CN114195707A - High-efficiency broad-spectrum plant antibacterial agent BZ - Google Patents
High-efficiency broad-spectrum plant antibacterial agent BZ Download PDFInfo
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- CN114195707A CN114195707A CN202111548423.3A CN202111548423A CN114195707A CN 114195707 A CN114195707 A CN 114195707A CN 202111548423 A CN202111548423 A CN 202111548423A CN 114195707 A CN114195707 A CN 114195707A
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Abstract
The invention relates to a phenylhydrazone compound, a synthetic method thereof, a medicine containing the compound and application thereof. The hydrazone compound has the advantages of simple structure, easiness in synthesis, strong antibacterial activity, wide antibacterial spectrum, low toxicity to animals and plants and low components, and can be used as an effective component or a synergistic component for developing a novel efficient broad-spectrum plant antibacterial agent.
Description
Technical Field
The invention relates to a plant antibacterial drug, in particular to a phenylhydrazone compound, a synthetic method thereof, a drug containing the compound and application thereof.
Background
Most plant diseases are caused by phytopathogenic fungi. Plant mycoses not only seriously affect the growth, yield and quality of agricultural products of plants, but also cause food safety problems in some cases.
The application of chemical antibacterial agents is the main means for preventing and treating plant pathogenic mycosis at present. Due to the generation of drug resistance and the continuous increase of the requirements of people on modern pesticides, some traditional pesticides are continuously exiting the market. Therefore, the research and development of new pesticides have important significance.
The existing plant antibacterial agent generally has the defect of narrow antibacterial spectrum. In agricultural production, mixed infection of multiple pathogenic bacteria often occurs in the same plant. In this regard, a method of mixing a plurality of antibacterial agents is often used in production. This approach is not only difficult to achieve the desired results in many cases, but also increases the cost of the pesticide application. Therefore, the development of agricultural antibacterial agents with strong broad spectrum is of great practical significance.
Hydrazone compounds are widely present in bacteria, fungi, plants and marine organisms and have good environmental compatibility (bioorg. Med. chem.2014,22, 6529-. Meanwhile, the hydrazone compound also has various biological activities such as antibiosis, disinsection, weeding, antivirus and anticancer, and the like, and has the obvious advantages of simple preparation, strong activity and small toxicity, so the hydrazone compound plays an important role in the creation of new pesticides. Heretofore, some hydrazone-based antibacterial agents such as quinoximehydrazone (Benquinox), pyriizone (ferimzone), and dizoxolon (Drazoxolon) have been successfully developed.
To date, only a few reports have been made on the antifungal activity of the hydrazone compounds to which this patent relates. Clark M T et al have reported the control of fungal grape downy mildew (Plasmopara viticola), barley powdery mildew (Erysiphe graminis), wheat brown rust (Erysiphe graminis), and broad bean rust (Uromyces fabae) by 3/4-pyridylaldehyde phenylhydrazone, 2/3-pyridylaldehyde-4' -chlorophenylhydrazone, and 2/3-pyridylaldehyde-N-formylphenylhydrazone (Clark M T and Ten Haken P.Ger.Offen., DE 2744385A 1,1978; Clark M tend Ten Haken P.U.S., US 4212868A, 1980). In addition, no report is found about the inhibitory activity of the compound on other plant pathogenic fungi, and no report is found about the antifungal activity of any other similar compound.
In the synthesis of hydrazone compounds, all the literature reports methods use the condensation of hydrazine or a substituent hydrazine with an aldehyde or a ketone. Since hydrazine compounds are expensive, hydrazone compounds prepared by the literature method are difficult to meet the low-cost requirement of the hydrazine compounds as pesticides.
Disclosure of Invention
The invention provides a phenylhydrazone compound, a synthesis method thereof, a medicine containing the compound and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a phenylhydrazone compound is characterized in that: the molecular formula is:
wherein:
R1is pyridyl, thienyl, pyrrolyl, etc.; r2Is hydrogen or methyl; r3、R4Are the same or different hydrogen, alkyl, alkoxy, halogen, nitro, cyano, trifluoromethyl, and the like; r3、R4The position (b) is ortho, para or meta on the benzene ring.
