CN115093343B - Pinonyl oxime ester compound, preparation method and application - Google Patents

Abstract

本发明所述化合物具有广谱的杀菌活性，尤其对水稻纹枯病菌、番茄灰霉病菌、小麦赤霉病菌、苹果腐烂病菌、番茄枯萎病菌和黄瓜炭疽病菌具有明显的抑制效果，可以作为杀菌剂用于上述植物病害的防治。The invention discloses a pinone oxime ester compound, a preparation method and an application. The invention introduces different oximes into pinone acid to obtain a class of compounds with novel structures. The structure of the compound is shown in formula I:

The compound of the present invention has broad-spectrum bactericidal activity, especially has obvious inhibitory effect on rice sheath blight, tomato cinerea, wheat scab, apple rot, tomato wilt and cucumber anthracnose, and can be used as a bactericidal agent. The agent is used for the control of the above-mentioned plant diseases.

Description

A kind of pinone oxime ester compound, preparation method and application

technical field

The invention belongs to the technical field of pathogenic bacteria control, and in particular relates to a pinone oxime ester compound, a preparation method and an application.

Background technique

my country is a large agricultural country, and plant diseases caused by pathogenic bacteria have caused significant economic losses to my country's agricultural production. Phytopathogenic bacteria will not only reduce the quality of fruits and vegetables and shorten the storage period; some fungi can also produce toxins, which are harmful to human and animal health. For example, rice sheath blight caused by Rhizoctonia solani Kuhn is one of the important diseases threatening rice production, which can cause up to 45% yield loss (Margani R et al, Iop Conference, 2018, 142) . At present, the main means of prevention and control of plant diseases is still chemical control. However, the widespread and uncontrolled use of pesticides has caused problems such as drug resistance and residues. Therefore, it is imperative to invent a kind of low toxicity, environmental protection, high-efficiency bactericide.

Natural products with relatively low toxicity and less environmental risk are often used as lead compounds for the discovery of new pesticides. Turpentine is the most productive natural monoterpene compound in the world, and its main component is α-pinene. Among the derivatives of α-pinene, four-membered ring compounds are a special class of compounds, and compounds with four-membered ring structures in nature often have good biological activity. α-pinene can be oxidized to obtain pinone acid containing four-membered rings. In recent years, the active groups of pinone acid—carboxyl group and ketone carbonyl group have been modified, and many compounds with agricultural activity have been derived.

Oxime compounds (oxime ethers and oxime esters) have a wide range of biological activities, including antitumor, herbicidal, insecticidal, antiviral and antifungal activities (Regnier T et al, Postharvest Biol.Tec.2009, 2, 254-258) . This type of compound also has the characteristics of high efficiency, low toxicity, and low residue. As a class of active substances, it has been widely used in the fields of pesticides and medicine. In particular, oxime derivatives such as pyraclostrobin, trifloxystrobin, and oxastrobin are used as commercial fungicides to control fungal diseases such as Botrytis cinerea, wheat scab, and wheat white powder.

In order to discover new agricultural fungicides, the inventors introduced different oxime compounds into pinone acid to obtain a class of compounds with novel structures, and found that they have good effects on preventing and controlling plant pathogenic bacteria. At present, there is no report on the pinone oxime ester compound in the present invention. Therefore, the present invention discloses the application of a class of pinone oxime ester compound with novel structure as an agricultural fungicide.

Contents of the invention

The object of the present invention is to provide a kind of pinone oxime ester compound, preparation method and application.

A kind of pinone oxime ester compound, is the compound shown in formula I;

R ₁ is selected from one of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, five-membered or six-membered aromatic heterocycle and phenyl; R The substitution mode of ₁ is single substitution or double substitution;

R ₂ is selected from one of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, five-membered or six-membered aromatic heterocycle and phenyl; R The substitution mode of ₂ is monosubstitution or double substitution.

A kind of pinone oxime ester compound, is the compound shown in formula I;

Each substituent in formula I is specifically shown in the following table:

A preparation method of a pinone oxime ester compound, wherein the pinone oxime ester compound is the pinone oxime ester compound described in claim 1 or 2;

The method comprises the following steps: reacting the compound shown in formula II and the compound shown in formula III in an organic solvent to obtain the compound shown in formula I;

Optionally, an additive is mixed into the organic solvent, and the additive is selected from one of 4-dimethylaminopyridine, dicyclohexylcarbodiimide and triethylamine; the organic solvent is selected from dichloromethane, One of toluene and ethyl acetate.

