CN112250598A - Paeonol hydrazone derivative, preparation method and application thereof, and pesticide - Google Patents

Paeonol hydrazone derivative, preparation method and application thereof, and pesticide Download PDF

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CN112250598A
CN112250598A CN202011231908.5A CN202011231908A CN112250598A CN 112250598 A CN112250598 A CN 112250598A CN 202011231908 A CN202011231908 A CN 202011231908A CN 112250598 A CN112250598 A CN 112250598A
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paeonol
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hydrogen
nitro
hydrazone derivative
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CN112250598B (en
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董钧锋
车志平
孙亚兰
田月娥
刘圣明
陈根强
林晓民
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Henan University of Science and Technology
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond

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Abstract

The invention relates to a paeonol hydrazone derivative, a preparation method and application thereof, and an insecticide, and belongs to the technical field of botanical pesticides. The paeonol hydrazone derivative has a structure shown in a formula I, wherein X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y and nitro or X, Y and hydrogen; r1、R2、R3Are respectively and independently selected from hydrogen and R4One of (1); the R is4is-F, -Cl, -Br, nitro or alkyl. The paeonol hydrazone derivative has the final corrected death rate of over 40 percent and the highest corrected death rate of over 70 percent under the concentration of 1mg/mL and is used for controlling the spodoptera frugiperdaObviously, can be used as a new medicine for preparing botanical pesticide.

Description

Paeonol hydrazone derivative, preparation method and application thereof, and pesticide
Technical Field
The invention relates to a paeonol hydrazone derivative, a preparation method and application thereof, and an insecticide, and belongs to the technical field of botanical pesticides.
Background
Paeonol is a phenolic ketone compound extracted and separated from root bark of Paeonia suffruticosa (Paeonia suffruticosa) of Ranunculaceae and whole plant of Cynanchum paniculatum (Cynanchum paniculatum) of Asclepiadaceae, and has wide pharmacological action and agricultural biological activity. At present, paeonol is widely applied in the aspect of medicine and mainly used for treating fever-reducing pain-easing, rheumatism-resisting and eczema, and 3 types of preparations sold on the market are paeonol tablets, injections and ointments respectively. The paeonol has the main characteristics in the aspect of agricultural biological activity: the fruit and vegetable fresh-keeping agent has fresh-keeping effect on fruits and vegetables; has inhibitory effect on plant pathogenic fungi, bacteria and viruses; has fumigating and contact killing effects on pests, and has avoidance effect on egg laying.
Spodoptera frugiperda (J.E. Smith) is a specific pest in the American area, a family Noctuidae of the Lepidoterata family of the Lepidoptera, also known as fall armyworm. Spodoptera frugiperda has emerged as a pest in Africa since 2016, and has now become the major corn pest in the midwest of Africa. The pest invades Yunnan and Guangxi of China from southeast Asia in 2019, is now harmful in 18 provinces (cities and autonomous regions), and seriously threatens grain production of corns and the like in China. The spodoptera frugiperda has strong adaptability and migration capability, can eat 353 plants including corn, rice, sorghum, millet, sugarcane, vegetables, cotton and other crops, and can cause great loss if the prevention and treatment measures are insufficient. At present, the control of spodoptera frugiperda mainly depends on chemical pesticides. However, Spodoptera frugiperda, which relies primarily on chemical pesticides to control its occurrence as a pest, is also continuously detecting resistance to pesticides with their use. In the middle of the 80's of the 20 th century, drug resistance of spodoptera frugiperda to carbaryl, methyl parathion and trichlorfon was generally detected in the southeast region of the united states, and sensitivity of spodoptera frugiperda field population to methomyl appeared to be significantly reduced. In the middle and south America, the Spodoptera frugiperda field population has low to medium-level drug resistance to carbaryl, phoxim, methyl parathion, trichlorfon and methomyl. At present, the development of new drug varieties with good insecticidal effect on spodoptera frugiperda is urgently needed.
Disclosure of Invention
The invention aims to provide the paeonol hydrazone derivative which has a good control effect on spodoptera frugiperda.
The invention also provides a preparation method of the paeonol hydrazone derivative and application of the paeonol hydrazone derivative in control of Spodoptera frugiperda.