A method for synthesizing a phenylhydrazone compound,
has the following synthetic route:
wherein:
R1is pyridyl, thienyl, pyrrolyl, etc.; r2Is hydrogen or methyl; r3、R4Are the same or different hydrogen, alkyl, alkoxy, halogen, nitro, cyano, trifluoromethyl, and the like; r3、R4The position (b) is ortho, para or meta on the benzene ring.
Application of phenylhydrazone compounds in preparing antibacterial medicines for plants is disclosed.
The phenylhydrazone compounds have obvious inhibitory activity on the following plant pathogenic bacteria:
cotton fusarium wilt pathogenic bacteria, watermelon fusarium wilt pathogenic bacteria, potato dry rot pathogenic bacteria, wheat gibberellic disease pathogenic bacteria, tomato early blight pathogenic bacteria, cabbage black spot pathogenic bacteria, tobacco brown spot pathogenic bacteria, maize curvularia pathogenic bacteria, apple anthracnose pathogenic bacteria, pumpkin fusarium wilt pathogenic bacteria, apple rot pathogenic bacteria, rice blast pathogenic bacteria, apple ring rot pathogenic bacteria, melon powdery mildew pathogen and grape downy mildew pathogen.
A medicine containing a phenylhydrazone compound.
The medicine is used as plant antibacterial medicine.
The medicine has obvious inhibitory activity to plant diseases caused by the following pathogenic bacteria:
cotton fusarium wilt pathogenic bacteria, watermelon fusarium wilt pathogenic bacteria, potato dry rot pathogenic bacteria, wheat gibberellic disease pathogenic bacteria, tomato early blight pathogenic bacteria, cabbage black spot pathogenic bacteria, tobacco brown spot pathogenic bacteria, maize curvularia pathogenic bacteria, apple anthracnose pathogenic bacteria, pumpkin fusarium wilt pathogenic bacteria, apple rot pathogenic bacteria, rice blast pathogenic bacteria, apple ring rot pathogenic bacteria, melon powdery mildew pathogen and grape downy mildew pathogen.
Compared with the prior art, the invention has the following advantages:
1) the method for synthesizing the hydrazone compound has the advantages of simple operation, high yield, high purity, low cost and suitability for large-scale production.
2) The hydrazone compound has high-efficiency and broad-spectrum inhibitory activity on more than ten common plant pathogenic fungi, has the advantages of low animal and plant toxicity and good environmental compatibility, is superior to most of antibacterial agents used in the existing agricultural production in the aspects of activity intensity and antibacterial spectrum, and can be used as an effective ingredient for preventing and treating plant mycosis caused by single pathogen or mixed infection of multiple pathogens.
3) The hydrazone compound has the characteristic of good water solubility, and can be used for preparing an aqueous agent with the characteristic of environmental friendliness.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The phenylhydrazone compounds have the following molecular structure characteristics:
wherein:
R1is pyridyl, thienyl, pyrrolyl, etc.; r2Is hydrogen or methyl; r3、R4Are the same or different hydrogen, alkyl, alkoxy, halogen, nitro, cyano, trifluoromethyl, and the like; r3、R4The position (b) is ortho, para or meta on the benzene ring.
The synthetic method of the phenylhydrazone compound has the following synthetic route of 'one pot boiling':
wherein:
R1is pyridyl, thienyl, pyrrolyl, etc.; r2Is hydrogen or methyl; r3、R4Are the same or different hydrogen, alkyl, alkoxy, halogen, nitro, cyano, trifluoromethyl, and the like; r3、R4The position (b) is ortho, para or meta on the benzene ring.
An application of phenylhydrazone compounds in preparing antibacterial medicines for plant is disclosed.
The phenylhydrazone compounds have obvious inhibitory activity on the following plant pathogenic bacteria:
cotton fusarium wilt pathogenic bacteria, watermelon fusarium wilt pathogenic bacteria, potato dry rot pathogenic bacteria, wheat gibberellic disease pathogenic bacteria, tomato early blight pathogenic bacteria, cabbage black spot pathogenic bacteria, tobacco brown spot pathogenic bacteria, maize curvularia pathogenic bacteria, apple anthracnose pathogenic bacteria, pumpkin fusarium wilt pathogenic bacteria, apple rot pathogenic bacteria, rice blast pathogenic bacteria, apple ring rot pathogenic bacteria, melon powdery mildew pathogen and grape downy mildew pathogen.
