CN112321455B - Paeonol acylhydrazone derivative, preparation method and application thereof, and pesticide - Google Patents
Paeonol acylhydrazone derivative, preparation method and application thereof, and pesticide Download PDFInfo
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Abstract
The invention relates to a paeonol acylhydrazone derivative, a preparation method and application thereof, and an insecticide, and belongs to the technical field of insecticides. The paeonol hydrazone derivative has a structure shown in a formula I, wherein X, Y is independently selectedFrom hydrogen, R 2 One of R 2 Is one of-Cl and nitro; r is R 1 Selected from C 1 ～ 7 Alkyl, aryl, heteroaryl, cyano-substituted C 1 ～ 7 One of the alkyl groups. The paeonol acylhydrazone derivative has remarkable spodoptera frugiperda killing activity, and can be used as a medicament for preparing botanical pesticides.
Description
Technical Field
The invention relates to a paeonol acylhydrazone derivative, a preparation method and application thereof, and an insecticide, and belongs to the technical field of insecticides.
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 paeonol acylhydrazone derivatives which have good control effect on spodoptera frugiperda.
The invention also provides a preparation method and application of the paeonohydrazone derivative.
In addition, the invention also provides an insecticide adopting the paeonohydrazone derivative.
In order to achieve the above purpose, the technical scheme adopted by the paeonol acylhydrazone derivative is as follows:
a paeonol acylhydrazone derivative has a structure shown in a formula I:
in formula I, X, Y is independently selected from hydrogen, R 2 One of R 2 is-Cl or nitro;
R 1 selected from C 1～7 Alkyl, aryl, heteroaryl, cyano-substituted C 1～7 One of the alkyl groups.
The paeonol acylhydrazone derivative has remarkable spodoptera frugiperda killing activity, and can be used as a novel medicament for preparing novel botanical pesticides. The final corrected mortality of the paeonol acylhydrazone derivatives measured by a small leaf dish adding method at the concentration of 1mg/mL is more than 25%, and is generally more than 35%, and the highest mortality can be more than 70%.
Further, X is selected from one of-Cl and nitro, Y is hydrogen, or X is selected from one of hydrogen and nitro, Y is nitro. At this time, the paeonol hydrazone derivative of the invention is shown as a formula I, wherein X is one of-Cl and nitro, Y is hydrogen, R 1 Selected from C 1～7 Alkyl, aryl, heteroaryl, cyano-substituted C 1～7 One of the alkyl groups. Or in the formula I, X is selected from one of hydrogen and nitro, Y is nitro, R 1 Selected from C 1～7 Alkyl, aryl, heteroaryl, cyano-substituted C 1～7 One of the alkyl groups.
Specifically, the C 1～7 The alkyl group may be methyl (Me), n-butyl (n-butyl) or n-heptyl (n-heptyl). Further, when there is no substituent, the C 1～7 Alkyl is C 4～7 An alkyl group.
Further, the aryl is phenyl (Ph), pyridyl or phenyl substituted by substituent; the substituent in the phenyl substituted by the substituent is C 1～3 Alkoxy, hydroxy, amino, -F, -Cl. The phenyl substituted by the substituent is phenyl substituted by a substituent. Further, the substituent is para to the substituent in the phenyl group substituted by the substituent. Further, the Pyridyl group is a 3-Pyridyl group (3-Pyridyl) or a 4-Pyridyl group (4-Pyridyl).
Further, the phenyl group substituted by the substituent is p-methoxyphenyl ((p-OMe) Ph), o-hydroxyphenyl ((o-OH) Ph), p-hydroxyphenyl (p-OH) Ph, p-aminophenyl ((p-NH) 2 ) Ph), p-fluorophenyl ((p-F) Ph), o-chlorophenyl ((o-Cl) Ph), or p-chlorophenyl ((p-Cl) Ph).
Further, the heteroaryl group is a five membered ring heteroaryl group. Still further, the heteroatom of the five membered ring heteroaryl is sulfur. The five-membered ring heteroaryl is thienyl. Further, the five-membered ring heteroaryl is 2-thienyl (2-thienyl).
