CN117326939A - Diterpenoid derivative and preparation method and application thereof - Google Patents
Diterpenoid derivative and preparation method and application thereof Download PDFInfo
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- CN117326939A CN117326939A CN202311145021.8A CN202311145021A CN117326939A CN 117326939 A CN117326939 A CN 117326939A CN 202311145021 A CN202311145021 A CN 202311145021A CN 117326939 A CN117326939 A CN 117326939A
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- 150000004141 diterpene derivatives Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 37
- 235000009566 rice Nutrition 0.000 claims abstract description 33
- 240000007594 Oryza sativa Species 0.000 claims abstract description 31
- 239000004009 herbicide Substances 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 14
- 239000000284 extract Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 241000209094 Oryza Species 0.000 claims description 7
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000004007 reversed phase HPLC Methods 0.000 claims description 6
- 239000010903 husk Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 16
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012044 organic layer Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 24
- 230000000723 chemosensory effect Effects 0.000 abstract description 7
- 229930000044 secondary metabolite Natural products 0.000 abstract description 6
- 230000002363 herbicidal effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000008635 plant growth Effects 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000012916 structural analysis Methods 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 14
- 230000012010 growth Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000003627 allelochemical Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- HFHZKZSRXITVMK-UHFFFAOYSA-N oxyphenbutazone Chemical group O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=C(O)C=C1 HFHZKZSRXITVMK-UHFFFAOYSA-N 0.000 description 4
- 239000008223 sterile water Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 240000008415 Lactuca sativa Species 0.000 description 3
- 235000003228 Lactuca sativa Nutrition 0.000 description 3
- 241000192043 Echinochloa Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000005100 correlation spectroscopy Methods 0.000 description 2
- 235000021186 dishes Nutrition 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 239000002024 ethyl acetate extract Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 2
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 1
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 1
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 235000011999 Panicum crusgalli Nutrition 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000036531 allelopathy Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 235000017807 phytochemicals Nutrition 0.000 description 1
- 229930000223 plant secondary metabolite Natural products 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/12—Saturated polycyclic compounds
- C07C61/125—Saturated polycyclic compounds having a carboxyl group bound to a condensed ring system
-
- 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
- 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
- A01N37/08—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 carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/95—Spiro compounds containing "not free" spiro atoms
- C07C2603/96—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members
- C07C2603/97—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members containing five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of medical intermediates, and discloses a diterpenoid derivative, a preparation method and application thereof. The invention utilizes modern separation and purification, structural analysis and other technologies to analyze the secondary metabolite of rice seed hulls in detail, and obtains a novel compound which has better chemosensory activity on plant growth, can be used as an active ingredient of novel herbicide, and has wide application.
Description
Technical Field
The invention belongs to the technical field of pesticide intermediates, and particularly relates to a novel diterpenoid derivative, a preparation method and application thereof.
Background
The allelochemicals are non-nutritive substances generated in organisms and can influence the growth, health, behavior or population relation of other plants, and the allelochemicals are media of allelochemicals and mainly are secondary metabolic substances of plants. The medium of phytochemicals is a chemical substance, called "chemosensory substance". The chemicals produced by plants that affect other biological growth, behavior, and population biology include not only inter-plant chemicals but also inter-plant and animal chemicals. Moreover, these chemicals need not enter the environment, but can also be performed in vivo. It has been found that many allelochemicals have an effect not only on plants but also on microorganisms, animals, in particular insects.
Rice is used as the most main grain crop in China, and paddy field weeds can cause 40% -60% yield reduction of the rice. Chemical herbicides are a common method for weeding rice fields, and large-scale use and annual increase of the dosage of the herbicides lead to the problems of '3R' such as continuous increase of weed resistance (resistance), pesticide residue (residue) and rampant of weeds. The rice seed husks are a layer of husks outside the rice, are the largest by-products in the rice processing process, and account for about 20% by weight of the rice. Comprehensive utilization of rice hulls has been widely studied for a long time at home and abroad, and a plurality of available ways are obtained. Recent researches show that the rice seed hulls contain a large amount of diterpenoid monomer compounds, and the compounds have certain allelochemicals activity, so that the modern separation means is utilized to deeply excavate natural products with enhanced allelochemicals activity from the rice seed hulls, and the natural products are used as precursors to develop novel herbicides, thereby providing a theoretical basis for further effectively utilizing the rice seed hulls and having better practical application value.
