CN1970566A - Epimedin C contrast preparation method and its product - Google Patents
Epimedin C contrast preparation method and its product Download PDFInfo
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- CN1970566A CN1970566A CN 200610201222 CN200610201222A CN1970566A CN 1970566 A CN1970566 A CN 1970566A CN 200610201222 CN200610201222 CN 200610201222 CN 200610201222 A CN200610201222 A CN 200610201222A CN 1970566 A CN1970566 A CN 1970566A
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- epimedin
- reference substance
- silica gel
- chloroform
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Abstract
The invention discloses a making method and product of chaohuoding C contrast product, which comprises the following steps: fetching epimedium drug; refluxing and extracting through 45-90% alcohol; recycling alcohol; condensing into concrete; extracting reciprocally through petroleum ether, chloroform, acetic ester and butanol sequently until the color is eliminated; recycling butanol to obtain rough concrete; proceeding silica gel column chromatographic fractionation and polyamide column chromatographic fractionation; obtaining the contrast product of chaohuoding C. The invention affirms optimal extracting technology of chaohuoding C, which separates and purifies chaohuoding C successfully.
Description
Technical field: the present invention relates to preparation method of a kind of epimedin reference substance and products thereof, belong to the extractive technique field of index components in the medicinal material.
Background technology: Herba Epimedii is a conventional Chinese medicine, has the effect of kidney-replenishing, strengthening the bones and muscles, wind-damp dispelling, is mainly used in impotence and seminal emission, and the muscles and bones impotence is soft, rheumatic arthralgia, numbness contracture, diseases such as climacteric hypertension.The contained total flavonoid composition of Herba Epimedii is one of efficient part, comprises the flavones ingredients more than at least six kinds such as icarin, and epimedin (epimedin C) is wherein a kind of.Learn after deliberation: the content of epimedin is higher than other flavones ingredients far away in the efficient part of Herba Epimedii (total flavones).And at present, the index composition of the epimedium herb that pharmacopeia requires only is an icarin.A kind of medicinal material is carried out the mensuration of multiple index thing, can more fully reflect the inner quality of medicinal material, quality control is had significance.
Therefore, the applicant is through great deal of experimental, submitted the patent application that name is called " content assaying method of icarin and epimedin in the XIANLING GUBAO ZHIJI " on April 6th, 2006 to State Intellectual Property Office, and application number is 2006102003226.This patent application has remedied the deficiency of existing quality inspection standard, makes the quality inspection standard of epimedium herb more perfect.But in application number is 2006102003226 patent application, be to be that reference substance is measured with the epimedin with the content of high effective liquid chromatography for measuring epimedin.And unit and the mechanism that the epimedin reference substance can be provided, the relevant report of yet not seeing the preparation method of relevant epimedin reference substance do not arranged at present at home as yet.So the applicant has carried out correlative study to the preparation of epimedin reference substance simultaneously in the process of the content assaying method of research epimedin.
Summary of the invention:
The objective of the invention is to: preparation method of a kind of epimedin reference substance and products thereof is provided.The present invention investigates by the extraction process to epimedium herb comprehensively, has determined the optimum extraction process of epimedin, and successfully epimedin has been carried out separation and purifying, and prepared compound can be confirmed as epimedin through tight spectroscopic identification.
The present invention is achieved in that the preparation method of epimedin reference substance is: extract (1): get epimedium herb, be cut into disconnected, add alcohol reflux 2-5 time that 10-40 doubly measures 45-90%, each 0.5-2h, merge all extracting solutions, reclaim ethanol, and relative density is 1.13-1.20 when being condensed into 60 ℃; The concentrated solution adding distil water is placed in right amount, abandons precipitation, gets supernatant liquor, and reconcentration gets medicinal extract; Use sherwood oil, chloroform, ethyl acetate extraction to closely colourless successively, be extracted to closely colourlessly again with propyl carbinol repeatedly, reclaim propyl carbinol and contain the epimedin crude extract to doing, promptly getting; (2) separate: contain the epimedin crude extract with dissolve with methanol, the thin-layer chromatography silica gel mixed sample, silica gel column chromatography separates, with chloroform: methyl alcohol=100: 17, carried out gradient elution in 100: 20,100: 22, following the tracks of inspection with the silica gel precoated plate knows, Rf value Rf behind the recovery solvent, promptly gets the epimedin crude product less than spot stream part of icarin on the prefabricated thin-layer chromatography TLC of the collection silica gel plate; The crude product dissolve with methanol, column chromatography is mixed sample with polymeric amide, polyamide column chromatography separates, with ethyl acetate: methyl alcohol: water=8: 1: 0, carry out gradient elution at 8: 1: 0.2, following the tracks of inspection with polyamide layer knows, collect polyamide layer thin-layer chromatography TLC and go up Rf value Rf spot stream part, behind the recovery solvent, promptly get the epimedin reference substance greater than icarin.