For the synthesis of the hydrazone compound, the invention provides the following specific methods and processes:
preparation of mono-and hydrazone compounds
To aniline or substituted aniline (0.1mol) was slowly added 6M hydrochloric acid (58.5mL) with vigorous stirring. Cooling the obtained system to-10-0 ℃. To the stirred solution above was added dropwise 25mL of an aqueous solution of sodium nitrite (8.45g) over about 10 minutes. After the addition was completed, stirring was continued for about 15 minutes to obtain a brown transparent solution. The resulting solution was quickly added dropwise over 10 minutes to a vigorously stirred 50mL aqueous solution of sodium sulfite (31.5g) at room temperature, and stirring was continued for 30 minutes after the addition was complete. The reaction flask was heated in a 72 deg.C oil bath for about 1.0h until the solid was completely dissolved to give a dark brown transparent solution. The reaction was cooled to about 50 deg.C, concentrated hydrochloric acid (8.5mL) was added thereto, and the mixture was stirred for 2h while warming to 72 deg.C, during which a large amount of precipitate formed. The reaction solution was cooled to about 40 ℃ and 2M sodium carbonate solution or 4M sodium hydroxide solution was added in portions with stirring. When the solid is completely dissolved (pH 10), the addition of the lye is stopped. An ethanol solution (50mL) of aldehyde or ketone (0.1mol) was slowly added under stirring, and the mixture was stirred at room temperature for 1 hour. Then, the mixture was stirred at 80 ℃ for 1 hour. Cooling the reaction system to room temperature, carrying out suction filtration under reduced pressure, and repeatedly washing the solid with deionized water for 3-4 times. And (3) carrying out vacuum drying on the obtained solid at 50-55 ℃ to obtain the required hydrazone compound, wherein the yield is 84-87%, and the purity can reach more than 98%.
2-pyridylaldehyde phenylhydrazone (1): pale yellow powder, yield 86%.1H NMR(400MHz,CDCl3)δ8.53(ddd,J＝5.0,1.7,1.0Hz,1H),8.19(s,1H),8.00(dt,J＝8.1,1.1Hz,1H),7.81(s,1H),7.68(td,J＝7.8,1.8Hz,1H),7.29(dd,J＝8.6,7.3Hz,2H),7.20–7.09(m,3H),6.91(tt,J＝7.3,1.2Hz,1H).
2-pyridylaldehyde-2' -fluorophenylhydrazone (2): yellow powder, yield 86%.1H NMR(400MHz,CDCl3)δ8.56(ddd,J＝4.9,1.8,1.0Hz,1H),8.08(s,1H),8.01(dt,J＝8.1,1.1Hz,1H),7.90(s,1H),7.71(td,J＝7.8,1.7Hz,1H),7.62(td,J＝8.2,1.6Hz,1H),7.20(ddd,J＝7.5,4.9,1.2Hz,1H),7.17–6.99(m,2H),6.84(dddd,J＝8.2,7.4,5.0,1.7Hz,1H).
2-pyridylaldehyde-3' -fluorophenylhydrazone (3): white powder, yield 92%.1H NMR(400MHz,CDCl3)δ8.54(ddd,J＝5.0,1.8,1.0Hz,1H),8.22(s,1H),8.00(dt,J＝8.1,1.1Hz,1H),7.82(s,1H),7.71(td,J＝7.8,1.8Hz,1H),7.25–7.14(m,2H),6.97(dt,J＝11.1,2.3Hz,1H),6.80(ddd,J＝8.2,2.1,0.9Hz,1H),6.59(tdd,J＝8.4,2.5,0.9Hz,1H).
