CN112250598B - 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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CN112250598B
CN112250598B CN202011231908.5A CN202011231908A CN112250598B CN 112250598 B CN112250598 B CN 112250598B CN 202011231908 A CN202011231908 A CN 202011231908A CN 112250598 B CN112250598 B CN 112250598B
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paeonol
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hydrogen
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nitro
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CN112250598A (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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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 plant source pesticides. The paeonol hydrazone derivative has a structure shown in a formula I, wherein in the formula I, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y is nitro or X, Y is hydrogen at the same time; r is R 1 、R 2 、R 3 Are respectively and independently selected from hydrogen and R 4 One of the following; the R is 4 is-F, -Cl, -Br, nitro or alkyl. The final corrected mortality rate of the paeonol hydrazone derivative measured by a small leaf disc addition method at the concentration of 1mg/mL can reach more than 40 percent, and can reach more than 70 percent at maximum, has remarkable control effect on spodoptera frugiperda, and can be used as a new drug variety for preparing botanical insecticide.

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 plant source pesticides.
Background
Paeonol (Paeonol) is a phenolic ketone compound extracted and separated from root bark of Paeonia suffruticosa (Paeonia suffruticosa) belonging to Ranunculaceae and whole plant of Cynanchum paniculatum (Cynanchum paniculatum) belonging to Asclepiadaceae, and has wide pharmacological action and agricultural bioactivity. Currently, paeonol has wide application in medicine, and is mainly used for treating fever and pain, rheumatism and eczema, and 3 commercially available dosage forms are paeonol tablets, injection and ointment respectively. Paeonol is mainly expressed in terms of agricultural biological activity: the fruit and vegetable fresh-keeping agent has fresh-keeping effect on fruits and vegetables; has inhibiting effect on plant pathogenic fungi, bacteria and viruses; has fumigating and contact killing effects on pests, and has repellent effect on spawning.
Spodoptera frugiperda Spodoptera frugiperda (j.e. smith) belongs to Lepidoptera, notuisae, nocturnal, also known as fall armyworm, and is a specific pest in america. Spodoptera frugiperda has been the major corn pest in africa since 2016 when it was outbreaked in africa. The pests invade from southeast Asia to Yunnan and Guangxi in China in 1 month in 2019, are harmful in 18 provinces (municipal and autonomous areas) at present, and seriously threaten grain production of corns and the like in China. Spodoptera frugiperda has strong adaptability and migration ability, and can feed 353 plants including corn, rice, sorghum, millet, sugarcane, vegetables, cotton and other crops, and if the prevention and control measures are inadequate, serious loss can be caused. At present, the prevention and control of spodoptera frugiperda mainly depend on chemical pesticides. However, spodoptera frugiperda, which mainly relies on chemical pesticides to control the occurrence of the pest, also continuously detects the problem of drug resistance to pesticides along with the use of the pesticides. Drug resistance of spodoptera frugiperda to carbaryl, methyl parathion and trichlorfon is commonly detected in the mid-80 s of the 20 th century in the southeast region of the united states, and the sensitivity of spodoptera frugiperda field populations in florida to methomyl is obviously reduced. In the middle and south america, spodoptera frugiperda field populations exhibit low to moderate resistance to carbaryl, phoxim, methylparaben, trichlorfon, and methomyl. At present, development of a new drug variety with good insecticidal effect on spodoptera frugiperda is urgently needed.
Disclosure of Invention
The invention aims to provide a 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 preventing and controlling 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 in a formula I:
in the formula I, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y and X, Y are simultaneously nitro; r is R 1 、R 2 、R 3 Are respectively and independently selected from hydrogen and R 4 One of the following; the R is 4 is-F, -Cl, -Br, nitro or alkyl.
The final corrected mortality rate of the paeonol hydrazone derivative measured by a small leaf disc addition method at the concentration of 1mg/mL can reach more than 40 percent, and can reach more than 70 percent at maximum, has remarkable control effect on spodoptera frugiperda, and can be used as a new drug variety for preparing botanical insecticide.
Further, the alkyl group has 1 to 3 carbon atoms.
