CN105218615A - A kind of natural new compound and Synthesis and applications thereof - Google Patents
A kind of natural new compound and Synthesis and applications thereof Download PDFInfo
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- CN105218615A CN105218615A CN201510614197.2A CN201510614197A CN105218615A CN 105218615 A CN105218615 A CN 105218615A CN 201510614197 A CN201510614197 A CN 201510614197A CN 105218615 A CN105218615 A CN 105218615A
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- leaf
- root
- saponin
- dolichos
- falcate dolichos
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Abstract
The invention discloses a kind of natural new compound and Synthesis and applications thereof.This compound structure is novel, anti-tumor activity is strong, be separated from dolichos falcatus Klein (Dolichos? falcata? Klein) root Root or leaf of Falcate dolichos, also disclose its preparation method, alcohol extracting Root or leaf of Falcate dolichos meal, concentrating under reduced pressure, through silica gel column chromatography, with chloroform-methanol gradient elution, separating-purifying obtains described compound, and this new compound outward appearance is white powder, for triterpenoid saponin, molecular formula is C
36h
56o
10, called after: Root or leaf of Falcate dolichos saponin(e C.
Description
Technical field
The invention belongs to medical art, be specifically related to a kind of natural new compound structure and preparation method thereof and application.
Background technology
Root or leaf of Falcate dolichos is the root of pulse family Dolichos plant dolichos falcatus Klein (DolichosfalcataKlein), is commonly called as fiber crops in fiber crops, fiber crops three sections, beans leaf Euphorbia sessiliflora Roxb, medicinal on the ground such as Yunnan, Guizhou, has expelling wind and activating blood circulation, the effects such as hemostasis and pain-relieving.By Literature Consult Root or leaf of Falcate dolichos chemical composition and pharmacology activity research less, the people such as Chongqing, Hunan, Pu carried out the research of chemical composition to it, find that wherein main saponin constituent is Root or leaf of Falcate dolichos saponin A [Chongqing, Hunan, Pu etc., the triterpene saponin component (1) of Root or leaf of Falcate dolichos, Yunnan plant research 1984,6 (3) 321-324].70 ~ eighties of 20th century Guiyang Medical College, yellow thickly the people such as to engage carry out rough antitumous effect research to Root or leaf of Falcate dolichos total saponins.From Root or leaf of Falcate dolichos, be not also separated the report obtaining Root or leaf of Falcate dolichos saponin(e C at present, the report that new and literature query does not have Root or leaf of Falcate dolichos saponin(e C is yet looked in the online version database Scifinder data of chemical abstracts, for new natural compounds, up to the present the active report carrying out furtheing investigate of monomer component of Root or leaf of Falcate dolichos saponin(e was not also carried out, especially without the relevant report of Root or leaf of Falcate dolichos saponin monomer component comprises anti-tumor activity.We carry out comprehensive chemical constitution study to Root or leaf of Falcate dolichos, are separated first and obtain natural new compound Root or leaf of Falcate dolichos saponin(e C, carry out anti-tumor activity first study the single saponin constituent of Root or leaf of Falcate dolichos natural new compound Root or leaf of Falcate dolichos saponin(e C from Root or leaf of Falcate dolichos.
Summary of the invention
Blank for prior art, the present invention is new activeconstituents Root or leaf of Falcate dolichos saponin(e C openly, and it can obtain from the root of natural phant dolichos falcatus Klein, and its novel structure, anti-tumor activity are strong, also disclose its preparation method.
Technical scheme of the present invention is as follows:
1. natural new compound Root or leaf of Falcate dolichos saponin(e C or its pharmacy acceptable salt shown in formula I:
2. the preparation method of the natural new compound Root or leaf of Falcate dolichos saponin(e C described in technical scheme 1, the method comprises: alcohol extracting Root or leaf of Falcate dolichos meal, and concentrating under reduced pressure, through silica gel column chromatography, with chloroform-methanol gradient elution, separating-purifying obtains the natural new compound Root or leaf of Falcate dolichos saponin(e C described in technical scheme 1.