2-pyridylaldehyde-4' -fluorophenylhydrazone (4): bright yellow flaky solid, yield 94%.1H NMR(400MHz,CDCl3)δ8.53(ddd,J＝4.9,1.8,0.9Hz,1H),8.15(s,1H),7.97(dt,J＝8.1,1.1Hz,1H),7.82(s,1H),7.70(td,J＝7.7,1.7Hz,1H),7.19(ddd,J＝7.4,5.0,1.2Hz,1H),7.16–7.04(m,2H),7.05–6.91(m,2H).
2-pyridylaldehyde-4' -chlorophenylhydrazone (5): yellow-green flaky solid, yield 92%.1H NMR(400MHz,CDCl3)δ8.60–8.45(m,1H),8.23(s,1H),7.96(d,J＝8.1Hz,1H),7.83(s,1H),7.71(t,J＝7.7Hz,1H),7.25–7.15(m,3H),7.09(d,J＝8.4Hz,2H).
2-pyridylaldehyde-4' -bromophenylhydrazone (6): orange yellow powder, yield 93%.1H NMR(400MHz,CDCl3)δ8.54(ddd,J＝5.1,1.7,1.0Hz,1H),8.14(s,1H),7.97(dt,J＝8.0,1.1Hz,1H),7.81(s,1H),7.70(td,J＝7.7,1.8Hz,1H),7.42–7.31(m,2H),7.20(ddd,J＝7.5,5.0,1.2Hz,1H),7.11–6.98(m,2H)。
2-pyridylaldehyde-4' -iodophenylhydrazone (7): yellow flaky solid, yield 86%.1H NMR(400MHz,CDCl3)δ8.54(dt,J＝5.0,1.3Hz,1H),8.15(s,1H),7.96(d,J＝8.0Hz,1H),7.80(s,1H),7.70(td,J＝7.7,1.7Hz,1H),7.62–7.48(m,2H),7.20(ddd,J＝7.5,4.9,1.2Hz,1H),7.02–6.86(m,2H)。
2-pyridylaldehyde-3 ',4' -difluorophenylhydrazone (8): off-white powder, yield 87%.1H NMR(400MHz,DMSO-d6)δ10.94(s,1H),8.60–8.39(m,1H),7.98(d,J＝8.0Hz,1H),7.91(s,1H),7.79(td,J＝7.7,1.7Hz,1H),7.45–7.20(m,2H),7.13(ddd,J＝13.1,7.1,2.6Hz,1H),6.97–6.73(m,1H)。
2-pyridinecarboxaldehyde-2' -methoxyphenylhydrazone(9): ginger yellow powder, yield 84%.1H NMR(400MHz,CDCl3)δ8.54(ddd,J＝4.9,1.7,1.0Hz,1H),8.35(s,1H),8.02(dt,J＝8.1,1.1Hz,1H),7.86(s,1H),7.68(td,J＝7.8,1.8Hz,1H),7.56(d,J＝7.9Hz,1H),7.16(ddd,J＝7.5,5.0,1.2Hz,1H),7.02–6.93(m,1H),6.93–6.75(m,2H),3.90(s,3H)。
2-pyridylaldehyde-3' -methoxyphenylhydrazone (10): pale yellow powder, yield 94%.1H NMR(400MHz,CDCl3)δ8.54(ddd,J＝4.9,1.8,1.0Hz,1H),8.09(s,1H),8.00(dt,J＝8.0,1.1Hz,1H),7.81(s,1H),7.69(td,J＝7.8,1.7Hz,1H),7.23–7.13(m,2H),6.80(t,J＝2.3Hz,1H),6.69(ddd,J＝8.1,2.1,0.9Hz,1H),6.47(ddd,J＝8.2,2.5,0.9Hz,1H),3.83(s,3H)。
2-pyridylaldehyde-4' -methoxyphenylhydrazone (11): orange yellow powder, yield 93%.1H NMR(400MHz,CDCl3)δ8.52(ddd,J＝5.1,1.7,0.9Hz,1H),8.09(s,1H),7.97(dt,J＝8.1,1.1Hz,1H),7.80(s,1H),7.68(td,J＝7.8,1.8Hz,1H),7.16(ddd,J＝7.5,5.0,1.2Hz,1H),7.12–7.05(m,2H),6.95–6.80(m,2H),3.79(s,3H)。
2-pyridylaldehyde-2' -methylphenylhydrazone (12): orange yellow powder, yield 88%.1H NMR(400MHz,CDCl3)δ8.54(ddd,J＝5.0,1.8,1.0Hz,1H),8.03(dt,J＝8.0,1.1Hz,1H),7.89(s,1H),7.83(s,1H),7.69(td,J＝7.8,1.8Hz,1H),7.57(dd,J＝8.1,1.3Hz,1H),7.24–7.14(m,2H),7.11(d,J＝7.4Hz,1H),6.86(td,J＝7.4,1.3Hz,1H),2.27(s,3H)。