The cyano group substituted C 1～7 The alkyl group is preferably cyano-substituted methyl, i.e., cyanomethylene (cyanomethyl).
The preparation method of the paeonol acylhydrazone derivative adopts the following technical scheme:
the preparation method of the paeonol hydrazone derivative comprises the following steps: carrying out reflux reaction on a compound shown in a formula II and a compound shown in a formula III;
in formula II, X, Y is independently selected from hydrogen, R 2 One of R 2 is-Cl or nitro;
in formula III, R 1 Selected from C 1～7 Alkyl, aryl, heteroaryl, cyano-substituted C 1～7 One of the alkyl groups.
The preparation method of the paeonol hydrazone derivatives has simple process, the yield of the paeonol hydrazone derivatives is more than 38%, and the production cost of the paeonol hydrazone derivatives can be reduced.
Further, the reaction is carried out in a solvent. The product does not need column chromatography separation after the reflux reaction is finished, because a large amount of solid products are generated in the reaction process, the crude product is obtained by direct filtration, the separation cost is reduced to a great extent, and the mass production is convenient.
Further, the reflux reaction uses ethanol as a solvent and glacial acetic acid as a catalyst.
Further, the compound of formula II is 5-chloropaeonol, 3-nitropaeonol, 5-nitropaeonol or 3, 5-dinitropaeonol. Wherein, the 5-chloropaeonol is prepared by adopting the method comprising the following steps: the paeonol and N-chlorosuccinimide are reacted in a solvent at 50-70 ℃. The molar ratio of paeonol to N-chlorosuccinimide is 1:1-1.4. The preparation method of the 5-rate paeonol also comprises the steps of adding water and an organic solvent into a reaction system for extraction, washing an extracted organic phase, removing the organic solvent after the organic phase is dehydrated, and separating by column chromatography. Preferably, the organic solvent is ethyl acetate. The washing is carried out by adopting saturated sodium carbonate solution and saturated saline water in turn. The dehydration adopts anhydrous sodium sulfate. The organic solvent is removed by evaporation.
Further, in formula III, the C 1～7 Alkyl is methyl (Me), n-butyl (n-butyl) or n-heptyl (n-heptyl). The aryl is phenyl (Ph), pyridyl or phenyl substituted by substituent. Further, the substituent in the phenyl substituted by the substituent is C 1～3 Alkoxy, hydroxy, amino, -F, -Cl. Further, the substituent group in the phenyl group substituted by the substituent group is located at the para position. The substituent-substituted phenyl is a substituent-substituted phenyl, such as p-chlorophenyl.
Further, the heteroaryl group is a five membered ring heteroaryl group. Still further, the heteroatom of the five membered ring heteroaryl is sulfur. The five-membered ring heteroaryl is thienyl. The thienyl group is preferably 2-thienyl.
Further, the compound of the formula III is one of acethydrazide, valeryl hydrazide, octanoyl hydrazide, cyano acethydrazide, benzoyl hydrazine, p-methoxy benzoyl hydrazine, 2-hydroxy benzoyl hydrazine, 4-hydroxy benzoyl hydrazine, p-amino benzoyl hydrazine, p-fluoro benzoyl hydrazine, 2-chlorobenzoyl hydrazine, 4-chlorobenzoyl hydrazide, 2-thiophene formyl hydrazine, nicotinic acid acyl hydrazine and isoniazid.
The application of the paeonol acylhydrazone derivative in spodoptera litura killing activity adopts the following technical scheme:
an application of the paeonohydrazone derivatives in preventing and controlling spodoptera frugiperda.
The paeonohydrazone derivative has remarkable insecticidal activity when being used for preventing and controlling spodoptera frugiperda.
The technical scheme adopted by the pesticide of the invention is as follows:
an insecticide contains any one of the above paeonol hydrazone derivatives as effective component.
The pesticide contains the paeonohydrazone derivative and has obvious spodoptera littoralis killing activity.
Further, the pesticide of the present invention is a botanical pesticide.