3. natural new compound Root or leaf of Falcate dolichos saponin(e C shown in the formula I described in technical scheme 1 or its pharmacy acceptable salt are preparing the application in antitumor drug.
4. the application described in technical scheme 3, described tumour is lung cancer or liver cancer.
5. prevent and/or treat a medicine for tumour, its activeconstituents is natural new compound Root or leaf of Falcate dolichos saponin(e C or its pharmacy acceptable salt shown in the formula I described in technical scheme 1.
6. according to technical scheme 5, prevent and/or treat the medicine of tumour, described medicine is injection, powder injection, tablet, capsule, granule or dripping pill.
7. according to technical scheme 5 or 6, prevent and/or treat the medicine of tumour, described tumour is lung cancer or liver cancer.
Compared with prior art, beneficial effect of the present invention:
The present invention is separated the Root or leaf of Falcate dolichos saponin(e C obtaining and have novel chemical structure first, it is a kind of natural new compound, this Root or leaf of Falcate dolichos saponin(e C has stronger antitumour activity, can the growth of remarkable Tumor suppression, has no significant effect the thymus index of tumor-bearing mice and spleen index simultaneously.
Accompanying drawing explanation
Fig. 1 is Root or leaf of Falcate dolichos saponin(e C plane structure chart.
Fig. 2 is Root or leaf of Falcate dolichos saponin(e C relative configuration figure.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Following embodiment test materials used all can be bought from commercial channel except the compounds of this invention prepared.
Embodiment 1: component separating
Root or leaf of Falcate dolichos 10Kg, extracts 3 times with 70% alcohol heat reflux, the medicinal extract 1250g of concentrating under reduced pressure after pulverizing, through silica gel column chromatography, with chloroform-methanol gradient elution, gradient is chloroform: the volume ratio of methyl alcohol is 50:1,30:1,20:1,10:1,5:1,3:1,1:1, detect through TLC, same section combines, and is divided into 6 parts, is numbered Fr.1, Fr.2, Fr.3, Fr.4, Fr.5, Fr.6 respectively; Wherein Fr.3 is through silica gel column chromatography, and dextran gel column chromatography separating-purifying obtains the compound of 500mg, called after Root or leaf of Falcate dolichos saponin(e C.
Embodiment 2: Root or leaf of Falcate dolichos saponin(e C-structure is identified
Root or leaf of Falcate dolichos saponin(e C is white powder, is dissolved in methyl alcohol, and for determining that its chemical structure has made following collection of illustrative plates to Root or leaf of Falcate dolichos saponin(e C: (1) spectrum has done optical rotational activity spectrum, UV spectrum and infrared spectra, (2) nucleus magnetic resonance one dimension spectrum has been done
1h,
13c and DEPT compose, (3) Two-dimensional NMR Map be HMBC, HSQC and
1h-
1hCOSY composes, and (4) NOE tests.
Below total qualification process is described in detail: compose according to one dimension nuclear-magnetism
1h,
13cNMR and DEPT composes, and be tentatively judged as a triterpenoid saponin, by literature survey, the people such as Chongqing, Hunan, Pu were once separated triterpenoid saponin Root or leaf of Falcate dolichos glucoside A (DolirosideA) obtained from this plant, and both nuclear magnetic datas have very large similarity.It is C that the quasi-molecular ion peak 671 ([M+Na]+) provided according to ESI+-MS, HRESIMS ([M+Na]+, m/z671.3769) and NMR data obtain its molecular formula
36h
56o
10, degree of unsaturation is 9.In infrared spectra, 3423cm
-1for hydroxyl group absorption peak, 2945,2928cm
-1for methyl, methylene radical absorption peak, 1712cm
-1for carbonyl absorption peak.By the further confirmation of two-dimensional nucleus magnetic spectrum data, especially in HMBC spectrum, H2-1 (δ 2.30,2.25,2H, ABd, J=-17.0Hz) and H-3 (δ 4.58,1H, s) is simultaneously relevant to C-2 (δ 213.3); And H2-23 (δ 3.53,3.39,2H, ABd, J=-9.3Hz) and C-3 (δ 83.8), C-5 (δ 47.7), C24 (δ 13.7) is correlated with, H-3, H-5 (δ 1.95,1H, overlapped), H3-24 (δ 0.65,3H, s) is relevant to C-23 (δ 64.1).The functional group that these conclusions show with infrared spectra conforms to.By further HSQC, HMBC and
1h-
1hCOSY spectrum analysis (table 1), and similar compound NMR comparing, the two dimensional structure finally determining this compound is Fig. 1.