2-pyridylaldehyde-3' -methylphenylhydrazone (13): pale yellow powder, yield 90%.1H NMR(400MHz,CDCl3)δ8.53(ddd,J＝5.0,1.8,1.0Hz,1H),8.06(s,1H),8.01(dt,J＝8.1,1.1Hz,1H),7.79(s,1H),7.69(td,J＝7.7,1.8Hz,1H),7.22–.11(m,2H),6.99(d,J＝2.0Hz,1H),6.93(dd,J＝8.1,2.2Hz,1H),6.78–6.64(m,1H),2.35(s,3H)。
2-pyridylaldehyde-4' -methylphenylhydrazone (14): ginger yellow powder, yield 91%.1H NMR(500MHz,DMSO-d6):δ7.81(1H,d,J＝16.1Hz),7.69(1H,dd,J＝7.7,1.3Hz),7.40(1H,2×t,J＝8.5,1.5Hz),7.09(1H,d,J＝8.3Hz),6.98(1H,t,J＝7.5Hz),6.50(1H,d,J＝16.1Hz),3.87(3H,s),1.82(2H,q,J＝7.5Hz),1.44(6H,s),0.88(3H,t,J＝7.5Hz)。
2-pyridylaldehyde-4' -ethylphenylhydrazone (15): yellow powder, yield 89%.1H NMR(400MHz,CDCl3)δ8.52(ddd,J＝5.0,1.7,1.0Hz,1H),8.09(s,1H),7.99(dt,J＝8.1,1.1Hz,1H),7.80(s,1H),7.68(td,J＝7.8,1.8Hz,1H),7.20–6.98(m,5H),2.60(q,J＝7.6Hz,2H),1.22(t,J＝7.6Hz,3H)。
2-pyridylaldehyde-3 ',4' -dimethylphenylhydrazone (16): yellow powder, yield 87%.1H NMR(400MHz,CDCl3)δ8.52(ddd,J＝5.0,1.8,0.9Hz,1H),8.08(s,1H),7.99(dt,J＝8.1,1.1Hz,1H),7.80(s,1H),7.70(td,J＝7.8,1.8Hz,1H),7.17(ddd,J＝7.5,5.0,1.2Hz,1H),7.04(d,J＝8.1Hz,1H),6.98(d,J＝2.4Hz,1H),6.89(dd,J＝8.1,2.4Hz,1H),2.26(s,3H),2.21(s,3H)。
3-pyridinecarboxaldehyde phenylhydrazone (17): pale yellow powder, yield 91%.1H NMR(400MHz,CDCl3)δ8.76(d,J＝2.3Hz,1H),8.52(dd,J＝4.8,1.7Hz,1H),8.05(dt,J＝8.0,2.0Hz,1H),7.89(s,1H),7.67(s,1H),7.30(ddd,J＝8.6,5.9,3.2Hz,3H),7.19–7.04(m,2H),6.97–6.84(m,1H)。
3-pyridylaldehyde-2' -fluorophenylhydrazone (18): pale pink powder, yield 89%.1H NMR(400MHz,CDCl3)δ8.80(d,J＝2.1Hz,1H),8.54(dd,J＝4.8,1.7Hz,1H),8.05(dt,J＝8.0,2.0Hz,1H),8.00(s,1H),7.78(s,1H),7.60(td,J＝8.2,1.6Hz,1H),7.31(dd,J＝8.0,4.8Hz,1H),7.17–7.09(m,1H),7.04(ddd,J＝11.8,8.2,1.3Hz,1H),6.94–6.76(m,1H)。
3-pyridylaldehyde-3' -fluorophenylhydrazone (19): off-white powder, yield 90%.1H NMR(400MHz,CDCl3)δ8.76(d,J＝2.1Hz,1H),8.54(dd,J＝4.8,1.7Hz,1H),8.06(dt,J＝8.0,2.0Hz,1H),8.02(s,1H),7.69(s,1H),7.32(dd,J＝8.0,4.8Hz,1H),7.21(td,J＝8.2,6.4Hz,1H),6.93(dt,J＝11.0,2.3Hz,1H),6.79(ddd,J＝8.1,2.2,0.9Hz,1H),6.58(tdd,J＝8.3,2.5,0.9Hz,1H)。
3-pyridylaldehyde-4' -fluorophenylhydrazone (20): off-white powder, yield 92%.1H NMR(400MHz,CDCl3)δ8.75(d,J＝2.1Hz,1H),8.51(dd,J＝4.8,1.7Hz,1H),8.02(dt,J＝8.0,1.9Hz,1H),7.90(s,1H),7.67(s,1H),7.30(dd,J＝8.0,4.8Hz,1H),7.17–7.03(m,2H),7.03–6.95(m,2H)。
4-pyridylaldehyde phenylhydrazone (21): orange yellow powder, yield 91%.1H NMR(400MHz,CDCl3)δ8.63–8.52(m,2H),8.10(s,1H),7.59(s,1H),7.54–7.46(m,2H),7.38–7.28(m,2H),7.21–7.12(m,2H),6.98–6.90(m,1H)。
