CN1342654A - C21 steriod glycoside extracted from white fleece flower root with antineoplastic function - Google Patents
C21 steriod glycoside extracted from white fleece flower root with antineoplastic function Download PDFInfo
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Abstract
The present invention relates to a kind of 4 novel antineoplastic C-21 steroglycosides and the mixture containing them. They are extracted from white fleece flower root, and can suppress cancer cells and induce wither of cervical cancer cells.
Description
The present invention relates to the antineoplastic compound of a class novelty, especially extraction separation obtains having the novel carbon-21 (C of antitumor action from the Chinese medicine Root of Bunge Auriculate
21) steroidal glycoside, be applicable to the inhibition growth of tumor.
Tumour is a big class serious threat people's life and healthy frequently-occurring disease and common disease, and the whole world has 7,000,000 people that tumour takes place every year, and 5,000,000 people are devitalized by tumour, and existing tumour patient is more than 10,000,000 people.More and more become serious health problem in China's tumour, at the beginning of liberation, tumour only accounts for the 9th or the tenth of the population cause of the death, to the seventies, risen to the 3rd, estimate at present, the annual tumor invasion number about 1,600,000 in the whole nation, the number that neoplastic disease is died from the whole nation every year has reached 1,300,000 people, and still on the rise, and it is surpassing cardiovascular disorder and is forming first reason into the human mortality.Therefore, the study on prevention of tumour is all paid much attention in countries in the world.
Now, operative treatment, radiotherapy, chemotherapy remain the most frequently used most important oncotherapy means, though chemotherapy developing history wherein is shorter, but in the complex therapy of tumour, play an increasingly important role, and, obtained quite high curative ratio as chorioepithelioma, acute lymphoblastic leukemia etc. for some tumour.But chemotherapy exists very big shortcoming, and this mainly is that existing antitumor drug is strong to the selectivity inhibition of tumour cell, systemic administration toxicity is big and major part has immunosuppressive action, and this has limited its use to a certain extent.Therefore, searching research high-efficiency low-toxicity, the novel antitumor drug of structure are still a very urgent and important global problem.
The objective of the invention is novel C with antitumor action according to theory of traditional Chinese medical science extraction separation high-efficiency low-toxicity, enhancing body immunity, novel structure from the Chinese medicine Root of Bunge Auriculate
21Steroidal glycoside.
The present invention's extraction separation from the Chinese medicine Root of Bunge Auriculate has the novel C of antitumor action
21Steroidal glycoside separates the C that obtains 4 kinds of novelties
21Steroidal glycoside is: Auriculoside A glycosides A, Auriculoside A glycosides B, the new glycosides A of Root of Bunge Auriculate, the new glycosides B of Root of Bunge Auriculate and include this 4 kinds of novel C
21The mixture radix cynanchi bungei total glucoside B (CGB) of steroidal glycoside, the C of 4 kinds of novelties
21Steroidal glycoside is the chemical structural formula with following formula, and wherein R is a sugar chain.
The chemical structure of Auriculoside A glycosides A: wherein R is β-D-glucopyanosyl base-(1 → 4)-α-L-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.
The chemical structure of Auriculoside A glycosides B: wherein R is β-D-glucopyanosyl base-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-digoxigenin pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.
The chemical structure of the new glycosides A of Root of Bunge Auriculate: wherein R is β-D-glucopyanosyl base-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.
The chemical structure of the new glycosides B of Root of Bunge Auriculate: wherein R is β-D-glucopyanosyl base-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-digoxigenin pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.
The Chinese medicine Root of Bunge Auriculate is the piece root of Asclepiadaceae (Asclepiadaceae) Cynanchum plant Auriculoside A (Cynanchum auriculatum Royle ex Wight), mountain on the other way round cynanchum auriculatum Royle ex Wight (C.wifordii Hemsl) and Bunge Swallowwort Root plants such as (C.bangei Decne), has the beneficial liver of nourishing blood, effects such as the benefit of reinforcing the kidney essence, strengthening the muscles and bones.Modern pharmacological research shows the C that Root of Bunge Auriculate contains
21Steroidal glycoside has antitumor and immuno-potentiation.
The C of novelty provided by the invention
21Steroidal glycoside and the C that includes novelty
21The mixture radix cynanchi bungei total glucoside B of steroidal glycoside, they be from Root of Bunge Auriculate (the piece root of Auriculoside A) through alcohols such as ethanol as extracting solvent, the medicinal extract that concentrates gained separates through macroporous resin column chromatography, collect ethanol eluate, concentrate the radix cynanchi bungei total glucoside ， Longitude silica gel column chromatography that obtains and separate, check chromatography stream part with thin-layer chromatography, stream part with identical single spot merges, and concentrates, and gets radix cynanchi bungei total glucoside B.Stream part 2 is wherein separated and purifying through Rp-18 lower pressure column or HPLC (high performance liquid chromatography) again, gets Auriculoside A glycosides A, Auriculoside A glycosides B, the new glycosides A of Root of Bunge Auriculate, the new glycosides B of Root of Bunge Auriculate.
By acid hydrolysis and ultraviolet spectrometer, infrared spectrometer, high resolution fast atom bombardment MS instrument, hydrogen nuclear magnetic resonance spectrometer, carbon-13 nmr spectra instrument, the relevant spectrometer of heteronuclear volume, spectral analysis techniques such as the relevant spectrometer of heteronuclear multikey, 4 kinds of C
21The chemical structure of steroidal glycoside has been separated bright, is respectively: announcement reaches booth (caudatin)-β-D-glucopyanosyl base-(1 → 4)-α-L-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside; Announcement reaches booth-β-D-glucopyanosyl base-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-digoxigenin pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside; Announcement reaches booth-β-D-glucopyanosyl base-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside; Announcement reaches booth-β-D-glucopyanosyl base-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-digoxigenin pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.And difference called after: Auriculoside A glycosides A (auriculoside A, I), Auriculoside A glycosides B (auriculoside B, II), the new glycosides A of Root of Bunge Auriculate (cynanauriculoside A, III), the new glycosides B of Root of Bunge Auriculate (cynanauriculoside B, IV).
The present invention compared with prior art has high-efficiency low-toxicity, antitumor, enhancing body immunization, be in the natural resource extraction separation as antineoplastic new drug.The C that these are novel
21Steroidal glycoside and include these novel C
21The composition radix cynanchi bungei total glucoside B of steroidal glycoside is to Human Prostate Cancer Cells PC
3, human lung carcinoma cell PAA, human cervical carcinoma cell Hela, colorectal cancer cells Hcc-8693 has the obvious suppression effect, and the apoptosis of energy induced Hcla cell, in the anticancer in animal body test, to mice transplanted tumor S
180Sarcoma and EC ascites carcinoma solid tumor also have the obvious suppression effect.The research and development anti-cancer agent brings glad tidings to tumour patient, has important science and actual value, and department is to produce bigger social benefit and economic benefit.
