CN114230484A - Oxime ester-containing cyclopentyl acetate compound and preparation and application thereof - Google Patents
Oxime ester-containing cyclopentyl acetate compound and preparation and application thereof Download PDFInfo
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- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
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- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
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Abstract
The invention discloses an oxime ester-containing cyclopentyl acetate compound and preparation and application thereof, wherein the structural formula of the oxime ester-containing cyclopentyl acetate compound is shown as a formula I:
Description
Technical Field
The invention belongs to the technical field of agricultural pest control, and particularly relates to preparation of a cyclopentyl acetate compound containing oxime ester and application of the compound in agricultural pest control.
Background
Aphids are agricultural pests with serious harm and have the characteristics of numerous varieties, rapid propagation, easy generation of resistance and the like. A series of problems such as drug resistance and ecological environment pollution brought by the traditional pesticide for preventing and treating aphids are more and more emphasized by people. Therefore, there is a need to develop efficient, environmentally friendly new green aphid control and to ensure rapid development of modern high quality agriculture.
Methyl dihydrojasmonate is a natural product containing a cyclopentanone structure, and belongs to one of jasmonic acid compounds in plant growth regulators. As a hormone in plants, it can induce the synthesis of some special proteins in plants and avoid the damage of the undamaged plant tissues. The jasmonic acid compounds can directly or indirectly resist pests by inducing plants to produce factors which influence the normal physiological activities of pests, such as compounds with the effects of resisting digestion, resisting nutrition and toxicity of the pests and the like. In addition, methyl jasmonate can induce plants to produce compounds that attract parasitic or predatory natural enemies. Methyl jasmonate can interfere with aphid targeting, feeding, etc. (Slesak, E.et al.J Chem Ecol.2001,27: 2529-. However, few studies have been made on whether jasmonates can produce a direct repellent effect on aphids via the sharp olfactory system of insects. Therefore, it is of great significance to research whether the jasmonic acid compounds can be used as potential aphid repellents for comprehensive control of aphids in modern agriculture.
The aphid pheromone (E-beta-farnesene, EBF) is a volatile substance secreted by aphids when the aphids are in danger, and can ensure that other aphids receiving the information substance can quickly escape from the site to avoid the danger. EBF can effectively drive field aphids, reduce the population density and reduce the harm to crops (Bowers W.S.et al.J.Insect Physiol.1977,23(6): 697-. EBF as an eco-friendly aphid behavior control agent candidate has important theoretical significance and potential application value in the field of modern high-quality agricultural pest control. However, the EBF structure contains unsaturated conjugated double bonds, which are easily decomposed by photooxidation in nature and further affect the field application. Therefore, it is expected that through appropriate chemical structure modification, appropriate pharmacodynamic functional fragments are introduced, and the repellent biological activity is retained or improved on the premise of improving the molecular stability.
Oxime ester compounds exhibit a wide range of physiological and pharmacological activities, such as plant virus resistance, bacteriostasis (Xialajuan et al. Fine chemistry 2017,34(07):834-840.), insecticide (Shiyujun et al. organic chemistry 2015,35(08):1785-1791.) and herbicidal activity (Lanxiang X.et al. pest Manag Sci.2020,76(6):2058-2067) due to their multiple polar functional atoms. In addition, the oxime ester fragment is also a common structure in a plurality of commercial pesticide varieties, such as trifloxystrobin, methomyl, pyribenzoxim and the like. Therefore, the oxime ester structure plays an important role in creating new pesticides, and important attention should be paid.
Disclosure of Invention
The invention aims to provide a cyclopentyl acetate compound containing oxime ester and preparation and application thereof.
The invention firstly provides an oxime ester-containing cyclopentyl acetate compound, the structural formula of which is shown in the formula I:
in the formula: r is C1-C10 straight chain or branched chain alkyl or C1-C10 alkyl chain substituted by halogen atoms at the tail end; or C3-C6 cycloalkyl, C2-C6 alkenyl chain, amino, phenyl or aryl; or alkyl, halogen, alkoxy substituted C3-C6 naphthenic base, C2-C6 alkenyl chain, amino, phenyl or aryl.