Better leaching process is: get epimedium herb, be cut into disconnectedly, add 20 times of amount 70% alcohol refluxs 3 times, each 1h merges three times extracting solution, recovery ethanol, and relative density is 1.15 when being condensed into 60 ℃; The concentrated solution adding distil water is placed in right amount, abandons precipitation, gets supernatant liquor, and reconcentration gets medicinal extract; Use sherwood oil, chloroform, ethyl acetate extraction to closely colourless successively, be extracted to closely colourlessly again with propyl carbinol repeatedly, reclaim propyl carbinol and contain the epimedin crude extract to doing, promptly getting.
Wherein the development system of silica gel thin-layer chromatography TLC is a chloroform: methyl alcohol=100: 20.
The development system of polyamide layer thin-layer chromatography TLC is an ethyl acetate: ethanol: water=8: 1: 1.
According to the epimedin reference substance that the preparation method of above-mentioned epimedin reference substance prepares, its chemical structural formula is:
For reliability and the accuracy of verifying the inventive method, the applicant has carried out the structure evaluation to prepared product and confirmed, and is specific as follows:
1, structure is identified:
Products obtained therefrom is light yellow crystalline powder, hydrochloric acid-magnesium powder reaction, Molish reacting positive, and hydrolysis detects glucose and rhamnosyl on the silica-gel plate.Molecular formula C
39H
50O
19(MS+
13C NMR), degree of unsaturation Ω=15 in conjunction with hydrogen (carbon) spectrum, IR, UV data, are judged as three glucosides of flavonoid compound.
13C NMR data δ 178.2 reaches
1H NMR data δ 12.61 shows on this flavonoid compound C-5 that monohydroxy is arranged.
1Have five fragrant hydrogen protons on the H NMR data presentation 1, one of them proton signal is unimodal [6.63 (1H, s, 6-H)], four proton signals in addition are typical B ring 4 '-oxygen and replace [7.90 (2H, the d of system, J=8.8Hz, 2 ', 6 '-H), 7.13 (2H, d, J=8.8Hz, 3 ', 5 '-H)] show that 1 is 8 luxuriant and rich with fragrance pure type flavonoid compounds of camphane that replacement is arranged.Simultaneously, hydrogen (carbon) spectrum shows a methoxyl group signal on this compound [δ H 3.84 (3H, s); δ C 55.5], compare through carbon spectrum data with known compound, determine that 4 ' of this compound is that methoxyl group replaces.In addition,
13C NMR data δ 17.6 (q), 21.4 (t), 25.5 (q), 122.1 (d), 131.1 (s), and
1(3H, s), 1.67 (3H, s), 5.16 (1H, t J=5.2Hz) show that an isopentene group is arranged on 1 to H NMR data δ 1.59, and its C-7, C-9 carbon spectrum data illustrate that to high field displacement this isopentene group is positioned at 8, and therefore 1 aglycon is anhydroicartin.(m/z 368,353,313,165[A for the fragment peak that forms after the RDA cracking
1-C
4H
7]
+And 135[B
2]
+) further support this conclusion.
13C NMR has the resonance signal of 3 sugared end group carbon between 95-106ppm: δ c101.6,100.7,100.5ppm; And 15 sugar charcoal signals.Compare through standard carbon spectrum data, can determine that these three sugar are respectively rhamnosyl, rhamnosyl and glucose with sugar.Warp compares with the known compound data,
1H NMR,
13The report unanimity of relevant epimedin is an epimedin so can identify this kind compound in C NMR, MS, UV, IR data and the documents and materials.