Biological activity
CGB among the present invention and four compounds have been carried out the evaluation experimental of inside and outside anti-tumor activity.
One. Root of Bunge Auriculate C
21The extracorporeal anti-tumor function of steroidal glycoside:
1. method
1.1 the cell suspension that is determined at the certain density of adding on the 24 porocyte culture plates of growth curve, the 1.0ml/ hole; Cultivate the medicine that adds different concns after a day, three multiple holes are all established in the 1.0ml/ hole.Different time after dosing reaches dosing simultaneously, with the digestion of 0.25% trypsin solution, collecting cell is counted on cell counting count board, is ordinate zou, time to be the X-coordinate cell growth curve that draws with every ml cell count.
1.2 MTT chromogenic assay method adds the cell suspension of certain density on 96 porocyte culture plates, 100 μ l/ holes; Cultivate the medicine that one day (cell attachment) back adds different concns, four multiple holes are all established in 100 μ l/ holes, and other establishes control wells (only add cell, do not add medicine) and zeroing hole (only add nutrient solution, do not contain cell and medicine).At 37 ℃, 5%CO
2, cultivate 4d in the incubator of saturated humidity, take out, add the MTT100 μ l/ hole of 1.0mg/ml; Continue to cultivate after 2 hours, liquid in each hole of inclining adds 0.04N hydrochloric acid Virahol 150 μ l/ holes again, after 1 hour, at 570nm place surveys each hole optical density with microplate reader in 37 ℃ of placements.
1.3 protein determination adds the cell suspension of certain density, 1.0ml/ hole on 24 porocyte culture plates; Cultivate after one day, add the medicine of different concns, in incubator (37 ℃, 5%CO
2) the middle cultivation after four days.The liquid in each hole that inclines, through 0.25% trysinization, the PBS flushing, centrifugal collecting cell adds 0.3NNaOH 0.5ml, behind 100 ℃ of heating in water bath 30min, gets 0.2ml and adds 2ml and examine Ma Shi light blue solution, in 754 spectrophotometer 595nm places survey optical density.
1.4 on cover glass, cultivated after four days by the dosing simultaneously of administration group with the Hela cell inoculation for morphological observation, takes out cover glass with the dyeing of HE staining, observation and taking pictures under light microscopic.
1.5 data statistics IC
50(half-inhibition concentration) calculates with the NDST program.
2. result
2.1 the influence that CGB and Compound I are grown to the PAA cell: CGB and Compound I with different concns are handled the PAA cell, and the growth of visible PAA cell all is suppressed, and is concentration and time-dependent manner.The Compound I of the CGB of 150 μ g/ml and 150 μ g/ml to the PAA cell have tangible cytotoxicity (Fig. 1, Fig. 2).
2.2CGB and Compound I, II, III, IV are to the influence of the tumour cell of vitro culture: observed CGB and Compound I, II, III, IV human large intestine cancer Hce-8693, Human Prostate Cancer Cells PC to vitro culture with mtt assay
3, human lung carcinoma cell PAA and four kinds of solid tumor cells of human cervical carcinoma cell Hela influence, the result shows that CGB and Compound I, II, III, IV have stronger cytotoxicity (table 1,2,3,4,5) to tumour cell.
Table 1 CGB is to the cytotoxicity of four kinds of human cancer cell strains
| Drug level | ????Hce-8693(％) | ????PC 3(％) | ????Hela(％) | ????PAA(％) |
| ??75μg.ml -1 | ????55 | ????77 | ????70 | ????85 |
| ??150μg.ml -1 | ????74 | ????93 | ????89 | ????93 |
| ??IC 50(μg.ml -1) | ????102.53 | ????53.72 | ????61.37 | ????50.08 |
The cytotoxicity of table 2 Compound I
| Drug level | ????Hce-8693(％) | ????PC 3(％) | ????Hela(％) | ????PAA(％) |
| ??49μmol.L -1??(60μg.ml -1) | ????65 | ????83 | ????84 | ????82 |
| ??245μmol.L -1??(300μg.ml -1) | ????80 | ????94 | ????96 | ????92 |
| ??IC 50(μg.ml -1) | ????52.60 | ????26.55 | ????32.57 | ????35.89 |
The cytotoxicity of table 3 Compound I I
| Drug level | ?Hce-8693(％) | ????PC 3(％) | ????Hela(％) | ????PAA(％) |
| ??49μmol.L -1??(60μg.ml -1) | ????46 | ????79 | ????70 | ????88 |
| ??245μmol.L -1??(300μg.ml -1) | ????78 | ????91 | ????87 | ????92 |
| ??IC 50(μg.ml -1) | ????94.07 | ????33.47 | ????43.50 | ????30.37 |
The cytotoxicity of table 4 compound III
| Drug level | Hce-8693(％) | ????PC 3(％) | ????Hela(％) | ????PAA(％) |
| ??55μmol.L -1??(60μg.ml -1) | ????51 | ????71 | ????68 | ????70 |
| ??275μmol.L -1??(300μg.ml -1) | ????74 | ????94 | ????89 | ????93 |
| ??IC 50(μg.ml -1) | ????72.40 | ????35.56 | ????40.95 | ????44.99 |
The cytotoxicity of table 5 compound IV
| Drug level | ????Hce-8693(％) | ????PC 3(％) | ????Hela(％) |
| ??56μmol.L -1??(60μg.ml -1) | ????64 | ????72 | ????74 |
| ??280μmol.L -1??(300μg.ml -1) | ????75 | ????87 | ????87 |
| ??IC 50(μg.ml -1) | ????9830 | ????38.31 | ????41.97 |
2.3 CGB and Compound I are to the influence of Hela cell protein content: CGB and Compound I with different concns were handled the Hela cell respectively after 96 hours, the protein content of cell reduces to some extent, and the protein decrement increases (table 6) along with the increase of CGB and Compound I concentration.Each concentration group difference is checked with statistical method, and P (0.05, show that restraining effect is concentration dependent.
Table 6 CGB and Compound I are to the influence of Hela cell protein content
| Medicine | Concentration (μ g.ml -1) | Protein decrement (%) |
| ????CGB | ????37.5 | ????5.46±3.06 |
| ????75 | ????20.79±1.36 | |
| ????150 | ????46.10±2.58 | |
| Compound I | ????15 | ????5.98±2.80 |
| ????30 | ????22.05±4.19 | |
| ????60 | ????48.53±6.87 |
2.4 CGB and Compound I are to the influence of Hela cellular form: morphological observation shows, and is vigorous without the cell growth of drug treating, is Polygons, and the cell growth of handling through CGB and Compound I obviously is subjected to press down cell rounding, pyknosis, dense poly-(Fig. 3).
