CN103125502A - Purpose of (-)-sumatrol serving as agricultural fungicide - Google Patents
Purpose of (-)-sumatrol serving as agricultural fungicide Download PDFInfo
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- CN103125502A CN103125502A CN201110396842XA CN201110396842A CN103125502A CN 103125502 A CN103125502 A CN 103125502A CN 201110396842X A CN201110396842X A CN 201110396842XA CN 201110396842 A CN201110396842 A CN 201110396842A CN 103125502 A CN103125502 A CN 103125502A
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- sumatrol
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- shrubby flase
- flase indigo
- adverse current
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Abstract
The invention first separates amorpha fruticosa seeds to obtain (-)-sumatrol with agricultural fungicide activity and discloses (-)-sumatrol having strong restrain and disinfection functions on phytopathogen. The (-)-sumatrol can be prepared into agricultural fungicide, widens using ranges of leguminous plant amorpha fruticosa and provides reliable technical base for development of plant pesticide.
Description
Technical field
The invention belongs to the pesticides application field, relate to the comprehensive utilization of leguminous plant shrubby flase indigo, be specifically related to a kind of active substance (-) that separation and purification obtains from the shrubby flase indigo seed-sumatrol as the purposes of disinfectant use in agriculture.
Background technology
Shrubby flase indigo (Amorpha fruticosa L.) is pulse family (Leguminosae) Amorpha fallen leaves bush.Approximately 25 kinds, the Amorpha plant whole world originates in the North America, and the shrubby flase indigo that China introduces cultivation only has a kind of.China's the South and the North all has the cultivation of shrubby flase indigo, and its applicability is strong, have a very wide distribution, and have well windproof, the function of fixing the sand, conserve water and soil, northern China particularly desert area be mainly used in water and soil conservation.In addition, cultivation can supply to view and admire, and is again nectariferous plant, and branch can be used for braiding, and leaf can be made green manure.
In the last few years, people began the medical value of shrubby flase indigo is studied.Its root, stem, leaf can be done medicinal, and the volatile oil in fruit can be used as desirable natural perfume material, all contain the chemical composition that some insect is had toxic action in the root of shrubby flase indigo, trunk, bark, leaf and fruit and seed, and plant resources is very abundant.Zheng Min is handsome at " vetiver and the shrubby flase indigo leaching liquor Primary Study to the legume crop allelopathy " Chinese master's best paper database, has reported in shrubby flase indigo acrial part leaching liquor in 2008 and has contained multiple allelochemical, and Seed germination is had inhibitory action; Bai Liping is at " shrubby flase indigo fruit pharmacognostical study " Chinese master's best paper database, reported the pharmacologically active of shrubby flase indigo extract in 2004, its have antitumor, antiviral, phosphodiesterase suppresses, protect the liver, malicious fish, desinsection and insect inhibitory action.WO 9815269A1 has reported that the Medical sterilization of (-)-sumatrol is active, can be used for treating the microbial disease of helicobacter pylorus; Dae Sik Jang etc. are at " Potential cancer chemopreventive flavonoids from the stems of Tephrosia toxicaria " Journal of Natural Products, 2003,66 (9), reported in the 1166-1170 page that (-)-sumatrol has potential cancer chemoprevention effect.Seiferle etc. are at " Insecticides derived from plants " Journal of Industrial and Engineering Chemistry, 1948,40 (4), reported in the 683-691 page that the agricultural insecticidal of (-)-sumatrol is active.Ermias Dagne etc. are at " Flavonoids and isoflavonoids from Tephrosia fulvinervis and Tephrosia pentaphylla ", Phytochemistry, 28 (11), the chemical constitution of having reported (-)-sumatrol in the 3207-3210 page with and H spectrum ownership, C.T.T.BLATT etc. are at " Cytotoxic Flavonoids from the Stem Bark of Lonchocarpus aff.fluvialis ", Phytotherapy Research, 16, the chemical constitution of having reported (-)-sumatrol in the 320-325 page with and C spectrum ownership.But separate so far the report obtain (-)-sumatrol from the shrubby flase indigo seed, also have no (-)-sumatrol has the report of agricultural bactericidal activity.
Summary of the invention
The object of the invention is to separate the active substance that obtains can be used as disinfectant use in agriculture from the shrubby flase indigo seed, and determine its structure, for comprehensive utilization, the new botanical pesticide of exploitation that enlarges shrubby flase indigo provides technical basis.
