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

Pinonyl oxime ester compound, preparation method and application Download PDF

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CN115093343B
CN115093343B CN202210692032.7A CN202210692032A CN115093343B CN 115093343 B CN115093343 B CN 115093343B CN 202210692032 A CN202210692032 A CN 202210692032A CN 115093343 B CN115093343 B CN 115093343B
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高艳清
潘婷敏
雷鹏
陈光友
蔡崇林
马志卿
冯俊涛
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Northwest A&F University
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Abstract

The invention discloses a pinonyl oxime ester compound, a preparation method and application thereof. According to the invention, different oximes are introduced into pinonic acid to obtain a compound with a novel structure. The structure of the compound is shown as formula I:

Description

Pinonyl oxime ester compound, preparation method and application
Technical Field
The invention belongs to the technical field of pathogen control, and particularly relates to a pinonyl oxime ester compound, a preparation method and application thereof.
Background
The Chinese is agricultural large country, and the plant diseases caused by pathogenic bacteria cause great economic loss for agricultural production in China. The plant pathogenic bacteria not only can reduce the quality of fruits and vegetables, but also can shorten the storage period; some fungi also produce toxins that are harmful to human and animal health. For example, rhizoctonia solani (Rhizoctoniasolani Kuhn) caused rice sheath blight is one of the important diseases threatening rice production, and can cause up to 45% yield loss (Margani R et al, iop Conference,2018,142). At present, the main control means of plant diseases is still chemical control, but the wide use and the non-controlled use of pesticides cause the problems of drug resistance, residue and the like. Therefore, the invention is imperative to provide a low-toxicity, environment-friendly and efficient 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 a natural monoterpene compound with the largest yield in the world, and the main component is alpha-pinene. Among the derivatives of alpha-pinene, the four-membered ring compound is a special compound, and the compound with the four-membered ring structure in nature has good biological activity. The alpha-pinene can be oxidized to obtain pinonic acid containing quaternary ring, and in recent years, the active groups of the pinonic acid, namely carboxyl and ketocarbonyl, are modified to obtain a plurality of compounds with agricultural activity.
Oximes (oxime ethers and oxime esters) have a wide range of biological activities including anti-tumor, herbicidal, insecticidal acaricidal, antiviral and antifungal activity (Regnier T et al, postharv biol.tec.2009,2, 254-258). The compounds have the characteristics of high efficiency, low toxicity, low residue and the like, and are widely applied to the fields of pesticides and medicines as active substances. In particular, oxime derivatives such as pyraclostrobin, trifloxystrobin, enestroburin and the like are used as commercial bactericides for controlling fungal diseases such as botrytis cinerea, gibberella wheat, wheat powdery mildew and the like.
In order to find out novel agricultural bactericides, the inventor introduces different oxime compounds into pinonic acid to obtain a compound with a novel structure, and finds out that the compound has good effect of preventing and treating plant pathogenic bacteria. At present, no pinonyl oxime ester compound is reported, and therefore, the invention discloses application of pinonyl oxime ester compounds with novel structures as agricultural bactericides.
Disclosure of Invention
The invention aims to provide a pinonyl oxime ester compound, a preparation method and application.
A pinonyl oxime ester compound which is shown in a formula I;
Figure BDA0003700367730000021
R 1 selected from hydrogen, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 3 -C 6 One of cycloalkyl, five-or six-membered aromatic heterocycle and phenyl; r is R 1 The substitution pattern of (a) is mono-substitution or di-substitution;
R 2 selected from hydrogen, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 3 -C 6 One of cycloalkyl, five-or six-membered aromatic heterocycle and phenyl; r is R 2 The substitution pattern of (C) is mono-substitution or di-substitution.
A pinonyl oxime ester compound which is shown in a formula I;
Figure BDA0003700367730000022
the substituents in formula I are specifically shown in the following table:
Figure BDA0003700367730000023
Figure BDA0003700367730000031
Figure BDA0003700367730000041
a method for preparing a pinonyl oxime ester compound, wherein the pinonyl oxime ester compound is the pinonyl oxime ester compound in claim 1 or 2;
the method comprises the following steps: reacting a compound shown in a formula II with a compound shown in a formula III in an organic solvent to obtain a compound shown in a formula I;
Figure BDA0003700367730000042
optionally, mixing an additive into the organic solvent, wherein the additive is selected from one of 4-dimethylaminopyridine, dicyclohexylcarbodiimide and triethylamine; the organic solvent is selected from one of dichloromethane, toluene and ethyl acetate.
Optionally, the reaction temperature of the reaction is-25 ℃ and the reaction time is 5 min-24 h;
optionally, the molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1: (1-1.2).
The pinonyl oxime ester compound is used for preparing a plant bactericide.
