CN107163058B - Preparation and application of alloimperatorin derivative - Google Patents
Preparation and application of alloimperatorin derivative Download PDFInfo
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- CN107163058B CN107163058B CN201710327572.4A CN201710327572A CN107163058B CN 107163058 B CN107163058 B CN 107163058B CN 201710327572 A CN201710327572 A CN 201710327572A CN 107163058 B CN107163058 B CN 107163058B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
- A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
- A23B7/154—Organic compounds; Microorganisms; Enzymes
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Abstract
The invention discloses a preparation method and application of an alloimperatorin derivative. The compound has a structure shown in formula (I), has good inhibitory activity on apple main diseases such as apple canker, apple ring rot and apple anthracnose, and has minimum inhibitory concentrations of 0.256, 0.128 and 0.128mg/mL respectively. Therefore, the compound can be used as a lead compound or a novel pesticide component with bactericidal action. The compound shown in the formula I is separated from plants, and compared with a chemical synthetic pesticide, the compound serving as a natural product has the advantages of low pesticide residue, difficulty in generating resistance, good environmental compatibility and the like.
Description
Technical Field
The invention relates to a botanical fungicide, in particular to a preparation method and application of an alloisocorychophragmus lactone derivative.
Background
Apples are the main economic crops in China, particularly, Jiaodong apples are reputed to be nationwide, and bring huge economic benefits to the local, but meanwhile, the influence of apple diseases on the quality and the yield of apples is more and more serious. The apple canker can directly damage the cortex of a fruit tree, so that the apple tree is gradually weakened and seriously even withered; apple ring rot, also known as rough skin disease and ring rot, commonly occurs in apple gardens in China and is often mixed with apple anthracnose and the like to cause diseases. Apple ring spot and apple anthracnose not only jeopardize the growth process of apples, but also can affect the storage of apples after picking, causing huge economic loss.
In recent years, with the use of a large amount of chemical pesticides, the apple diseases have increasingly serious drug resistance, and the problems of pesticide residue exceeding standards, environmental pollution, even poisoning of people and livestock and the like are caused along with the drug resistance. Compared with chemical pesticides, botanical pesticides have the advantages of high selectivity, low toxicity, easy degradation, difficult generation of resistance by pests and diseases, and the like, and become an important direction for the development of green and friendly pesticides in the future.
Disclosure of Invention
The invention aims to provide a preparation method and application of an alloimperatorin derivative. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an alloisoimperatorin derivative has a structure shown in formula (I),
a preparation method of an alloimperatorin derivative is characterized in that:
1) pulverizing dried rhizome of Notopterygium incisum Ting ex H.Chang, sieving, and extracting with organic solvent to obtain extract;
2) subjecting the extract to silica gel column chromatography, gradient eluting with petroleum ether-ethyl acetate and chloroform-methanol, collecting eluate, and detecting by thin layer chromatography;
3) sequentially separating and purifying the petroleum ether-ethyl acetate gradient elution components in the step 2) in a reverse phase silica gel column chromatography, a Sephadex LH-20 gel column chromatography and a preparative high performance liquid chromatography, and collecting the retention time tRThe content of 14.1-16.1min to obtain the final product.
The step 3) of collecting the retention time tRThe component with value of 15.3min to obtain the final product.
The preparation method comprises the following steps of 1) crushing dried rhizomes of Notopterygium root Notopterygium incisum Ting ex H. Chang, sieving with a 20-30-mesh sieve, and extracting with one or more of methanol, ethanol, ethyl acetate, acetone and water as an organic solvent to obtain an extract.
In the step 2), the petroleum ether-ethyl acetate elution gradient is 80:1 to 1:1, and the chloroform-methanol elution gradient is 40:1 to 1: 1.
The reverse silica gel column chromatography eluent in the step 3) is methanol-water with the volume ratio of 4:1, the Sephadex LH-20 gel column chromatography eluent is acetone, the high performance liquid chromatography condition is acetonitrile-water with the volume ratio of 3:2, the flow rate is 3mL/min, and the detection wavelength is 230 nm.
An application of an alloisoimperatorin derivative is disclosed, wherein the alloisoimperatorin derivative shown in the formula (I) can be used for preparing an active lead compound or a new pesticide component for preventing and treating apple diseases.
The apple diseases are apple rot, apple ring rot or apple anthracnose.
The invention has the advantages that: the alloimperatorin derivative shown in the formula (I) has better inhibitory activity on main apple diseases such as apple canker, apple ring rot and apple anthracnose, the minimum inhibitory concentration is 0.256, 0.128 and 0.128mg/mL respectively, and the alloimperatorin derivative can be used for preparing an active lead compound or a new pesticide component for preventing and treating apple diseases; the alloimperatorin derivative shown in the formula I is obtained by extracting and separating dried rhizome of Notopterygium incisum Ting ex H.Chang, is used as a plant source natural product, and has the advantages of difficult generation of drug resistance, safety to non-target organisms, good environmental compatibility and the like.
