-inflammatory, bactericidal, herbicidal, and insecticidal. Our previous studies have shown that the natural product cinnamic acid exhibits good agricultural antibacterial activity, especially against the EC of rapeseed sclerotinia. 50 The value is 18.77 mg / L (Plant Disease, 2019, 103, 944).

[0004] To discover new agricultural fungicides, the inventors introduced cinnamic acid into oxime ester structures, resulting in a new class of compounds represented by Formula I. These compounds have been shown to be effective in controlling plant pathogens. The present invention discloses a class of novel cinnamic acid oxime ester compounds and their use as agricultural fungicides. Summary of the Invention

[0005] The present invention aims to provide a cinnamic acid oxime ester compound, a preparation method and an application thereof.

[0006] A cinnamic acid oxime ester compound, a compound represented by formula I

[0007]

[0008] Where: R 1 At least one selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkyl, halogenated C1-C4 alkoxy, cyano and nitro;

[0009] R 2 At least one selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkyl, halogenated C1-C4 alkoxy, cyano and nitro;

[0010] R 1 and R 2 is mono-substituted, di-substituted or tri-substituted;

[0011] Wherein: when R 1 is hydrogen, R 2 is not chlorine, methoxy or ethoxy; when R 1 is substituted with 2 methoxy groups or 3 methoxy groups, R 2 is not substituted with 2 methoxy groups or 3 methoxy groups;

[0012] or a salt of the compound shown in formula I.

[0013] Optionally, specifically, the said R 1 is selected from at least one of methyl, methoxy, fluorine, chlorine, bromine and trifluoromethyl;

[0014] The said R 2 is selected from at least one of methyl, tert-butyl, methoxy, fluorine, chlorine, bromine, trifluoromethyl and trifluoromethoxy.

[0015] A cinnamic acid oxime ester compound is the compound shown in formula I

[0016]

[0017] The specific substituents of the compound shown in formula I are shown in the following table:

[0018]

[0019]

[0020] The preparation method of the cinnamic acid oxime ester compound according to any one of the present invention includes the following steps: adding the compound shown in formula III or the compound shown in formula IV and the compound shown in formula II into an organic solvent for reaction to obtain the compound shown in formula I;

[0021]

[0022] Optionally, the said organic solvent is selected from at least one of dichloromethane, chloroform, toluene, ethyl acetate and tetrahydrofuran.

[0023] Optionally, an additive is further added to the organic solvent, and the said additive is selected from at least one of triethylamine, pyridine and dicyclohexylcarbodiimide.

[0024] Optionally, the reaction temperature of the said reaction is -25 to 50 °C, and the reaction time is 5 min to 24 h;

[0025] The molar ratio of the compound shown in Formula II to the compound shown in Formula III or the compound shown in Formula IV is 1.0:(1.0 - 1.2).

[0026] Use of the cinnamic acid oxime ester compound according to any one of the present invention for preparing a plant fungicide.

[0027] Optionally, the plant fungicide is used for controlling Sclerotinia sclerotiorum, Botrytis cinerea, Valsa mali and / or Gaeumannomyces graminis var. tritici.

[0028] A plant fungicide, wherein the plant fungicide uses the cinnamic acid oxime ester compound according to any one of the present invention as an active ingredient;

[0029] The weight percentage content of the active ingredient is 0.1% - 99%.

[0030] The beneficial effects of the present invention are as follows:

[0031] The present invention introduces cinnamic acid, a natural product with excellent biological activity, into the oxime ester compound. The obtained compound has a novel structure and broad-spectrum bactericidal activity, and particularly has an obvious inhibitory effect on Botrytis cinerea, Valsa mali and Gaeumannomyces graminis var. tritici. Description of the Drawings

[0032] The drawings are used to provide a further understanding of the present disclosure, and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure, but do not constitute a limitation to the present disclosure. In the drawings:

[0033] Figure 1 is the hydrogen spectrum of Compound I-05 of the present invention;

[0034] Figure 2 is the carbon spectrum of Compound I-05 of the present invention;

[0035] Figure 3 is the hydrogen spectrum of Compound I-22 of the present invention;

[0036] Figure 4 is the hydrogen spectrum of Compound I-22 of the present invention. Specific Embodiments

[0037] The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to these examples. The methods, unless otherwise specified, are all conventional methods. The materials, unless otherwise specified, can all be obtained from public commercial channels.