4-pyridylaldehyde-2' -fluorophenylhydrazone (22): pale yellow powder, yield 90%.1H NMR(400MHz,Chloroform-d)δ8.69–8.52(m,2H),8.27–8.08(m,1H),7.70(d,J＝1.2Hz,1H),7.61(td,J＝8.3,1.6Hz,2H),7.58–7.46(m,1H),7.20–7.09(m,1H),7.05(ddd,J＝11.8,8.2,1.4Hz,1H),6.94–6.79(m,1H)。
4-pyridylaldehyde-3' -fluorophenylhydrazone (23): pale yellow powder, yield 91%.1H NMR(400MHz,CDCl3)δ8.67–8.52(m,2H),8.17(s,1H),7.61(d,J＝1.1Hz,1H),7.54–7.43(m,2H),7.24–7.15(m,1H),6.95(dt,J＝10.9,2.3Hz,1H),6.81(ddd,J＝8.2,2.1,0.9Hz,1H),6.61(tdd,J＝8.4,2.6,0.9Hz,1H)。
4-pyridylaldehyde-4' -fluorophenylhydrazone (24): yellow powder, yield 93%.1H NMR(400MHz,DMSO-d6)δ10.78(s,1H),8.65–8.36(m,2H),7.79(s,1H),7.65–7.50(m,2H),7.12(td,J＝5.6,5.1,3.2Hz,4H)。
2-thiophenecarboxaldehyde phenylhydrazone (25): off-white powder, yield 89%.1HNMR(400MHz,DMSO-d6)δ10.31(s,1H),8.06(s,1H),7.65–6.29(m,8H)。
2-thiophenecarboxaldehyde-3' -fluorophenylhydrazone (26): pale yellow powder, yield 90%.1H NMR(400MHz,DMSO-d6)δ10.54(s,1H),8.09(s,1H),7.49(dt,J＝4.9,0.9Hz,1H),7.26(dd,J＝3.7,1.2Hz,1H),7.25–7.17(m,1H),7.07(dd,J＝5.1,3.6Hz,1H),6.82–6.69(m,2H),6.60–6.43(m,1H)。
2-thiophenecarboxaldehyde-4' -fluorophenylhydrazone (27): off-white powder, yield 89%.1H NMR(400MHz,DMSO-d6)δ10.29(s,1H),8.05(s,1H),7.45(dt,J＝5.1,1.0Hz,1H),7.21(dd,J＝3.6,1.1Hz,1H),7.11–7.01(m,3H),7.01–6.93(m,2H)。
2-pyrrolecarboxaldehyde phenylhydrazone (28): brick red powder, yield 95%.1H NMR(400MHz,DMSO-d6)δ11.11(s,1H),9.89(s,1H),7.73(s,1H),7.22–7.12(m,2H),7.09–6.97(m,2H),6.81(q,J＝2.3Hz,1H),6.74–6.60(m,1H),6.24(dt,J＝3.8,1.8Hz,1H),6.07(q,J＝2.7Hz,1H)。
2-acetylpyridine-4' -fluorophenylhydrazone (29): pale yellow powder, yield 90%.1H NMR(400MHz,DMSO-d6)δ9.51(s,1H),8.53(dd,J＝5.2,1.9Hz,1H),8.11(d,J＝7.9Hz,1H),7.77(td,J＝7.7,1.9Hz,1H),7.40–7.22(m,3H),7.18–6.96(m,2H),2.35(s,3H)。
3-acetylpyridine-4' -fluorophenylhydrazone (30): pale yellow powder, yield 85%.1H NMR(400MHz,DMSO-d6)δ9.45(s,1H),8.98(d,J＝2.4Hz,1H),8.49(dd,J＝4.7,1.6Hz,1H),8.13(dt,J＝8.1,2.0Hz,1H),7.40(dd,J＝8.1,4.7Hz,1H),7.30–7.19(m,2H),7.08(t,J＝8.9Hz,2H),2.28(s,3H)。
II, antibacterial activity
1. In vitro antibacterial Activity
The test bacteria are cotton fusarium wilt pathogenic bacteria (FOV), watermelon fusarium wilt pathogenic bacteria (FON), potato dry rot pathogenic bacteria (FS), wheat scab pathogenic bacteria (FG), tomato early blight pathogenic bacteria (AS), cabbage black spot pathogenic bacteria (AB), tobacco brown spot pathogenic bacteria (AA), corn curvularia pathogenic bacteria (CL), apple anthracnose pathogenic bacteria (CG), pumpkin fusarium wilt pathogenic bacteria (FB), apple rot pathogenic bacteria (VM), rice blast pathogenic bacteria (PO) and apple ring rot pathogenic Bacteria (BN).