In order to realize purpose of the present invention, the present invention to shrubby flase indigo seed (commercially available) carry out ethyl acetate extraction, silicagel column rough segmentation, silicagel column segmentation, high speed adverse current chromatogram separates for the first time and the high speed adverse current chromatogram secondary separation, separate first to obtain having the extract of agricultural bactericidal active substance and proved that its structure is (-)-sumatrol from the shrubby flase indigo seed.Concrete process for separation and purification is as follows:
1. Soxhlet is extracted
At first using miniature plant sample cracker is pulverized shrubby flase indigo seed (buying by oneself), after it is crushed to the 40-80 order, according to shrubby flase indigo seed meal quality (Kg) and solvent volume (L) 1: 4-1: 6 ratio, adopt the Soxhlet extraction equipment, extract under reflux temperature, until till the solvent under backflow was not with color from the apparatus,Soxhlet's extraction tube, extraction time was approximately 4-6h.Solvent used is respectively benzinum, ethyl acetate, ethanol, respectively extract is concentrated ligroin extraction, ethyl acetate extract and the ethanol extract that obtains the shrubby flase indigo seed.Three parts of extracts are carried out respectively desinsection (killing mite), sterilization and Herbicidal.Insecticidal activity assay selects diamond-back moth, beet armyworm and black peach aphid etc. as supplying the examination insect, acaricidal activity selects Tetranychus cinnabarinus as supplying the examination mite, as supplying the examination germ, activity of weeding selects barnyard grass and pepper grass as the examination material to bactericidal activity with Botrytis cinerea, Pyricularia oryzae, tomato late blight bacterium, wheat powdery mildew, cucumber downy mildew, corn rust and cucumber anthracnose etc.Living test is tested result and is shown, the ethyl acetate extract of shrubby flase indigo seed has certain pesticide activity.
2. silica gel column chromatography separates for the first time
The ethyl acetate extract that upper part is had the shrubby flase indigo seed of certain pesticide activity carries out the silicagel column rough segmentation.Take 100-140 order silica gel as fixing phase, carry out wash-out take benzinum, carrene, ethyl acetate, acetone, methyl alcohol as mobile phase respectively, the variation according to colour band on pillar, initial gross separation obtain 5 elution fraction.The elution fraction that separation obtains is carried out respectively biological activity determination (method is with for the first time), the second active result of secondary survey shows that the eluent ethyl acetate part pesticide activity after the silicagel column rough segmentation is best, therefore it is carried out next step silica gel column chromatography secondary separation.
3. silica gel column chromatography secondary separation
Ethyl acetate part that first separation obtains to silicagel column is proceeded the silica gel column chromatography secondary separation, eluant, eluent is selected benzinum, benzinum and ethyl acetate (v: v, down together) (10: 1), benzinum and ethyl acetate (5: 1), benzinum and ethyl acetate (1: 1), benzinum and ethyl acetate (1: 2), benzinum and ethyl acetate (1: 5), benzinum and ethyl acetate (1: 10), ethyl acetate, ethanol carry out wash-out, and collect each part elution fraction.The elution fraction that separation obtains is carried out respectively biological activity determination (method is with for the first time), benzinum after the secondary separation of the silicagel column of biologically active result demonstration for the third time: ethyl acetate (1: 1) part elution fraction bactericidal activity is best, therefore its high speed adverse current chromatogram that carries out next step is separated.
4. high speed adverse current chromatogram (HSCCC) is first separates
The benzinum that secondary separation is collected to silicagel column: ethyl acetate (1: 1) part is carried out high speed adverse current chromatogram and is separated for the first time, solvent system selection n-hexane: ethyl acetate: ethanol: water=1: 0.8: 1.3: 1 separates, flow velocity 2ml/min, applied sample amount 300mg, positive rotating speed 850r/min, the fast 600r/min that reverses, 30 ℃ of temperature.Carry out the collection of elution fraction according to the absworption peak of the UV-detector (254nm wave band) of instrument configuration, obtain altogether 11 duplicate samples in the forward elution process, obtain altogether 4 duplicate samples in the counter-rotating elution process.The sample that obtains is given birth to respectively test and is tested (method is the same), and result shows that wherein forward the 10th duplicate samples has stronger bactericidal activity.This duplicate samples detects through high performance liquid chromatography, and therefore purity should further purify only in 50% left and right.Next step separates continuation and selects high speed adverse current chromatogram to carry out.