Disclosure of Invention
In view of the above, the present invention aims to provide a diterpenoid derivative or a pharmaceutically acceptable salt thereof, which can be used as a chemosensory compound and can be used for preparing novel herbicides, and a preparation method thereof.
The diterpene derivative provided by the invention is a compound with a structural formula I, and is a novel diterpene derivative disclosed for the first time.
The invention also provides a preparation method of the diterpenoid derivative, which comprises the following steps:
1) Primary extraction: extracting rice seed hulls with 95% ethanol, concentrating under reduced pressure at room temperature to dry to obtain rice seed hull extract; the rice seed hulls are preferably those of Oryza sativa l;
2) Extraction: adding the rice seed hull extract into 1.5L of water solution to prepare suspension, simultaneously adding equal volume of ethyl acetate for extraction, and concentrating an ethyl acetate layer under reduced pressure at room temperature until the ethyl acetate layer is dried to obtain the rice seed hull extract;
3) Purifying by normal phase silica gel chromatographic column: adding the rice seed hull extract obtained in the step 2) to a chromatographic column filled with normal phase silica gel filler, and sequentially adopting the following steps of: 0 petroleum ether-ethyl acetate solution with the volume ratio of 100:1 petroleum ether-ethyl acetate solution with the volume ratio of 100:2, the volume ratio of the petroleum ether-ethyl acetate solution is 100:4 petroleum ether-ethyl acetate solution with a volume ratio of 100:10 petroleum ether-ethyl acetate solution with a volume ratio of 100:20, and a petroleum ether-ethyl acetate solution with a volume ratio of 0:100, by taking a petroleum ether-ethyl acetate solution with a volume ratio of 100:10 petroleum ether-ethyl acetate solution fraction;
4) Purifying by reverse phase silica gel chromatographic column: adding the fractions obtained in the step 3) to a chromatographic column filled with reverse phase silica gel packing, eluting with 40% by volume of methanol solution, 50% by volume of methanol solution, 60% by volume of methanol solution, 70% by volume of methanol solution, 80% by volume of methanol solution, 90% by volume of methanol solution and 100% by volume of methanol solution in sequence, and collecting the fractions eluted by 80% by volume of methanol solution;
5) Reversed phase high performance liquid chromatography purification: and (3) separating and purifying the fraction obtained in the step (4) by reverse-phase high performance liquid chromatography to obtain the diterpene derivative.
Preferably, the rice seed hulls in step 1) of the above method are those of Oryza satival.
Preferably, the organic solvent in step 1) of the above method is ethanol with a concentration of 95%.
Preferably, the organic solvent in step 2) of the above method is ethyl acetate.
Preferably, in step 5), the mobile phase elution system selected by the high performance liquid phase is a methanol-water system.
Preferably, in step 5), the volume ratio of methanol to water in the methanol-water system is 78:22.
The invention also provides application of the diterpenoid derivative or the diterpenoid derivative prepared by the preparation method in preparing herbicide.
The invention utilizes the modern separation and purification technology to systematically separate the secondary metabolite of rice (Oryza sativa L.) seed hulls, thus obtaining a new diterpenoid derivative, which has better chemosensory activity and can be used as an active ingredient of novel herbicide and has wide application.
Drawings
FIG. 1 is a high performance liquid chromatography of the compound obtained in example 1 of the present invention;
FIG. 2 is a graph showing the hydrogen spectrum of the compound obtained in example 1 of the present invention;
FIG. 3 is a graph showing carbon spectrum data of the compound obtained in example 1 of the present invention;
FIG. 4 is a two-dimensional nuclear magnetic resonance data map (COSY) of the compound according to example 1 of the present invention;
FIG. 5 is a two-dimensional nuclear magnetic resonance data graph (HSQC) of the compound obtained in example 1 of the present invention;
FIG. 6 is a two-dimensional nuclear magnetic resonance data plot (HMBC) of the compound obtained in example 1 of the present invention;
FIG. 7 is a high resolution mass spectrum (HRESIMS) data plot of the compound of example 1 of the present invention.
FIG. 8 is a graph showing the results of screening for chemosensory activity of the compound according to example 1 of the invention.
Detailed Description
In order to further illustrate the present invention, the diterpene derivatives and the preparation method thereof provided by the present invention are described in detail below with reference to examples.