In addition, the invention also provides an insecticide adopting the paeonol hydrazone derivative.
In order to achieve the above purpose, the technical scheme adopted by the paeonol hydrazone derivatives of the invention is as follows:
a paeonol hydrazone derivative has a structure shown as a formula I:
Figure BDA0002765500780000021
in the formula I, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y and nitro or X, Y and hydrogen; r1、R2、R3Are respectively and independently selected from hydrogen and R4One of (1); the R is4is-F, -Cl, -Br, nitro or alkyl.
The paeonol hydrazone derivative has a final corrected death rate of over 40 percent and a maximum corrected death rate of over 70 percent under the concentration of 1mg/mL and is remarkable in control effect on spodoptera frugiperda, and can be used as a novel medicament for preparing botanical insecticides.
Further, the number of carbon atoms of the alkyl group is 1 to 3.
Further, in the formula I, R1、R2、R3Not hydrogen at the same time.
Further, in the formula I, R2Is hydrogen.
Further, in the formula I, R1Is R4、R3Is hydrogen or R1Is hydrogen, R3Is R4。
Further, in the formula I, R1、R3Are all R4。
Further, the paeonol hydrazone derivative has a structure shown as a formula II:
Figure BDA0002765500780000022
in the formula II, R1、R3Are all R4。
Further, in the formula II, R1is-F, -Cl, -Br or nitro, R3Is hydrogen.
The preparation method of the paeonol hydrazone derivative adopts the technical scheme that:
the preparation method of the paeonol hydrazone derivative comprises the following steps: carrying out reflux reaction on the compound shown in the formula III and the compound shown in the formula IV or hydrochloride of the compound shown in the formula IV;
Figure BDA0002765500780000031
in the formula III, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y and nitro or X, Y and hydrogen;
in the formula IV, R1、R2、R3Are respectively and independently selected from hydrogen and R4One of (1); the R is4is-F, -Cl, -Br, nitro or alkyl.
The preparation method of the paeonol hydrazone derivative has the advantages of simple process and low raw material cost, and the yield of the paeonol hydrazone derivative is more than 59 percent, so that the production cost of the paeonol hydrazone derivative is greatly reduced.
Further, ethanol is used as a solvent in the reflux reaction, and glacial acetic acid is used as a catalyst.
Further, the number of carbon atoms of the alkyl group is 1 to 3.
Further, the compound shown in the formula III is 3-nitro paeonol, 5-nitro paeonol or 3, 5-dinitropaeonol.
Further, in the formula IV, R2Is hydrogen.
Further, in the formula IV, R1Is R4，R3Is hydrogen. Or in the formula IV, R1、R3Are all R4. Or in the formula IV, R1Is R4、R3Is hydrogen. Or in the formula IV, R1Is hydrogen, R3Is R4. Still further, the compound of formula IV has the following structure:
Figure BDA0002765500780000032
in the formula VI, R1、R3Are all R4。
Further, in the formula VI, R1is-F, -Cl, -Br or nitro, R3Is hydrogen.
Further, the compound of formula IV is one of phenylhydrazine, m-toluylhydrazine, p-methylphenylhydrazine, 2-fluorophenylhydrazine, 3-fluorophenylhydrazine, 4-fluorophenylhydrazine, 3, 4-difluorophenylhydrazine, 2-chlorophenylhydrazine, 3-chlorophenylhydrazine, 2-bromophenylhydrazine, 3-bromophenylhydrazine, 2-nitrophenylhydrazine, 3-nitrophenylhydrazine and 4-nitrophenylhydrazine.
The technical scheme adopted by the application of the paeonol hydrazone derivative in the control of Spodoptera frugiperda is as follows:
an application of the paeonol hydrazone derivative in preventing and treating Spodoptera frugiperda.
The paeonol hydrazone derivative has obvious spodoptera frugiperda killing activity when being used for preventing and controlling spodoptera frugiperda at the groove bottom, and the prevention and control effect of a part of compounds on spodoptera frugiperda is better than that of a commercial botanical insecticide, namely toosendanin.
The technical scheme adopted by the pesticide of the invention is as follows:
an insecticide contains any one of the above derivatives as effective component.
The pesticide contains the paeonol hydrazone derivative, and has remarkable spodoptera exigua killing activity.