Optionally, the reaction temperature of the reaction is -25-25°C, and the reaction time is 5min-24h;

Optionally, the molar ratio of the compound represented by formula II to the compound represented by formula III is 1: (1-1.2).

The application of any pinone oxime ester compound described in the present invention in the preparation of plant fungicides.

Optionally, the plant fungicide is used to control rice sheath blight, tomato gray mold, apple rot, wheat head blight, tomato wilt or cucumber anthracnose.

The application of the pinone yloxime ester compound prepared by any one of the preparation methods described in the present invention for the preparation of plant fungicides.

Optionally, the plant fungicide is used to control rice sheath blight, tomato gray mold, apple rot, wheat head blight, tomato wilt or cucumber anthracnose.

The beneficial effects of the present invention are:

The present invention introduces different oxime compounds into pinone acid derived from natural product α-pinene, and the obtained compound has a novel structure and good fungicidal activity, especially for rice sheath blight and tomato gray mold Disease, apple rot, wheat head blight, tomato wilt and cucumber anthracnose have obvious inhibitory effect.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present disclosure, and constitute a part of the description, together with the following specific embodiments, are used to explain the present disclosure, but do not constitute a limitation to the present disclosure. In the attached picture:

Fig. 1 is the hydrogen spectrogram of compound I-01 of the present invention;

Fig. 2 is the hydrogen spectrogram of compound I-02 of the present invention;

Fig. 3 is the hydrogen spectrogram of compound I-18 of the present invention;

Figure 4 is the hydrogen spectrum of compound I-26 of the present invention.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to these examples. Said method, if not specified, is a conventional method. The materials, unless otherwise specified, can be obtained from open commercial channels.

The pinone oxime ester compound disclosed by the present invention has the general structural formula of formula I;

R ₁ is selected from one of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, five-membered or six-membered aromatic heterocycle and phenyl; R The substitution mode of ₁ is monosubstituted or double substituted; _R2 is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₃ -C ₆ cycloalkyl, five-membered or six-membered aromatic One of heterocycle and phenyl; the substitution mode of _R2 is mono-substituted or double-substituted.

For more details, see the data listed in Table 1:

Table 1

Unless otherwise specified below, the reagent ratios used are volume ratios.

Example 1: Preparation of compound benzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-01)

Benzaldehyde oxime (3mmol) and pinone acid chloride (3mmol) were added into a 25mL one-necked bottle, and dichloromethane was used as a solvent, and stirred overnight at room temperature. Purified by column chromatography (petroleum ether: ethyl acetate = 4:1), and dried to obtain 0.68 g of a light yellow solid with a yield of 80% and a melting point of 46.5-47.6°C. ¹ H NMR (400MHz, CDCl ₃ )δ8.33(s,1H),7.74–7.68(m,2H),7.49–7.37(m,3H),2.92–2.86(m,1H),2.51–2.46(m ,1H),2.46–2.38(m,2H),2.08–2.04(m,1H),2.03(s,3H),2.00–1.93(m,1H),1.35(s,2H),1.26–1.22(m ,1H), 0.89(s,3H).

Example 2: Preparation of compound 2-chlorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-02)

Add pinone acid chloride (3mmol), 2-chlorobenzylaldoxime (3mmol) and dicyclohexylcarbodiimide (3mmol) sequentially into a 25mL single-necked bottle, and react overnight at room temperature with dichloromethane as a solvent. Purified by column chromatography and dried to obtain 0.72 g of light yellow liquid with a yield of 75%. ¹ H NMR (400MHz, CDCl ₃ )δ8.79(s,1H),8.06(d,J=7.1Hz,1H),7.44–7.38(m,2H),7.33–7.29(m,1H),3.03– 2.89(m,1H),2.70–2.52(m,1H),2.52–2.44(m,2H),2.09(s,1H),2.06(s,3H),2.04–1.96(m,1H),1.38( s,2H), 1.26(s,1H), 1.08(s,1H), 0.92(s,2H).