Example 1 preparation of Compounds of formula i
The invention adopts the steps of extraction, purification and the like under the conventional condition of laboratory culture conditions to prepare the compound. Wherein the plant used is the rice seed coat (Oryza sativa l.).
The process of the specific compound is as follows:
1) Extraction of
Rice seed hulls (10 kg) were collected, dried in the shade, pulverized, extracted with 95% ethanol at room temperature (5 L.times.3), and the extract was concentrated under reduced pressure to dryness to give about 187g of a transformant residue (i.e., rice seed hull extract).
2) Extraction
The rice seed hull extract was dissolved in 1.5L of water to prepare a suspension, and simultaneously an equal volume of ethyl acetate was added to extract (1.5L of x 3), and the extract was concentrated to dryness under reduced pressure to obtain about 83g of a rice seed hull ethyl acetate extract (abbreviated as rice seed hull extract).
3) Normal phase silica gel column chromatography
Adding the rice seed hull ethyl acetate extract obtained in the step 2) to a chromatographic column (200-300 meshes) filled with 500g normal phase silica gel filler, performing gradient elution (0% -100%) by using a petroleum ether-ethyl acetate system, collecting elution components, and taking the elution components with the volume ratio of 100:10 petroleum ether-ethyl acetate solution fraction;
4) Reversed phase silica gel chromatographic column purification
The fraction obtained in step 3) was applied to a column packed with 120g of reverse phase silica gel (120 angstrom, 30-50 mesh), and eluted with a gradient of methanol-water system (40% -100% methanol), and the eluted fraction was collected and eluted with a methanol solution having a volume concentration of 80%.
5) Reversed phase high performance liquid chromatography purification
And 4) separating and purifying the fractions obtained in the step 4) by using reverse-phase high performance liquid chromatography. The separation conditions are as follows: chromatographic column Hedera C 18 A-5 μm,4.6mm I.D.times.250 mm (Jiangsu Hanbang technology), the elution system is methanol-water isocratic elution, the specific conditions are: methanol-water (78:22, V/V) at a flow rate of 3.0mL/min. The detection wavelength is 203nm, the column temperature is 25 ℃, and the reaction is carried outThe sample amount was 100. Mu.L. The compound with the structural formula of formula i is obtained, and a high performance liquid chromatography, a hydrogen spectrum data graph, a carbon spectrum data graph, a two-dimensional nuclear magnetic resonance data graph (COSY), a two-dimensional nuclear magnetic resonance data graph (HSQC), a two-dimensional nuclear magnetic resonance data graph (HMBC) and a high resolution mass spectrum (HRESIMS) data graph are shown in figures 1-7.
Compound I, syn-demoden-18-oic acid, white amorphous powder.
The nmr hydrogen spectrum and carbon spectrum data of compound I are shown in table 1;
high resolution ESI mass spectrometry data for compound i: (-) -HR-ESIMS m/z 301.2196[ M-H] - (Calcd.for C 20 H 29 O 2 ,301.2168).
TABLE 1 Hydrogen Spectrometry and carbon Spectrometry data for Compound 1 (deuterated chloroform)
The above results indicate that the resulting compounds are structurally correct.
Example 2: chemosensory Activity of Compound I of the invention
(1) Experimental materials
Instrument and reagent: constant temperature and humidity incubator. The plant seeds used were tested: echinochloa crusgalli (l.) beauv (barnyard grass seeds), samlusparvirflow raf (chinese cabbage seeds), lactuca sativa l.angustana irish.b (lettuce seeds), purchased from the national academy of sciences.
Test sample: the purity of the secondary metabolite I is more than 90%; dissolving in DMSO, and standing.
(2) Experimental method
The selected plant seeds were sterilized with 10% hydrogen peroxide for 5min, then washed with sterile water 5 times, and drained. The sterilized plant seeds were spread on a wet petri dish (two layers of filter paper were filled) and then the petri dish was placed in a constant temperature and humidity incubator (temperature set to 25 ℃) until the white buds were exposed.