Further, the pesticide is a botanical pesticide.
Drawings
FIG. 1 is a hydrogen spectrum of compound I-1a prepared in the example of the process for preparing a paeonol hydrazone derivative;
FIG. 2 is a hydrogen spectrum of compound I-1b prepared in the example of the method for preparing a paeonol hydrazone derivative.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Examples 1 to 18 of Paeonol Hydrazone derivatives
The paeonol hydrazone derivatives of the embodiments 1 to 18 have the structures shown as the formula II or the formula V:
Figure BDA0002765500780000041
the specific structure of the paeonol hydrazone derivatives and the corresponding structural formula of X, Y, R in the examples1、R3The corresponding groups are shown in table 1.
TABLE 1 Structure of the paeonol hydrazone derivatives of examples 1 to 18 and X, Y, R in the structure1、R3Corresponding radicals
Figure BDA0002765500780000042
Figure BDA0002765500780000051
Examples of the preparation of Paeonol Hydrazone derivatives
The 3-nitro paeonol and 5-nitro paeonol adopted in the embodiment of the preparation method of the paeonol hydrazone derivative can be prepared according to the following methods: dissolve 1mmol of paeonol (Compound 1) in 5mL of concentrated H at-30 deg.C2SO4Then 1mmol of concentrated HNO is added3Continuously reacting for 0.5 h; pouring the reaction solution into 50mL of ice water, stirring to separate out a large amount of solid, filtering, and washing with water to be neutral; dissolving, drying with anhydrous sodium sulfate, and separating the products 2 (3-nitro paeonol) and 3 (5-nitro paeonol) by silica gel column chromatography.
The properties of the isolated product 2 were as follows:
1) light yellow solid, melting point 125-126 ℃, yield 29%.
2) Nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: 13.03(s,1H),8.50(s,1H),6.55(s,1H),4.01(s,3H),2.64(s, 3H).
3) ESI-MS of this Compound, M/z (%) 210([ M-H ]]+,100)。
The properties of the isolated product 3 were as follows:
1) light yellow solid, the melting point is 132-133 ℃, and the yield is 13%.
2) Nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: 13.06(s,1H),7.83(d, J ═ 8.8Hz 1H),6.58(d, J ═ 9.2Hz,1H),3.97(s,3H),2.61(s, 3H).
3) ESI-MS of this Compound, M/z (%) 210([ M-H ]]+,100)。
The preparation method of the 3-nitro paeonol and the 5-nitro paeonol comprises the following chemical reactions:
Figure BDA0002765500780000061
the 3, 5-dinitropaeonol adopted in the examples of the preparation method of the paeonol hydrazone derivative can be prepared according to the following method: dissolve 1mmol of paeonol (Compound 1) in 5mL of concentrated H at-30 deg.C2SO4Then 3mmol of concentrated HNO is added3Continuously reacting for 5 hours; pouring the reaction solution into 50mL of ice water, stirring to separate out a large amount of solid, filtering, washing with water to be neutral, and recrystallizing with ethyl acetate to obtain a product 4.
The properties of product 4 were as follows:
1) pale yellow solid, melting point 129-130 ℃, yield 74%.
2) Nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
substitution of deuterium with CDCl3TMS is an internal standard, where the peak assignments are: 13.43(s,1H),8.62(s,1H),4.09(s,3H),2.74(s, 3H).
3) ESI-MS of this Compound, M/z (%) 255([ M-H ]]+,100)。
The preparation method of the 3, 5-dinitropaeonol comprises the following chemical reactions:
Figure BDA0002765500780000062
in addition to the preparation of 3-nitropaeonol, 5-nitropaeonol and 3, 5-dinitropaeonol according to the methods listed above, other commercially available products can be prepared or purchased directly by using other prior art methods. For example, Yaoaishen et al reported the synthesis of paeonol nitration products (Yaoaishen, Li Fang, Deng Sheng, Zhongguo, Synthesis of paeonol mono-nitration and di-nitration derivatives, proceedings of Combined Fertilizer industry university, 2009,32: 177-.