Optionally, the plant fungicide is used for controlling rice sheath blight, tomato gray mold, apple rot, wheat scab, tomato wilt or cucumber anthracnose.
The pinonyl oxime ester compound prepared by any one of the preparation methods is applied to preparation of plant bactericides.
Optionally, the plant fungicide is used for controlling rice sheath blight, tomato gray mold, apple rot, wheat scab, tomato wilt or cucumber anthracnose.
The beneficial effects of the invention are as follows:
according to the invention, different oxime compounds are introduced into pinonic acid derived from a natural product alpha-pinene, and the obtained compound has novel structure and good bactericidal activity, and particularly has obvious inhibition effects on rice sheath blight, tomato gray mold, apple rot, wheat scab, tomato wilt and cucumber anthracnose.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a hydrogen spectrum of compound I-01 of the present invention;
FIG. 2 is a hydrogen spectrum of compound I-02 of the present invention;
FIG. 3 is a hydrogen spectrum of the compound I-18 of the present invention;
FIG. 4 is a hydrogen spectrum of the compound I-26 of the present invention.
Detailed Description
The invention is further illustrated below in connection with specific examples, but the invention is not limited to these examples. The methods are conventional methods unless otherwise specified. Such materials, unless otherwise indicated, are commercially available from public sources.
The pinonyl oxime ester compound disclosed by the invention has a structural general formula shown in a formula I;
Figure BDA0003700367730000051
R 1 selected from hydrogen, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 3 -C 6 One of cycloalkyl, five-or six-membered aromatic heterocycle and phenyl; r is R 1 The substitution pattern of (a) is mono-substitution or di-substitution; r is R 2 Selected from hydrogen, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 3 -C 6 One of cycloalkyl, five-or six-membered aromatic heterocycle and phenyl; r is R 2 The substitution pattern of (C) is mono-substitution or di-substitution.
For more details, see the data set forth in Table 1:
TABLE 1
Figure BDA0003700367730000061
Figure BDA0003700367730000071
Figure BDA0003700367730000081
The reagent ratios used are all volume ratios unless specifically stated below.
Example 1: preparation of the Compound benzaldehyde O- (2- ((1S, 3S) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-01)
Figure BDA0003700367730000082
To a 25mL single-necked flask were added benzaldehyde oxime (3 mmol) and pinonic acid chloride (3 mmol), and the mixture was stirred overnight at room temperature with methylene chloride as a solvent. Column chromatography purification (petroleum ether: ethyl acetate=4:1) gives after drying 0.68g of a pale yellow solid, yield 80%, melting point: 46.5-47.6 ℃. 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 the Compound 2-chlorobenzaldehyde O- (2- ((1S, 3S) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-02)
Figure BDA0003700367730000083
To a 25mL single-necked flask, pinonic acid chloride (3 mmol), 2-chlorobenzaldehyde oxime (3 mmol) and dicyclohexylcarbodiimide (3 mmol) were sequentially added, and the mixture was reacted overnight at room temperature with methylene chloride as a solvent. Purification by column chromatography and drying gave 0.72g of pale yellow liquid in 75% yield. 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: preparation of the Compound 2-chloro, 6-fluorobenzaldehyde O- (2- ((1S, 3S) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-18)
Figure BDA0003700367730000091
A single-port 25mL bottle was charged with pinonic acid chloride (3 mmol), 2-chloro, 6-fluorobenzaldehyde oxime (3 mmol), triethylamine (3 mmol) and toluene as a solvent, and reacted at 25℃for 5 minutes. Column chromatography purification (petroleum ether: ethyl acetate=4:1) afforded after drying 0.61g of a yellow liquid in 60% yield. 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: preparation of Compound (E) -3- (4-chlorophenyl) acrolein O- (2- ((1S, 3S) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-26)
Figure BDA0003700367730000092
To a 25mL single flask were added pinonic acid chloride (3 mmol), (E) -3- (4-chlorophenyl) aldoxime (3.6 mmol), 4-dimethylaminopyridine (3 mmol), 10mL ethyl acetate, and stirred at-25℃for 24h. Column chromatography purification (petroleum ether: ethyl acetate=4:1) gives after drying 0.62g of yellow solid, yield 60%, melting point: 63.6-64.2 ℃. 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)。
R was prepared in the same manner as in the preparation of Compound I-02 described above 2 The oxime is replaced by various oximes, and the oxime reacts with pinonic acid chloride to obtain corresponding products I-03 to I-17, I-19 to I-25, and the appearance, melting point, yield and purity of the compound 1 The H NMR spectrum data are shown below.