2, structural confirmation:
(1) instrument and reagent
Infrared spectrometer (German VECTOR22 type), nuclear magnetic resonance spectrometer (the Varian 400MHz of VARIAN Oncology Systems NMR spectrometer with superconducting magnet), electrospray mass spectrometer (GC-MS 5973 types), UV, visible light spectrophotometer (HP8453E).Thin-layer chromatography is with silica gel H (Qingdao Marine Chemical Co., Ltd.), silica gel precoated plate (subsidiary factory of Haiyang Chemical Plant, Qingdao), and polymeric amide (Taizhou city, 80～120mesh Zhejiang Province road and bridge four blue or green biochemical material factory), solvent is that technical grade heavily steams use.
(2) fusing point: by " " melting point determination " method under an appendix VII of Chinese pharmacopoeia version in 2005 the C item is measured.It is an amount of to get product of the present invention, and porphyrize in 105 ℃ of dryings 2 hours, divides and gets an amount of sample, measures in accordance with the law, and measurement result is 198～200 ℃.
(3) ultraviolet: by " " ultraviolet-visible spectrophotometry " under an appendix VA of Chinese pharmacopoeia version in 2005 item measured.Product UV λ max of the present invention
MeOHNm is 271,316,351.UV spectrum shows flavones characteristic absorbance λ max
MeOHNm:351 and 271.
(4) infrared: by " " infrared spectrophotometry " under an appendix VC of Chinese pharmacopoeia version in 2005 item measured.IR(KBr)cm
-1：3417(OH)，2925，1651(α，β-unsaturated?C＝O)，1598，1511(C＝C)，1491，1440，1377，1343，1305，1260，1220，1181，1062，983，940，919，838，810。
(5) yellow powder (ethyl acetate methanol), mp198-200 ℃.HCl Mg reaction is rose-red color, and brown ring (positive), FeCl appear in the Molish reaction
3Reacting positive (blackish green).
ESI-MS?m/z：823.3[M+H]
+，677.2[M-rha+H]
+，531.1[M-2×rha+H]
+。
EI-MS?m/z：368[M-glc-2×rha]
+，353[M-glc-2×rha-CH
3]
+，313[M-glc-2×rha-C
4H
8]
+，300，177，165，146，135，85，73，60。
1H-NMR(DMSO-d6)：12.61(1H，s，5-OH)，7.90(2H，d，J＝8.8?Hz，H-2’，6’)，7.13(2H，d，J＝8.8Hz，H-3’，5’)，6.63(1H，s，H-6)，5.16(1H，t，J＝5.2Hz，H-12)，5.00(1H，d，J＝6.4Hz，Glc-H-1)，3.84(3H，s，OCH
3)，1.67(3H，s，H-15)，1.59(3H，s，H-14)，1.10(3H，d，J＝6.0Hz，Rha’H-6)，0.80(3H，d，J＝4.8Hz，Rha-H-6)。
5.38(1H，d，J＝1.5Hz，Rha-H-1)，4.87(1H，d，J＝1.0Hz，Rha’-H-1)，
13C-NMR(DMSO-d6)：157.3(C-2，s)，134.6(C-3，s)，178.2(C-4，s)，159.1(C-5，s)，98.1(C-6，d)，160.6(C-7，s)，108.3(C-8，s)，153.0(C-9，s)，105.5(C-10，s)，21.4(C-11，t)，122.1(C-12，d)，131.1(C-13，s)，25.5(C-14，q)，17.6(C-15，q)，122.1(C-1’，s)，130.6(C-2’，d)，114.1(C-3’，d)，161.5(C-4’，s)，114.1(C-5’，d)，130.6(C-6’，d)，55.5(OCH
3，q)，100.5(Glc-C-1，d)，73.3(Glc-C-2，d)，76.6(Glc-C-3，d)，68.8(Glc-C-4，d)，77.2(Glc-C-5，d)，60.6(Glc-C-6，t)，100.7(Rha-C-1，d)，75.5(Rha-C-2，d)，70.4(Rha-C-3，d)，71.9(Rha-C-4，d)，70.2(Rha-C-5，d)，17.6(Rha-C-6，q)，101.6(Rha’-C-1，d)，70.7(Rha’-C-2，d)，70.1(Rha’-C-3，d)，71.3(Rha’-C-4，d)，69.6(Rha’-C-5，d)，17.5(Rha’-C-6，q)。Acid hydrolysis, TLC checks that sugar moieties is glucose, rhamnosyl and rhamnosyl.