Further, in formula I, R 1 、R 2 、R 3 Not both hydrogen.
Further, in formula I, R 2 Is hydrogen.
Further, in formula I, R 1 Is R 4 、R 3 Is hydrogen or R 1 Is hydrogen, R 3 Is R 4 。
Further, in formula I, R 1 、R 3 All are R 4 。
Further, the paeonol hydrazone derivative has a structure shown in a formula II:
in formula II, R 1 、R 3 All are R 4 。
Further, in formula II, R 1 is-F, -Cl, -Br or nitro, R 3 Is hydrogen.
The preparation method of the paeonol hydrazone derivative adopts the following technical scheme:
the preparation method of the paeonol hydrazone derivative comprises the following steps: reflux reaction is carried out 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;
in the formula III, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y and X, Y are simultaneously nitro;
in formula IV, R 1 、R 2 、R 3 Are respectively and independently selected from hydrogen and R 4 One of the following; the R is 4 is-F, -Cl, -Br, nitro or alkyl.
The preparation method of the paeonol hydrazone derivatives has the advantages of simple process and low raw material cost, and the yield of the paeonol hydrazone derivatives is more than 59%, so that the production cost of the paeonol hydrazone derivatives is greatly reduced.
Further, the reflux reaction uses ethanol as a solvent and glacial acetic acid as a catalyst.
Further, the alkyl group has 1 to 3 carbon atoms.
Further, the compound of formula III is 3-nitropaeonol, 5-nitropaeonol or 3, 5-dinitropaeonol.
Further, in formula IV, R 2 Is hydrogen.
Further, in formula IV, R 1 Is R 4 ，R 3 Is hydrogen. Or in formula IV, R 1 、R 3 All are R 4 . Or in formula IV, R 1 Is R 4 、R 3 Is hydrogen. Or in formula IV, R 1 Is hydrogen, R 3 Is R 4 . Further, the compound of formula IV has the following structure:
in formula VI, R 1 、R 3 All are R 4 。
Further, in formula VI, R 1 is-F, -Cl, -Br or nitro, R 3 Is hydrogen.
Further, the compound of the formula IV is one of phenylhydrazine, m-tolylhydrazine, 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 application of the paeonol hydrazone derivative in preventing and controlling spodoptera frugiperda adopts the following technical scheme:
an application of the paeonol hydrazone derivatives in preventing and controlling spodoptera frugiperda.
The paeonol hydrazone derivative has remarkable spodoptera littoralis killing activity when being used for preventing and controlling spodoptera littoralis at the bottom of a tank, wherein the preventing and controlling effect of partial compounds on the spodoptera littoralis is better than that of a commercial plant source pesticide toosendanin.
The technical scheme adopted by the pesticide of the invention is as follows:
an insecticide contains one of the above paeonol hydrazone derivatives as effective component.
The pesticide provided by the invention contains the paeonol hydrazone derivative and has obvious spodoptera frugiperda killing activity.
Further, the pesticide of the present invention is a botanical pesticide.
Drawings
FIG. 1 is a hydrogen spectrum of a compound I-1a prepared in an example of a preparation method of paeonol hydrazone derivatives;
FIG. 2 is a hydrogen spectrum of the compound I-1b prepared in an example of a preparation method of paeonol hydrazone derivatives.
Detailed Description
The technical scheme of the invention is further described below in connection with the specific embodiments.
Examples 1 to 18 of paeonol hydrazone derivatives
The paeonol hydrazone derivatives of examples 1 to 18 have a structure as shown in formula II or formula V:
specific structure of paeonol hydrazone derivatives of each embodiment and corresponding structure formula X, Y, R 1 、R 3 The corresponding groups are shown in Table 1.
TABLE 1 Structure of Paeonol hydrazone derivatives of examples 1 to 18 and X, Y, R in the Structure 1 、R 3 Corresponding groups
Examples of the preparation method of Paeonol hydrazone derivatives
The 3-nitropaeonol and 5-nitropaeonol adopted in the examples of the preparation method of the paeonol hydrazone derivatives can be prepared according to the following methods: 1mmol of paeonol (Compound 1) was dissolved in 5mL of concentrated H at-30 ℃ 2 SO 4 After that, 1mmol of concentrated HNO is added 3 The reaction was continued for 0.5h; pouring the reaction solution into 50mL of ice water, stirring to separate out a large amount of solids, filtering, and washing with water to neutrality; dissolving, drying with anhydrous sodium sulfate, and separating the products 2 (3-nitropaeonol) and 3 (5-nitropaeonol) by silica gel column chromatography.
