CN101121739B - Hydrolysable tannin and application thereof - Google Patents

Hydrolysable tannin and application thereof Download PDF

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Publication number
CN101121739B
CN101121739B CN200710030117A CN200710030117A CN101121739B CN 101121739 B CN101121739 B CN 101121739B CN 200710030117 A CN200710030117 A CN 200710030117A CN 200710030117 A CN200710030117 A CN 200710030117A CN 101121739 B CN101121739 B CN 101121739B
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methanol
eluted fractions
water
collect
methyl alcohol
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CN101121739A (en
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姜志宏
吴少瑜
田中山中崇
文晓芸
刘中秋
岩田弘美
河野高畑勋
吴曙光
广濑小野
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Southern Medical University
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Southern Medical University
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Abstract

The invention provides a novel hydrolytic tannin of the pyran glucose category containing the coffee acyl. The chemical structure is as shown in formula (1); the compound of the invention can inhibitthe proliferation of tumor; the compound has the better anti-tumor activity and can be used to prepare the anti-tumor drugs.

Description

A kind of hydrolysable tannin and application thereof
Technical field
The present invention relates to organic chemistry filed, be specifically related to contain the Glucopyranose class hydrolysable tannin of coffee acyl.
Background technology
Tannin is called vegatable tannin again, is that a class extensively is present in the intravital complicated pluralism phenolic compound of plant, and wherein hydrolysable tannin is ester or the glycosides that phenolic acid and polyvalent alcohol form.
People such as Zhi-hong Jiang and Yoko Hirose have found the multiple Glucopyranose class hydrolysable tannin that contains coffee acyl and galloyl in calendar year 2001 in Balaenoptera borealis Lesson (Balanophora japonica Makino); as: 1-O-(E)-coffee acyl-3-O-galloyl-β-D-Glucopyranose; this compound is a kind of yellow amorphous powder, [α] D 15-48.9 ° (c=0.8, MeOH), hydrolyzable is gallic acid and 1-O-(E)-coffee acyl-β-D-Glucopyranose under the effect of tannase; 3-O-(E)-coffee acyl-4-O-galloyl-D-Glucopyranose, this compound are a kind of yellow amorphous powders, [α] D 15-144.2 ° of (c=0.7; MeOH); hydrolyzable is gallic acid and 3-O-(E)-coffee acyl-D-Glucopyranose [Caffeoyl under the effect of tannase; Coumaroyl; Galloyl; and Hexahydxydiphenoyl Glucoses from Balanophora japonica.Zhi-hongJiang, Yoko Hirose et.Chem.Pharm.Bull.49 (7) 887-892 (2001)].But do not have to disclose the purposes of this compounds in the above-mentioned literary composition, do not see other reports yet.
Summary of the invention
The object of the present invention is to provide a kind of new Glucopyranose class hydrolysable tannin that contains coffee acyl.
Another object of the present invention is to provide this new Glucopyranose class hydrolysable tannin application in pharmacy that contains coffee acyl.
The Glucopyranose class hydrolysable tannin that contains coffee acyl that the present invention is new is:
A kind of hydrolysable tannin, its chemical structure is
A kind of hydrolysable tannin that this compound is separated from Balaenoptera borealis Lesson (Balanophora japonica Makino mainly is distributed in south China and Japan) is the unformed powder of brown, molecular formula C 28H 24O 17, specific rotatory power [α] D 16-219.3 ° (c=0.6 MeOH), is a kind of hydrolysable tannin, is compound d and Verbindung with its back hydrolyzable in alkaline solution that methylates, and hydrolysis reaction is shown in (II).
Figure G2007100301174D00021
The compounds of this invention can extract acquisition by following method from Balaenoptera borealis Lesson:
(1) get Balaenoptera borealis Lesson, 70% methyl alcohol or alcohol immersion 24 hours are at room temperature used in chopping, filter, and filtrate decompression is removed alcohol, get general extractive;
(2) general extractive dilutes with suitable quantity of water, uses ether, ethyl acetate extraction then successively, the molten part of fetching water;
(3) with water-soluble portion through MCI-gel CHP20P column chromatography, wash the desaccharification compounds earlier with water, use 10%～40% methyl alcohol gradient elution then, collect the methanol-eluted fractions thing;