The method for preparing the paeonol hydrazone derivative of embodiment 1 to 18, comprising the steps of:
1) weighing 1mmol of a compound shown as a formula III and 1mmol of hydrochloride of a compound shown as a formula IV, putting the compounds into a 50mL flask, adding 10mL of absolute ethanol to completely dissolve the hydrochloride of the compounds shown as the formula III and the formula IV, then dropwise adding 1-2 drops of glacial acetic acid, carrying out reflux reaction, generating a large amount of solids through the reflux reaction, and carrying out TLC tracking detection until the raw materials completely react; the reflux reaction time is 2-12 h;
2) and then, standing and cooling to room temperature to completely crystallize, carrying out vacuum filtration to obtain a crude product, washing the crude product with frozen ethanol (-20 ℃) for 3 times (the dosage of the frozen ethanol is 10mL each time), then washing the crude product with petroleum ether for 3 times (the dosage of the petroleum ether is 10mL each time), and drying to obtain a yellow solid product. The product yield was then calculated.
When the paeonol hydrazone derivatives of examples 1 to 18 were prepared by the preparation method, the compound of formula III, the compound of formula IV, the time of the reflux reaction, and the yield of the final product used are shown in table 2, and the yellow solid products obtained when the paeonol hydrazone derivatives of each example were prepared are numbered in table 2.
TABLE 2 specific substances of the compounds of formulae III and IV and the time of the reflux reaction, the yields of the final products and the product numbers used in the methods of preparing the paeonol hydrazone derivatives of examples 1 to 18
Figure BDA0002765500780000071
Figure BDA0002765500780000081
The physicochemical properties of the products numbered in table 2 are as follows:
compound I-1 a:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 15.80(s,1H),10.04(s,1H),8.38(s,1H),7.36(t, J ═ 8.0Hz,2H),7.07(d, J ═ 8.0Hz,2H),6.94(t, J ═ 7.2Hz,1H),3.94(s,3H),2.48(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H15N4O6([M+H]+) 347.0986; found, 347.0990. The hydrogen spectrum is shown in FIG. 1.
The chemical reactions involved in the preparation of compound I-1a are:
Figure BDA0002765500780000082
compound I-1 b:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: 15.72(s,1H),9.99(s,1H),8.36(s,1H),7.23(t, J ═ 8.0Hz,1H),6.84-6.89(m,2H),6.75(d, J ═ 7.2Hz,1H),3.94(s,3H),2.46(s,3H),2.28(s, 3H).
2) HRMS (ESI) of the compound Calcd for C16H17N4O6([M+H]+) 361.1143; found, 361.1145. The hydrogen spectrum is shown in FIG. 2.
The chemical reactions involved in the preparation of compound I-1b are:
Figure BDA0002765500780000091
compound I-1 c:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: 15.87(s,1H),9.95(s,1H),8.35(s,1H),7.15(d, J ═ 8.4Hz,2H),6.97(d, J ═ 8.4Hz,2H),3.94(s,3H),2.45(s,3H),2.23(s, 3H).
2) HRMS (ESI) of the compound Calcd for C16H17N4O6([M+H]+),361.1143；found,361.1148。
The chemical reactions involved in the preparation of compound I-1c are:
Figure BDA0002765500780000092
compound I-1 d:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: delta 9.92(s,1H),8.41(s,1H),7.17-7.29(m,3H),6.96-7.02(m,1H),3.94(s,3H),2.49(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14FN4O6([M+H]+),365.0892；found,365.0896。
The chemical reactions involved in the preparation of compound I-1d are:
Figure BDA0002765500780000101
compound I-1 e:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: delta 10.19(s,1H),8.38(s,1H),7.33-7.39(m,1H),6.87-6.89(m,1H),6.79-6.83(m,1H),6.69-6.74(m,1H),3.94(s,3H),2.46(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14FN4O6([M+H]+),365.0892；found,365.0893。
The chemical reactions involved in the preparation of compound I-1e are:
Figure BDA0002765500780000102
compound I-1 f:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: 15.57(s,1H),10.01(s,1H),8.37(s,1H),7.16-7.21(m,2H),7.03-7.09(m,2H),3.94(s,3H),2.46(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14FN4O6([M+H]+),365.0892；found,365.0899。
The chemical reactions involved in the preparation of compounds I-1f are:
Figure BDA0002765500780000111
compound I-1 g:
nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: delta 10.24(s,0.8H),9.85(s,0.2H),8.35(s,0.8H),8.15(s,0.2H),7.31-7.43(m,1H),7.05-7.11(m,0.8H),6.96-7.02(m,0.2H),6.86-6.90(m,0.8H),6.81-6.83(m,0.2H),3.93(s,2.4H),3.06(s,0.6H),2.45(s,2.4H),2.36(s, 0.6H).