Anti-tumor in vivo effect 1. methods of two .CGB
1.1 to murine sarcoma S
180Therapeutic action: get the inoculation back 10 days well-grown tumor-bearing mices, aseptic according to a conventional method separation S
180Tumor tissue, press knurl: physiological saline=homogenate in 1: 3, be inoculated in the ICR mouse armpit subcutaneous (0.2ml/ mouse) of 18～22g, random packet after inoculating 24 hours is divided oral and the two kinds of administrations in abdominal cavity, every day 1 time, totally 1 time, animal is put to death in it back, weighs, knurl is heavy, calculates the tumour inhibiting rate of medicine.
1.2 the result plants back 8 days well-grown tumor-bearing mices to mouse EC ascites carcinoma solid tumor, aseptic extraction ascites, with 10 times of dilutions of physiological saline, be inoculated in the ICR mouse armpit subcutaneous (0.2ml/ mouse) of 18～22g, random packet behind inoculation 24h, divide oral and two kinds of administrations in abdominal cavity, every day 1 time, totally 10 times, put to death animal after 11 days, weigh, knurl is heavy, calculates the tumour inhibiting rate of medicine.
2. result
Three batches of result of experiment (table 7) show that oral and intraperitoneal administration all can obviously suppress S
180The growth of sarcoma and EC ascites carcinoma solid tumor.
Table 7CGB is to mice transplanted tumor S
180Restraining effect medicine knurl strain route of administration dosage (mg/kg) tumour inhibiting rate (%) of sarcoma and EC solid tumor
20???????????35.1
Oral 40 39.7CGB S180 80 47.7
40???????????43.1
20 22.4EC abdominal cavities 40 29.2
80 44.3 3. toxicity test: the oral medium lethal dose of CGB mouse is 4890mg/kg
Example 1: after preparation radix cynanchi bungei total glucoside B Root of Bunge Auriculate dried root 10kg pulverizes, extract 3 times with methanol eddy, each 2 hours, united extraction liquid, decompression and solvent recovery gets ethanol extraction.This extract is used chloroform heating in water bath 2 hours, cooled and filtered, and the reclaim under reduced pressure chloroform gets chloroform extract.With in the chloroform extract impouring normal hexane, reflux 2 times, gets the insoluble part of normal hexane, i.e. radix cynanchi bungei total glucoside at each half an hour again.Radix cynanchi bungei total glucoside is carried out silica gel column chromatography, carry out gradient elution with chloroform-ethanol, check chromatography stream part with thin-layer chromatography, the stream part with identical single spot merges, and concentrates, and gets radix cynanchi bungei total glucoside B.
The fallow powder of radix cynanchi bungei total glucoside B.Lieberman-Burchard and Keller-Killiani reaction all are positive, and show to be all the steroidal compounds that contains the 2-desoxy sugar.The high-efficient liquid phase chromatogram of radix cynanchi bungei total glucoside B is seen Fig. 4.
Example 2:
Preparation Auriculoside A glycosides A
After Root of Bunge Auriculate dried root 10kg pulverizes, extract 3 times with methanol eddy, each 2 hours, united extraction liquid, decompression and solvent recovery gets ethanol extraction.This extract is used chloroform heating in water bath 2 hours, cooled and filtered, and the reclaim under reduced pressure chloroform gets chloroform extract.With in the chloroform extract impouring normal hexane, reflux 2 times, gets the insoluble part of normal hexane at each half an hour again.The insoluble part of normal hexane is carried out silica gel column chromatography, carry out gradient elution with chloroform-ethanol, check that with thin-layer chromatography chromatography flows part, the stream part with identical single spot merges, and concentrates, and gets stream part 1,2,3,4,5, will wherein flow part 2 through HPLC (MeOH:H
2O) separation, purifying obtain Auriculoside A glycosides A.
The unformed powder of Auriculoside A glycosides A white.mp：151-154℃。[α]
D 28＝-32.1°-(C＝0.04，EtOH)。UV λ
Max EthanolNm (log ε): 222.5 (4.05) .IR ν
Max KBr.cm
-1: 3449,2971,2935,1713,1645,1225,1165.HR-FAB-MS m/z:1227.6495[(C
62H
100O
24-H)
-, theoretical value 1227.6526].FAB-MS：m/z?1251[M+Na]
+，1071[1251-H
2O-glc]
+，761[M+1-H
2O-glc-cym-cym]
+，617[761-ole]
+，473[617-cym]
+。
1H NMR,
13C NMR and HMBC data see Table 8.
Table 8. compound 1
1H,
13C NMR and HMBC data aglycon part
13C?NMR???
1H?NMR???????????HMBC1α???????????39.0(t)????1.09-1.12，m??????C-2，C-101β?????????????????????????????????1.77-1.83，m2α???????????29.9(t)????1.77-1.83，m??????C-1，C-32β?????????????????????????????????2.00-2.14，m3??????77.7(d)????3.85，m???????????C-2，C-5，Sa-C-14α???????????39.3(t)????1.78，m???????????C-3，C-54β??????????????????????????????????2.41，m????5??????139.4(s)6??????119.2(d)???5.28，br?s????????C-8，C-107α???????????34.9(t)????2.017β?????????????????????????????????2.12，m???????????C-8，C-98??????74.3(s)????[5.04，br?s(OH)]??C-8，C-9，C-149??????44.6(d)????1.72，br?d(12.9)??C-8，C-10，C-1110?????37.1(s)11α?????????25.1(t)????2.14，m???????????C-9，C-10，C-1211β??????????????????????????????2.25，m12?????72.6(d)????5.03，m???????????C-11，C-13，C-17，C-1′13?????58.0(s)14?????89.5(s)????[6.12，s(OH)]15?????33.9(t)????2.07，m???????????C-14，C-16，C-17，C-1816α?????????33.0(t)????2.02，m???????????C-13，C-14，C-15，C-17，16β??????????????????????????????3.25，m17?????92.4(s)????[6.44，s(OH)]?????C-13，C-17，C-2018?????10.8(q)????1.97，s???????????C-12，C-13，C-14，C-1719?????18.2(q)????1.31，s???????????C-1，C-9，C-1020?????209.5(s)21?????27.6(q)????2.50，d(0.8)??????C-201′????166.0(s)2′????114.2(d)???5.85，s???????????C-1′，C-3′，C-4′，C-7′3′????165.5(s)4′????38.2(d)????2.41，m???????????C-7′C-5′，C-6′5′????21.0(q)????0.94，d(7.6)??????C-3′，C-4′，C-6′，C-7′6′????20.9(q)????0.96，d(7.6)??????C-3′，C-4′，C-5′，C-7′7′????16.5(q)????2.26，s???????????C-2′，C-3′，C-4′
Table 8 is continuous
Sugar moieties
13CNMR????