[0038] The cinnamic acid oxime ester compound of the present invention refers to a compound having the structure shown in Formula I:

[0039]

[0040] Wherein: R 1 is selected from at least one of hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkyl, halogenated C1-C4 alkoxy, cyano and nitro;

[0041] R 2 is selected from at least one of hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkyl, halogenated C1-C4 alkoxy, cyano and nitro;

[0042] R 1 and R 2 are substituted in a mono-substituted, di-substituted or tri-substituted manner, and the substitution numbers of R 1 and R 2 can be the same or different. For example, when R 1 is mono-substituted, R 2 can be mono-substituted, di-substituted or tri-substituted; the so-called mono-substitution means that R 1 selects one substituent for substitution, or R 2 selects one substituent for substitution; di-substitution means that R 1 and R 2 can select two substituents for substitution, and the two substituents can be the same or different; tri-substitution means that R 1 and R 2 can select three substituents for substitution, and the three substituents can be the same or different. For example, 1 halogen plus 1 alkyl is two different substitutions;

[0043] Wherein: when R 1 is hydrogen, R 2 is not chlorine, methoxy or ethoxy; when R 1 is substituted with 2 methoxy groups or 3 methoxy groups, R 2 is not substituted with 2 methoxy groups or 3 methoxy groups;

[0044] or a salt of the compound represented by formula I.

[0045] Preferably, R 1 is selected from at least one of methyl, methoxy, fluorine, chlorine, bromine and trifluoromethyl; R 2 The substituents are selected from at least one of methyl, tert-butyl, methoxy, fluorine, chlorine, bromine, trifluoromethyl and trifluoromethoxy; the substitution manner is mono-substituted, di-substituted or tri-substituted;

[0046] or a salt of the compound represented by formula I.

[0047] More specifically, see the data listed in Table 1:

[0048] Table 1

[0049]

[0050]

[0051] The compound shown in Formula I is prepared by the following method:

[0052] A method for preparing a cinnamic acid oxime ester compound, comprising the following steps: adding the compound shown in Formula III or the compound shown in Formula IV and the compound shown in Formula II to an organic solvent for reaction to obtain the compound shown in Formula I;

[0053]

[0054] The organic solvent is selected from at least one of dichloromethane, chloroform, toluene, ethyl acetate, and tetrahydrofuran.

[0055] An additive is further added to the organic solvent, and the additive is selected from at least one of triethylamine, pyridine, and dicyclohexylcarbodiimide.

[0056] The reaction temperature of the reaction is -25 to 50 °C, and the reaction time is 5 min to 24 h;

[0057] The molar ratio of the compound shown in Formula II to the compound shown in Formula III or the compound shown in Formula IV is 1.0:(1.0 - 1.2).

[0058] Use of the cinnamic acid oxime ester compound according to any one of the present invention for preparing a plant fungicide. The plant fungicide is used for controlling Sclerotinia sclerotiorum, Botrytis cinerea, Valsa mali, and / or Gaeumannomyces graminis var. tritici.

[0059] A plant fungicide, wherein the plant fungicide uses the cinnamic acid oxime ester compound according to any one of the present invention as an active ingredient; the weight percentage content of the active ingredient is 0.1% - 99%.

[0060] The following specifically describes the solution of the present invention with specific examples.

[0061] Example 1: Preparation of Compound 2 - Bromobenzaldehyde - O - (-3-(4 - Trifluoromethylphenyl)acryloyl)oxime (I - 06)

[0062]