The chemical reactions involved in the preparation of compound I-1g are:
Figure BDA0002765500780000112
compound I-1 h:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: 9.09(s,1H),8.46(s,1H),7.50(dd, J ═ 8.0Hz,1.6Hz,1H),7.36-7.41(m,1H),7.23(dd, J ═ 8.0Hz,1.6Hz,1H),7.00-7.04(m,1H),3.95(s,3H),2.54(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14ClN4O6([M+H]+),381.0596；found,381.0599。
The chemical reactions involved in the preparation of compound I-1h were:
Figure BDA0002765500780000121
compound I-1I:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 10.15(s,1H),8.39(s,1H),7.37(t, J ═ 8.0Hz,1H),7.08(t, J ═ 2.0Hz,1H),6.99-7.02(m,1H),6.93-6.96(m,1H),3.94(s,3H),2.46(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14ClN4O6([M+H]+),381.0596；found,381.0601。
The chemical reactions involved in the preparation of compound I-1I are:
Figure BDA0002765500780000122
compound I-1 j:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 8.89(s,1H),8.46(s,1H),7.65(dd, J ═ 8.0Hz,1.6Hz,1H),7.40-7.44(m,1H),7.21(dd, J ═ 8.0Hz,1.6Hz,1H),6.94-6.98(m,1H),3.95(s,3H),2.53(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14BrN4O6([M+H]+),425.0091；found,425.0095。
The chemical reactions involved in the preparation of compound I-1j are:
Figure BDA0002765500780000131
compound I-1 k:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 10.13(s,1H),8.38(s,1H),7.31(t, J ═ 8.0Hz,1H),7.23(t, J ═ 2.0Hz,1H),7.02-7.08(m,2H),3.94(s,3H),2.46(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14BrN4O6([M+H]+),425.0091；found,425.0093。
The chemical reactions involved in the preparation of compound I-1k are:
Figure BDA0002765500780000132
compound I-1 l:
nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 10.76(s,0.8H),10.72(s,0.2H),8.37(s,0.8H),8.20(dd, J ═ 8.8Hz,1.2Hz,0.8H),8.05(s,0.2H),7.85(dd, J ═ 8.8Hz,1.2Hz,0.2H),7.77(dd, J ═ 8.8Hz,6.8Hz,1H),7.64-7.68(m,0.8H),7.58-7.61(m,0.2H),7.00-7.04(m,0.8H),6.80-6.84(m,0.2H),3.90(s,2.4H),3.06(s,0.6H),2.45(s,2.4H),2.29(s, 0.6H).
The chemical reactions involved in the preparation of compound I-1l are:
Figure BDA0002765500780000133
compound I-1 m:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 10.39(s,1H),8.40(s,1H),7.90(t, J ═ 2.4Hz,1H),7.71-7.73(m,1H),7.63(t, J ═ 8.4Hz,1H),7.43-7.46(m,1H),3.95(s,3H),2.48(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H14N5O8([M+H]+),392.0837；found,392.0841。
The chemical reactions involved in preparing compound I-1m are:
Figure BDA0002765500780000141
compound I-1 n:
nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 10.87(s,0.6H),10.64(s,0.4H),8.32(s,0.6H),8.15-8.20(m,2H),8.13(s,0.4H),7.30(d, J ═ 8.8Hz,1.2H),7.20(d, J ═ 8.8Hz,0.8H),3.90(s,1.8H),3.06(s,1.2H),2.48(s,1.8H),2.41(s, 1.2H).