1HNMR???????????????HMBCD-cym.Sa-C1??????96.5(d)????5.27，br?d(11.3)?????C3，Sa-C2Sa-C2??????37.5(t)????1.89，m；2.32，m?????Sa-C1，Sa-C3Sa-C3??????78.1(d)????4.07，br?s???????????Sa-C1，Sa-C5Sa-C4??????83.4(d)????3.51，m??????????????Sa-C3，Sa-C5，Sa-C6，Sb-C1Sa-C5??????69.1(d)????4.22，m??????????????Sa-C1，Sa-C6Sa-C6??????18.7(q)????1.38，d(6.5)?????????Sa-C4，Sa-C5Sa-3-OCH
3?58.9(q)????3.60，d(0.9)?????????Sa-C3D-ole.Sb-C1??????101.9(d)???4.66，br?d(9.7)??????Sa-C4，Sb-C2Sb-C2??????37.2(t)????1.63，m；2.25，m?????Sb-C1，Sb-C3Sb-C3??????78.7(d)????4.20，m??????????????Sb-C1，Sb-C4，Sb-C5Sb-C4??????83.1(d)????3.44，m??????????????Sb-C3，Sb-C5，Sb-C6，Sc-C1Sb-C5??????71.9(d)????3.46，dd(2.3，9.1)???Sb-C1，Sb-C6Sb-C6??????18.7(q)????1.38，d(6.5)?????????Sb-C4，Sb-C5Sb-3-OCH
3?56.5(q)????3.33，d(0.8)?????????Sb-C3D-cym.Sc-C1??????100.5(d)???5.11，br?d(9.7)??????Sb-C4，Sc-C2Sc-C2??????37.5(t)????1.78，m；2.29，m?????Sc-C1，Sc-C3Sc-C3??????77.8(d)????3.99，m??????????????Sc-C4，Sc-C4Sc-C4??????81.7(d)????3.36，br?d(8.95)?????Sc-C3，Sc-C5，Sc-C6，Sd-C1Sc-C5??????69.0(d)????4.16，m??????????????Sc-C1，Sc-C6Sc-C6??????18.6(q)????1.37，d(6.5)?????????Sc-C4，Sc-C5Sc-3-OCH
3?59.0(q)????3.55，d(0.9)?????????Sc-C3L-cym.Sd-C1??????97.4(d)????5.06，br?d(2.6)??????Sc-C4，Sd-C2，Sd-C5Sd-C2??????34.9(t)????1.78，m；2.32，m?????Sd-C1，Sd-C3Sd-C3??????73.7(d)????3.96，m??????????????Sd-C1，Sd-C4，Sd-C5Sd-C4??????79.1(d)????3.42，dd(2.7，9.1)???Sd-C3，Sd-C5，Sd-C6，Se-C1Sd-C5??????64.8(d)????4.80，dq(6.5，7.6)???Sd-C1，Sd-C3，Sd-C4，Sd-C6Sd-C6??????18.4(q)????1.50，d(6.0)?????????Sd-C4，Sd-C5Sd-3-OCH
3?57.1(q)????3.49，d(0.8)?????????Sd-C3D-glc.Se-C1??????102.3(d)???5.01，br?d(7.7)??????Sd-C-4，Se-C-5Se-C2??????75.4(d)????3.98，m??????????????Se-C1，Se-C3Se-C3??????78.5(d)????4.23，m??????????????Se-C1，Se-C2，Se-C4Se-C4??????72.1(d)????4.20，m??????????????Se-C3，Se-C5，Se-C6Se-C5??????79.2(d)????3.99，m??????????????Se-C4，Se-C6Se-C-6??????63.0(t)???4.37，dd(5.4，11.6)??Se-C4，Se-C5
4.56，br?d(11.6)?????Se-C4
Example 3:
Preparation Auriculoside A glycosides B
After Root of Bunge Auriculate dried root 10kg pulverizes, extract 3 times with methanol eddy, each 2 hours, united extraction liquid, decompression and solvent recovery gets ethanol extraction.This extract is used chloroform heating in water bath 2 hours, cooled and filtered, and the reclaim under reduced pressure chloroform gets chloroform extract.With in the chloroform extract impouring normal hexane, reflux 2 times, gets the insoluble part of normal hexane at each half an hour again.The insoluble part of normal hexane is carried out silica gel column chromatography, carry out gradient elution with chloroform-ethanol, check that with thin-layer chromatography chromatography flows part, the stream part with identical single spot merges, and concentrates, and gets stream part 1,2,3,4,5, will wherein flow part 2 through HPLC (MeOH:H
2O) separation, purifying obtain Auriculoside A glycosides B.
The unformed powder of Auriculoside A glycosides B white.mp：141-146℃。[α]
D 28＝+4.4°(C＝0.16，EtOH)。UV λ
Max EthanolNm (log ε): 222.5 (4.04) .IR ν
Max KBrCm
-1: 3447,2971,2935,1712,1646,1225,1164.HR-FAB-MS m/z:1213.6337[(C
61H
98O
24-H)
-, theoretical value 1213.6370].FAB-MS：m/z?1237[M+Na]
+，909[M+1-glc-cym]
+，765[909-glc-cym-ole]
+，473[M+1?chain-H
2O]
+，473[617-cym]
+。
1H NMR,
13C NMR and HMBC data see Table 9.
Table 9. compound 2
1H,
13C NMR and HMBC data
The aglycon part
13C?NMR???