Compound 3-ChlorobenzeneFormaldehyde O- (2- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-03): pale yellow solid; the yield thereof was found to be 73%; melting point: 66.4-67.5 ℃; 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- ((1 s,3 s) -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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-05): pale yellow liquid; the yield was 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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-06): pale 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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-07): pale yellow solid; the yield thereof was found to be 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- ((1 s,3 s) -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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-09): pale yellow solid; the yield thereof was found to be 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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-10): pale yellow solid; the yield thereof was found to be 63%; melting point: 61.2-62.9 ℃; 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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-11): pale yellow liquid; the yield thereof was found to be 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- ((1 s,3 s) -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- ((1 s,3 s) -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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-14): pale yellow solid; yield 78%; melting point: 65.2-66.8 ℃.
Compound 4-cyanobenzaldehyde O- (2- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-15): pale yellow solid; the yield thereof was found to be 77%; melting point: 62.5-65.1 ℃.
Compound 4-nitrobenzaldehyde O- (2- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-16): pale yellow solid; the yield thereof was found to be 69%; melting point: 69.5-70.6 ℃.
The compound 2, 4-fluorobenzaldehyde O- (2- ((1 s,3 s) -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- ((1 s,3 s) -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- ((1 s,3 s) -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- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-20): pale yellow liquid; the yield thereof was found to be 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)。
the compound thiophene-2-carbaldehyde O- (2- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-21): pale yellow liquid; the yield thereof was found to be 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)。
the compound 3-bromothiophene-2-carbaldehyde O- (2- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-22): pale yellow liquid; yield 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)。
the compound 3-methylthiophene-2-carbaldehyde O- (2- ((1 s,3 s) -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)。
the compound 5-chlorothiophene-2-carbaldehyde O- (2- ((1 s,3 s) -3-acetyl-2, 2-dimethylcyclobutyl) acetyl) oxime (I-24): pale yellow liquid; the yield thereof was found to be 50%.
The compound 5-nitrothiophene-2-carbaldehyde O- (2- ((1 s,3 s) -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)。
example 5: inhibitory Activity of Compounds of formula I against 6 plant pathogenic bacteria
The bactericidal activity of the compound shown in the formula I is measured by adopting a hypha growth rate method. The test strains were rice sheath blight, tomato gray mold, apple rot, wheat scab, tomato blight and cucumber anthracnose.
Weighing the compound of formula I respectively, preparing mother liquor with concentration of 10000mg/L by using dimethyl sulfoxide, sucking the prepared mother liquor with concentration of 10000mg/L by using a transfer gun respectively, adding the mother liquor into sterilized and cooled Potato Dextrose Agar (PDA) culture medium, uniformly mixing to prepare 50mg/L culture medium with medicine, pouring the culture medium into culture dishes with diameter of 9cm, 15mL of each dish, and repeating each medicine for 3 times. After the medicated culture medium in the dish is condensed, the medicated PDA plate is made. Dimethyl sulfoxide was used as a solvent blank. The cultured pathogenic bacteria flat plate is prepared into bacterial cakes with the diameter of 0.5cm along the edge of bacterial colony by a puncher, and the bacterial cakes are respectively inoculated into the PDA flat plate with medicine and blank control and placed into a incubator with the temperature of 25 ℃ for dark culture. After the colonies grew sufficiently in the equal blank PDA plates, the diameters of the colonies treated were measured by the crisscross method, and the average value was obtained.
The hypha growth inhibition rate was calculated using the following formula:
Figure BDA0003700367730000131
the in vitro bactericidal activity data of the compounds are shown in table 2.
TABLE 2 results of in vitro bactericidal activity of compounds of formula I (inhibition%)
Figure BDA0003700367730000132
Figure BDA0003700367730000141
Note that: + represents that the inhibition rate of the compound to pathogenic bacteria is 0-40%, ++ represents that the inhibition rate of the compound to pathogenic bacteria is 41-79%, ++ means that the inhibition rate of the compound against pathogenic bacteria is 80% -100%.
As can be seen from the table, the compounds of the formula I provided by the invention have certain inhibitory activity on the 6 plant pathogenic bacteria tested. Wherein, the inhibition rate of the compounds I-02, I-05, I-18, I-19 and I-23 to the Rhizoctonia solani is more than 80 percent; the inhibition rate of the compounds I-02, I-05, I-18, I-19, I-23 and I-25 to the botrytis cinerea is more than 80%; the inhibition rate of the compound I-23 to the wheat gibberella is more than 80%; the inhibition rate of the compounds I-05 and I-23 to apple rot germs is more than 80 percent; the inhibition rate of the compound I-23 to tomato fusarium wilt is more than 80%.
The data show that the compound of the formula I has better inhibition effect on Rhizoctonia solani, botrytis cinerea, malus canker, alternaria wheat, botrytis cinerea and anthracnose of cucumber, and can be used as a bactericide for preventing and controlling the plant pathogenic bacteria.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (7)