The chemical reactions involved in the preparation of compound I-1n are:
Figure BDA0002765500780000142
compound I-2 a:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 14.03(s,1H),9.65(s,1H),8.15(s,1H),7.32(t, J ═ 8.8Hz,2H),7.06(d, J ═ 8.8Hz,2H),6.88(t, J ═ 7.2Hz,1H),6.75(s,1H),3.93(s,3H),2.39(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H16N3O4([M+H]+),302.1135；found,302.1142。
The chemical reactions involved in the preparation of compound I-2a are:
Figure BDA0002765500780000151
compound I-2 b:
nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 13.37(s,0.8H),12.79(s,0.2H),10.35(s,0.2H),10.11(s,0.8H),8.51(s,0.2H),8.19(s,0.8H),7.91(t, J ═ 2.4Hz,0.2H),7.88(t, J ═ 2.4Hz,0.8H),7.73(dd, J ═ 7.6Hz,2.4Hz,0.2H),7.68(dd, J ═ 7.6Hz,2.4Hz,0.8H),7.59(d, J ═ 8.4Hz,0.2H),7.57(d, J ═ 8.4Hz,0.8H),7.46(dd, J ═ 7.6, 2.4, 0.2H), 7.81 (dd, 6H, 7.6H, 6H), 6.6H, 6H, 2.6H, 6H, 3.6H, 6H, 3.6H, 2H, and s (d).
The chemical reactions involved in the preparation of compound I-2b are:
Figure BDA0002765500780000152
compound I-3 a:
nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ:14.47(s,0.6H),13.05(s,0.4H),10.27(s,0.6H),9.72(s,0.4H),8.14-8.18(m,0.4H),7.69-7.73(m,0.6H),7.26-7.32(m,2H),6.77-7.06(m,4H),3.98(s,1.2H),3.89(s,1.8H),2.64(s,1.2H),2.41(s, 1.8H).
The chemical reactions involved in the preparation of compound I-3a are:
Figure BDA0002765500780000161
compound I-3 b:
the physicochemical properties of the compound are as follows:
1) nuclear magnetic resonance spectrum of the compound (1H NMR, 400MHz) characteristics:
deuterated DMSO is used as a solvent, TMS is used as an internal standard substance, and the attribution of each peak is as follows: δ 13.88(s,1H),10.11(s,1H),7.85(t, J ═ 2.4Hz,1H),7.77(d, J ═ 9.2Hz,1H),7.69(dd, J ═ 8.0Hz,1.6Hz,1H),7.60(t, J ═ 8.0Hz,1H),7.41(dd, J ═ 8.0Hz,1.6Hz,1H),6.84(d, J ═ 8.8Hz,1H),3.91(s,3H),2.44(s, 3H).
2) HRMS (ESI) of the compound Calcd for C15H15N4O6([M+H]+),347.0986；found,347.0991。
The chemical reactions involved in the preparation of compound I-3b are:
Figure BDA0002765500780000162
in addition, the paeonol hydrazone derivative of example 1 can be prepared by a method comprising the following steps:
1) weighing 1mmol of formula 3, 5-dinitropaeonol and 1mmol of phenylhydrazine hydrochloride, placing the materials in a 50mL flask, adding 10mL of absolute ethyl alcohol to completely dissolve the 3, 5-dinitropaeonol and the phenylhydrazine hydrochloride, then dropwise adding 1-2 drops of glacial acetic acid, carrying out reflux reaction to generate a large amount of solid, and carrying out TLC tracking detection until the raw materials are completely reacted;
2) and then, standing and cooling to room temperature to completely crystallize, carrying out vacuum filtration to obtain a crude product, washing the crude product with frozen ethanol (-20 ℃) for 3 times (the dosage of the frozen ethanol is 10mL each time), then washing the crude product with petroleum ether for 3 times (the dosage of the petroleum ether is 10mL each time), and drying to obtain a yellow solid product. The chemical reaction involved is:
Figure BDA0002765500780000171
examples of insecticides
The pesticide of the embodiment is a botanical pesticide, wherein the effective component is the paeonol hydrazone derivative of any one of embodiments 1 to 18. In the preparation of the insecticide of this example, with reference to the conventional method for preparing insecticides, only the effective insecticidal component was replaced with the paeonol hydrazone derivative of the corresponding example in examples 1 to 18. For example, the effective components of the commercial toosendanin botanical insecticide can be replaced by the paeonol hydrazone derivatives of the corresponding examples in examples 1-18 with equal concentration.
Examples of the experiments
The experimental example is an activity determination experiment for killing lepidoptera pests Spodoptera frugiperda.