Example 3: Compound 2-chloro, 6-fluorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-18) preparation of

Add pinone acid chloride (3mmol), 2-chloro, 6-fluorobenzaldehyde oxime (3mmol), triethylamine (3mmol) into a 25mL single-necked bottle with toluene as solvent, and react at 25°C for 5min. Purified by column chromatography (petroleum ether: ethyl acetate = 4:1), and dried to obtain 0.61 g of a yellow liquid with a yield of 60%. ¹ H NMR (400MHz, CDCl ₃ ) δ8.66(s, 1H), 7.41–7.34(m, 1H), 7.28(d, J=5.8Hz, 1H), 7.11(t, J=8.5Hz, 1H) ,3.03–2.89(m,1H),2.61–2.52(m,1H),2.52–2.45(m,2H),2.09(s,1H),2.06(s,3H),2.03–1.97(m,1H) ,1.38(s,2H),1.26(s,1H),1.08(s,1H),0.92(s,2H).

Example 4: Compound (E)-3-(4-chlorophenyl)acrolein O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl) Preparation of Oxime (I-26)

Add pinone acid acid chloride (3mmol), (E)-3-(4-chlorophenyl)propenaldoxime (3.6mmol), 4-dimethylaminopyridine (3mmol) and 10ml ethyl acetate in a 25mL single-necked bottle, Stir at -25°C for 24h. Purified by column chromatography (petroleum ether: ethyl acetate = 4:1), and dried to obtain 0.62 g of a yellow solid with a yield of 60% and a melting point of 63.6-64.2°C. ¹ H NMR (400MHz, CDCl ₃ ) δ8.20–8.11(m,1H),7.47–7.35(m,4H),6.98(d,J=7.7Hz,2H),2.97–2.90(m,1H), 2.54–2.48(m,1H), 2.49–2.40(m,2H), 2.14–2.05(m,4H), 2.04–1.97(m,1H), 1.39(s,3H), 0.93(s,3H).

According to the same method as above for the preparation of compound I-02, _R2 is replaced with various oximes and reacted with pinone acid chloride to obtain the corresponding products I-03～I-17, I-19～I-25, compound The appearance, melting point, yield and ¹ H NMR spectrum data of are shown below.

Compound 3-chlorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-03): pale yellow solid; yield 73 %; melting point: 66.4-67.5°C; ¹ H NMR (400MHz, CDCl ₃ ) δ8.32(s, 1H), 7.77(s, 1H), 7.59(d, J=7.7Hz, 1H), 7.44(d, J＝8.1Hz, 1H), 7.37(t, J＝7.8Hz, 1H), 3.03–2.90(m, 1H), 2.60–2.49(m, 1H), 2.48–2.40(m, 2H), 2.09(s ,1H), 2.06(s,3H), 2.03–1.94(m,1H), 1.38(s,2H), 1.26(s,1H), 1.08(s,1H), 0.91(s,2H).

Compound 4-chlorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-04): pale yellow solid; yield 75 %; Melting point: 83.2-84.1℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.32(s, 1H), 7.68(d, J=8.6Hz, 2H), 7.41(d, J=8.5Hz, 2H) ,3.01–2.88(m,1H),2.67–2.50(m,1H),2.49–2.41(m,2H),2.09(s,1H),2.06(s,3H),2.03–1.96(m,1H) ,1.38(s,2H),1.25(s,1H),1.08(s,1H),0.91(s,2H).

Compound 2-bromobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-05): light yellow liquid; yield 60 %; ¹ H NMR (400MHz, CDCl ₃ ) δ8.77 (s, 1H), 8.09–8.01 (m, 1H), 7.64–7.59 (m, 1H), 7.39–7.30 (m, 2H), 3.03–2.88 (m,1H),2.71–2.52(m,1H),2.51–2.43(m,3H),2.09(s,1H),2.07(s,3H),2.04–1.97(m,1H),1.39(s ,2H), 1.26(s,1H), 1.09(s,1H), 0.92(s,2H).

Compound 3-bromobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-06): light yellow solid; yield 75 %; Melting point: 54.2-55.7℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.30(s,1H),7.93(s,1H),7.66–7.58(m,2H),7.33–7.28(m,1H ),3.04–2.89(m,1H),2.68–2.51(m,1H),2.51–2.40(m,2H),2.09(s,1H),2.06(s,3H),2.03–1.96(m,1H ), 1.38(s,2H), 1.27(s,1H), 1.08(s,1H), 0.91(s,2H).