The antibacterial activity was measured by a hyphal linear growth rate method. The test bacteria are: cotton wilt pathogen (MK); watermelon wilt pathogen (XK); potato dry rot pathogen (MG); wheat scab original (XC); tomato early blight pathogen (FZ); cabbage black spot pathogen (BH); alternaria alternate (YC); curvularia zeae pathogenic bacteria (YW); apple anthracnose Pathogen (PT); pumpkin wilt pathogen (NK); apple rot Pathogen (PF); pathogenic rice blast (SD); apple ring rot Pathogen (PL). The culture medium is PDA. Test solutions of compounds were prepared using 5% aqueous DMSO (v/v). The concentrations of the test compounds in PDA medium were all 100. mu.g/mL. The positive control drug was azoxystrobin (98% purity). Each experimental setup was performed in triplicate and repeated three times. The measurement results are expressed as the average inhibition ratio.
2. Pot culture test for resisting peronospora parasitica
Preparing a test solution: test compounds were formulated in 160mg/mL solutions with 10% OP-10 in dimethyl sulfoxide (DMSO). Before the test, the test leaves were diluted 533 times with water and then subjected to a spray treatment.
The test bacteria are plasmopara viticola. The test was carried out by the spore germination method on leaves. The spore of the grape downy mildew is prepared into the concentration of 105The spores/ml suspension was inoculated by spraying onto the back of the leaves of the grape. Placing the inoculated plants in an isolation room with high humidity and environmental temperature for 24h, transferring the plants into a greenhouse with environmental humidity and temperature for 48h, and finally transferring the plants into a high humidity environment for 24 h. The plants were then moved to the natural environment. After the water content on the plant surface had naturally evaporated, the infected leaves were removed from the plant and sprayed with a test solution of 300. mu.g/mL. After the moisture on the liquid surface is naturally volatilized, the petioles of the leaves are immersed in water and then are placed in a high-humidity environment for incubation for 72 hours. The effect of the test was evaluated by comparing the percentage of the spore coverage area on the leaf surfaces of the test group and the control group.