Drawings
FIG. 1 is a hydrogen spectrum of a compound I-a prepared in an example of a preparation method of paeonol hydrazone derivatives;
FIG. 2 is a hydrogen spectrum of the compound I-b 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 21 of paeonol acylhydrazone derivatives
The paeonol acylhydrazone derivatives of examples 1 to 21 have the structure shown in formula I:
x, Y, R of the paeonol hydrazone derivatives of the examples are of formula I 1 The corresponding groups are shown in Table 1.
TABLE 1 paeonol acylhydrazone derivatives of examples 1 to 21 of formula X, Y, R 1 Corresponding groups
Examples of the preparation method of Paeonol acylhydrazone derivatives
The 5-chlorophenol used in the examples of the preparation method of paeonol acylhydrazone derivatives can be prepared according to the following method:
1mmol of paeonol (compound 1) was weighed into a 50mL flask, N' -dimethylformamide (DMF, 10 mL) was added thereto, and then the mixture was left at room temperature (r.t.), N-chlorosuccinimide (NCS, 1.2 mmol) was added thereto, and then the reaction was continued at 60℃for 48 hours, followed by TLC detection. To the reaction solution was added water (30 mL), followed by extraction with ethyl acetate 3 times (60 mL of ethyl acetate each time), and the organic phases were combined. The organic phase was washed with a saturated sodium carbonate solution (30 mL. Times.3), saturated brine (30 mL) and dried over anhydrous sodium sulfate. The solvent was then removed under reduced pressure, and the product 2 was isolated by silica gel column chromatography in 73% yield. The physicochemical properties of product 2 are as follows:
1) Pale yellow solid, melting point 112-113 ℃.
2) Nuclear magnetic resonance spectrum 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: delta 12.65 (s, 1H), 7.69 (s, 1H), 6.47 (s, 1H), 3.92 (s, 3H), 2.55 (s, 3H).
3) ESI-MS, M/z (%) 201 ([ M+H) of the compound] + ,100)。
The chemical reaction involved in the preparation method of the 5-chloropaeonol is as follows:
the 5-chloropaeonol can be prepared according to the method, and can also be directly purchased and used as a commercial product.
The 3-nitropaeonol and 5-nitropaeonol adopted in the examples of the preparation method of the paeonol acylhydrazone derivatives can be prepared according to the following methods: paeonol (1 mmol) was dissolved in 5mL of concentrated H at-30deg.C 2 SO 4 After that, 1mmol of concentrated HNO is added 3 Continuous reverseShould be 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 products 3 and 4 by silica gel column chromatography.
Wherein, the physicochemical properties of the product 3 are as follows:
1) Pale yellow solid, melting point 132-133 ℃, yield 13%.
2) Nuclear magnetic resonance spectrum 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 physicochemical properties of product 4 are as follows:
1) Pale yellow solid, melting point 125-126 ℃, yield 29%.
2) Nuclear magnetic resonance spectrum 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 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 acylhydrazone derivatives can be prepared by the following method:
paeonol (1 mmol) was dissolved in 5mL of concentrated H at-30deg.C 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 5. Physicochemical properties of product 5 such asThe following steps:
1) Pale yellow solid, melting point 129-130 ℃, yield 74%.
2) Nuclear magnetic resonance spectrum 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 paeonol hydrazone derivatives involves the chemical reaction that:
besides the preparation method, 3-nitropaeonol, 5-nitropaeonol and 3, 5-dinitropaeonol can also be prepared by adopting other prior art or directly purchased and used in commercial products.
The preparation method of the paeonol hydrazone derivatives of examples 1 to 21 comprises the following steps:
1) Weighing 1mmol of a compound of formula II and 1mmol of a compound of formula III, placing the compounds into a 50mL flask, adding 10mL of absolute ethyl alcohol to dissolve the compounds, then dropwise adding 1-2 drops of glacial acetic acid, and carrying out reflux reaction to generate a large amount of solids, wherein TLC (thin layer chromatography) tracking detection is carried out until the raw materials are completely reacted; the reflux reaction time is 2-8 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 the product. The yield was then calculated.
When the paeonol acylhydrazone derivatives of examples 1 to 21 were prepared by the preparation method, the compound of formula II, the compound of formula III, the reflux reaction time and the yield of the final product are shown in table 2, and the products obtained when the paeonol acylhydrazone derivatives of each example were prepared are numbered, as shown in table 2.