Compound 4-bromobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-07): pale yellow solid; yield 73 %; Melting point: 65.2-67.1℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.31(s, 1H), 7.59(q, J=8.7Hz, 4H), 3.03-2.89(m, 1H), 2.67- 2.50(m,1H),2.50–2.40(m,2H),2.09(s,1H),2.06(s,3H),2.03–1.94(m,1H),1.38(s,2H),1.25(s, 1H), 1.08(s,1H), 0.91(s,2H).

Compound 2-fluorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-08): pale yellow liquid; yield 71 %; ¹ H NMR (400MHz, CDCl ₃ ) δ8.63(s, 1H), 8.02(t, J=7.4Hz, 1H), 7.53–7.43(m, 1H), 7.20(t, J=7.6Hz, 1H),7.15–7.09(m,1H),3.01–2.89(m,1H),2.68–2.51(m,1H),2.49–2.43(m,2H),2.09(s,1H),2.07(s, 3H), 2.03–1.97(m,1H), 1.38(s,2H), 1.26(s,1H), 1.08(s,1H), 0.92(s,2H).

Compound 3-fluorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-09): pale yellow solid; yield 65 %; Melting point: 51.2-52.4℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.33(s, 1H), 7.54–7.46(m, 2H), 7.44–7.37(m, 1H), 7.22–7.14(m ,1H),3.02–2.90(m,1H),2.70–2.51(m,1H),2.51–2.41(m,2H),2.09(s,1H),2.07(s,3H),2.03–1.95(m ,1H), 1.38(s,2H), 1.26(s,1H), 1.08(s,1H), 0.92(s,2H).

Compound 4-fluorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-10): pale yellow solid; yield 63 %; melting point: 61.2-62.9°C; ¹ H NMR (400MHz, CDCl ₃ ) δ8.33 (s, 1H), 7.78–7.72 (m, 2H), 7.12 (t, J=8.7Hz, 2H), 3.03– 2.90(m,1H),2.60–2.49(m,1H),2.49–2.40(m,2H),2.09(s,1H),2.06(s,3H),2.01–1.95(m,1H),1.38( s,2H), 1.26(s,1H), 1.08(s,1H), 0.91(s,2H).

Compound 2-methylbenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-11): pale yellow liquid; yield 68%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.62 (s, 1H), 7.88–7.80 (m, 1H), 7.41–7.31 (m, 1H), 7.23 (t, J=8.4Hz, 2H) ,3.04–2.87(m,1H),2.54–2.49(m,1H),2.47(s,4H),2.45–2.41(m,1H),2.09(s,1H),2.06(s,3H),2.03 –1.97(m,1H),1.38(s,2H),1.26(s,1H),1.08(s,1H),0.92(s,2H).

Compound 3-methylbenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-12): pale yellow liquid; yield 71%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.32(s, 1H), 7.60(s, 1H), 7.48(d, J=7.3Hz, 1H), 7.33–7.27(m, 2H), 3.02 –2.88(m,1H),2.68–2.49(m,1H),2.49–2.40(m,2H),2.37(s,3H),2.08(s,1H),2.05(s,3H),2.00–1.93 (m,1H), 1.37(s,2H), 1.25(s,1H), 1.07(s,1H), 0.91(s,2H).

Compound 4-methylbenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-13): pale yellow liquid; yield 71%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.31(s, 1H), 7.62(d, J=8.1Hz, 2H), 7.23(d, J=7.9Hz, 2H), 3.03–2.86(m ,1H),2.55–2.48(m,1H),2.48–2.43(m,2H),2.39(s,3H),2.08(s,1H),2.06(s,3H),2.02–1.94(m,1H ), 1.38(s,2H), 1.25(s,1H), 1.08(s,1H), 0.91(s,3H).

Compound 4-methoxybenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-14): pale yellow solid; The yield is 78%; melting point: 65.2-66.8°C.

Compound 4-cyanobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-15): pale yellow solid; yield 77%; melting point: 62.5-65.1°C.

Compound 4-nitrobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-16): pale yellow solid; yield 69%; melting point: 69.5-70.6°C.

Compound 2,4-fluorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-17): pale yellow liquid; Yield 78%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.56 (s, 1H), 8.09–8.01 (m, 1H), 7.00–6.91 (m, 1H), 6.91–6.84 (m, 1H), 3.03 –2.89(m,1H),2.68–2.50(m,1H),2.50–2.43(m,2H),2.09(s,1H),2.06(s,3H),2.03–1.96(m,1H),1.38 (s,3H),1.08(s,1H),0.92(s,3H).