1H?NMR???????????HMBC1α???????????39.0(t)????1.12，m???????????C2，C91β?????????????????????????????????1.70，m???????????C2，C9，C102α???????????29.9(t)????1.71，m???????????C1，C32β?????????????????????????????????2.14，m???????????C1，C3，C103??????77.7(d)????3.83，m???????????Sa-C14α???????????39.3(t)????1.71，m???????????C2，C5，C104β?????????????????????????????????2.44，m???????????C2，C5，C6，C105??????139.4(s)6??????119.2(d)???5.24，br?s????????C8，C107α???????????34.8(t)????2.03，m???????????C5，C6，C8，C97β?????????????????????????????????2.44，m8??????74.3(s)????[5.00，s(OH)]?????C8，C9，C149??????44.6(d)????1.67，br?d(12.9)??C10，C14，C1910?????36.8(s)11α?????????25.1(t)????2.10，m???????????C8，C9，C10，C1211β???????????????????????????????2.21，m12?????72.6(d)????5.01，br?d(11.4)??C11，C13，C17，C18，C′113?????58.0(s)14?????89.5(s)????[6.12，s(OH)]15?????33.9(t)????2.03，m???????????C13，C14，C16，C1716α?????????33.0(t)????2.06，m???????????C13，C14，C15，C1716β???????????????????????????????3.24，m17?????92.4(s)????[6.42，s(OH)]?????C13，C17，C2018?????10.7(q)????1.97，s???????????C12，C13，C14，C1719?????18.7(q)????1.30，s???????????C1，C5，C9，C1020?????209.4(s)21?????27.6(q)????2.48，s???????????C20C-1′??166.0(s)C-2′??114.2(d)???5.85，s???????????C1′，C3′，C4′，C7′C-3′??165.4(s)C-4′??38.2(d)????2.40，m???????????C7′C-5′??21.0(q)????0.94，d(7.0)??????C3′，C4′，C6′，C7′C-6′??20.9(q)????0.96，d(7.6)??????C3′，C4′，C5′，C7′C-7′??16.5(q)????2.27，s???????????C3′，C4′，C6′
Table 9 is continuous
Sugar moieties Sa-C1 96.4 (d) 5.45, br d (9.3) C-3, Sa-C2Sa-C2 37.4 (t) 1.78, m; 2.27, m Sa-C1, Sa-C3Sa-C3 78.2 (d) 3.97, m Sa-C1, Sa-C5Sa-C4 82.6 (d) 3.37, br d (9.7) Sa-C3, Sa-C5, Sa-C6, Sb-C1Sa-C5 68.6 (d) 4.23-4.26, m Sa-C1, Sa-C6Sa-C6 18.7 (q) 1.41, br d (4.9) Sa-C4, Sa-C5Sa-3-OCH
357.5 (q) 3.45, s Sa-C3D-digit.Sb-C1 98.4 (d) 5.21, br d (10.4) Sa-C4, Sb-C2Sb-C2 37.4 (t) 1.78, m; 2.27, m Sb-C1, Sb-C3Sb-C3 69.1 (d) 4.12-4.25, m Sb-C4, Sb-C5Sb-C4 83.2 (d) 3.50, m Sb-C3, Sb-C5, Sb-C6, Sc-C1Sb-C5 67.6 (d) 4.23-4.26, m Sb-C1, Sb-C6Sb-C6 18.7 (q) 1.37, br d (4.3) Sb-C4, Sb-C5D-ole.Sc-C1 102.0 (d) 4.64, br d (9.8) Sb-C4, Sc-C2Sc-C2 37.8 (t) 1.64, m; 2.24, m Sc-C1, Sc-C3Sc-C3 78.4 (d) 3.97, m Sc-C1, Sc-C4, Sc-C5Sc-C4 83.2 (d) 3.46, br d (9.3) Sc-C3, Sc-C5, Sc-C6, Sd-C1Sc-C5 71.8 (d) 3.45, d (6.3) Sc-C1, Sc-C6Sc-C6 18.7 (q) 1.37, d (4.3) Sc-C4, Sc-C5Sc-3-OCH
358.7 (q) 3.49, s Sc-C3D-cym.Sd-C1 99.8 (d) 5.14, br d (9.4) Sc-C4, Sd-C2, Sd-C5Sd-C2 37.4 (t) 1.78, m; 2.27, m Sd-C1, Sd-C3Sd-C3 77.7 (d) 3.97, m Sd-C1, Sd-C4, Sd-C5Sd-C4 83.4 (d) 3.65, br d (9.8) Sd-C3, Sd-C5, Sd-C6, Se-C1Sd-C5 69.7 (d) 4.15, m Sd-C1, Sd-C6Sd-C6 18.7 (q) 1.62, d (ca.6) Sd-C4, Sd-C5Sd-3-OCH
358.9 (q) 3.53, s Sd-C3D-glc.Se-C1 106.6 (d) 4.90, br d (ca.7) Sd-C4, Se-C5Se-C2 75.4 (d) 3.97, m Se-C1, Se-C3Se-C3 78.4 (d) 4.14, m Se-C1, Se-C2, Se-C4Se-C4 71.9 (d) 4.12, m Se-C3, Se-C5Se-C5 78.8 (d) 4.03, m Se-C1, Se-C4, Se-C6Se-C6 63.1 (t) 4.37, m Se-C4, Se-C5
4.56，br?d(7.3)?????Se-C4
Example 4:
The new glycosides A of preparation Root of Bunge Auriculate
After Root of Bunge Auriculate dried root 10kg pulverizes, extract 3 times with methanol eddy, each 2 hours, united extraction liquid, decompression and solvent recovery gets ethanol extraction.This extract is used chloroform heating in water bath 2 hours, cooled and filtered, and the reclaim under reduced pressure chloroform gets chloroform extract.With in the chloroform extract impouring normal hexane, reflux 2 times, gets the insoluble part of normal hexane at each half an hour again.The insoluble part of normal hexane is carried out silica gel column chromatography, carry out gradient elution with chloroform-ethanol, check that with thin-layer chromatography chromatography flows part, the stream part with identical single spot merges, and concentrates, and gets stream part 1,2,3,4,5, will wherein flow part 2 through HPLC (MeOH:H
2O) separation, purifying obtain the new glycosides A of Root of Bunge Auriculate.
The unformed powder of the new glycosides A white of Root of Bunge Auriculate.mp：172-176℃。α]
D 28＝0°(C＝0.80，EtOH)。UV λ
Max EthanolNm (1og ε): 221.5 (4.05) .IR ν
Max KBrCm
-1: 3448,2969,2935,1713,1646,1226,1166.HR-FAB-MS m/z:1083.5739 ([C
55H
88O
21-H]
-, theoretical value 1083.5740).FAB-MS：m/z?1091[M+Li]
+，911[1091-H
2O-glc]
+，617[M+1-H
2O-glc-cym-ole]
+，473[617-H
2O-glc-cym-ole-cym]
+。
1H NMR,
13C NMR and HMBC data see Table 10.
Table 10. compound 3
1H,
13C NMR and HMBC data
The aglycon part
13C?NMR????