[0063] In a 25 mL single-necked flask, 1.00 g (5 mmol) of 2-bromobenzaldoxime, 0.5060 g (5 mmol) of triethylamine, and 10 mL of dichloromethane were added. At room temperature, a solution of 1.173 g (5 mmol) of 4-trifluoromethylcinnamoyl chloride in 10 mL of dichloromethane was added dropwise thereto. After the addition was complete, the reaction was carried out for 30 minutes. Purification by column chromatography (petroleum ether:ethyl acetate = 8:1), and a white solid was obtained after drying. The yield was 73%, m.p. 138.2 - 139.1 °C. 1 1H NMR (400 MHz, CDCl3) δ: 8.86 (s, 1H), 8.10 (dd, J = 7.5, 1.9 Hz, 1H), 7.88 (d, J = 16.1 Hz, 1H), 7.66 (s, 4H), 7.60 (dd, J = 7.7, 1.2 Hz, 1H), 7.38 - 7.30 (m, 2H), 6.64 (d, J = 16.1 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ: 163.81, 155.78, 144.72, 137.45, 133.28, 132.96, 132.11 (q, J = 32.7 Hz), 129.56, 128.82, 128.41, 127.84, 125.94 (q, J = 3.7 Hz), 125.01, 123.77 (q, J = 273.4 Hz), 117.85. HRMS: C 17 H 11 BrF3NO [M + H] + , calculated value 397.9998, measured value 397.9994.

[0064] Example 2: Preparation of compound 2-fluorobenzaldehyde - O - ((E)-3-(4-methoxyphenyl)acryloyl)oxime (I-14)

[0065]

[0066] 0.696 g (5 mmol) of 2-fluorobenzaldoxime, 0.891 g (5 mmol) of 4-methoxycinnamic acid, and 1.032 g (5 mmol) of dicyclohexylcarbodiimide were added to 20 mL of dichloromethane, and the reaction was carried out at room temperature with stirring for 24 h. After concentration by a rotary evaporator, purification was carried out by silica gel column chromatography, and the mobile phase ratio was petroleum ether:ethyl acetate = 10:1. Rotary evaporation and concentration gave a white solid. The yield was 70%, m.p. 104.2 - 105.7 °C. 11H NMR (400 MHz, CDCl3) δ: 8.73 (s, 1H), 8.12 - 8.07 (m, 1H), 7.84 (d, J = 15.9 Hz, 1H), 7.54 (d, J = 8.7 Hz, 2H), 7.50 - 7.44 (m, 1H), 7.22 (t, J = 7.5 Hz, 1H), 7.13 (t, J = 9.3 Hz, 1H), 6.93 (d, J = 8.7 Hz, 2H), 6.43 (d, J = 16.0 Hz, 1H), 3.86 (s, 3H). 13 13C NMR (100 MHz, CDCl3) δ: 164.83, 161.78, 161.60 (d, J = 252.36 Hz), 149.62 (d, J = 5.0 Hz), 146.37, 133.40 (d, J = 8.7 Hz), 130.05, 127.84 (d, J = 2.1 Hz), 126.91, 124.61 (d, J = 3.5 Hz), 118.30 (d, J = 10.2 Hz), 115.96 (d, J = 20.9 Hz), 114.42, 112.43, 55.40. HRMS: C 17 H 14 FNO2 [M + H] + , calculated value 300.1030, measured value 300.1032.

[0067] Other compounds of the present invention can be prepared with reference to the above embodiments.

[0068] Appearance, melting point and structure identification data of some compounds are as follows:

[0069] Compound I - 01: White solid. m.p. 177.6 - 178.2 °C. 1 1H NMR (500 MHz, CDCl3) δ 8.88 (s, 1H), 8.28 (d, J = 16.1 Hz, 1H), 8.13 (dd, J = 7.7, 1.7 Hz, 1H), 7.68 (dd, J = 7.5, 1.6 Hz, 1H), 7.63 (dd, J = 7.9, 1.0 Hz, 1H), 7.45 (dd, J = 7.8, 1.2 Hz, 1H), 7.40 - 7.30 (m, 4H), 6.58 (d, J = 16.0 Hz, 1H).

[0070] Compound I - 02: White solid. m.p. 139.9 - 141.2 °C. 11H NMR (500 MHz, CDCl3) δ 8.87 (s, 1H), 8.12 (d, J = 7.2 Hz, 1H), 7.81 (d, J = 16.0 Hz, 1H), 7.62 (d, J = 7.7 Hz, 1H), 7.56 (s, 1H), 7.44 (d, J = 7.1 Hz, 1H), 7.39 - 7.32 (m, 4H), 6.57 (d, J = 16.0 Hz, 1H).

[0071] Compound I-03: White solid. m.p. 153.0 - 153.6 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.86 (s, 1H), 8.11 (dd, J = 7.6, 1.9 Hz, 1H), 7.82 (d, J = 16.0 Hz, 1H), 7.61 (dd, J = 7.8, 1.2 Hz, 1H), 7.50 (d, J = 8.5 Hz, 2H), 7.39 - 7.31 (m, 4H), 6.54 (d, J = 16.0 Hz, 1H).