Compound 2-chloro,6-fluorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-18): pale yellow liquid ; Yield 76%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.66(s, 1H), 7.41–7.34(m, 1H), 7.28(d, J=5.8Hz, 1H), 7.11(t, J ＝8.5Hz,1H),3.03–2.89(m,1H),2.61–2.52(m,1H),2.52–2.45(m,2H),2.09(s,1H),2.06(s,3H),2.03– 1.97(m,1H),1.38(s,2H),1.26(s,1H),1.08(s,1H),0.92(s,2H).

Compound 5-bromo,2-fluorobenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-19): pale yellow solid ; Yield 61%; Melting point: 75.2-77.1℃; ¹ H NMR (400MHz, CDCl ₃ ) δ8.55(s, 1H), 8.20–8.12(m, 1H), 7.60–7.52(m, 1H), 7.03 (t,J=9.2Hz,1H),3.04–2.89(m,1H),2.58–2.50(m,1H),2.50–2.42(m,2H),2.09(s,1H),2.07(s,3H ), 2.03–1.95(m,1H), 1.39(s,2H), 1.26(s,1H), 1.08(s,1H), 0.92(s,2H).

Compound 3,5-trifluoromethylbenzaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-20): pale yellow Liquid; Yield 65%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.46(s, 1H), 8.21(s, 2H), 8.00(d, J=15.6Hz, 1H), 3.04–2.91(m, 1H),2.60–2.53(m,1H),2.51–2.44(m,2H),2.10(s,1H),2.08(s,3H),2.03–1.95(m,1H),1.40(s,2H) ,1.27(s,1H),1.09(s,1H),0.93(s,2H).

Compound thiophene-2carbaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-21): pale yellow liquid; yield 44% ; ¹ H NMR (400MHz, CDCl ₃ ) δ8.50(s,1H),7.50(d,J=5.0Hz,1H),7.41(d,J=3.7Hz,1H),7.13–7.07(m,1H ),3.01–2.87(m,1H),2.53–2.46(m,1H),2.46–2.39(m,2H),2.09(s,1H),2.06(s,3H),2.01–1.95(m,1H ), 1.37(s,3H), 0.91(s,3H).

Compound 3-bromothiophene-2carbaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-22): pale yellow liquid; 45%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.56(s, 1H), 7.47(d, J=5.3Hz, 1H), 7.06(d, J=5.3Hz, 1H), 3.01–2.89( m,1H),2.56–2.47(m,1H),2.47–2.40(m,2H),2.09(s,1H),2.06(s,3H),2.02–1.96(m,1H),1.38(s, 2H), 1.25(s,1H), 1.08(s,1H), 0.91(s,2H).

Compound 3-methylthiophene-2carbaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-23): pale yellow liquid; Yield 43%; ¹ H NMR (400MHz, CDCl ₃ ) δ8.53(s, 1H), 7.38(d, J=5.0Hz, 1H), 6.90(d, J=5.1Hz, 1H), 3.00–2.89 (m,1H),2.48(d,J=7.1Hz,1H),2.46–2.39(m,2H),2.37(s,3H),2.06(s,3H),2.04(d,J=3.2Hz, 1H), 2.02–1.96(m,1H), 1.38(s,3H), 0.91(s,3H).

Compound 5-chlorothiophene-2carbaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-24): pale yellow liquid; rate 50%.

Compound 5-nitrothiophene-2carbaldehyde O-(2-((1S,3S)-3-acetyl-2,2-dimethylcyclobutyl)acetyl)oxime (I-25): pale yellow solid; Yield 48%; Melting point: 101.4-102.5℃.; ¹ H NMR (400MHz, CDCl ₃ ) δ8.44(s, 1H), 7.91–7.87(m, 1H), 7.34(d, J=4.2Hz, 1H ),2.97–2.90(m,1H),2.56–2.49(m,1H),2.49–2.44(m,2H),2.07(s,3H),2.05(s,1H),2.03–1.97(m,1H ), 1.38(s,2H), 1.25(s,1H), 1.08(s,1H), 0.91(s,2H).

Embodiment 5: the inhibitory activity of formula I compound to 6 kinds of plant pathogenic bacteria

The bactericidal activity of the compound of formula I was determined by the mycelium growth rate method. The tested strains were rice sheath blight, tomato gray mold, apple rot, wheat head blight, tomato fusarium wilt and cucumber anthracnose.