TABLE 2 specific substances of Compounds of formulas II and III, time of reflux reaction, yield of final product, product number employed in the preparation methods of Paeonol acylhydrazone derivatives of examples 1 to 21
The physicochemical properties of each numbered product in table 2 are as follows:
compound I-a:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 232-233 ℃.
2) Nuclear magnetic resonance 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 14.54 (s, 1H), 11.11 (s, 1H), 8.20 (s, 1H), 6.74 (s, 1H), 3.93 (s, 3H), 2.38 (s, 3H), 2.08 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 11 H 14 N 3 O 5 ([M+H] + ) 268.0928; found,268.0931. The hydrogen spectrum is shown in FIG. 1.
The chemical reactions involved in the preparation of compound I-a are:
compound I-b:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 218-219 ℃.
2) Nuclear magnetic resonance 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 14.57 (s, 1H), 11.07 (s, 1H), 8.20 (s, 1H), 6.74 (s, 1H), 3.93 (s, 3H), 2.35-2.38 (m, 5H), 1.54-1.61 (m, 2H), 1.28-1.37 (m, 2H), 0.92 (t, J=7.6 Hz, 3H).
3) HRMS (ESI) of the compound Calcd for C 14 H 20 N 3 O 5 ([M+H] + ) 310.1397; found,310.1399. The hydrogen spectrum is shown in FIG. 2.
The chemical reactions involved in the preparation of compound I-b are:
compound I-c:
the physicochemical properties of this compound are as follows:
1) Pale yellow solid, melting point 153-154 ℃.
2) Nuclear magnetic resonance spectrum of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: 14.56 (s, 1H), 11.05 (s, 1H), 8.20 (s, 1H), 6.74 (s, 1H), 3.93 (s, 3H), 2.38 (s, 3H), 2.31-2.35 (m, 2H), 1.55-1.62 (m, 2H), 1.25-1.31 (m, 8H), 0.88 (t, j=7.2 hz, 3H).
3) HRMS (ESI) of the compound Calcd for C 17 H 26 N 3 O 5 ([M+H] + ),352.1867；found,352.1870。
The chemical reactions involved in the preparation of compounds I-c are:
compound I-d:
the physicochemical properties of this compound are as follows:
1) Yellow solid with a melting point of 242-243 ℃.
2) Nuclear magnetic resonance 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 14.13 (s, 1H), 11.47 (s, 1H), 8.23 (s, 1H), 6.77 (s, 1H), 3.96 (s, 2H), 3.94 (s, 3H), 2.39 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 12 H 13 N 4 O 5 ([M+H] + ),293.0880；found,293.0873。
The chemical reactions involved in the preparation of compounds I-d are:
compound I-e:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point 258-259 ℃.
2) Nuclear magnetic resonance 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 14.68 (s, 1H), 11.53 (s, 1H), 8.28 (s, 1H), 7.95 (d, j=7.2 hz, 2H), 7.62-7.66 (m, 1H), 7.53-7.57 (m, 2H), 6.80 (s, 1H), 3.96 (s, 3H), 2.52 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 16 N 3 O 5 ([M+H] + ),330.1084；found,330.1085。
The chemical reactions involved in the preparation of compounds I-e are:
compounds I-f:
the physicochemical properties of this compound are as follows:
1) Pale yellow solid with melting point 264-265 ℃.
2) Nuclear magnetic resonance 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 14.73 (s, 1H), 11.33 (s, 1H), 8.26 (s, 1H), 7.95 (d, j=8.8 hz, 2H), 7.06-7.10 (m, 2H), 6.78 (s, 1H), 3.95 (s, 3H), 3.85 (s, 3H), 2.50 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 17 H 18 N 3 O 6 ([M+H] + ),360.1190；found,360.1196。
The chemical reactions involved in the preparation of compounds I-f are:
compound I-g:
the physicochemical properties of this compound are as follows:
1) Yellow solid, melting point 243-244 ℃.