Detailed Description
To clarify the understanding of the characteristics of the present invention, the invention will be further illustrated with reference to the following non-limiting examples.
Example 1: the alloisoimperatorin derivative is shown as formula (I), (the Arabic numerals in the structure are the mark positions of carbon atoms)
Example 2: preparation of alloimperatorin derivatives
1) Separating and purifying
Pulverizing dried rhizome of Notopterygium incisum Ting ex H. Chang, sieving with 20 mesh sieve, ultrasonic extracting with ethyl acetate for 3 times, mixing extractive solutionsAnd distilling under reduced pressure to obtain extract. Subjecting to silica gel VLC (liquid chromatography) flash column chromatography, and performing gradient elution with petroleum ether-ethyl acetate (flow rate of 120mL/min) in a volume ratio of 80:1 to 1:1 and chloroform-methanol (flow rate of 120mL/min) in a volume ratio of 40:1 to 1:1 according to the ascending order of the polarity of the eluent. Collecting eluate, detecting by thin layer chromatography, wherein anisaldehyde-concentrated sulfuric acid is used as color developing agent according to RfValues and color rendering to incorporate the same or similar parts. Collecting the gradient elution components of petroleum ether-ethyl acetate with the volume ratio of 1:1, carrying out reversed phase silica gel column chromatography on the collected components, sequentially carrying out gradient elution by using methanol-water (the flow rate is 5mL/min) with the volume ratio of 1:9 to 1:0, and collecting the methanol-water elution components with the volume ratio of 4: 1. The component is subjected to gel column chromatography, acetone is used as an eluting solution (flow rate is 1mL/min), and finally the component is separated and purified by preparative high performance liquid chromatography (the chromatographic condition is acetonitrile-water with volume ratio of 3:2, flow rate is 3mL/min, detection wavelength is 230nm), and the collection retention time t isRThe component with value of 15.3min to obtain the final product.
2) Structural identification
The alloimperatorin derivative shown in the formula (I) is light yellow crystal, HRESIMS M/z 359.1155[ M + Na ]]+The molecular formula is shown as C21H20O4Which is1H-and13the C-NMR data are shown in Table 1.
TABLE 1 methods of alloimperatorin derivatives of formula (I)1H NMR (500MHz) and13c NMR (125MHz) data (MeOD, delta/ppm)
Example 3: test for bacteriostatic Activity
The bacteriostatic activity of the compound shown in the formula (I) on apple rot pathogen, apple ring rot pathogen and apple anthracnose pathogen is determined by a microdilution method (from natural products to a new pesticide creation-principle method, Wuwenjun, 2006, chemical industry publishing Co.).
1) Preparation of the bacterial suspension
After the test fungus was inoculated on the surface of PDA medium and cultured at 28 ℃ for 72 hours, 2mL of a sterile 0.85% NaCl solution (containing 0.25% Tween-20) was aspirated to wash the culture, and the colonies were gently scraped off with a glass scraper. The appropriate amount of bacterial suspension was pipetted into a sterile test tube and adjusted to 0.5 McLeod (equivalent to 1.5X 10)8CFU/mL) for use.
2) Preparation of samples
1mg of a sample to be tested (a compound shown in the formula (I)) is dissolved in 100 mu L of 50% DMSO, and after the mixture is sufficiently mixed, 50 mu L of the sample solution is sucked into another centrifuge tube, and then 50 mu L of 50% DMSO is added to obtain a sample solution with the concentration reduced by half. According to this method, 6 sets of sample solutions were obtained with successively halved concentrations.
3) MIC determination method
(1) By adopting aseptic operation, sample solutions with different concentrations after dilution in multiple proportion are respectively added into an aseptic 96-well polystyrene plate, 5 mu L of the sample solution is respectively added into the 1 st to 6 th wells, the wells without the sample are used as blank controls, and the wells with 5 mu L of 50% DMSO solution are used as solvent controls.
(2) After diluting the indicator suspension corresponding to 0.5 McLeod's turbidity 1000 times with PDB medium, 95. mu.L of the indicator suspension was added to a 96-well plate in order to make the sample concentrations in the 1 st to 6 th wells 512, 256, 128, 64, 32, 16. mu.g/mL in order. All the above samples were repeated three times. After gently shaking and mixing, the 96-well plate is sealed and placed in a biochemical incubator at 28 ℃ for culturing for 72 hours.