For determining the relative configuration of Root or leaf of Falcate dolichos saponin(e C, we have done NOE experiment, H-3 and H-1 α in ROESY spectrogram, and H-5, H-23a are relevant, prove that H-3 is α configuration; H-23a and H-3 is correlated with, and H3-24 and H3-25 is correlated with simultaneously, proves that hydroxyl is substituted in C-23 position instead of C-24 position.By comprehensive REOSY spectrum analysis (data are as table 1), other substituent configuration and Root or leaf of Falcate dolichos glucoside A configuration completely the same as Fig. 2.This compound specific rotation light value [α] 25.5D+42.43 (c0.31, MeOH), with other analogues be all on the occasion of, and the triterpenoid saponin of the type is all oleanane type but not its enantiomorph, consider it is relationship type on the product and such triterpene source of students that simultaneously obtain in same plant, composition graphs modal data and literature survey finally determine that the chemical structure of Root or leaf of Falcate dolichos saponin(e C is such as formula shown in I.This compound structure is unique, and the functional group on C-2 position and C-4 position and known compound have bigger difference, are defined as new compound, called after Root or leaf of Falcate dolichos saponin(e C through scifinder site search.
Compound structure data are as follows:
Molecular formula is C
36h
56o
10, molecular weight is 648; [α] 25.5D+42.43 (c0.31, MeOH); UV (MeOH) λ
max(log ε): 203 (3.13) nm; IR (KBr) ν
max3423,2945,2928,1712,1631,1462,1394,1279,1261,1164,1077,1052,644cm
– 1; PositiveESIMS:m/z671 [M+Na]
+; PositiveHRESIMS [M+Na]
+m/z671.3769 (calcdforC
36h
56o
10na [M+Na]
+, 671.3766);
1h,
13the nuclear magnetic datas such as C are as table 1.
Table 1. Root or leaf of Falcate dolichos saponin(e C nuclear magnetic data table (inMeOD, δ inppm (JinHz).
The experimental study of the anti-tumor activity of embodiment 2 the compounds of this invention
(1) Root or leaf of Falcate dolichos saponin(e C is to the tumor-inhibiting action of Lewis lung cancer mouse
1. material
1.1 knurl strains
Lewis lung cancer is purchased from China Medicine University's tumor experiment room.
1.2 animal
C57BL/6 (C57BL/6JMouse) mouse, 50, male, body weight 18 ~ 22g, purchased from Kunming Chu Shang Science and Technology Ltd., animal conformity certification SCXK (Hunan) K2012-0002.
1.3 medicine
Root or leaf of Falcate dolichos saponin(e C is prepared by embodiment 1 by research institute of Yunnan Plant Pharmaceutical Industry Co., Ltd. laboratory; Endoxan (CY) purchased from SHANXI POWERDONE PHARMACEUTICAL.,LTD, lot number: 20141102.Root or leaf of Falcate dolichos saponin(e C is according to mouse preliminary result, if high, medium and low three dosage: 50mg/kg, 100mg/kg, 200mg/kg.
1.4 instrument
Inverted microscope, Chongqing optical instrument factory; Bechtop, Suzhou Decontamination Equipment Plant; LXJ2I type whizzer, Shanghai medical analytical instrument factory; Three use electric heating constant-temperature water-bath tank, Chang'an, Beijing scientific instrument factory; Vortex mixer, Zhejiang Le Cheng electrical apparatus factory.