[0072] Compound I-04: White solid. m.p. 149.6 - 149.9 °C. 1 1H NMR (500 MHz, CDCl3) δ 8.87 (s, 1H), 8.13 (dd, J = 7.7, 1.7 Hz, 1H), 7.86 (d, J = 16.0 Hz, 1H), 7.63 (dd, J = 7.9, 1.0 Hz, 1H), 7.58 (dd, J = 8.6, 5.4 Hz, 2H), 7.40 - 7.32 (m, 2H), 7.12 (t, J = 8.6 Hz, 2H), 6.50 (d, J = 16.0 Hz, 1H).

[0073] Compound I-05: White solid. m.p. 140.7 - 141.2 °C. 1 1H NMR (500 MHz, CDCl3) δ 8.87 (s, 1H), 8.12 (dd, J = 7.7, 1.7 Hz, 1H), 7.82 (d, J = 16.0 Hz, 1H), 7.62 (dd, J = 7.9, 1.0 Hz, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.40 - 7.32 (m, 2H), 6.56 (d, J = 16.0 Hz, 1H). 1H NMR and 13C NMR spectra are shown in Figure 1 and 2 .

[0074] Compound I-07: White solid. m.p. 117.2 - 118.3 °C. 11H NMR (400 MHz, CDCl3) δ 8.85 (s, 1H), 8.12 (dd, J = 7.6, 1.8 Hz, 1H), 7.86 (d, J = 16.0 Hz, 1H), 7.60 (dd, J = 7.9, 1.1 Hz, 1H), 7.47 (d, J = 8.1 Hz, 2H), 7.38 - 7.29 (m, 2H), 7.21 (d, J = 8.0 Hz, 2H), 6.52 (d, J = 16.0 Hz, 1H), 2.38 (s, 3H).

[0075] Compound I-08: White solid. m.p. 141.2 - 142.1 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.86 (s, 1H), 8.13 (dd, J = 7.6, 1.8 Hz, 1H), 7.85 (d, J = 16.0 Hz, 1H), 7.62 (dd, J = 7.9, 0.9 Hz, 1H), 7.54 (d, J = 8.7 Hz, 2H), 7.40 - 7.31 (m, 2H), 6.94 (d, J = 8.7 Hz, 2H), 6.44 (d, J = 16.0 Hz, 1H), 3.86 (s, 3H).

[0076] Compound I-09: White solid. m.p. 128.5 - 129.3 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.38 (s, 1H), 7.97 (s, 1H), 7.83 (d, J = 16.0 Hz, 1H), 7.68 (d, J = 7.8 Hz, 1H), 7.61 - 7.59 (m, 1H), 7.53 (d, J = 8.7 Hz, 2H), 7.31 (t, J = 7.9 Hz, 1H), 6.93 (d, J = 8.7 Hz, 2H), 6.42 (d, J = 15.9 Hz, 1H), 3.85 (s, 3H).

[0077] Compound I-10: White solid. m.p. 182.7 - 183.9 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.40 (s, 1H), 7.83 (d, J = 15.9 Hz, 1H), 7.66 (d, J = 8.5 Hz, 2H), 7.59 - 7.56 (m, 2H), 7.53 (d, J = 8.7 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.42 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0078] Compound I-11: White solid. m.p. 103.2 - 104.7 °C. 11H NMR (400 MHz, CDCl3) δ 8.90 (s, 1H), 8.16 - 8.14 (m, 1H), 7.85 (d, J = 16.0 Hz, 1H), 7.54 (t, J = 8.7 Hz, 2H), 7.44 - 7.39 (m, 2H), 7.35 - 7.31 (m, 1H), 6.93 (d, J = 8.8 Hz, 2H), 6.44 (d, J = 16.0 Hz, 1H), 3.85 (s, 3H).