The invention also provides a preparation method of the oxime ester-containing cyclopentyl acetate compound, and the preparation process of the oxime ester-containing cyclopentyl acetate compound shown in the formula I is as follows:
reacting a compound methyl dihydrojasmonate 1 in a mixed solvent of water and tetrahydrofuran of lithium hydroxide at room temperature for 1h to obtain a compound 2, and reacting the compound 2 with geraniol in a dichloromethane solvent for 1h under the action of DCC and DMAP to obtain a compound D1. And refluxing the compound D1, hydroxylamine hydrochloride and sodium ethoxide in a mixed solvent of ethanol and water at 50 ℃ for 1.5h to obtain a compound ZJT. The compound ZJT reacts with different substituted acyl chloride in dichloromethane in the presence of triethylamine for 1.5h to obtain the target compound with the structure of the formula I.
The synthetic route of the formula I is as follows:
the cyclopentyl acetate compound containing oxime ester can be applied to the prevention and control of agricultural pests, in particular to the prevention and control of aphids.
In a specific case, the invention also provides an aphid repellent, the active component of which is the oxime ester-containing cyclopentyl acetate compound. The dosage form is a pharmaceutically acceptable dosage form; the formulation comprises at least one of missible oil, wettable powder, suspending agent, powder, soluble powder, aqueous solution, water dispersible powder, smoke agent, granules and seed coating agent.
The invention reasonably splices the drug effect fragments of the oxime ester-containing cyclopentyl acetate structure and the fat long chain, invents a class of oxime ester-containing cyclopentyl acetate compound, and has important significance for screening and discovering new modern eco-friendly insect behavior control agents.
Detailed Description
The invention is further described with reference to the following examples, but the scope of the invention is not limited thereto. The methods in the following examples are conventional methods unless otherwise specified; the materials used are commercially available from the open literature unless otherwise specified.
Example 1: preparation of cyclopentyl acetate compound containing oxime ester
50mL of water, 50mL of THF, methyl jasmonate 1(15.7g, 70mmol, 1equiv) were added to a 250mL reaction flask, 5.6g of LiOH was dissolved in water and added dropwise to the reaction flask, stirred at room temperature for 1h, and the reaction was monitored by spotting. Extraction with ethyl acetate, combining the aqueous phases, acidification with 1mol/L hydrochloric acid, further extraction with ethyl acetate 3 times, combining the organic phases, drying over anhydrous magnesium sulfate, filtration, rotary evaporation to give compound 2 as a yellow oily liquid, about 13.6g, in about 92% yield.
Geraniol (10.27g, 66.7mmol, 1equiv), DCC (13.75g, 66.7mmol, 1equiv) and DMAP (0.8g, 6.67mmol, 0.1equiv) were mixed and dissolved in 30mL DCM, compound 2(13.6g, 66.7mmol, 1equiv) was added dropwise to the reaction solution, stirred under ice bath, and the reaction was completed after 1 h. The solution appeared white turbid, the reaction was diluted with DCM and filtered to remove white solid to give a pale yellow oily liquid which was concentrated on the column after rotary evaporation, PE: EA ═ 40: 1, passing a first point, then turning 20: 1 to 10: 1 to yield 17.44g of compound D1 with a yield of about 87%.
To a 250mL reaction flask was added compound D1(10.46g, 30mmol, 1equiv), hydroxylamine hydrochloride (3.13g, 45mmol, 1.5equiv), sodium ethoxide (6.15g, 75mmol, 2.5equiv), 20mL ethanol and 20mL water, heated to 50 deg.C, refluxed for 1.5h, and the reaction monitored by TLC for 1h completion. Removing most ethanol and water by rotary evaporation, extracting by ethyl acetate, and then performing column chromatography separation, wherein the PE is selected from the following components in percentage by weight, namely EA is 30: 1-20: 1,10: 1,5: 1, separating to obtain cis-isomer (upper point) and trans-isomer (lower point). The step can also be carried out without column chromatography, and the next step is to continue separation, and the product still can be isomeric at normal temperature after separation and still is a mixture.
0.54g of ZJT (1.04g, 3mmol, 1equiv) is taken out and put into a 100mL reaction bottle, 10mL of DCM, triethylamine (0.61g, 6mmol, 2equiv) and acyl chloride (4.5mmol, 1.5equiv) are dissolved in 10mL of DCM, then the mixture is dripped into the reaction liquid in ice bath, the dripping is finished, the reaction is started, and after about 1.5h, the reaction is completed, and the color becomes yellow clear liquid. DCM is used for extraction, drying, filtration and rotary evaporation are carried out, and then column chromatography separation is carried out, wherein PE: EA is 30: 1-20: 1, obtaining light yellow oily liquid as target objects I-01-I-25, wherein the yield of the majority object is about 60-80%.
The appearance and yield of the above compounds are shown in table 1, and the nmr hydrogen spectrum data are shown in table 2.