1H?NMR??????????????HMBC1α???????????????39.0(t)?????1.17，m??????????????C2，C9，C101β???????????????????????????????????????1.82，m??????????????C2，C9，C102α???????????????29.9(t)?????1.82，m；????????????C10，C1，C3；2β???????????????????????????????????????2.13，m??????????????C10，C13????????77.7(d)?????3.87，m??????????????Sa-C14α???????????????39.3(t)?????1.82，m??????????????C2，C5，C6，C104β???????????????????????????????????????2.53，dd(4.7，12.0)??C2，C5，C6，C105????????139.4(s)6????????119.3(d)????5.26，br?s???????????C8，C107α???????????????34.8(t)?????2.15，m??????????????C8，C9，C5，C67β???????????????????????????????????????2.45，m??????????????C8，C9，C5，C68????????74.3(s)?????[5.07，s(OH)]????????C7，C8，C9，C149????????44.6(d)?????1.75，t(10.5)????????C10，C19，C1410???????37.3(s)11α?????????????25.1(t)?????2.15?????????????????C8，C9，C10，C1211β?????????????????????????????????????2.20?????????????????C8，C9，C10，C1212???????72.6(d)?????5.04，dd(4.1，11.7)??C11，C13，C17，C18，C′113???????58.0(s)14???????89.5(s)?????[6.13，s(OH)]????????C8，C14，C1515α????????????33.9(t)?????2.15，m??????????????C815β????????????????????????????????????2.45，m??????????????C816α????????????33.0(t)?????2.13，m??????????????C14，C15，C2016β????????????????????????????????????3.29，m??????????????C14，C15，C2017???????92.4(s)?????[6.45，s(OH)]????????C13，C17，C2018???????10.8(q)?????1.98，s??????????????C13，C12，C14，C1719???????18.2(q)?????1.32，s??????????????C1，C5，C9，C1020???????209.5(s)21???????27.6(q)?????2.50，d(0.9)?????????C17，C20C-1′????166.0(s)C-2′????114.2(d)????5.58，s??????????????C1′，C3′，C4′，C7′C-3′????165.4(s)C-4′????38.2(d)?????2.45，m??????????????C3′，C5′，C6′C-5′????21.0(q)?????0.93，d(7.6)?????????C4′，C6?′C-6′????20?9(q)?????0.96，d(7.0)?????????C4′，C5′C-7′????16.5(q)?????2.27，s??????????????C2′，C3′，C4′
Table 10 is continuous
Sugar moieties
13C?NMR???
1H?NMR????????????????HMBCD-cym.Sa-C1??????96.4(d)????5.26，br?d(8.0)????????C3，Sa-C2Sa-C2??????37.4(t)????2.33，m；1.82，m???????Sa-C1，Sa-C3Sa-C3??????78.8(d)????4.25，m????????????????Sa-C1，Sa-C4，Sa-C5，Sa-C4??????83.6(d)????3.49，m????????????????Sa-C3，Sa-C5，Sa-C6，Sb-C1Sa-C5??????69.0(d)????4.21，m????????????????Sa-C1，Sa-C4，Sa-C6Sa-C6??????18.7(q)????1.43，d(5.9)???????????Sa-C4，Sa-C5Sa-3-OCH
3?57.5(q)????3.51，d(1.0)???????????Sa-C3D-ole.Sb-C1??????102.0(d)???4.69，br?d(9.7)????????Sa-C4，Sb-C2Sb-C2??????37.8(t)????2.33，m；1.78，m???????Sb-C1，Sb-C3Sb-C3??????78.2(d)????4.10，m????????????????Sb-C1，Sb-C4Sb-C4??????82.7(d)????3.47，m????????????????Sb-C1，Sb-C5，Sb-C6，Sc-C1Sb-C5??????71.8(d)????3.48，m????????????????Sb-C1，Sb-C6Sb-C6??????18.7(q)????1.41，d(5.3)???????????Sb-C4，Sb-C5Sb-3-OCH
3?58.7(q)????3.52，d(1.0)???????????Sh-C3D-cym.Sc-C1??????98.4(d)????5.25，br?d(7.6)????????Sb-C4，Sc-C2Sc-C2??????36.8(t)????2.33，m；1.78，m???????Sc-C1，Sc-C3Sc-C3??????77.9(d)????4.19，m????????????????Sc-C1，Sc-C4，Sc?C5Sc-C4??????83.2(d)????3.68，dd(2.8，9.6)?????Sc-C1，Sc-C5，Sc-C6，Sd-C1Sc-C5??????69.7(d)????4.28，m????????????????Sc-C6，Sc-C4，Sc-C1Sc-C6??????18.7(q)????1.62，d(6.0)???????????Sc-C4，Sc-C5Sc-3-OCH
3?58.9(q)????3.56，d(1.0)???????????Sc-C3D-glcSd-C1??????106.6(d)???4.93，br?d(7.7)????????Sc-C4，Sd-C5Sd-C2??????75.4(d)????3.98，m????????????????Sd-C1，Sd-C3Sd-C3??????78.5(d)????4.23，m????????????????Sd-C2，Sd-C4Sd-C4??????71.9(d)????4.17，m????????????????Sd-C3，Sd-C5，Sd-C6Sd-C5??????78.4(d)????3.98，m????????????????Sd-C4，Sd-C6Sd-C6??????63.1(t)????4.40，dd(5.5，11.6)????Sd-C4，Sd-C5
4.54，dd(2.1，11.6)????Sd-C4
Example 5:
The new glycosides B of preparation Root of Bunge Auriculate
After Root of Bunge Auriculate dried root 10kg pulverizes, extract 3 times with methanol eddy, each 2 hours, united extraction liquid, decompression and solvent recovery gets ethanol extraction.This extract is used chloroform heating in water bath 2 hours, cooled and filtered, and the reclaim under reduced pressure chloroform gets chloroform extract.With in the chloroform extract impouring normal hexane, reflux 2 times, gets the insoluble part of normal hexane at each half an hour again.The insoluble part of normal hexane is carried out silica gel column chromatography, carry out gradient elution with chloroform-ethanol, check that with thin-layer chromatography chromatography flows part, the stream part with identical single spot merges, and concentrates, and gets stream part 1,2,3,4,5, will wherein flow part 2 through HPLC (MeOH:H
2O) separation, purifying obtain the new glycosides B of Root of Bunge Auriculate.
The unformed powder of the new glycosides B white of Root of Bunge Auriculate.[α]
D 28＝11.2°(C＝0.50，EtOH)。UVλ
max ethanol?nm(logε)：221.5(4.02)。IRν
max KBr?cm
-1：3446，2971，2935，1713，1646，1225，1165。HR-FAB-MS m/z:1069.5499 ([C
54H
86O
21-H]
-, theoretical value: 1069.5583).FAB-MS：m/z?1093[M+Na]
+，909[M+1-glc]
+，765[M+1-glc-cym]
+，635[M+1-glc-cym-digit]
+，473[M+1-sugar?chain-H
2O]
+。
1H NMR,
13C NMR, HMQC and HMBC data see Table 11.
Table 11. compound 4
1H,
13C NMR and HMBC data
The aglycon part
13C?NMR???