2) Nuclear magnetic resonance 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 14.43 (s, 1H), 11.73 (s, 1H), 11.60 (s, 1H), 8.28 (s, 1H), 7.97 (dd, J=8.0 Hz,1.6Hz, 1H), 7.43-7.48 (m, 1H), 6.98-7.05 (m, 2H), 6.81 (s, 1H), 3.96 (s, 3H), 2.45 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 16 N 3 O 6 ([M+H] + ),346.1034；found,346.1033。
The chemical reactions involved in the preparation of compounds I-g are:
compound I-h:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 288-289 ℃.
2) Nuclear magnetic resonance 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 14.76 (s, 1H), 11.23 (s, 1H), 10.20 (s, 1H), 8.26 (s, 1H), 7.85 (dd, j=6.4 hz,2.0hz, 2H), 6.87-6.90 (m, 2H), 6.77 (s, 1H), 3.95 (s, 3H), 2.49 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 16 N 3 O 6 ([M+H] + ),346.1034；found,346.1030。
The chemical reactions involved in the preparation of compounds I-h are:
compound I-I:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 262-263 ℃.
2) Nuclear magnetic resonance 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 14.88 (s, 1H), 11.02 (s, 1H), 8.25 (s, 1H), 7.71 (d, j=8.8 hz, 2H), 6.77 (s, 1H), 6.60-6.63 (m, 2H), 5.92 (s, 2H), 3.95 (s, 3H), 2.48 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 17 N 4 O 5 ([M+H] + ),345.1193；found,345.1195。
The chemical reactions involved in the preparation of compounds I-I are:
compound I-j:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 251-252 ℃.
2) Nuclear magnetic resonance 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 14.64 (s, 1H), 11.52 (s, 1H), 8.28 (s, 1H), 8.05 (dd, J=8.4 Hz,5.6Hz, 2H), 7.37-7.42 (m, 2H), 6.79 (s, 1H), 3.95 (s, 3H), 2.52 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 15 FN 3 O 5 ([M+H] + ),348.0990；found,348.0996。
The chemical reactions involved in the preparation of compounds I-j are:
compound I-k:
the physicochemical properties of this compound are as follows:
1) Yellow solid, melting point 241-242 ℃.
2) Nuclear magnetic resonance 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 14.46 (s, 1H), 11.81 (s, 1H), 8.26 (s, 1H), 7.65 (dd, J=7.2 Hz,2.4Hz, 1H), 7.55-7.61 (m, 2H), 7.50 (dd, J=7.2 Hz,2.4Hz, 1H), 6.81 (s, 1H), 3.96 (s, 3H), 2.44 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 15 ClN 3 O 5 ([M+H] + ),364.0695；found,364.0699。
The chemical reactions involved in the preparation of compounds I-k are:
compound I-l:
the physicochemical properties of this compound are as follows:
1) Yellow solid with a melting point of 242-243 ℃.
2) Nuclear magnetic resonance 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 14.58 (s, 1H), 11.54 (s, 1H), 8.27 (s, 1H), 7.98 (dd, J=6.4 Hz,2.0Hz, 2H), 7.61-7.63 (m, 2H), 6.79 (s, 1H), 3.95 (s, 3H), 2.51 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 15 ClN 3 O 5 ([M+H] + ),364.0695；found,364.0701。
The chemical reactions involved in the preparation of compounds I-l are:
compound I-m:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 246-247 ℃.
2) Nuclear magnetic resonance 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 14.48 (s, 1H), 11.44 (s, 1H), 8.27 (s, 1H), 8.07 (dd, J=4.0 Hz,1.2Hz, 1H), 7.94 (dd, J=5.2 Hz,1.2Hz, 1H), 7.27 (dd, J=5.2 Hz,3.6Hz, 1H), 6.79 (s, 1H), 3.95 (s, 3H), 2.51 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 14 H 14 N 3 O 5 S([M+H] + ),336.0649；found,336.0645。
The chemical reactions involved in the preparation of compounds I-m are:
compound I-n:
the physicochemical properties of this compound are as follows:
1) Yellow solid with a melting point of 256-257 ℃.