(4) eluate of step (3) gained is through Chromatorex ODS, with behind the water elution with 10～80% methanol-eluted fractions, collect 40～80% meoh eluates, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; Go up MCI-gel CHP20P again, with behind the water elution with 10～80% methanol-eluted fractions, collect 40～80% meoh eluates, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; Go up Sephadex LH-20 chromatography then, with behind the water elution with 10～80% methanol-eluted fractions, collect 40-80% methanol-eluted fractions thing, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; After TSK gel Toyopearl HW-40F column chromatography, with behind the water elution with 10～80% methanol-eluted fractions, collect that TLC goes up FeCl in 30～50% methanol-eluted fractions things 3Solution shows the flow point of mazarine spot, merges the wash-out flow point of the column chromatography that contains single spot, waves most solvent, gets final product.
The compounds of this invention has anti-tumor activity, can suppress the propagation of tumour cell, can be used to prepare the medicine for the treatment of tumour, and this medicine is made up of The compounds of this invention and medically acceptable auxiliary material, and wherein the content of The compounds of this invention is 5～20% (W/W).
To prove that The compounds of this invention has anti-tumor activity by anticancer experiment in vitro below.
One, adopts human hepatoma cell strain HepG 2The anti-tumor activity that carries out The compounds of this invention for model detects.
1, experimental technique:
1) HepG 2When cell cultures grows to exponential phase of growth, promptly with 0.25% tryptic digestion, the centrifugal 3min of 1000 * g, cell precipitation is adjusted to 6 * 10 with the DMEM substratum of 10%FBS 4Individual/ml, 190 μ l are inoculated in the every hole of 96 well culture plates, place 37 ℃, 5%CO 2And cultivated 24 hours under the saturated humidity condition.
2) establish 5 multiple holes for every group, add 10 μ l The compounds of this invention in every hole, continue under the above-mentioned condition to cultivate 48 hours.Experiment repeats 3 times.
3) cell cultures is after 48 hours, and every hole adds CCK-8 (the cell counting kit 8) reagent of 10 μ l, 37 ℃, 5%CO 2And continue under the saturated humidity condition to cultivate 1.5 hours.
4) be determined at the absorbance that wavelength is the 450nm place (OD) with microplate reader, 650nm is as the reference wavelength, and inhibitory rate of cell growth by formula; Inhibiting rate=(control wells OD value-experimental port OD value)/control wells OD value) * 100% calculate, and with the IC of each component of compusyn computed in software 50
2, experimental result:
Table 1 The compounds of this invention is to HepG 2The influence of cell proliferation
Figure G2007100301174D00031
The normal HepG that cultivates 2Cell is monolayer growth, and cell density uniform distribution, cell are the fusiformis well-grown.Add the Balaenoptera borealis Lesson component after 48 hours in culturing cell, cell retraction occurs, becomes circle, and is floating, and along with time lengthening, the buoyant cell increases.The The compounds of this invention of each dosage is to HepG 2The inhibiting rate of cell growth is as shown in table 1, and The compounds of this invention is to HepG 2The inhibition degree of cell proliferation and the positive correlation that increases progressively into of dosage, visible the present invention can suppress the propagation of tumour cell, has anti-tumor activity.
Two, The compounds of this invention is to the influence of lotus S180 mouse tumor size
1, under aseptic condition, extracted S180 knurl source mouse out knurl liquid in back 10 days in the inoculation of going down to posterity, adjust oncocyte number to 5 * 10 with stroke-physiological saline solution from the abdominal cavity 6Individual/ml.
2, get 21 mouse (18-22g/ is only), the knurl liquid 0.2ml of inoculation step 1 gained is divided into following 5 groups at random in the subcutaneous back of right thigh respectively:
(1) The compounds of this invention low dose group: give the The compounds of this invention treatment, 5.0mg/kg;
(2) dosage group in the The compounds of this invention: give the The compounds of this invention treatment, 10.0mg/kg;