1H-NMR,
13C-NMR, MS, IR, the report unanimity of relevant epimedin in UV data and the documents and materials.So this compound identification is an epimedin.
Compared with prior art, this carries out study tour by the extraction process to epimedium herb, has determined the optimum extraction process of epimedin, and successfully epimedin has been carried out separation and purifying; The compound of gained can be confirmed as epimedin through spectroscopic identification.The assay of epimedin that is prepared as in the epimedium herb of epimedin reference substance provides effective reference substance source, thereby for epimedium herb carries out the mensuration of multiple index thing, lays a good foundation more fully to reflect its inner quality.
Embodiment:
Embodiments of the invention 1:
(1) extraction process:
Get epimedium herb, be cut into disconnectedly, add 20 times of 70% alcohol reflux 3 times, each 1h merges three times extracting solution, recovery ethanol, and relative density is 1.15 when being condensed into 60 ℃.The concentrated solution adding distil water is placed in right amount, abandons precipitation, gets supernatant liquor, and reconcentration gets medicinal extract.Use sherwood oil, chloroform, ethyl acetate extraction to closely colourless successively, be extracted to closely colourlessly again with propyl carbinol repeatedly, reclaim propyl carbinol, promptly obtain containing the crude extract of epimedin to doing.
(2) separating technology:
1. the separation of silica gel column chromatography:
With above-mentioned gained crude extract dissolve with methanol, the thin-layer chromatography silica gel mixed sample, silica gel column chromatography separates, with chloroform: methyl alcohol (100: 17,100: 20,100: 22) gradient elution, follow the tracks of inspection with the silica gel precoated plate and know, development system is a chloroform: methyl alcohol=100: 20, and collect silica gel precoated plate TLC and go up Rf value spot stream part less than icarin, after reclaiming solvent, promptly get the epimedin crude product.
2. the separation of polyamide column chromatography:
Epimedin crude product dissolve with methanol, column chromatography is mixed sample with polymeric amide, polyamide column chromatography separates, with ethyl acetate: methyl alcohol: water (8: 1: 0,8: 1: 0.2) gradient elution, follow the tracks of inspection with polyamide layer and know, development system is an ethyl acetate: ethanol: water=8: 1: 1, collect polyamide layer TLC and go up Rf value spot stream part, behind the recovery solvent, promptly get the epimedin reference substance greater than icarin.
Embodiments of the invention 2:
Extraction process: get epimedium herb, be cut into disconnectedly, add 10 times of 90% alcohol reflux 2 times, each 2h merges twice extracting solution, recovery ethanol, and relative density is 1.13 when being condensed into 60 ℃.The concentrated solution adding distil water is placed in right amount, abandons precipitation, gets supernatant liquor, and reconcentration gets medicinal extract.Use sherwood oil, chloroform, ethyl acetate extraction to closely colourless successively, be extracted to closely colourlessly again with propyl carbinol repeatedly, reclaim propyl carbinol, promptly obtain containing the crude extract of epimedin to doing.
The separating technology of epimedin crude extract is described with embodiment 1.
Embodiments of the invention 3:
Extraction process: get epimedium herb, be cut into disconnectedly, add 40 times of 45% alcohol reflux 5 times, each 0.5h merges five times extracting solution, recovery ethanol, and relative density is 1.20 when being condensed into 60 ℃.The concentrated solution adding distil water is placed in right amount, abandons precipitation, gets supernatant liquor, and reconcentration gets medicinal extract.Use sherwood oil, chloroform, ethyl acetate extraction to closely colourless successively, be extracted to closely colourlessly again with propyl carbinol repeatedly, reclaim propyl carbinol, promptly obtain containing the crude extract of epimedin to doing.