The properties of the isolated product 2 are as follows:
1) Pale yellow solid, melting point 125-126 ℃, yield 29%.
2) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
with deuterated CDCl 3 As solvent, TMS is an internal standard, where each peak is assigned to: 13.03 (s, 1H), 8.50 (s, 1H), 6.55 (s, 1H), 4.01 (s, 3H), 2.64 (s, 3H).
3) ESI-MS, M/z (%) 210 ([ M-H) of the Compound] + ,100)。
The properties of the isolated product 3 are as follows:
1) Pale yellow solid, melting point 132-133 ℃, yield 13%.
2) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
with deuterated CDCl 3 As solvent, TMS is an internal standard, where each peak is assigned to: 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, M/z (%) 210 ([ M-H) of the Compound] + ,100)。
The preparation method of the 3-nitropaeonol and 5-nitropaeonol involves the chemical reaction that:
the 3, 5-dinitropaeonol used in the examples of the preparation method of paeonol hydrazone derivatives can be prepared according to the following method: 1mmol of paeonol (Compound 1) was dissolved in 5mL of concentrated H at-30 ℃ 2 SO 4 After that, 3mmol of concentrated HNO is added 3 The reaction is continued for 5 hours; pouring the reaction solution into 50mL of ice water, stirring to separate out a large amount of solids, filtering, washing with water to be neutral, and recrystallizing with ethyl acetate to obtain a product 4.
The properties of product 4 are as follows:
1) Pale yellow solid, melting point 129-130 ℃, yield 74%.
2) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
with deuterated CDCl 3 As solvent, TMS is an internal standard, where each peak is assigned to: 13.43 (s, 1H), 8.62 (s, 1H), 4.09 (s, 3H), 2.74 (s, 3H)。
3) ESI-MS, M/z (%) 255 ([ M-H) of the compound] + ,100)。
The preparation method of the 3, 5-dinitropaeonol involves the chemical reaction that:
in addition to the preparation of 3-nitropaeonol, 5-nitropaeonol and 3, 5-dinitropaeonol according to the methods listed above, other prior art processes can be used to prepare or directly purchase commercial products. For example Yao Risheng et al report the synthesis of paeonol nitration products (Yao Risheng, li Fa, deng Shengsong, guoyong. Synthesis of paeonol mononitration and dinitration derivatives. Proc. Of the joint fertilizer industry, 2009, 32:177-180).
The preparation method of the paeonol hydrazone derivatives in examples 1 to 18 comprises the following steps:
1) Weighing 1mmol of the compound shown in the formula III and 1mmol of the hydrochloride of the compound shown in the formula IV, placing the compounds in a 50mL flask, adding 10mL of absolute ethyl alcohol to completely dissolve the hydrochloride of the compound shown in the formula III and the hydrochloride of the compound shown in the formula IV, then dropwise adding 1-2 drops of glacial acetic acid, carrying out reflux reaction, generating a large amount of solids by the reflux reaction, and tracking and detecting that the raw materials are completely reacted by TLC; the reflux reaction time is 2-12 h;
2) And then cooling to room temperature to completely crystallize, vacuum filtering 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), washing 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 paeonol hydrazone derivatives of examples 1 to 18 were prepared by the preparation method, the compound of formula III, the compound of formula IV, and the time of reflux reaction and the yield of the final product are shown in table 2, and yellow solid products obtained when paeonol hydrazone derivatives of each example were prepared were numbered, as shown in table 2.