[0079] Compound I - 12: White solid. m.p. 124.5 - 125.1 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.40 (s, 1H), 7.86 - 7.82 (m, 2H), 7.65 (d, J = 7.6 Hz, 1H), 7.54 (d, J = 8.7 Hz, 2H), 7.47 - 7.44 (m, 1H), 7.38 (t, J = 7.8 Hz, 1H), 6.93 (d, J = 8.7 Hz, 2H), 6.43 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0080] Compound I - 13: White solid. m.p. 163.2 - 163.9 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.41 (s, 1H), 7.83 (d, J = 16.0 Hz, 1H), 7.72 (d, J = 8.5 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H), 6.92 (d, J = 8.7 Hz, 2H), 6.42 (d, J = 15.9 Hz, 1H), 3.85 (s, 3H).

[0081] Compound I - 15: White solid. m.p. 120.7 - 121.8 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.42 (s, 1H), 7.84 (d, J = 15.9 Hz, 1H), 7.56 - 7.52 (m, 4H), 7.44 - 7.37 (m, 1H), 7.18 (td, J = 8.3, 2.8 Hz, 1H), 6.93 (d, J = 8.7 Hz, 2H), 6.43 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0082] Compound I - 16: White solid. m.p. 119.4 - 119.9 °C. 11H NMR (400 MHz, CDCl3) δ 8.42 (s, 1H), 7.85 - 7.77 (m, 3H), 7.54 (d, J = 8.7 Hz, 2H), 7.14 (t, J = 8.6 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.42 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0083] Compound I-17: White solid. m.p. 109.2 - 110.8 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.72 (s, 1H), 7.92 (d, J = 7.7 Hz, 1H), 7.84 (d, J = 15.9 Hz, 1H), 7.54 (d, J = 8.7 Hz, 2H), 7.37 (t, J = 7.2 Hz, 1H), 7.28 - 7.23 (m, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.46 (d, J = 16.0 Hz, 1H), 3.86 (s, 3H), 2.51 (s, 3H).

[0084] Compound I-18: White solid. m.p. 112.3 - 113.2 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.42 (s, 1H), 7.83 (d, J = 16.0 Hz, 1H), 7.67 (s, 1H), 7.55 - 7.52 (m, 3H), 7.35 - 7.26 (m, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.44 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H), 2.40 (s, 3H).

[0085] Compound I-19: White solid. m.p. 114.9 - 115.6 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.41 (s, 1H), 7.82 (d, J = 16.0 Hz, 1H), 7.67 (d, J = 8.1 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 7.25 (d, J = 9.7 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.43 (d, J = 16.0 Hz, 1H), 3.85 (s, 3H), 2.40 (s, 3H).

[0086] Compound I-20: White solid. m.p. 173.2 - 173.5 °C. 11H NMR (400 MHz, CDCl3) δ 8.49 (s, 1H), 7.91 (d, J = 8.1 Hz, 2H), 7.85 (d, J = 16.0 Hz, 1H), 7.71 (d, J = 8.3 Hz, 2H), 7.54 (d, J = 8.7 Hz, 2H), 6.94 (d, J = 8.7 Hz, 2H), 6.43 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0087] Compound I-21: White solid. m.p. 116.7 - 117.4 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.45 (s, 1H), 7.86 - 7.82 (m, 3H), 7.54 (d, J = 8.7 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.42 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0088] Compound I-22: White solid. m.p. 124.7 - 125.1 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.42 (s, 1H), 7.82 (d, J = 16.0 Hz, 1H), 7.71 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H), 6.92 (d, J = 8.7 Hz, 2H), 6.43 (d, J = 16.0 Hz, 1H), 3.85 (s, 3H), 1.34 (s, 9H). 1H NMR and 13C NMR spectra are shown in Figure 3 and 4 .

[0089] Compound I-23: White solid. m.p. 127.4 - 128.1 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.38 (s, 1H), 7.83 (d, J = 15.9 Hz, 1H), 7.73 - 7.68 (m, 1H), 7.53 (d, J = 8.7 Hz, 2H), 7.47 (dd, J = 4.2, 1.9 Hz, 1H), 7.22 (d, J = 8.3 Hz, 1H), 6.93 (d, J = 8.7 Hz, 2H), 6.41 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0090] Compound I-24: White solid. m.p. 132.1 - 132.7 °C. 11H NMR (400 MHz, CDCl3) δ 8.54 (s, 1H), 8.24 (s, 2H), 7.98 (s, 1H), 7.87 (d, J = 15.9 Hz, 1H), 7.55 (d, J = 8.7 Hz, 2H), 6.94 (d, J = 8.7 Hz, 2H), 6.42 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0091] Compound I-25: White solid. m.p. 169.1 - 169.7 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.33 (s, 1H), 7.84 (d, J = 15.9 Hz, 1H), 7.53 (d, J = 8.7 Hz, 2H), 7.45 (t, J = 7.3 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.40 (d, J = 15.9 Hz, 1H), 3.86 (s, 3H).