5. high speed adverse current chromatogram (HSCCC) secondary separation
High speed adverse current chromatogram is separated the 10th duplicate samples that forward receives for the first time carry out the high speed adverse current chromatogram Re-isolation, solvent system selection n-hexane: ethyl acetate: ethanol: water=(1: 2: 1: 1) separate, flow velocity 2ml/min, applied sample amount 300mg, positive rotating speed 850r/min, the fast 600r/min that reverses, 30 ℃ of temperature.Collect according to the absworption peak of the UV-detector (254nm wave band) of instrument configuration, obtain altogether 3 duplicate samples in the forward elution process, obtain altogether 1 duplicate samples in the counter-rotating elution process.Detect through high performance liquid chromatography, wherein forward the 3rd duplicate samples purity more than 95%, has good bactericidal activity.It is (-)-sumatrol that above-mentioned separator detects this duplicate samples composition of proof through nuclear-magnetism, mass spectrum etc.
Adopt said method, (-)-sumatrol outward appearance that the extraction separation obtains from the shrubby flase indigo seed is light yellow solid, and structure is suc as formula shown in (I):
(I) (-)-sumatrol
ESI-MS (-) m/z 409[M-H]
-, ESI-MS (+) m/z 411[M+H]
+, relative molecular mass is 410.
1H NMR (300MHz, CDCl
3): δ 12.44 (1H, s, 11-OH), 6.86 (1H, s, H-1), 6.46 (1H, s, H-4), 6.01 (1H, s, H-10), 5.20 (1H, t, H-2 '), 5.06 and 4.93 (2H, s, 4 '-CH
2), 4.88 (1H, t, H-6a), 4.59 (1H, dd, H-6), 4.16 (1H, d, H-6), (3.84 1H, d, H-12a), 3.79 and 3.82 (each 3H, s, 2,3-OMe), 3.23 (1H, q, H-1 '), 2.85 (1H, q, H-1 '), 1.75 (3H, s, 5 '-CH
3).H spectrum data and " Flavonoids and isoflavonoids from Tephrosia fulvinervis and Tephrosia pentaphylla ", Phytochemistry, 28 (11), the H spectrum data consistent of (-) that reports in the 3207-3210 page-sumatrol.
13C NMR (75MHz, CDCl
3): 110.3 (C-1), 104.6 (C-1a), 142.9 (C-2), 149.7 (C-3), 101.0 (C-4), 147.2 (C-4a), 66.0 (C-6), 71.7 (C-6a), 156.3 (C-7a), 104.1 (C-8), 166.1 (C-9), 91.9 (C-10), 169.1 (C-11), 101.2 (C-11a), 193.6 (C-12), 43.7 (C-12a), (30.5 C-1 '), (88.1 C-2 '), (144.0 C-3 '), (112.7 C-4 '), (17.0 C-5 '), 55.9 and 56.3 (2,3-OMe).C spectrum data and C.T.T.BLATT etc. are at " Cytotoxic Flavonoids from the Stem Bark of Lonchocarpus aff.fluvialis ", Phytotherapy Research, the C spectrum data consistent of (-) that reports in 16,320-325 page-sumatrol.
Detect proof through biologically active, the present invention extracts (-)-sumatrol that obtains first from the shrubby flase indigo seed has phytopathogen and suppresses and killing action, should be as the active component of the disinfectant use in agriculture of a kind of efficient, low toxicity, environmental protection.Therefore, the present invention has found the purposes of (-)-sumatrol as disinfectant use in agriculture first, has expanded the comprehensive utilization of leguminous plant shrubby flase indigo, has not only realized purpose of the present invention, and provides reliable technical basis for the exploitation of botanical pesticide.
Embodiment
Following examples are used for further describing the present invention.(-)-sumatrol that extracts from the shrubby flase indigo seed is according to the method described above carried out the agricultural bactericidal active testing.