(3) The compounds of this invention high dose group group: give the The compounds of this invention treatment, 20.0mg/kg;
(4) positive controls: give NVP-XAA 723 (Epigallocatechin-3-gallate, EGCG) treatment, 20mg/kg;
(5) blank group: physiological saline is irritated stomach.
Inoculation while next day gastric infusion, dosage 0.2ml, be administered once every day, and continuous 10 days, drug withdrawal was weighed next day, peeled off the subcutaneous tumors body after the dissection, claimed knurl heavy.Be calculated as follows tumour inhibiting rate (%)=(the average knurl of the average knurl weight-administration of control group group is heavy)/average knurl of control group heavy * 100%.
Table 2 The compounds of this invention is to the influence of lotus S180 mouse tumor size
Figure G2007100301174D00041
The result is as shown in table 2, and The compounds of this invention increases with dosage the restraining effect of lotus S180 mouse tumor, and its effect and EGCG are suitable.
Embodiment
Preparation example
1, the acquisition of The compounds of this invention
(1) get Balaenoptera borealis Lesson, 70% methyl alcohol or alcohol immersion 24 hours are at room temperature used in chopping, filter, and filtrate decompression is removed alcohol, get general extractive;
(2) general extractive dilutes with suitable quantity of water, uses ether, ethyl acetate extraction then successively, the molten part of fetching water;
(3) with water-soluble portion through MCI-gel CHP20P column chromatography, wash the desaccharification compounds earlier with water, use 10%～40% methyl alcohol gradient elution then, collect the methanol-eluted fractions thing;
(4) eluate of step (3) gained is through Chromatorex ODS, with behind the water elution with 10～80% methanol-eluted fractions, collect 40～80% meoh eluates, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; Go up MCI-gel CHP20P again, with behind the water elution with 10～80% methanol-eluted fractions, collect 40～80% meoh eluates, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; Go up Sephadex LH-20 chromatography then, with behind the water elution with 10～80% methanol-eluted fractions, collect 40-80% methanol-eluted fractions thing, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; After TSK gel Toyopearl HW-40F column chromatography, with behind the water elution with 10～80% methanol-eluted fractions, collect that TLC goes up FeCl in 30～50% methanol-eluted fractions things 3Solution shows the flow point of mazarine spot, merges the wash-out flow point of the column chromatography that contains single spot, waves most solvent, promptly gets The compounds of this invention, and its purity is greater than 95%.
2, this compound identification and analysis:
1) method
(1) specific rotation is measured by JASCO DIP-370 digital polarimeter;
(2) 1H and 13C-NMR is measured by Varian Unity plus 500 and Varian Gemini 300 spectrometers;
Coupling constant (J) is represented with Hz, chemical shift is represented with δ (ppm), tetramethylsilane is interior mark, high resolution ESI mass spectrum is by Q-TOF mass spectrometer (Bruker Daltonics, MA, USA) measure, EI and FAB mass spectrum are measured by JEOL JMSDX-303 spectrometer, and glycerine is the mass spectral matrix of FAB.
(3) thin-layer chromatography Kieselgel 60 F 254(0.2mm thick, Merck), spot is by ultraviolet lamp and 2%FeCl for pre-bed board 3With 10% sulfuric acid spraying colour developing.
(4) hydrolysis reaction: extract 54mg is at anhydrous acetone 15ml, dimethylsulfate 1.5ml and K 2CO 31.5h refluxes in the mixing solutions of 2g.Filtering the back concentrates and silica gel column chromatography (2-20% MeOH in CHCl 3) purifying, (2ml) stirs 2hr in the methanol solution of adding 2%NaOMe in purified product, and with the HCl neutralization, water layer obtains the methylate compound with ether extraction.The column chromatography filler is by silica gel Kieselgel 60 (70-230 mesh, Merck), Sephadex LH-20 (25-100mm, Pharmacia Fine Chemical Co.Ltd.), MCI-gel CHP 20P (75-150mm, MitsubishiChemical Co.Ltd.), TSK gel Toyopearl HW-40F (Tosoh), Chromatorex ODS (100-200mesh, FujiSilysia Chemical), Bondapak C18 (125um, Waters).