2) Nuclear magnetic resonance 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 14.54 (s, 1H), 11.71 (s, 1H), 9.09 (d, J=2.4 Hz, 1H), 8.80 (dd, J=4.8 Hz,1.6Hz, 1H), 8.28-8.31 (m, 2H), 7.61 (dd, J=8.0 Hz,4.8Hz, 1H), 6.82 (d, J=2.4 Hz, 1H), 3.96 (s, 3H), 2.53 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 15 H 15 N 4 O 5 ([M+H] + ),331.1037；found,331.1035。
The chemical reactions involved in the preparation of compounds I-n are:
compound I-o:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 253-254 ℃.
2) Nuclear magnetic resonance 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 14.46 (s, 1H), 11.76 (s, 1H), 8.81 (dd, j=4.4 hz,2.0hz, 2H), 8.29 (s, 1H), 7.86 (dd, j=4.4 hz,2.0hz, 2H), 6.81 (s, 1H), 3.96 (s, 3H), 2.53 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 15 H 15 N 4 O 5 ([M+H] + ),331.1037；found,331.1031。
The chemical reactions involved in the preparation of compound I-o are:
compound II-a:
the physicochemical properties of this compound are as follows:
1) Pale yellow solid, melting point 233-234 ℃.
2) Nuclear magnetic resonance 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 14.84 (s, 1H), 11.14 (s, 1H), 7.75 (d, j=9.2 hz, 1H), 6.79 (d, j=9.2 hz, 1H), 3.90 (s, 3H), 2.37 (s, 3H), 2.07 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 11 H 14 N 3 O 5 ([M+H] + ),268.0928；found,268.0933。
The chemical reactions involved in the preparation of compound II-a are:
compound II-b:
the physicochemical properties of this compound are as follows:
1) Yellow solid with melting point of 253-254 ℃.
2) Nuclear magnetic resonance 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 14.96 (s, 1H), 11.52 (s, 1H), 7.94 (d, j=7.2 hz, 2H), 7.82 (d, j=8.8 hz, 1H), 7.65 (t, j=7.6 hz, 1H), 7.57 (t, j=7.6 hz, 2H), 6.83 (d, j=9.2 hz, 1H), 3.92 (s, 3H), 2.51 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 16 N 3 O 5 ([M+H] + ),330.1084；found,330.1085。
The chemical reactions involved in the preparation of compound II-b are:
compound III-a:
the physicochemical properties of this compound are as follows:
1) Pale yellow solid, melting point 239-240 ℃.
2) Nuclear magnetic resonance 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 11.57 (s, 1H), 8.45 (s, 1H), 3.94 (s, 3H), 2.48 (s, 3H), 2.11 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 11 H 13 N 4 O 7 ([M+H] + ),313.0779；found,313.0783。
The chemical reaction involved in the preparation of compound III-a is of the formula:
compound III-b:
the physicochemical properties of this compound are as follows:
1) Pale yellow solid with a melting point of 250-251 ℃.
2) Nuclear magnetic resonance spectrum of the compound 1 H NMR,400 MHz) characterization:
deuterated DMSO as solvent, TMS as internal standard, wherein each peak was assigned to: δ 11.98 (s, 1H), 8.52 (s, 1H), 7.97 (d, j=7.6 hz, 2H), 7.68 (t, j=7.6 hz, 1H), 7.58 (t, j=7.6 hz, 2H), 3.96 (s, 3H), 2.62 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 15 N 4 O 7 ([M+H] + ),375.0935；found,375.0937。
The chemical reactions involved in the preparation of compound III-b are:
compound IV-a:
the physicochemical properties of this compound are as follows:
1) Pale yellow solid, melting point 210-211 ℃.
2) Nuclear magnetic resonance 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 13.79 (s, 1H), 11.33 (s, 1H), 7.94 (d, j=7.2 hz, 2H), 7.65 (s, 1H), 7.62 (d, j=7.6 hz, 1H), 7.56 (t, j=7.6 hz, 2H), 6.69 (s, 1H), 3.38 (s, 3H), 2.45 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 16 ClN 2 O 3 ([M+H] + ),319.0844；found,319.0847。
The chemical reactions involved in the preparation of compound IV-a are:
compound IV-b:
the physicochemical properties of this compound are as follows:
1) Pale yellow solid, melting point 203-204 ℃.