The mensuration of embodiment 1 (-)-sumatrol bactericidal activity
With (-) that extract-sumatrol sample, the fungal disease of plant has been carried out the test of live body prolection from the shrubby flase indigo seed.Control cucumber downy mildew protection effect test method is as follows:
Select the consistent potted plant cucumber seedling of growth, cut off growing point and keep two true leaves, as test material.Carry out foliar spray with extract (-)-sumatrol according to design concentration and process, separately establish the blank of spray clear water, 3 repetitions.Second day inoculation cucumber downy mildew sporangia suspension after processing, then be positioned over phytotron (temperature: 25 ℃ of daytimes, 20 ℃ of nights, relative moisture: 95-100%) moisturizing is cultivated, and is positioned over greenhouse (25+2 ℃) and normal management after 24 hours, 5 days " Invest, Then Investigate " control efficiency.Disease scale calculates control efficiency with reference to State Standard of the People's Republic of China " pesticide field efficacy medicine test criterion " with disease index.
Result of the test shows that (-)-sumatrol has stronger bactericidal activity, when being 250mg/L as (-)-sumatrol concentration, the preventive effect of cucumber downy mildew has been reached 98%.
Claims (4)
1. (-)-sumatrol is as the purposes of disinfectant use in agriculture.
2. purposes according to claim 1 is characterized in that: described (-)-sumatrol separates from the shrubby flase indigo seed and obtains.
3. purposes according to claim 2, described (-)-sumatrol adopts following methods separating-purifying from the shrubby flase indigo seed to obtain: 1) Soxhlet is extracted, 2) silica gel column chromatography separates for the first time, 3) silica gel column chromatography secondary separation, 4) high speed adverse current chromatogram separates for the first time, and 5) the high speed adverse current chromatogram secondary separation; It is characterized in that: high speed adverse current chromatogram is separated the 10th duplicate samples that forward receives for the first time carry out the high speed adverse current chromatogram Re-isolation, the 3rd duplicate samples that obtains in the forward elution process is (-)-sumatrol.
4. purposes according to claim 3 is characterized in that: adopt described process for separation and purification to separate the chemical constitution of (-)-sumatrol that obtains from the shrubby flase indigo seed as follows:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110742079A (en) * | 2019-10-29 | 2020-02-04 | 四川国光农化股份有限公司 | Pesticide composition for promoting root growth and increasing yield of edible leguminous crops, preparation and application |
| CN111903718A (en) * | 2020-07-16 | 2020-11-10 | 海南欧兰德农业高科发展有限公司 | Low-pollution pesticide for green soybean planting |
| CN113200995A (en) * | 2021-04-27 | 2021-08-03 | 河北大学 | Compound Sterigmatocystin, preparation method thereof and application thereof in pesticide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998015269A1 (en) * | 1996-10-08 | 1998-04-16 | Mitsubishi Chemical Corporation | Drugs containing rotenoids |
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2011
- 2011-12-02 CN CN201110396842.XA patent/CN103125502B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998015269A1 (en) * | 1996-10-08 | 1998-04-16 | Mitsubishi Chemical Corporation | Drugs containing rotenoids |
Non-Patent Citations (2)
| Title |
|---|
| DAE SIK JANG,ET AL: "Potential Cancer Chemopreventive Flavonoids from the stems of tephrosia toxicaria", 《JOURNAL OF NATURAL PRODUCTS》, vol. 66, no. 9, 20 August 2003 (2003-08-20), pages 1166 - 1170 * |
| 纪明山，等: "紫穗槐种子杀蚜活性初探", 《江苏农业科学》, vol. 39, no. 2, 15 April 2011 (2011-04-15), pages 208 - 210 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110742079A (en) * | 2019-10-29 | 2020-02-04 | 四川国光农化股份有限公司 | Pesticide composition for promoting root growth and increasing yield of edible leguminous crops, preparation and application |
| CN110742079B (en) * | 2019-10-29 | 2021-10-08 | 四川国光农化股份有限公司 | Pesticide composition for promoting root growth and increasing yield of edible leguminous crops, preparation and application |
| CN111903718A (en) * | 2020-07-16 | 2020-11-10 | 海南欧兰德农业高科发展有限公司 | Low-pollution pesticide for green soybean planting |
| CN113200995A (en) * | 2021-04-27 | 2021-08-03 | 河北大学 | Compound Sterigmatocystin, preparation method thereof and application thereof in pesticide |
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| CN103125502B (en) | 2014-06-18 |
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