(5) PGME Amide's is synthetic: extract 10.2mg, (S)-PGME 10mg, PyBop 18mg, HOBT 9mg and methylmorphorine 20ul in the solution of DMF (1mg) at stirring at room 2hr.Add water 15ml and extract with 15mln-butanol. the organic layer anhydrous Na 2SO 4Dry and concentrated, use silicagel column purifying CHCl at last 3-MeOH-H 2O (8: 2: 0.2).
2) result:
[α] D 16-219.3 ° of (c=0.6, MeOH) .Anal.Calcd for C 28H 24O 175/4 H 2O:C, 51.34; H, 4.08.Found:C, 51.39; H, 4.22.Negative FAB-MS m/z:631[M-H] -.Negative HR-ESI-MS m/z:631.0970[M-H] -(calcd.for C 28H 23O 17: 631.0935). 1H-NMR (500MHz, CD 3OD): δ 7.07 (1H, d, J=2Hz, caf-2), 6.78 (1H, d, J=8Hz, caf-5), 6.97 (1H, dd, J=2,8Hz, caf-6), 7.67 (1H, d, J=16Hz, caf-7), 6.31 (1H, d, J=16Hz, caf-8), 5.70 (1H, d, J=8Hz, glc-1), 3.64 (1H, t, J=8Hz, glc-2), 3.90 (1H, t, J=9Hz, glc-3), 4.93 (1H, t, J=9Hz, glc-4), 4.05 (1H, m, glc-5), 4.16 (1H, t, J=11Hz, glc-6a), 4.08 (1H, dd, J=3,11Hz, glc-6b), 7.24 (1H, s, 4,6-acyl-3 '), 4.70 (1H, d, J=2Hz, 4,6-acyl-2), 3.66 (1H, ddd, J=2,3,11Hz, 4,6-acyl-3), 2.18 (1H, dd, J=11,17Hz, 4,6-acyl-4a), 1.81 (1H, dd, J=3,17Hz, 4,6-acyl-4b). 13C-NMR data sees Table 2.
This compound of table 2 13C-NMR (125MHz) Spectral Data
High resolution ESI mass spectrum determines that this compound molecule formula is C 28H 24O 17. 1H-NMR shows a caffeoyl group, and one 1,4,6 three acidylate glucosyl group groups. 13Except the signal of glucose and caffeoyl group, find that also two ester carbonyl groups are arranged, interior ester carbonyl group, carboxylic acid carbonyl, two methynes (CH) among the C-NMR, a methylene radical (CH 2) and the signal of five phenyl ring that replace.According to 1H and 134,6 acyl group structure fragment and euphormisinM in this compound of the data-speculative of C-NMR 2 [3]Unanimity.This compound is methylated and basic hydrolysis obtains derivative 3d and confirmed above deduction.The coherent signal of anomeric proton and carbonyl carbon (formula III) determines that the position of coffee acyl is connected in the end group of glucose among the HMBC, and other acyl ester chain is connected in the C-4 of glucose, on 6 the hydroxyl.At last, adopt the PGME method to analyze (seeing formula IV) to compound 3, determine to be connected in sugared C-4, C-3 is configured as S in 6 the acyl group structure fragment.In sum, the molecular structure that can determine this compound is the structure shown in the formula (I).
Figure G2007100301174D00071
Application examples
Example one:
[preparation prescription]
Hydrolysable tannin 20g
Microcrystalline Cellulose 48g
Zulkovsky starch 30g
Talcum powder 2g
Make 1000 altogether, every contains this compound 100mg.
[preparation method]
Take by weighing this compound 20g, be diluted to 50g with Zulkovsky starch, mixing takes by weighing Microcrystalline Cellulose 48g again, and with 95% ethanol system softwood, the granulation of sieving, 50 ℃ of dryings of low temperature, whole grain adds talcum powder 2g, mixing, and compressing tablet (every 0.1g), quality inspection, packing, promptly.
[usage and dosage]
Each 3, every day 3 times.
[being suitable for the crowd]
Be suitable for various tumour patients.
Example two:
[preparation prescription]
Hydrolysable tannin 10g
Microcrystalline Cellulose 48g
Zulkovsky starch 40g
Talcum powder 2g
Make 1000 altogether, every contains this compound 100mg.
[preparation method]
Take by weighing this compound 10g, be diluted to 50g with Zulkovsky starch, mixing takes by weighing Microcrystalline Cellulose 48g again, and with 95% ethanol system softwood, the granulation of sieving, 50 ℃ of dryings of low temperature, whole grain adds talcum powder 2g, mixing, and compressing tablet (every 0.1g), quality inspection, packing, promptly.
[usage and dosage]
Each 3, every day 3 times.
[being suitable for the crowd]
Be suitable for various tumour patients.
Example three:
[preparation prescription]
Hydrolysable tannin 5g
Microcrystalline Cellulose 48g
Zulkovsky starch 30g
Talcum powder 2g
Make 1000 altogether, every contains this compound 100mg.
[preparation method]
Take by weighing this compound 5g, be diluted to 50g with Zulkovsky starch, mixing takes by weighing Microcrystalline Cellulose 48g again, and with 95% ethanol system softwood, the granulation of sieving, 50 ℃ of dryings of low temperature, whole grain adds talcum powder 2g, mixing, and compressing tablet (every 0.1g), quality inspection, packing, promptly.
[usage and dosage]
Each 3, every day 3 times.
[being suitable for the crowd]
Be suitable for various tumour patients.