3. Potting test against powdery mildew
The preparation of the test solution is the same as the above-mentioned potted plant antibacterial test for downy mildew. The test bacteria are melon powdery mildew. The test is carried out by adopting a spore germination method on leaves, and the specific method is basically the same as the potted plant antibacterial test of the peronospora parasitica. The number of melon seedlings used in each trial was about 30, and the melon seedlings were grown in compost containing sterilized water. The melon plants inoculated with the sweet melon powdery mildew spore suspension are placed in a high-humidity environment for 24 hours and then are subjected to spray treatment by using 300 mu g/mL of test solution. After 5 days, the antibacterial effect was evaluated in the same manner as in the above-mentioned potting antibacterial test for downy mildew.
TABLE 1 inhibitory Activity of the Compounds on 13 phytopathogenic fungi
TABLE 2 index of control of the compounds against powdery mildew of melon and downy mildew of grapevine*
*0 represents that the control effect is less than 50 percent; 1 represents that the control effect is 50-80%; 2 represents that the control effect is more than 80 percent
The result of antibacterial activity shows that at the concentration of 100 mug/mL, the hydrazone compound disclosed by the patent shows excellent inhibitory activity and a wide antibacterial spectrum on 12 plant pathogenic bacteria, shows a high control effect on 2 plant pathogenic bacteria, and has great potential as an effective component for preparing plant antibacterial drugs.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (7)
1. A phenylhydrazone compound is characterized in that: the molecular formula is:
wherein:
R1is pyridyl, thienyl, pyrrolyl, etc.; r2Is hydrogen or methyl; r3、R4Are the same or different hydrogen, alkyl, alkoxy, halogen, nitro, cyano, trifluoromethyl, and the like; r3、R4The position (b) is ortho, para or meta on the benzene ring.
2. The method for synthesizing a phenylhydrazone compound according to claim 1,
has the following synthetic route:
wherein:
R1is pyridyl, thienyl, pyrrolyl, etc.; r2Is hydrogen or methyl; r3、R4Are the same or different hydrogen, alkyl, alkoxy, halogen, nitro, cyano, trifluoromethyl, and the like; r3、R4The position (b) is ortho, para or meta on the benzene ring.
3. The use of a phenylhydrazone compound according to claim 1, wherein:
application of phenylhydrazone compounds in preparing antibacterial medicines for plants is disclosed.
4. The use of a phenylhydrazone compound according to claim 5, wherein:
the phenylhydrazone compounds have obvious inhibitory activity on the following plant pathogenic bacteria:
cotton fusarium wilt pathogenic bacteria, watermelon fusarium wilt pathogenic bacteria, potato dry rot pathogenic bacteria, wheat gibberellic disease pathogenic bacteria, tomato early blight pathogenic bacteria, cabbage black spot pathogenic bacteria, tobacco brown spot pathogenic bacteria, maize curvularia pathogenic bacteria, apple anthracnose pathogenic bacteria, pumpkin fusarium wilt pathogenic bacteria, apple rot pathogenic bacteria, rice blast pathogenic bacteria, apple ring rot pathogenic bacteria, melon powdery mildew pathogen and grape downy mildew pathogen.
5. A pharmaceutical comprising the phenylhydrazone compound according to claim 1.
6. The drug containing a phenylhydrazone compound according to claim 5, wherein: the medicine is used as plant antibacterial medicine.
7. The drug containing a phenylhydrazone compound according to claim 6, wherein: the medicine has obvious inhibitory activity to plant diseases caused by the following pathogenic bacteria:
cotton fusarium wilt pathogenic bacteria, watermelon fusarium wilt pathogenic bacteria, potato dry rot pathogenic bacteria, wheat gibberellic disease pathogenic bacteria, tomato early blight pathogenic bacteria, cabbage black spot pathogenic bacteria, tobacco brown spot pathogenic bacteria, maize curvularia pathogenic bacteria, apple anthracnose pathogenic bacteria, pumpkin fusarium wilt pathogenic bacteria, apple rot pathogenic bacteria, rice blast pathogenic bacteria, apple ring rot pathogenic bacteria, melon powdery mildew pathogen and grape downy mildew pathogen.
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