(3) The absorbance of each well was measured using a microplate reader at a wavelength of 600nm, and the lowest sample concentration at which the growth of the indicator bacteria was completely inhibited in the wells was taken as the MIC of the compound. (Note: it is only meaningful to indicate that the bacteria grows significantly in the negative control wells; the highest concentration of drug inhibiting the growth of the strain should be recorded when a single jump occurs in the experiment; if multiple jumps occur, no results should be reported, and the experiment should be repeated.)
The test results are as follows: the compound shown in the formula I has good inhibitory activity on main apple diseases such as apple canker, apple ring rot and apple anthracnose, the minimum inhibitory concentration is 0.256, 0.128 and 0.128mg/mL respectively, and the compound has good bacteriostatic activity.
The experimental results prove that the compound has good bacteriostatic activity and can be used for preparing an active lead compound or a new pesticide component for preventing and treating apple diseases.
Claims (5)
1. An alloimperatorin derivative characterized by: the structure of the alloisoimperatorin derivative is shown as a formula (I),
2. a method for preparing alloisoimperatorin derivatives according to claim 1, characterized in that:
1) pulverizing dried rhizome of Notopterygium incisum Ting ex H.Chang, sieving, and extracting with ethyl acetate to obtain extract;
2) subjecting the above extract to silica gel column chromatography, gradient eluting with petroleum ether-ethyl acetate 80: 1-1: 1 and chloroform-methanol 40: 1-1: 1, collecting eluate, and detecting by thin layer chromatography;
3) performing reverse phase silica gel column chromatography on the elution components with the petroleum ether-ethyl acetate volume ratio of 1:1 in the step 2), performing gradient elution with methanol-water of 1:9 to 1:0, and collecting eluent;
4) sequentially carrying out Sephadex LH-20 gel column chromatography and preparative high performance liquid chromatography on the elution components with the methanol-water volume ratio of 4:1 gradient in the step 3), separating and purifying, collecting retention time tRThe component with value of 15.3min to obtain the isoimperatorin derivative shown in formula (I); the eluent of the Sephadex LH-20 gel column chromatography is acetone, and the prepared high performance liquid chromatography conditions are acetonitrile-water with the volume ratio of 3:2, the flow rate is 3mL/min, and the detection wavelength is 230 nm.
3. Use of the alloisoimperatorin derivative of claim 1, wherein: the alloimperatorin derivative shown in the formula (I) is used for preparing an active lead compound for preventing and treating apple diseases.
4. Use of the alloisoimperatorin derivative of claim 1, wherein: the alloisoimperatorin derivative shown in the formula (I) is used for preparing a new pesticide component.
5. Use according to claim 3, characterized in that: the apple diseases are apple rot, apple ring rot or apple anthracnose.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265552A (en) * | 2013-05-22 | 2013-08-28 | 南京泽朗医药科技有限公司 | Method for extracting imperatorin by subcritical fluid technique |
| CN104193700A (en) * | 2014-08-22 | 2014-12-10 | 青岛农业大学 | Dithiocarbamate compound containing amide group as well as preparation method and application thereof |
| CN104326918A (en) * | 2014-10-10 | 2015-02-04 | 青岛农业大学 | Compound 3-fluoro-4-hydroxy-5-nitro-1-phenyl butanone and preparation method and agricultural biological activity thereof |
| CN104326919A (en) * | 2014-10-10 | 2015-02-04 | 青岛农业大学 | Compound 2-hydroxy-3-fluoro-5-nitro-1-phenyl butanone and preparation method and agricultural biological activity thereof |
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- 2017-05-11 CN CN201710327572.4A patent/CN107163058B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265552A (en) * | 2013-05-22 | 2013-08-28 | 南京泽朗医药科技有限公司 | Method for extracting imperatorin by subcritical fluid technique |
| CN104193700A (en) * | 2014-08-22 | 2014-12-10 | 青岛农业大学 | Dithiocarbamate compound containing amide group as well as preparation method and application thereof |
| CN104326918A (en) * | 2014-10-10 | 2015-02-04 | 青岛农业大学 | Compound 3-fluoro-4-hydroxy-5-nitro-1-phenyl butanone and preparation method and agricultural biological activity thereof |
| CN104326919A (en) * | 2014-10-10 | 2015-02-04 | 青岛农业大学 | Compound 2-hydroxy-3-fluoro-5-nitro-1-phenyl butanone and preparation method and agricultural biological activity thereof |
Non-Patent Citations (2)
| Title |
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| 羌活提取物对8种植物病原真菌抑制活性研究初报;薛俊鹏等;《中国植保导利》;20141231(第10期);第5-7页 * |
| 茜草等25种中药材对5种植物病原真菌的抑制活性;牛赡光等;《植物保护》;20151231;第41卷(第4期);第111-116页 * |
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