The secondary metabolite I was diluted with sterile water to prepare solutions with concentrations of 5, 10 and 20. Mu.g/mL, two layers of filter paper were laid on each dish, and the solutions of different concentrations of secondary metabolite I were added to the dishes until the filter paper was completely wetted (5 mL). 15 plant seedlings with consistent germination were selected from each of the above dishes, and repeated 3 times, and the control was the growth of plants cultivated in sterile water. Culturing in an illumination incubator (25 deg.C, illumination for 12 h/d) for 2d, and measuring root length and seedling height of the plant. The growth inhibition rate was calculated as follows:
growth inhibition ratio (%) = [ (control growth amount-treatment growth amount)/control growth amount ] ×100
Wherein the control growth amount is the plant growth amount cultivated by sterile water, and the treatment growth amount is the growth amount of each plant seed after the secondary metabolite I with different concentrations is added.
(3) Experimental results
The experimental results are shown in table 2 and fig. 8.
TABLE 2 screening of compounds for allelopathy
The result shows that the compound I has better chemosensory activity, shows a certain inhibition effect on the growth of barnyard grass seedlings, cabbage seedlings and lettuce seedlings, and can be used as an active ingredient of a novel herbicide.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A diterpenoid derivative or a pharmaceutically acceptable salt thereof, which is characterized in that the diterpenoid derivative is syn-stemoden-18-oic acid and has a structure shown in formula i:
2. the method for producing diterpenoid derivatives according to claim 1, comprising the steps of:
1) Primary extraction: extracting rice seed hulls with an organic solvent, and concentrating under reduced pressure at room temperature to dry to obtain rice seed hull extract;
2) Extraction: dissolving the rice seed shell extract in an aqueous solution to prepare a suspension, simultaneously adding an equal volume of organic solvent for extraction, and concentrating and drying an organic layer under reduced pressure at room temperature to obtain the rice seed shell extract;
3) Separating by normal phase silica gel column chromatography: adding the rice seed hull extract obtained in the step 2) to a chromatographic column filled with reverse phase silica gel, eluting with a petroleum ether-ethyl acetate solution with a volume ratio of 100:0, a petroleum ether-ethyl acetate solution with a volume ratio of 100:1, a petroleum ether-ethyl acetate solution with a volume ratio of 100:2, a petroleum ether-ethyl acetate solution with a volume ratio of 100:4, a petroleum ether-ethyl acetate solution with a volume ratio of 100:10, a petroleum ether-ethyl acetate solution with a volume ratio of 100:20 and a petroleum ether-ethyl acetate solution with a volume ratio of 0:100 in sequence, and taking petroleum ether-ethyl acetate solution fractions with a volume ratio of 100:10;
4) Purifying by reverse phase silica gel chromatographic column: adding the fractions obtained in the step 3) to a chromatographic column filled with reverse phase silica gel packing, eluting with 40% by volume of methanol solution, 50% by volume of methanol solution, 60% by volume of methanol solution, 70% by volume of methanol solution, 80% by volume of methanol solution, 90% by volume of methanol solution and 100% by volume of methanol solution in sequence, and taking the fractions eluted by the 80% by volume of methanol solution;
5) Reversed phase high performance liquid chromatography purification: and (3) separating and purifying the fraction obtained in the step (4) by reverse-phase high performance liquid chromatography to obtain the diterpene derivative.
3. The method according to claim 2, wherein the rice seed husk is a seed husk of Oryza sativa l.
4. The method according to claim 2, wherein in step 1), the organic solvent is 95% ethanol.
5. The method according to claim 2, wherein in step 2), the organic solvent is ethyl acetate.
6. The method according to claim 2, wherein in step 5), the mobile phase elution system selected for the high performance liquid phase is a methanol-water system.
7. The method according to claim 2, wherein in step 5), the volume ratio of methanol to water in the methanol-water system is 78:22.
8. The diterpenoid derivative as defined in claim 1 or the diterpenoid derivative prepared by the preparation method as defined in any one of claims 2-7, and the application thereof in preparing herbicides.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311145021.8A CN117326939A (en) | 2023-09-06 | 2023-09-06 | Diterpenoid derivative and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311145021.8A CN117326939A (en) | 2023-09-06 | 2023-09-06 | Diterpenoid derivative and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN117326939A true CN117326939A (en) | 2024-01-02 |
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|---|---|---|---|
| CN202311145021.8A Pending CN117326939A (en) | 2023-09-06 | 2023-09-06 | Diterpenoid derivative and preparation method and application thereof |
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| Country | Link |
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