TABLE 2 specific substances of Compounds of formula III and formula IV, and time of reflux reaction, yield of final product, product number employed in the preparation methods of Paeonol hydrazone derivatives of examples 1 to 18
The physicochemical properties of each numbered product in table 2 are as follows:
compound I-1a:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 15.80 (s, 1H), 10.04 (s, 1H), 8.38 (s, 1H), 7.36 (t, j=8.0 hz, 2H), 7.07 (d, j=8.0 hz, 2H), 6.94 (t, j=7.2 hz, 1H), 3.94 (s, 3H), 2.48 (s, 3H).
2) HRMS (ESI) of the compound Calcd for C 15 H 15 N 4 O 6 ([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:
compound I-1b:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 15.72 (s, 1H), 9.99 (s, 1H), 8.36 (s, 1H), 7.23 (t, j=8.0 hz, 1H), 6.84-6.89 (m, 2H), 6.75 (d, j=7.2 hz, 1H), 3.94 (s, 3H), 2.46 (s, 3H), 2.28 (s, 3H).
2) HRMS (ESI) of the compound Calcd for C 16 H 17 N 4 O 6 ([M+H] + ) 361.1143; found,361.1145. Hydrogen gasThe spectrum is shown in FIG. 2.
The chemical reactions involved in the preparation of compound I-1b are:
compound I-1c:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 15.87 (s, 1H), 9.95 (s, 1H), 8.35 (s, 1H), 7.15 (d, j=8.4 hz, 2H), 6.97 (d, j=8.4 hz, 2H), 3.94 (s, 3H), 2.45 (s, 3H), 2.23 (s, 3H).
2) HRMS (ESI) of the compound Calcd for C 16 H 17 N 4 O 6 ([M+H] + ),361.1143；found,361.1148。
The chemical reactions involved in the preparation of compound I-1c are:
compound I-1d:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 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 C 15 H 14 FN 4 O 6 ([M+H] + ),365.0892；found,365.0896。
The chemical reactions involved in the preparation of compound I-1d are:
compound I-1e:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 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 C 15 H 14 FN 4 O 6 ([M+H] + ),365.0892；found,365.0893。
The chemical reactions involved in the preparation of compound I-1e are:
compound I-1f:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 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 C 15 H 14 FN 4 O 6 ([M+H] + ),365.0892；found,365.0899。
The chemical reactions involved in the preparation of compounds I-1f are:
compound I-1g:
nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 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:
compound I-1h:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 9.09 (s, 1H), 8.46 (s, 1H), 7.50 (dd, j=8.0 hz,1.6hz, 1H), 7.36-7.41 (m, 1H), 7.23 (dd, j=8.0 hz,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 C 15 H 14 ClN 4 O 6 ([M+H] + ),381.0596；found,381.0599。
The chemical reactions involved in the preparation of compound I-1h are:
compound I-1I:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 10.15 (s, 1H), 8.39 (s, 1H), 7.37 (t, J=8.0 Hz, 1H), 7.08 (t, J=2.0 Hz, 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 C 15 H 14 ClN 4 O 6 ([M+H] + ),381.0596；found,381.0601。
The chemical reactions involved in the preparation of compound I-1I are:
compound I-1j:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 8.89 (s, 1H), 8.46 (s, 1H), 7.65 (dd, J=8.0 Hz,1.6Hz, 1H), 7.40-7.44 (m, 1H), 7.21 (dd, J=8.0 Hz,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 C 15 H 14 BrN 4 O 6 ([M+H] + ),425.0091；found,425.0095。
The chemical reactions involved in the preparation of compound I-1j are:
compound I-1k:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 10.13 (s, 1H), 8.38 (s, 1H), 7.31 (t, J=8.0 Hz, 1H), 7.23 (t, J=2.0 Hz, 1H), 7.02-7.08 (m, 2H), 3.94 (s, 3H), 2.46 (s, 3H).
2) HRMS (ESI) of the compound Calcd for C 15 H 14 BrN 4 O 6 ([M+H] + ),425.0091；found,425.0093。
The chemical reactions involved in the preparation of compound I-1k are:
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compound I-1l:
nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 10.76 (s, 0.8H), 10.72 (s, 0.2H), 8.37 (s, 0.8H), 8.20 (dd, j=8.8 hz,1.2hz, 0.8H), 8.05 (s, 0.2H), 7.85 (dd, j=8.8 hz,1.2hz, 0.2H), 7.77 (dd, j=8.8 hz,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:
compound I-1m:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data spectrum of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 10.39 (s, 1H), 8.40 (s, 1H), 7.90 (t, j=2.4 hz, 1H), 7.71-7.73 (m, 1H), 7.63 (t, j=8.4 hz, 1H), 7.43-7.46 (m, 1H), 3.95 (s, 3H), 2.48 (s, 3H).