[0092] Compound I-26: White solid. m.p. 97.3 - 98.9 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.74 (s, 1H), 7.85 (d, J = 16.0 Hz, 1H), 7.53 (d, J = 8.7 Hz, 2H), 7.40 - 7.34 (m, 1H), 7.28 (d, J = 8.7 Hz, 1H), 7.12 (t, J = 9.0 Hz, 1H), 6.93 (d, J = 8.7 Hz, 2H), 6.48 (d, J = 15.9 Hz, 1H), 3.85 (s, 3H).

[0093] Compound I-27: White solid. m.p. 143.7 - 144.1 °C. 1 1H NMR (400 MHz, CDCl3) δ 8.53 (s, 1H), 8.23 (s, 2H), 7.97 (s, 1H), 7.85 (d, J = 15.9 Hz, 1H), 7.53 (d, J = 8.7 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 6.41 (d, J = 15.9 Hz, 1H), 3.85 (s, 3H).

[0094] Example 3: In vitro antibacterial activity of Compound I against 6 plant pathogens

[0095] The bactericidal activity of Compound I was determined by the mycelial growth rate method. The test strains were Rhizoctonia solani, Gibberella zeae, Sclerotinia sclerotiorum, Botrytis cinerea, Valsa mali, and Gaeumannomyces graminis var. tritici.

[0096] Weigh the compound of formula I separately, and prepare a stock solution with a concentration of 10,000 mg / L using dimethyl sulfoxide. Then, use a pipette to aspirate the prepared 10,000 mg / L stock solution and add it to the sterilized and cooled potato dextrose agar (PDA) medium. After mixing, prepare a medicated medium with a concentration of 50 mg / L, pour it into a petri dish with a diameter of 9 cm, 15 mL per dish, and repeat each agent 4 times. After the medicated medium in the dish has solidified, make a medicated PDA plate. Set dimethyl sulfoxide as the solvent blank control. Use a punch to prepare a mycelial disc with a diameter of 0.7 cm along the edge of the colony of the cultured pathogen plate, and inoculate it into the medicated and blank control PDA plates respectively, and place them in a 25°C incubator for dark culture. After the colonies in the blank control PDA plate have grown sufficiently, measure the colony diameter of each treatment by the cross method and take the average value.

[0097] Calculate the mycelial growth inhibition rate using the following formula:

[0098]

[0099] The in vitro bactericidal activity data of some compounds are shown in Table 1.

[0100] Table 1 In vitro bactericidal activity results of the compound of formula I (inhibition rate %)

[0101]

[0102] As can be seen from Table 1, the compound of formula I provided by the present invention has certain inhibitory activities against the 4 kinds of plant pathogens tested. Among them, compounds I-09, I-21, I-22, and I-24 against Gaeumannomyces graminis var. tritici, and I-14 and I-26 against Botrytis cinerea and Valsa mali, all showed inhibition rates exceeding 90%; the inhibition rates of compounds I-06, I-07, I-08, I-11, I-17, I-18, I-24, and I-27 against Botrytis cinerea exceeded 80%, showing relatively good activity. In addition, compounds I-01 to I-27 also have certain antibacterial activities against Rhizoctonia solani and Gibberella zeae.

[0103] Example 4: In vivo bactericidal activity of some compounds of formula I

[0104] Pharmacodynamic determination of the compound against apple canker. The control effect of the compound on apple branches was determined by the scald inoculation method. One-year-old branches were selected, cut into sections, then soaked in 1% sodium hypochlorite solution for 5 min for disinfection, and then taken out to dry, and the two ends of the branches were coated with paraffin to prevent water loss and infection by miscellaneous bacteria. (1) Protective effect: Punch holes in the epidermis of apple branches with a puncher with a diameter of 5 mm, spray the required concentration of the liquid medicine at the wound site, and inoculate the pathogenic bacteria 24 h after spraying the medicine; (2) Therapeutic effect: Punch holes in the epidermis of apple branches with a puncher with a diameter of 5 mm and inoculate the pathogenic bacteria, and then spray the required concentration of the liquid medicine 24 h after inoculating the bacteria. Use clear water as the blank control. Investigate the control effect after moisturizing and culturing for 5 - 7 days.