TABLE 1 physicochemical data for oxime ester containing cyclopentyl acetate compounds (formula I)
TABLE 2 NMR data on target compounds of formula I
Example 2: oxime ester-containing cyclopentyl acetate compound has aphid repelling activity
The repellent activity of the pea aphids and the green peach aphids of the target compound is measured by using a T-type olfactometer (HDSM 3-150). More than 20 adult aphids without wings are released from a release port, and moist air passing through activated carbon and distilled water is introduced into each arm at 0.2L/min through an air pump. The test arm introduced moist air through 5 μ g of a source of oxime ester containing cyclopentyl acetate compound, the other arm served as a control arm, and the introduced moist air through a control solvent. The number of aphids on each arm at 15min of sample introduction was recorded. The olfactometer and the leather hose are cleaned by absolute ethyl alcohol, the filter paper sheet is replaced and the two arms are exchanged for use every time of repetition, and each sample experiment is repeated three times. The control group or the treatment group was counted by crossing the center of the olfactometer by 2cm, and aphids that did not cross were counted as non-reaction groups.
The corrected repellency rate was calculated as follows:
the repellent rate is (number of insects in control group-number of insects in treatment group)/(number of insects in control group + number of insects in treatment group) × 100%
All the bioassay experiments of the invention are 3 times, and the test results of the repellency activity to pea aphids and green peach aphids are shown in table 3.
TABLE 3 repellent Activity of Cyclopentylacetate with Oxime esters (5. mu.g) against Piper pisum and Myzus persicae
The results show that: the cyclopentyl acetate compound containing oxime ester has good repelling activity on the pea aphids at low concentration, for example, the repelling rate of partial compounds I-02, I-03, I-06 and the like on the pea aphids under 5 mu g dosage reaches more than 50 percent. Further research finds that the compounds generally have excellent repelling effect on the green peach aphids, and even most of the compounds show the repelling effect superior to that on the pea aphids. For example, the repellent rate of the compounds I-03, I-08, I-09 and I-11 to the green peach aphids under the dosage of 5 mu g reaches over 60 percent, and over half of the compounds have the repellent rate to the green peach aphids over 50 percent. Therefore, the cyclopentyl acetate compound containing oxime ester not only has a good repelling effect on pea aphids, but also has a better repelling activity on peach aphids, and can be used as a broad-spectrum aphid repellent to control aphids on modern agricultural crops in the future.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (4)
1. An oxime ester-containing cyclopentyl acetate compound has a structural formula shown in formula I:
in the formula: r is C1-C10 straight chain or branched chain alkyl or C1-C10 alkyl chain substituted by halogen atoms at the tail end; or C3-C6 cycloalkyl, C2-C6 alkenyl chain, amino, phenyl or aryl; or alkyl, halogen, alkoxy substituted C3-C6 naphthenic base, C2-C6 alkenyl chain, amino, phenyl or aryl.
2. The preparation method of the oxime ester-containing cyclopentyl acetate compound (formula I) as claimed in claim 1 comprises the following steps:
reacting a compound methyl dihydrojasmonate 1 in a mixed solvent of water and tetrahydrofuran of lithium hydroxide at room temperature to obtain a compound 2, and reacting the compound 2 with geraniol in a dichloromethane solvent under the action of DCC and DMAP to obtain a compound D1; reacting the compound D1 with hydroxylamine hydrochloride and sodium ethoxide in a mixed solvent of ethanol and water to obtain a compound ZJT; reacting a compound ZJT with different substituted acyl chlorides in dichloromethane in the presence of triethylamine to obtain a target compound with a structure shown in a formula I;
the synthetic route of the formula I is as follows:
3. the use of the oxime ester-containing cyclopentyl acetate compound according to claim 1 for controlling agricultural pests.
4. An aphid repellent, the active component of which is the cyclopentyl acetate compound containing oxime ester according to claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117064A (en) * | 2016-05-18 | 2016-11-16 | 中国农业大学 | A kind of (instead) β farnesene analog containing jasmonic group and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117064A (en) * | 2016-05-18 | 2016-11-16 | 中国农业大学 | A kind of (instead) β farnesene analog containing jasmonic group and preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 夏丽娟 等: "1，4-戊二烯-3-酮肟酯类化合物的合成及生物活性", 《精细化工》 * |
| 杜少卿 等: "以气味相关蛋白为导向的新型EBF类似物的设计、合成和生物活性", 《中国化工学会农药专业委员会第十七届年会论文集》 * |
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