2) HRMS (ESI) of the compound Calcd for C 15 H 14 N 5 O 8 ([M+H] + ),392.0837；found,392.0841。
The chemical reactions involved in the preparation of compound I-1m are:
compound I-1n:
nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 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=8.8 Hz, 1.2H), 7.20 (d, J=8.8 Hz, 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 compounds I-1n are:
compound I-2a:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 14.03 (s, 1H), 9.65 (s, 1H), 8.15 (s, 1H), 7.32 (t, j=8.8 hz, 2H), 7.06 (d, j=8.8 hz, 2H), 6.88 (t, j=7.2 hz, 1H), 6.75 (s, 1H), 3.93 (s, 3H), 2.39 (s, 3H).
2) HRMS (ESI) of the compound Calcd for C 15 H 16 N 3 O 4 ([M+H] + ),302.1135；found,302.1142。
The chemical reactions involved in the preparation of compound I-2a are:
compound I-2b:
nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 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=2.4 hz, 0.2H), 7.88 (t, j=2.4 hz, 0.8H), 7.73 (dd, j=7.6 hz,2.4hz, 0.2H), 7.68 (dd, j=7.6 hz,2.4hz, 0.8H), 7.59 (d, j=8.4 hz, 0.2H), 7.57 (d, j=8.4 hz, 0.8H), 7.46 (dd, j=7.6 hz,2.4hz, 0.8H), 7.42 (dd, j=7.6 hz,2.4 hz), 7.6 (s, 6.4H), 7.82 (d, j=8.6 hz, 0.4H), 7.82 (s, 3.4H), 3.9 (d, j=8.6H), 0.4H).
The chemical reactions involved in the preparation of compound I-2b are:
compound I-3a:
nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 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:
compound I-3b:
the physicochemical properties of this compound are as follows:
1) Nuclear magnetic resonance data of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: delta 13.88 (s, 1H), 10.11 (s, 1H), 7.85 (t, J=2.4 Hz, 1H), 7.77 (d, J=9.2 Hz, 1H), 7.69 (dd, J=8.0 Hz,1.6Hz, 1H), 7.60 (t, J=8.0 Hz, 1H), 7.41 (dd, J=8.0 Hz,1.6Hz, 1H), 6.84 (d, J=8.8 Hz, 1H), 3.91 (s, 3H), 2.44 (s, 3H).
2) HRMS (ESI) of the compound Calcd for C 15 H 15 N 4 O 6 ([M+H] + ),347.0986；found,347.0991。
The chemical reactions involved in the preparation of compound I-3b are:
in addition, the paeonol hydrazone derivatives of example 1 can also be prepared by a method comprising the following steps:
1) Weighing 1mmol of 3, 5-dinitropaeonol and 1mmol of phenylhydrazine hydrochloride, placing the 3, 5-dinitropaeonol and the phenylhydrazine hydrochloride 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, generating a large amount of solids by the reflux reaction, and tracking and detecting that the raw materials are completely reacted by TLC;
2) And then cooling to room temperature to completely crystallize, vacuum filtering 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), washing 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:
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 pesticide of this example, the effective insecticidal component is replaced with the paeonol hydrazone derivative of the corresponding example in examples 1 to 18 by referring to the existing preparation method of the pesticide. For example, the active ingredient in the commercially available toosendanin botanical insecticide can be replaced by the paeonol hydrazone derivatives of the corresponding examples in examples 1 to 18 with equal concentration.
Experimental example
The experimental example is an activity measurement experiment of spodoptera littoralis which kills lepidoptera pest cordyceps sinensis.