[0105] In vivo control effect against apple canker:

[0106] At a dose of 200 mg / L, compounds I-14, I-26, etc., the protective activity and therapeutic activity against apple canker were both above 95%; at a dose of 100 mg / L, compounds I-14, I-26, etc., the protective activity and therapeutic activity against apple canker were both above 85%.

[0107] Pharmacodynamic determination of the compound against tomato gray mold. The pot method was used for determination: (1) Protective effect: Spray the required concentration of the liquid medicine, air dry naturally, and spray inoculate with a suspension with a concentration of 1×10 5 spores / mL 24 h later; (2) Therapeutic effect: Inoculate with a suspension with a concentration of 1×10 5 spores / mL 24 h before spraying the required concentration of the liquid medicine. Use clear water as the blank control. After inoculation, transfer to a humidity chamber and culture for 7 d, and then investigate the control effect.

[0108] In vivo control effect against tomato gray mold:

[0109] At a dose of 200 mg / L, compounds I-14, etc., the protective activity and therapeutic activity against tomato gray mold were both above 98%; at a dose of 100 mg / L, compounds I-14, etc., the protective activity and therapeutic activity against tomato gray mold were both above 88%.

[0110] The effect of the compound against gray mold on tomato fruits was determined by the acupuncture method. At doses of 200 mg / L and 100 mg / L, compounds I-14, etc., the protective activity and therapeutic activity against gray mold on tomato fruits were both above 90%;

[0111] The results of the bioactivity determination showed that the compound of formula I had good inhibitory effects on Gaeumannomyces graminis var. tritici, Botrytis cinerea, and Valsa mali, and could be used as a fungicide for the control of the above plant pathogenic bacteria.

[0112] The preferred embodiments of the present disclosure have been described in detail above. However, the present disclosure is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0113] In addition, it should be noted that, in the various specific technical features described in the above specific embodiments, they can be combined in any suitable manner without conflict. To avoid unnecessary repetition, the present disclosure will not separately describe various possible combination methods.

[0114] Furthermore, any combination can be made among various different embodiments of the present disclosure, as long as it does not violate the idea of the present disclosure, and it should also be regarded as the content disclosed by the present disclosure.

Claims

1. A cinnamic acid oxime ester compound, characterized in that, The compound shown in Formula I The specific substituents of the compound shown in Formula I are shown in the following table:

2. The preparation method of the cinnamic acid oxime ester compound according to claim 1, characterized in that, Comprising the following steps: Adding the compound shown in Formula III or the compound shown in Formula IV and the compound shown in Formula II into an organic solvent for reaction to obtain the compound shown in Formula I; 3. The preparation method of the cinnamic acid oxime ester compound according to claim 2, characterized in that, The organic solvent is selected from at least one of dichloromethane, chloroform, toluene, ethyl acetate and tetrahydrofuran.

4. The preparation method of the cinnamic acid oxime ester compound according to claim 2, wherein, An additive is further added into the organic solvent, and the additive is selected from at least one of triethylamine, pyridine and dicyclohexylcarbodiimide.

5. The preparation method of the cinnamic acid oxime ester compound according to claim 2, wherein, The reaction temperature of the reaction is -25 to 50 °C, and the reaction time is 5 min to 24 h; The molar ratio of the compound shown in Formula II to the compound shown in Formula III or the compound shown in Formula IV is 1.0:(1.0 - 1.2).

6. Use of the cinnamic acid oxime ester compound according to claim 1 for preparing a plant bactericide.

7. The application according to claim 6, wherein The plant bactericide is used for preventing and treating Sclerotinia sclerotiorum, Botrytis cinerea, Valsa mali and / or Gaeumannomyces graminis var. tritici.

8. A plant fungicide, characterized in that, The plant bactericide uses the cinnamic acid oxime ester compound according to claim 1 as an active ingredient; The weight percentage content of the active ingredient is 0.1% - 99%.

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