Take formula I compound respectively, be mixed with the mother liquor that concentration is 10000mg/L with dimethyl sulfoxide, draw the above-mentioned prepared mother liquor of 10000mg/L with pipetting gun respectively, join the potato dextrose agar that has sterilized, cooling ( PDA) medium, after mixing, prepare 50mg/L drug-carrying medium, pour it into a petri dish with a diameter of 9cm, 15mL per dish, and repeat 3 times for each medicament. After the drug-carrying medium in the dish is condensed, make a drug-carrying PDA plate. Dimethyl sulfoxide was used as the solvent blank control. The well-cultured pathogenic bacteria plate was prepared along the edge of the colony with a puncher to form a bacterium cake with a diameter of 0.5 cm, which was inoculated on the drug-carrying and blank control PDA plates respectively, and placed in a 25°C incubator for dark cultivation. After the colony in the blank control PDA plate grows sufficiently, the colony diameter of each treatment is measured by the cross method, and the average value is taken.

The mycelium growth inhibition rate was calculated by the following formula:

The in vitro bactericidal activity data of the compounds are shown in Table 2.

The in vitro bactericidal activity result (inhibition rate %) of the compound of table 2 formula I

Note: + indicates that the inhibitory rate of the compound on pathogenic bacteria is 0-40%, ++ indicates that the inhibitory rate of the compound on pathogenic bacteria is 41-79%, and +++ indicates that the inhibitory rate of the compound on pathogenic bacteria is 80%-100%.

It can be seen from the above table that the compound of formula I provided by the present invention has a certain inhibitory activity on the six tested plant pathogenic bacteria. Among them, compounds I-02, I-05, I-18, I-19 and I-23 have an inhibitory rate of more than 80% to rice sheath blight; compounds I-02, I-05, I-18, I -19, I-23 and I-25 have an inhibitory rate of more than 80% to Botrytis cinerea; the inhibitory rate of compound I-23 to wheat head blight is more than 80%; compound I-05 and I-23 have an inhibitory rate to apple The inhibitory rate of the rot pathogen is over 80%; the inhibitory rate of the compound I-23 on the tomato Fusarium wilt is over 80%.

The data show that the compound of formula I has a good inhibitory effect on rice sheath blight, tomato cinerea, apple rot, wheat scab, tomato wilt and cucumber anthracnose, and can be used as a fungicide for the above-mentioned plant pathogens prevention and treatment.

The preferred embodiments of the present disclosure have been described in detail above, but 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. These simple modifications All belong to the protection scope of the present disclosure.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner if there is no contradiction. The combination method will not be described separately.

In addition, various implementations of the present disclosure can be combined arbitrarily, as long as they do not violate the idea of the present disclosure, they should also be regarded as the content disclosed in the present disclosure.

Claims (7)

1. a pinone yloxime ester compound, is characterized in that, is the compound shown in formula I;

Each substituent in formula I is specifically shown in the following table:

2. a preparation method of pinone oxime ester compound, it is characterized in that, described pinone oxime ester compound is the pinone oxime ester compound described in claim 1; The method comprises the following steps: reacting the compound shown in formula II and the compound shown in formula III in an organic solvent to obtain the compound shown in formula I;

3. the preparation method of pinone yloxime ester compound according to claim 2 is characterized in that, in described organic solvent, is mixed with additive, and additive is selected from 4-dimethylaminopyridine, dicyclohexyl carbon One of diimine and triethylamine; the organic solvent is selected from one of methylene chloride, toluene and ethyl acetate. 4. according to the preparation method of the described pinone oxime ester compound of claim 2 or 3, it is characterized in that, the reaction temperature of described reaction is-25～25 ℃, and the reaction time is 5min～24h; 5. according to the preparation method of the described pinone oxime ester compound of claim 2 or 3, it is characterized in that, the mol ratio of the compound shown in described formula II and the compound shown in formula III is 1:(1～1.2 ). 6. the pinone yloxime ester compound as claimed in claim 1 is used for the application of preparation plant fungicide. 7. The application according to claim 6, wherein the plant fungicide is used for preventing and treating rice sheath blight, tomato gray mold, apple rot, wheat head blight, tomato fusarium wilt or cucumber anthracnose.

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