1. Test compounds: the paeonol hydrazone derivatives of examples 1 to 18.
2. Positive control: a commercial botanical insecticide, Toosendanin (Toosendanin).
3. Test organisms: spodoptera frugiperda (Spodoptera frugiperda) at the third instar.
4. The determination method comprises the following steps: feeding poison by adopting a small leaf dish adding method, changing normal corn leaves after 48 hours for feeding until eclosion, wherein the detailed method comprises the following steps:
firstly, the test insects are three-year-old early Spodoptera frugiperda, a small leaf disc addition method is adopted, toosendanin is used as a positive control, acetone is used as a blank control, and the concentration of a detected sample is 1 mg/mL;
three times of samples are set, 10 robust three-instar early spodoptera frugiperda with uniform size are repeatedly selected and raised in a culture dish with the diameter of 9cm, and a layer of filter paper is laid at the bottom of the culture dish for moisture preservation;
thirdly, fresh corn leaves are cut into 1 multiplied by 1cm2Soaking the small leaf disk in the prepared sample liquid medicine and the reference liquid medicine for 3 seconds, naturally airing, feeding the test insects, adding the small leaf disk in time after the test insects eat the small leaf disk, and feeding the normal leaves until emergence after 48 hours;
fourthly, feeding conditions are as follows: the temperature is 25 +/-2 ℃, the relative humidity is 65-80%, the illumination time is 12h, and the dark time is 12 h;
regularly recording the feeding amount, the number of survivals and the expression symptoms of the test insects, and calculating the corrected mortality (%) of the test insects in different periods according to the following formula:
Figure BDA0002765500780000181
5. the results of the insecticidal activity measurements are shown in Table 3.
TABLE 3 results of assaying Spodoptera frugiperda-killing activity of paeonol hydrazone derivatives of examples 1 to 18
Figure BDA0002765500780000182
As can be seen from the data in Table 3, the paeonol hydrazone derivatives have remarkable control effect on Spodoptera frugiperda (Spodoptera frugiperda), wherein the control effect of part of the paeonol hydrazone derivatives on Spodoptera frugiperda is better than that of a commercial botanical insecticide, namely toosendanin, and the paeonol hydrazone derivatives can be used for preparing the botanical insecticide.

Claims (10)

1. A paeonol hydrazone derivative is characterized in that: has a structure shown in formula I:
Figure FDA0002765500770000011
in the formula I, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y and nitro or X, Y and hydrogen; r1、R2、R3Are respectively and independently selected from hydrogen and R4One of (1); the R is4is-F, -Cl, -Br, nitro or alkyl.
2. The paeonol hydrazone derivative according to claim 1, wherein: the number of carbon atoms of the alkyl group is 1 to 3.
3. The paeonol hydrazone derivative according to claim 1 or 2, wherein: r2Is hydrogen.
4. The paeonol hydrazone derivative according to claim 3, wherein: r1Is R4、R3Is hydrogen or R1Is hydrogen, R3Is R4。
5. The paeonol hydrazone derivative according to claim 3, wherein: r1、R3Are all R4。
6. The paeonol hydrazone derivative according to claim 5, wherein: has a structure as shown in formula II:
Figure FDA0002765500770000012
in the formula II, R1、R3Are all R4。
7. The paeonol hydrazone derivative according to claim 6, wherein: r1is-F, -Cl, -Br or nitro, R3Is hydrogen.
8. A method for preparing the paeonol hydrazone derivative according to claim 1, wherein: the method comprises the following steps: carrying out reflux reaction on the compound shown in the formula III and the compound shown in the formula IV or hydrochloride of the compound shown in the formula IV;
Figure FDA0002765500770000021
in the formula III, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y is simultaneouslyNitro radicalOr X, Y are both hydrogen;
in the formula IV, R1、R2、R3Are respectively and independently selected from hydrogen and R4One of (1); the R is4is-F, -Cl, -Br, nitro or alkyl.
9. The use of a paeonol hydrazone derivative as defined in claim 1, for controlling spodoptera frugiperda.
10. An insecticide, characterized by: the effective component of the pesticide comprises the paeonol hydrazone derivative as defined in any one of claims 1 to 7.
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