2) Nuclear magnetic resonance 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 13.75 (s, 1H), 11.33 (s, 1H), 8.00-8.03 (m, 2H), 7.64 (s, 1H), 7.35-7.41 (m, 2H), 6.68 (s, 1H), 3.88 (s, 3H), 2.45 (s, 3H).
3) HRMS (ESI) of the compound Calcd for C 16 H 15 ClFN 2 O 3 ([M+H] + ),337.0750；found,337.0755。
The chemical reactions involved in the preparation of the compounds IV-b are:
examples of insecticides
The pesticide of the embodiment is a botanical pesticide, wherein the effective component is any one of paeonol hydrazone derivatives of the embodiments 1 to 21. In the preparation of the pesticide of this example, the preparation method of the existing pesticide is referred to, and the effective ingredient is replaced by the paeonol hydrazone derivatives of the corresponding examples in examples 1 to 21. For example, the effective components in the commercial toosendanin botanical insecticide can be replaced by the paeonol hydrazone derivatives of the corresponding examples in examples 1 to 21 with equal concentration.
Experimental example
The experimental example is an activity measurement experiment of spodoptera littoralis of lepidoptera pest killing cordyceps sinensis:
1. test compound: paeonol acylhydrazone derivatives of examples 1 to 21.
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 21 against Spodoptera frugiperda
As shown in the data of Table 3, the paeonohydrazone derivatives have remarkable control effect on spodoptera frugiperda (Spodoptera frugiperda), wherein the control effect of part of the paeonohydrazone derivatives on spodoptera frugiperda is superior to that of a commercial plant source pesticide toosendanin, and the paeonohydrazone derivatives can be used for preparing plant source pesticides.
Claims (8)
1. A paeonol acylhydrazone derivative is characterized in that: has a structure as shown in formula I:
in the formula I, X, Y are hydrogen and R 1 Selected from C 4 ～ 7 Alkyl-and cyano-substituted C 1 ～ 7 One of the alkyl groups;
or X, Y is independently selected from one of-Cl or nitro, R 1 Selected from C 1 ～ 7 Alkyl, aryl, heteroaryl, cyano-substituted C 1 ～ 7 One of the alkyl groups;
or X, Y one is hydrogen, one is-Cl or nitro, R 1 Selected from C 1 ～ 7 Alkyl, aryl, heteroaryl, cyano-substituted C 1 ～ 7 One of the alkyl groups;
the aryl is phenyl, pyridyl or phenyl substituted by substituent; the substituent in the phenyl substituted by the substituent is C 1 ～ 3 Alkoxy, hydroxy, amino, -F, -Cl; the pyridyl is 3-pyridyl or 4-pyridyl; the heteroaryl is a five membered ring heteroaryl.
2. The paeonol acylhydrazone derivative according to claim 1, wherein: x is selected from one of-Cl and nitro, Y is hydrogen, or X is selected from one of hydrogen and nitro, Y is nitro.
3. The paeonol acylhydrazone derivative according to claim 1, wherein: the C is 1 ～ 7 Alkyl is methyl, n-butyl or n-heptyl.
4. The paeonol acylhydrazone derivative according to claim 1, wherein: the phenyl substituted by the substituent is p-methoxyphenyl, m-hydroxyphenyl, p-aminophenyl, p-fluorophenyl, m-chlorophenyl or p-chlorophenyl.
5. The paeonol acylhydrazone derivative according to claim 1, wherein: the five-membered ring heteroaryl is 2-thienyl.
6. A process for the preparation of paeonol acylhydrazone derivatives as claimed in claim 1, characterized in that: the method comprises the following steps: carrying out reflux reaction on a compound shown in a formula II and a compound shown in a formula III;
x, Y in formula II and R in formula III 1 The method of claim 1.
7. Use of paeonohydrazone derivatives as claimed in claim 1 for controlling spodoptera frugiperda.
8. An insecticide, characterized in that: the effective insecticidal component of the insecticide comprises the paeonol hydrazone derivative according to any one of claims 1 to 5.
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