2. experimental technique
After selecting inoculation Lewis lung cancer 14d, the mice with tumor that generalized case is good, de-neck is put to death, and asepticly strips tumor tissues, homogenate, becomes 1 × 10 with normal saline dilution
7/ ml, living cell counting number >95%.Get 50 C57BL/6 mouse, every mouse right armpit subcutaneous vaccination 0.2mL tumor cell suspension.Then mouse is divided into 5 groups at random, often organizes 10, be respectively: lotus knurl model group, positive group, high, medium and low three the dosage groups of Root or leaf of Falcate dolichos saponin(e C.Each group of mouse administration as follows, every day 1 time, continuous 12 days: positive group intraperitoneal injection of cyclophosphamide 30mg/kg; The Root or leaf of Falcate dolichos saponin(e C of high, medium and low three dosage component of Root or leaf of Falcate dolichos saponin(e C other abdominal injection 200mg/kg, 100mg/kg, 50mg/kg; The physiological saline of the capacity such as lotus knurl model group abdominal injection, 0.1mL/10g.Within after administration the 13rd day, put to death mouse, strip knurl body and weigh, calculate tumour inhibiting rate; And win spleen and thymus gland, weigh, calculate spleen index and thymus index.Tumour inhibiting rate=(the heavy ﹣ medication group of the average knurl of control group average knurl weight) average knurl × 100% of/control group; Heavy (the chest gland weight)/body weight (unit: mg/g) of spleen index (thymus index)=spleen.
3. result
From table 2, the average knurl of model group is great in 1g, represents modeling success.Positive drug CY significantly can suppress the growth of Mice Bearing Lewis Lung Cancer, inhibitory rate 81.8%.Root or leaf of Falcate dolichos saponin(e C is high, middle, and dosage group has obvious restraining effect to Mice Bearing Lewis Lung Cancer, and tumour inhibiting rate is respectively 57.6% and 50.8%, compares have significant difference (P<0.01) with model group.Root or leaf of Falcate dolichos saponin(e C low dose group has certain restraining effect to Mice Bearing Lewis Lung Cancer, and tumour inhibiting rate is 27.3%, compares there was no significant difference (P>0.05) with model group.CY significantly can suppress thymus index and the spleen index (P<0.01) of tumor-bearing mice while tumor suppression, and Root or leaf of Falcate dolichos saponin(e C tri-dosage groups have no significant effect the thymus index of tumor-bearing mice and spleen index.
Table 2. Root or leaf of Falcate dolichos saponin(e C is to the restraining effect of Mice Bearing Lewis Lung Cancer transplanted tumor
* P<0.05, * * P<0.01, compares with model group
(2) Root or leaf of Falcate dolichos saponin(e C is to the tumor-inhibiting action of Heps liver cancer mouse
1. material
1.1 knurl strains
Rat liver cancer solid-type (Heps), purchased from China Medicine University's tumor experiment room.
1.2 animal
ICR mouse, 50, male and female half and half, body weight 18 ~ 22g, purchased from Kunming Chu Shang Science and Technology Ltd., animal conformity certification SCXK (Hunan) K2012-0002.
1.3 medicine
Root or leaf of Falcate dolichos saponin(e C is prepared by embodiment 1 by research institute of Yunnan Plant Pharmaceutical Industry Co., Ltd. laboratory; Endoxan (CY) purchased from SHANXI POWERDONE PHARMACEUTICAL.,LTD, lot number: 20141102.Root or leaf of Falcate dolichos saponin(e C is according to mouse preliminary result, if high, medium and low three dosage: 50mg/kg, 100mg/kg, 200mg/kg.
1.4 instrument
Inverted microscope, Chongqing optical instrument factory; Bechtop, Suzhou Decontamination Equipment Plant; LXJ2I type whizzer, Shanghai medical analytical instrument factory; Three use electric heating constant-temperature water-bath tank, Chang'an, Beijing scientific instrument factory; Vortex mixer, Zhejiang Le Cheng electrical apparatus factory.
