CN104592331B - A kind of quercetin derivative and its preparation technology and application - Google Patents
A kind of quercetin derivative and its preparation technology and application Download PDFInfo
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- CN104592331B CN104592331B CN201510054166.6A CN201510054166A CN104592331B CN 104592331 B CN104592331 B CN 104592331B CN 201510054166 A CN201510054166 A CN 201510054166A CN 104592331 B CN104592331 B CN 104592331B
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Abstract
The invention belongs to trees secondary metabolism active component prepares parsing and application, and in particular to from pulse family (Leguminosae) arbor Chinese scholar tree (Sophorajaponica), a kind of isolated new Quercetin (Quercetin) derivant is 3 O of Quercetin (4 " galloyl) α L rhamnopyranosyloxyhy glucosides (3 O of Quercetin (4 " galloyl) α L rhamnopyranoside) and the application in oxidation resistant product is prepared.Liquid-liquid extraction of the present invention and modern chromatographic separation preparation simple specification, it is easy to operation and industrialized production.
Description
Technical field
The invention belongs to trees secondary metabolism active component prepares parsing and application, and in particular to from pulse family
(Leguminosae) isolated a kind of new Quercetin in arbor Chinese scholar tree (Sophora japonica Linn.)
(Quercetin) derivant is Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides (Quercetin-3-O-
(4 "-galloyl)-α-L-rhamnopyranoside) and application.
Background technology
Chinese scholar tree (Sophora japonica Linn.), also known as middle Chinese scholar tree, Sophora japonica L., Fructus sophorae etc., it is pulse family
(Leguminosae) Sophora (Sophora Linn.) integrates medicinal, edible, timber-used and China's endemic tree viewed and admired.
The cultivated area of China is very wide, and from THE SOUTH OF NORTHEAST CHINA, northwest to Shaanxi, SOUTH OF GANSU, southwest is to Sichuan, Yunnan height above sea level in north
Below 2600m, south to the ground such as Guangdong, Guangxi (Sun Rongxi, etc., Jouranl of Agricultural University of Hebei, 2011,34 (3)：65-70).
The present invention utilizes liquid-liquid extraction and chromatographic separation technology to prepare from Chinese scholar tree (Sophora japonica Linn.)
Obtain a kind of new quercetin derivative i.e. Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides, the Cortex querci dentatae
The entitled Quercetin-3-O- of plain derivant English (4 "-galloyl)-α-L-rhamnopyranoside.
The content of the invention
It is an object of the invention to provide a kind of new quercetin derivative be Quercetin -3-O- (4 "-galloyl)-α -
L- rhamnopyranosyloxyhy glucosides (Quercetin-3-O- (4 "-galloyl)-α-L-rhamnopyranoside).
It is a further object to provide from pulse family (Leguminosae) Sophora (Sophora Linn.) arbor state
Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides is prepared in Chinese scholartree (Sophora japonica Linn.)
Technique.
Third object of the present invention is to provide Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides
Antioxidant activity effect application.
Technical scheme is summarized as follows：
The quercetin derivative of following chemical structural formulas：
The compound molecule formula of the present invention is C28H24O15, chemical entitled Quercetin -3-O- (4 "-galloyl)-α-L-
Rhamnopyranosyloxyhy glucosides, and its corresponding English entitled Quercetin-3-O- (4 "-galloyl)-α-L-rhamnopyranoside.
Quercetin -3-O- (4 "-galloyl)-α-L- pyrroles are prepared from Chinese scholar tree (Sophora japonica Linn.)
Mutter the technique of rhamnoside, comprise the steps：
(1) the Chinese scholar tree root bark plant material of crushing is taken, adds concentration expressed in percentage by volume to be 40% for 1: 1～1: 10 in mass ratio
～60% acetonitrile solution, heating or room temperature or microwave or ultrasonic assistant are extracted 1～5 time, 1～48 hour every time, are filtered,
Filtrate reduced in volume obtains crude extract to the 1%～15% of original volume；
(2) water of 1～5 times of crude extract quality, stirring is added to add the n-hexane extraction 1～5 of 1～5 times of crude extract quality
It is secondary, separate, remaining water layer is added into the chloroform extraction 1～5 time of 1～5 times of crude extract quality, is separated, by chloroform layer concentrating under reduced pressure
Obtain chloroform extraction phase；
(3) at least one of chloroform extraction phase Jing gel filtration chromatography and silica gel column chromatography prepares Quercetin -3-O-
(4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides.