Claims (5)

1. hydrolysable tannin, its molecular structure is
Figure F2007100301174C00011
2. the preparation method of the described hydrolysable tannin of claim 1, this method is made up of following steps:
(1) get Balaenoptera borealis Lesson, 70% methyl alcohol or alcohol immersion 24 hours are at room temperature used in chopping, filter, and filtrate decompression is removed alcohol, get general extractive;
(2) general extractive dilutes with suitable quantity of water, uses ether, ethyl acetate extraction then successively, water intaking dissolubility part;
(3) with water-soluble portion through MCI-gel CHP20P column chromatography, wash the desaccharification compounds earlier with water, use 10%～40% methyl alcohol gradient elution then, collect the methanol-eluted fractions thing;
(4) eluate of step (3) gained is through Chromatorex ODS, with behind the water elution with 10～80% methanol-eluted fractions, collect 40～80% meoh eluates, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; Go up MCI-gel CHP20P again, with behind the water elution with 10～80% methanol-eluted fractions, collect 40～80% meoh eluates, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; Go up Sephadex LH-20 chromatography then, with behind the water elution with 10～80% methanol-eluted fractions, collect 40-80% methanol-eluted fractions thing, reclaim under reduced pressure methyl alcohol, residue add a little dissolve with methanol; After TSK gel Toyopearl HW-40F column chromatography, with behind the water elution with 10～80% methanol-eluted fractions, collect that TLC goes up FeCl in 30～50% methanol-eluted fractions things 3Solution shows the flow point of mazarine spot, merges the wash-out flow point of the column chromatography that contains single spot, waves most solvent, gets final product.
3. the application of the described hydrolysable tannin of claim 1 in the preparation antitumor drug.
4. the described application of claim 3, wherein said medicine is made up of described hydrolysable tannin compound of claim 1 (I) and medically acceptable auxiliary material.
5. application as claimed in claim 4, the mass percentage content that it is characterized in that compound in the described medicine (I) is 5～20%.
CN200710030117A 2007-09-06 2007-09-06 Hydrolysable tannin and application thereof Expired - Fee Related CN101121739B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107459548A (en) * 2017-08-29 2017-12-12 云南养尊堂生物科技有限公司 A kind of method that extraction from dioecious balanophora herb prepares Balaenoptera borealis Lesson element

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1883646A (en) * 2006-05-19 2006-12-27 三峡大学 Sobering-up agent and preparation method thereof

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1883646A (en) * 2006-05-19 2006-12-27 三峡大学 Sobering-up agent and preparation method thereof

Non-Patent Citations (2)

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Title
腾荣伟等.蛇菰的化学成分.云南植物研究22 2.2000,22(2),225-233.
腾荣伟等.蛇菰的化学成分.云南植物研究22 2.2000,22(2),225-233. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107459548A (en) * 2017-08-29 2017-12-12 云南养尊堂生物科技有限公司 A kind of method that extraction from dioecious balanophora herb prepares Balaenoptera borealis Lesson element
CN107459548B (en) * 2017-08-29 2019-11-29 云南养尊堂生物科技有限公司 A method of extraction prepares Balaenoptera borealis Lesson element from dioecious balanophora herb

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