1. Test compound: paeonol hydrazone derivatives of examples 1 to 18.
2. Positive control: a commercial botanical pesticide, toosendanin (Toosendanin).
3. Test organism: spodoptera frugiperda at early age (Spodoptera frugiperda).
4. The measuring method comprises the following steps: the method adopts a small She Dietian addition method to feed poison, and after 48 hours, normal corn leaves are replaced to feed until eclosion, and the detailed method is as follows:
(1) the test insects are early-stage spodoptera frugiperda of three ages, a small leaf dish adding method is adopted, toosendanin is used as a positive control, acetone is used as a blank control, and the concentration of a measured sample is 1mg/mL;
(2) three repeats are arranged on each sample, 10 healthy and uniform-sized spodoptera frugiperda at early stage of three ages are selected from each repeat, and are fed into a culture dish with the diameter of 9cm, and a layer of filter paper is paved at the bottom of the culture dish so as to preserve moisture;
(3) fresh corn leaves were cut into 1X 1cm pieces 2 Immersing the small leaf disc in the pre-prepared sample liquid medicine and the control liquid medicine for 3 seconds, naturally airing, feeding the test insects, adding the small leaf disc in time after the test insects eat the small leaf disc, and feeding normal leaves until eclosion occurs after 48 hours of feeding;
(4) feeding conditions: the temperature is 25+/-2 ℃, the relative humidity is 65-80%, the illumination time is 12h, and the darkness time is 12h;
(5) regularly recording the feeding amount, the number of mouths, the symptoms and the like of the test insects, and calculating the corrected mortality (%) of the test insects in different periods according to the following formula:
5. the insecticidal activity was measured as shown in Table 3.
TABLE 3 determination of the Activity of the Paeonol hydrazone derivatives of examples 1 to 18
As shown in the data of Table 3, the paeonol hydrazone derivatives have remarkable control effect on spodoptera frugiperda (Spodoptera frugiperda), wherein the control effect of part of paeonol hydrazone derivatives on spodoptera frugiperda is superior to that of a commercial plant source pesticide toosendanin, and can be used for preparing the plant source pesticide.

Claims (8)

1. The application of paeonol hydrazone derivatives in preventing and controlling spodoptera frugiperda is characterized in that: the paeonol hydrazone derivative has a structure shown in a formula I:
in the formula I, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y is the same asNitro or X, Y and hydrogen; r is R 1 、R 2 、R 3 Are respectively and independently selected from hydrogen and R 4 One of the following; the R is 4 is-F, -Cl, -Br, nitro or alkyl.
2. The use of paeonol hydrazone derivatives according to claim 1 for controlling spodoptera frugiperda, characterized in that: the alkyl group has 1 to 3 carbon atoms.
3. Use of paeonol hydrazone derivatives according to claim 1 or 2 for controlling spodoptera frugiperda, characterized in that: r is R 2 Is hydrogen.
4. The use of paeonol hydrazone derivatives according to claim 3 for controlling spodoptera frugiperda, characterized in that: r is R 1 Is R 4 、R 3 Is hydrogen or R 1 Is hydrogen, R 3 Is R 4 。
5. The use of paeonol hydrazone derivatives according to claim 3 for controlling spodoptera frugiperda, characterized in that: r is R 1 、R 3 All are R 4 。
6. The use of paeonol hydrazone derivatives as claimed in claim 5 for controlling spodoptera frugiperda, characterized in that: has a structure as shown in formula II:
in formula II, R 1 、R 3 All are R 4 。
7. The use of paeonol hydrazone derivatives as claimed in claim 6 for controlling spodoptera frugiperda, characterized in that: r is R 1 is-F, -Cl, -Br or nitro, R 3 Is hydrogen.
8. The use of paeonol hydrazone derivatives according to claim 1 for controlling spodoptera frugiperda, characterized in that: the preparation method of the paeonol hydrazone derivative comprises the following steps: reflux reaction is carried out 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;
in the formula III, X is hydrogen, Y is nitro or X is nitro, Y is hydrogen or X, Y and X, Y are simultaneously nitro;
in formula IV, R 1 、R 2 、R 3 Are respectively and independently selected from hydrogen and R 4 One of the following; the R is 4 is-F, -Cl, -Br, nitro or alkyl.
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