1H?NMR?????????????HMBC1α???????????39.0(t)????1.11，m?????????????C2，C91β?????????????????????????????????1.82，m?????????????C2，C9，C102α???????????29.9(t)????1.82，m?????????????C1，C323????????????????2.12????????????????C1，C3，C103??????77.7(d)????3.85，m?????????????Sa-C14α???????????39.3(d)????1.82，m?????????????C2，C5，C1043????????????????2.25，m?????????????C2，C5，C6，C105??????139.4(s)6??????119.2(d)???5.26，br?s??????????C8，C107α??????????34.8(t)????2.15，m?????????????C5，C6，C8，C97β????????????????????????????????2.45，m8??????74.3(s)9??????44.6(d)????1.72，br?d(10.8)????C10，C14，C1910?????37.4(s)11α?????????25.1(t)????2.10，m?????????????C8，C9，C10，C1211β???????????????????????????????2.13，m12?????72.6(d)????5.03，dd(ca.4，12)??C11，C13，C17，C18，C＇-113?????58.0(s)14?????89.5(s)15α????????33.8(t)????2.15，m?????????????C13，C14，C16，C1715β??????????????????????????????2.45，m16α????????33.0(t)????2.13，m?????????????C13，C14，C15，C1716β??????????????????????????????3.25，m17?????92.4(s)18?????10.7(q)????1.97????????????????C12，C13，C14，C1719?????18.7(q)????1.30，s?????????????C1，C5，C9，C10，20?????209.4(s)21?????27.6(q)????2.49，s?????????????C1′，C3′，C4′，C7′1′????166.0(s)2′????114.2(d)???5.85，s?????????????C7′3′????165.4(s)4′????38.2(d)????2.45，m?????????????C3′，C4′，C5′，C7′5′????21.0(q)????0.94，d(6.7)????????C3′，C4′，C6′6′????20.9(q)????0.96，d(7.5)????????C3′，C4′，C5′7′????16.5(q)????2.26，s?????????????C2′，C3′，C4′
Table 11 is continuous
Sugar moieties
13C?NMR???
1H?NMR??????????????????????HMBCD-cym.Sa-C1??????96.4(d)????5.46，br?d(9.2)???????????????C-3，Sa-C2Sa-C2??????36.8(t)????1.70-1.75，m；2.42，m?????????Sa-C1，Sa-C3Sa-C3??????78.2(d)????3.25-3.75，m??????????????????Sa-C1，Sa-C5Sa-C4??????83.1(d)????3.37，d(7.2)??????????????????Sa-C3，Sa-C5，Sa-C6，Sb-C1Sa-C5??????68.6(d)????4.29，m???????????????????????Sa-C1，Sa-C6Sa-C6??????18.7(q)????1.37，d(4.2)??????????????????Sa-C4，Sa-C5Sa-3-OCH
3?59.0(q)????3.52，s???????????????????????Sa-C3D-digit.Sb-C1??????99.8(d)????5.15，br?d(8.9)???????????????Sa-C4，Sb-C2Sb-C2??????38.2(t)????1.70-1.75，m；2.32，m?????????Sb-C1，Sb-C3Sb-C3??????69.1(d)????4.14-4.20，m??????????????????Sb-C1，Sb-C5Sb-C4??????83.8(d)????3.70，br?d(8.8)???????????????Sb-C3，Sb-C5，Sb-C6，Sc-C1Sb-C5??????67.5(d)????4.14-4.20，m??????????????????Sb-C1，Sb-C6Sb-C6??????18.9(q)????1.42，d(5.3)??????????????????Sb-C4，Sb-C5D-ole.Sc-C1??????101.9(d)???4.67，br?d(9.4)???????????????Sb-C4，Sc-C2Sc-C2??????36.8(t)????1.54-1.62，m；2.39-2.46，m????Sc-C1，Sc-C3Sc-C3??????79.3(d)????3.75-4.25，m??????????????????Sc-C1，Sc-C5Sc-C4??????83.3(d)????3.50，br?d(9.5)???????????????Sc-C3，Sc-C5，Sc-C6，Sd-C1Sc-C5??????72.1(d)????3.50，m???????????????????????Sc-C1，Sc-C6Sc-C6??????18.5(q)????1.42，d(5.3)??????????????????Sc-C4，Sc-C5Sc-3-OCH
3?59.0(q)????3.56??????????????????????????Sb-C3D-glc.Sd-C1??????104.5(d)???5.10，br?d(ca.10)?????????????Sc-C4，Sd-C5Sd-C2??????75.7(d)????3.93-3.98，m??????????????????Sd-C1，Sd-C3Sd-C3??????78.4(d)????4.14-4.20，m??????????????????Sd-C2，Sd-C4Sd-C4??????72.0(d)????4.14-4.20，m??????????????????Sd-C3，Sd-C5Sd-C5??????78.7(d)????4.14-4.20，m??????????????????Sd-C4，Sd-C6Sd-C6??????63.1(t)????4.33，m4.51，br?d(11.6)???????Sd-C4，Sd-C5，Sd-C4，Sd-C5
The 0.1N H that each 30mg of Compound I, II, III and IV is dissolved in 3ml is respectively got in the acid hydrolysis of Compound I, II, III and IV
2SO
4In the methyl alcohol, reflux half an hour, methyl alcohol is removed in decompression, with saturated Ba (OH)
2The solution neutralization is filtered, and removes precipitation, and filtrate decompression is concentrated into dried, uses column chromatography (silica gel 10g, CHCl then
3: MeOH=200: 1 → 100: 1 → 60: 1 → 10: 1) separate, obtain the mixture of compound V and sugar.Compound V:UV (EtOH) λ
Max(log ε): 221.0 (4.20) nm, IR (KBr) ν
Max: 3446,2971,2935,1713,1680,1646cm
-1,
1HNMR,
13CNMR,
1H-
1H COSEY (the relevant spectrum of hydrogen-hydrogen) and HMBC data see Table 12, and through the thin-layer chromatography inspection, compound V is consistent with Caudatin standard substance Rf value.
Table 12. compound 5
1H,
13C NMR,
1H-
1H COSEY and HMBC data
13C?NMR???
1H?NMR?????????????????????