2. experimental technique
The ascites of the tumor-bearing mice of 8d after aseptic aspiration goes down to posterity, with stroke-physiological saline solution dilution, adjustment cell concn to 5.0 × 10
7/ ml, is inoculated in mouse right fore subcutaneous, every 0.2ml.Then mouse is divided into 5 groups at random, often organizes 10, be respectively: lotus knurl model group, positive group, high, medium and low three the dosage groups of Root or leaf of Falcate dolichos saponin(e C.Each group of mouse administration as follows, every day 1 time, continuous 12 days: positive group intraperitoneal injection of cyclophosphamide 30mg/kg; The Root or leaf of Falcate dolichos saponin(e C of high, medium and low three dosage component of Root or leaf of Falcate dolichos saponin(e C other abdominal injection 200mg/kg, 100mg/kg, 50mg/kg; The physiological saline of the capacity such as lotus knurl model group abdominal injection, 0.1mL/10g.Within after administration the 13rd day, put to death mouse, strip knurl body and weigh, calculate tumour inhibiting rate; And win spleen and thymus gland, weigh, calculate spleen index and thymus index.Tumour inhibiting rate=(the heavy ﹣ medication group of the average knurl of control group average knurl weight) average knurl × 100% of/control group; Heavy (the chest gland weight)/body weight (unit: mg/g) of spleen index (thymus index)=spleen.
3. result
From table 3, the average knurl of model group is great in 1g, represents modeling success.Positive drug CY significantly can suppress the growth of mice Heps liver cancer, inhibitory rate 69.0%.Root or leaf of Falcate dolichos saponin(e C high dose group has obvious restraining effect to mice Heps, and its inhibitory rate 31.7% compares with model group and has significant difference (P<0.01); In Root or leaf of Falcate dolichos saponin(e C, low dose group has certain restraining effect to mice Heps, and tumour inhibiting rate is respectively 19.0% and 9.5%, the difference (P>0.05) that compares with model group that there are no significant.CY significantly can suppress the thymus index of tumor-bearing mice while tumor suppression, and Root or leaf of Falcate dolichos saponin(e C high dose group can significantly improve the thymus index of tumor-bearing mice, in, low dose group has no significant effect the thymus index of tumor-bearing mice and spleen index.
Table 3 Root or leaf of Falcate dolichos saponin(e C is to the restraining effect of Transplanted murine tumors Heps
* P<0.05, * * P<0.01, compares with model group
Research shows: the tumour inhibiting rate of Root or leaf of Falcate dolichos saponin(e C of the present invention is high less than endoxan, but endoxan can significantly impact thymus index and the spleen index of mouse while tumor suppression, and Root or leaf of Falcate dolichos saponin(e C tri-dosage groups have no significant effect the thymus index of tumor-bearing mice and spleen index, and there is stronger antitumour activity.
Claims (7)
1. natural new compound Root or leaf of Falcate dolichos saponin(e C or its pharmacy acceptable salt shown in formula I:
2. the preparation method of natural new compound Root or leaf of Falcate dolichos saponin(e C according to claim 1, its spy is that the method comprises: alcohol extracting Root or leaf of Falcate dolichos meal, concentrating under reduced pressure, through silica gel column chromatography, with chloroform-methanol gradient elution, separating-purifying obtains natural new compound Root or leaf of Falcate dolichos saponin(e C according to claim 1.
3. natural new compound Root or leaf of Falcate dolichos saponin(e C shown in formula I according to claim 1 or its pharmacy acceptable salt are preparing the application in antitumor drug.
4. application according to claim 3, is characterized in that: described tumour is lung cancer or liver cancer.
5. prevent and/or treat a medicine for tumour, its activeconstituents is natural new compound Root or leaf of Falcate dolichos saponin(e C or its pharmacy acceptable salt shown in formula I according to claim 1.
6. prevent and/or treat the medicine of tumour according to claim 5, it is characterized in that: described medicine is injection, powder injection, tablet, capsule, granule or dripping pill.
7. according to claim 5 or 6, prevent and/or treat the medicine of tumour, it is characterized in that: described tumour is lung cancer or liver cancer.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003321369A (en) * | 2002-05-08 | 2003-11-11 | Kinji Ishida | Composition to be perorally administered for mitigating stress |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003321369A (en) * | 2002-05-08 | 2003-11-11 | Kinji Ishida | Composition to be perorally administered for mitigating stress |
Non-Patent Citations (1)
| Title |
|---|
| KAZUKO YOSHIKAWA ET AL.: "New Oleanene Triterpenoid Saponins from Madhuca longifolia", 《J. NAT. PROD.》 * |
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