The separating technology of epimedin crude extract is described with embodiment 1.
Claims (5)
1. the preparation method of an epimedin reference substance is characterized in that: (1) extraction: get epimedium herb, be cut into disconnected, add alcohol reflux 2-5 time that 10-40 doubly measures 45-90%, each 0.5-2h merges all extracting solutions, reclaim ethanol, and relative density is 1.13-1.20 when being condensed into 60 ℃; The concentrated solution adding distil water is placed in right amount, abandons precipitation, gets supernatant liquor, and reconcentration gets medicinal extract; Use sherwood oil, chloroform, ethyl acetate extraction to closely colourless successively, be extracted to closely colourlessly again with propyl carbinol repeatedly, reclaim propyl carbinol and contain the epimedin crude extract to doing, promptly getting; (2) separate: contain the epimedin crude extract with dissolve with methanol, the thin-layer chromatography silica gel mixed sample, silica gel column chromatography separates, with chloroform: methyl alcohol=100: 17, carried out gradient elution in 100: 20,100: 22, following the tracks of inspection with the silica gel precoated plate knows, Rf value Rf behind the recovery solvent, promptly gets the epimedin crude product less than spot stream part of icarin on the prefabricated thin-layer chromatography TLC of the collection silica gel plate; The crude product dissolve with methanol, column chromatography is mixed sample with polymeric amide, polyamide column chromatography separates, with ethyl acetate: methyl alcohol: water=8: 1: 0, carry out gradient elution at 8: 1: 0.2, following the tracks of inspection with polyamide layer knows, collect polyamide layer thin-layer chromatography TLC and go up Rf value Rf spot stream part, behind the recovery solvent, promptly get the epimedin reference substance greater than icarin.
2. according to the preparation method of the described epimedin reference substance of claim 1, it is characterized in that: described leaching process is: get epimedium herb, be cut into disconnected, add 20 times of amount 70% alcohol refluxs 3 times, each 1h, merge three times extracting solution, reclaim ethanol, and relative density is 1.15 when being condensed into 60 ℃; The concentrated solution adding distil water is placed in right amount, abandons precipitation, gets supernatant liquor, and reconcentration gets medicinal extract; Use sherwood oil, chloroform, ethyl acetate extraction to closely colourless successively, be extracted to closely colourlessly again with propyl carbinol repeatedly, reclaim propyl carbinol and contain the epimedin crude extract to doing, promptly getting.
3. according to the preparation method of the described epimedin reference substance of claim 1, it is characterized in that: the development system of silica gel thin-layer chromatography TLC is a chloroform: methyl alcohol=100: 20.
4. according to the preparation method of the described epimedin reference substance of claim 1, it is characterized in that: the development system of polyamide layer thin-layer chromatography TLC is an ethyl acetate: ethanol: water=8: 1: 1.
5. the epimedin reference substance for preparing of the preparation method of epimedin reference substance according to claim 1, its chemical structural formula is:
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|---|---|---|---|
| CNB2006102012225A CN100422200C (en) | 2006-12-06 | 2006-12-06 | Epimedin C contrast preparation method and its product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006102012225A CN100422200C (en) | 2006-12-06 | 2006-12-06 | Epimedin C contrast preparation method and its product |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607976A (en) * | 2008-06-19 | 2009-12-23 | 贵州省中国科学院天然产物化学重点实验室 | A kind of preparation method of icarin |
| CN101747393B (en) * | 2008-12-17 | 2012-04-11 | 中国科学院大连化学物理研究所 | Method for simultaneously preparing chemical references of icariin, epimedin A, epimedin B and epimedin C |
-
2006
- 2006-12-06 CN CNB2006102012225A patent/CN100422200C/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607976A (en) * | 2008-06-19 | 2009-12-23 | 贵州省中国科学院天然产物化学重点实验室 | A kind of preparation method of icarin |
| CN101747393B (en) * | 2008-12-17 | 2012-04-11 | 中国科学院大连化学物理研究所 | Method for simultaneously preparing chemical references of icariin, epimedin A, epimedin B and epimedin C |
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| Publication number | Publication date |
|---|---|
| CN100422200C (en) | 2008-10-01 |
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