1. The pinonyl oxime ester compound is characterized by being a compound shown in a formula I;
Figure FDA0004240040770000011
the substituents in formula I are specifically shown in the following table:
Figure FDA0004240040770000012
Figure FDA0004240040770000021
Figure FDA0004240040770000031
2. a method for preparing a pinonyl oxime ester compound, which is characterized in that the pinonyl oxime ester compound is the pinonyl oxime ester compound in claim 1;
the method comprises the following steps: reacting a compound shown in a formula II with a compound shown in a formula III in an organic solvent to obtain a compound shown in a formula I;
Figure FDA0004240040770000032
3. the method for preparing pinonyl oxime ester compound according to claim 2, wherein an additive is mixed in the organic solvent, the additive being one selected from 4-dimethylaminopyridine, dicyclohexylcarbodiimide and triethylamine; the organic solvent is selected from one of dichloromethane, toluene and ethyl acetate.
4. The method for preparing pinonyl oxime ester compounds according to claim 2 or 3, wherein the reaction temperature is-25 ℃ and the reaction time is 5 min-24 h;
5. the method for preparing pinonyl oxime ester compounds according to claim 2 or 3, wherein the molar ratio of the compound shown in formula II to the compound shown in formula III is 1: (1-1.2).
6. The use of pinonyl oxime ester compound of claim 1 for preparing plant bactericides.
7. The use according to claim 6, wherein the plant fungicide is used for controlling rice sheath blight, tomato gray mold, apple rot, wheat scab, tomato blight or cucumber anthracnose.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2018390864A1 (en) * 2017-12-20 2020-06-18 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of vegetable, tomato and potato plants by phytopathogenic microorganisms
CN113816902A (en) * 2020-06-18 2021-12-21 西北农林科技大学 Oxime ether (ester) compound, preparation method and application
CN114213311A (en) * 2021-12-27 2022-03-22 浙江工业大学 Substituted benzaldehyde oxime ester compound and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2018390864A1 (en) * 2017-12-20 2020-06-18 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of vegetable, tomato and potato plants by phytopathogenic microorganisms
CN113816902A (en) * 2020-06-18 2021-12-21 西北农林科技大学 Oxime ether (ester) compound, preparation method and application
CN114213311A (en) * 2021-12-27 2022-03-22 浙江工业大学 Substituted benzaldehyde oxime ester compound and preparation method and application thereof

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