2H-
1H???????HMBC1α????????????39.8(t)????1.17，m?????????????????????C-2H，C-9H????C2，C9，C101β??????????????????????????????????1.76，m???????????????????????????????????C2，C9，C102α????????????31.7(t)????1.80，m?????????????????????C-3H??????????C1，C3，C102β??????????????????????????????????2.32，br?d(6.8)???????????????????????????C1，C103α????????????73.20(d)???3.51，m?????????????????????C-2H??????????Sa-C14α????????????42.8(t)????1.88，m?????????????????????C-3H??????????C2，C5，C6，C104β??????????????????????????????????2.32，m???????????????????????????????????C2，C5，C6，C105??????140.5(s)6??????119.2(d)???5.36，br?s??????????????????C-7H??????????C8，C107??????34.2(t)????2.19，m?????????????????????C-6H??????????C5，C6，C8，C98??????74.9(s)??????????????????????????????????????????????C8，C9，C149??????45.2(d)????1.57，br?d(3.1)?????????????C-11H?????????C10，C14，C1910?????38.0(s)11α????????25.5(t)????1.70-1.77，m????????????????C-9H，C-12H???C8，C9，C10，C1211β??????????????????????????????1.93-1.95，m??????????????????????????????C8，C9，C10，C1212?????72.6(d)????4.55，dd(4.3，11.8)?????????C-11H?????????C11，C13，C17，C18，
C′113?????58.6(s)14?????89.9(s)15α???????34.2(t)????1.93-1.95，m????????????????C-16H?????????C815β??????????????????????????????2.00-2.07，m??????????????????????????????C816α???????33.3(t)????1.70-1.77，m????????????????C-15H?????????C14，C15，C2016β??????????????????????????????2.92，ddd(4.9，9.7，12.6)?????????????????C14，C15，C2017?????92.9(s)??????????????????????????????????????????????C13，C17，C2018?????10.5(q)????1.55，s???????????????????????????????????C13，C12，C14，C1719?????18.6(q)????1.19，s???????????????????????????????????C1，C5，C9，C1020?????209.0(s)21?????27.6(q)????2.22，s???????????????????????????????????C201′????167.4(s)2′????114.2(d)???5.58，s?????????????????????C-7′H????????C1′，C3′，C4′，C7′3′????165.4(s)4′????39.4(d)????2.46，qq(6.8)???????????????C5′，6′H????C3′，C5′，C6′5′????21.3(q)????2.13，d(6.7)????????????????C-4′H????????C4′，C6′6′????21.4(q)????1.13，d(6.7)????????????????C-4′H????????C4′，C6′7′????16.7(q)????2.16，d(1.2)????????????????C-2′H????????C2′，C3′，C4′
Claims (11)
1. extraction separation has the novel carbon-21 steroidal glycosides of antitumor action from the Chinese medicine Root of Bunge Auriculate, it is characterized in that separating the carbon-21 steroidal glycosides that obtains 4 kinds of novelties is: Auriculoside A glycosides A, Auriculoside A glycosides B, the new glycosides A of Root of Bunge Auriculate, the new glycosides B of Root of Bunge Auriculate and the mixture-radix cynanchi bungei total glucoside B that includes the carbon-21 steroidal glycosides of these 4 kinds of novelties, the carbon-21 steroidal glycosides of 4 kinds of novelties is the chemical structural formulas with following formula, and wherein R is a sugar chain.
2. novel carbon-21 steroidal glycosides according to claim 1, it is characterized in that among the Auriculoside A glycosides A that R is β-D-glucopyanosyl base-(1 → 4)-α-L-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl (1 → 4)-β-D-Apocynum cannabinum pyranoside.
3. novel carbon-21 steroidal glycosides according to claim 1, it is characterized in that among the Auriculoside A glycosides B that R is β-D-glucopyanosyl base-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-digoxigenin pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.
4. novel carbon-21 steroidal glycosides according to claim 1, it is characterized in that among the new glycosides A of Root of Bunge Auriculate that R is β-D-glucopyanosyl base-(1 → 4)-β-D-Apocynum cannabinum pyrans glycosyl-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.
5. novel carbon-21 steroidal glycosides according to claim 1, it is characterized in that among the new glycosides B of Root of Bunge Auriculate that R is β-D-glucopyanosyl base-(1 → 4)-β-D-Folium seu Cortex Nerii pyrans glycosyl-(1 → 4)-β-D-digoxigenin pyrans glycosyl-(1 → 4)-β-D-Apocynum cannabinum pyranoside.
6. mixture according to claim 1 is characterized in that radix cynanchi bungei total glucoside B is the carbon-21 steroidal glycosides that includes Auriculoside A glycosides A, Auriculoside A glycosides B, the new glycosides A of Root of Bunge Auriculate, new these the 4 kinds of novelties of glycosides B of Root of Bunge Auriculate
7. compound according to claim 1 and mixture is characterized in that the cytotoxic activity to four kinds of human cancer cell strains.
8. compound according to claim 1 and mixture, the apoptotic effect that it is characterized in that inducing human cervical carcinoma cell Hela etc.
9. mixture according to claim 1-radix cynanchi bungei total glucoside B is characterized in that mice transplanted tumor S
180The restraining effect of sarcoma, EC ascites carcinoma solid tumor.
10. compound according to claim 1, the pharmaceutical composition of forming with pharmaceutically acceptable carrier of its antitumor significant quantity.
11. mixture according to claim 1-radix cynanchi bungei total glucoside B, the pharmaceutical composition of forming with pharmaceutically acceptable carrier of its antitumor significant quantity.
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| CNB001363646A CN1152044C (en) | 2000-12-16 | 2000-12-16 | C21 steriod glycoside extracted from white fleece flower root with antineoplastic function |
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| CNB001363646A CN1152044C (en) | 2000-12-16 | 2000-12-16 | C21 steriod glycoside extracted from white fleece flower root with antineoplastic function |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357309C (en) * | 2005-09-15 | 2007-12-26 | 浙江省医学科学院 | Carbon-21 steroidal glycosides possessing immunological suppression action |
| CN100429217C (en) * | 2004-12-29 | 2008-10-29 | 中国人民解放军第二军医大学 | Saponin compound, general saponin of cynanchum bunaei and application in medication for treating disease of gstrointestinal tract |
| CN100450490C (en) * | 2007-02-07 | 2009-01-14 | 江苏省中医药研究院 | Use of caudatin-3-O-beta-D-cymaroside as medicament for treating tumour |
| CN113817614A (en) * | 2021-11-02 | 2021-12-21 | 盐城师范学院 | High-efficiency synthesis of C21Steroid glycoside colletotrichum gloeosporioides Z-44 and application thereof |
-
2000
- 2000-12-16 CN CNB001363646A patent/CN1152044C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429217C (en) * | 2004-12-29 | 2008-10-29 | 中国人民解放军第二军医大学 | Saponin compound, general saponin of cynanchum bunaei and application in medication for treating disease of gstrointestinal tract |
| CN100357309C (en) * | 2005-09-15 | 2007-12-26 | 浙江省医学科学院 | Carbon-21 steroidal glycosides possessing immunological suppression action |
| CN100450490C (en) * | 2007-02-07 | 2009-01-14 | 江苏省中医药研究院 | Use of caudatin-3-O-beta-D-cymaroside as medicament for treating tumour |
| CN113817614A (en) * | 2021-11-02 | 2021-12-21 | 盐城师范学院 | High-efficiency synthesis of C21Steroid glycoside colletotrichum gloeosporioides Z-44 and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1152044C (en) | 2004-06-02 |
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