The preparation technology has the characteristics of operational approach simple specification, yield are high, preparation cost is low.
Experiment confirms that Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhies glucosides has preferably to DPPH free radicals
Scavenging activity (IC50It is worth for 6.56 μM), its elimination effect is better than matched group α-Tocopherol (IC50It is worth for 6.82 μM) and
BHT(IC50It is worth for 6.88 μM).This shows Quercetin -3-O- (the 4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides for preparing
Antioxidant activity significantly, can be applied to food, medicine, health product and cosmetic industry as antioxidant.
Specific embodiment
With reference to the following example will be easier, the present invention is more fully understood, be given embodiment be in order to illustrate the present invention,
Rather than the present invention is limited by any way.
Embodiment 1：
The preparation of Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides
(1) the Chinese scholar tree root bark plant material of crushing is taken, and the acetonitrile that concentration expressed in percentage by volume is 45% is added for 1: 4 in mass ratio
Aqueous solution, extract at room temperature 4 times 36 hours every time, are filtered, the 5% of filtrate reduced in volume to original volume, obtain crude extract；
(2) water of 2 times of crude extract quality, stirring, the n-hexane extraction of 2 times of addition crude extract quality 2 times is added to separate,
Remaining water layer is added into the chloroform extraction 2 times of 2 times of crude extract quality, is separated, chloroform layer concentrating under reduced pressure is obtained into chloroform extraction phase；
(3) chloroform extraction phase Jing silica gel column chromatography prepares Quercetin -3-O- (4 "-galloyl)-α-L- pyrans
Rhamnoside.
Embodiment 2：
The preparation of Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides
(1) the Chinese scholar tree root bark plant material of crushing is taken, and the acetonitrile that concentration expressed in percentage by volume is 55% is added for 1: 3 in mass ratio
Aqueous solution, microwave extraction 3 times 2 hours every time, are filtered, the 6% of filtrate reduced in volume to original volume, obtain crude extract；
(2) water of 3 times of crude extract quality, stirring, the n-hexane extraction of 3 times of addition crude extract quality 3 times is added to separate,
Remaining water layer is added into the chloroform extraction 3 times of 3 times of crude extract quality, is separated, chloroform layer concentrating under reduced pressure is obtained into chloroform extraction phase；
(3) chloroform extraction phase Jing gel filtration chromatography prepares Quercetin -3-O- (4 "-galloyl)-α-L- pyrans
Rhamnoside.
The Structural Identification of the compound：
The compound1Proton signal [δ in H NMR spectras (data such as table 1)H6.23 (1H, d, J=2.3Hz, H-6)
And δH6.41 (1H, d, J=2.3Hz, H-8)] show the compound A rings be phloroglucinol type aromatic rings.And its13C NMR believe
Number [δC159.6 (C-2), 135.3 (C-3), 179.5 (C-4)] compound is disclosed for typical flavonol.The matter of the compound
Sub- peak [δH7.65 (1H, d, J=2.2Hz, H-2 '), δH6.92 (1H, d, J=8.3Hz, H-5 ') and δH7.52 (1H, dd, J
=8.3Hz, J=2.2Hz)] disclose the compound B rings be typical case's ABX formula aromatic rings.Therefore, the aglycon of the compound is true
It is set to Quercetin.
At which1In H H NMR spectroscopies, 1 terminal hydrogen δH5.31 (1H, br s, H-1 "), a methyl δH1.02 (3H, d, J=
6.3Hz, H-6 ") and four proton δH3.53-5.08 (4H, H-2 ", 3 ", 4 " and, 5 ") contain one in showing the compound molecule
α-L- rhamnopyranosyloxyhy glucosides.
The compound13C NMR signal [δC121.8 (C-1 " '), 109.9 (C-2 " ', 6 " '), 146.3 (C-3 " ',
5 " '), 139.8 (C-4 " ')] with reference to proton peak δH7.10 (2H, s, H-2 " ', 6 " ') show in the compound molecule comprising one
Galloyl.
HMBC spectrums show the rhamnose terminal hydrogen δ of the compoundH5.31 (the carbon of 1H, br s, H-1 ") and quercetin aglycon
Signal δC135.3 (C-3) have Long-Range Correlation, determine that α-L- rhamnopyranosyloxyhy glucosides is connected with quercetin aglycon C-3.And Fructus rhamni (Rhamnus davurica Pall.)
The proton signal δ of sugarH5.08 (the carbon peak δ on 1H, dd, J=10.1Hz, J=9.8Hz, H-4 ") and galloylC 168.4
(C-7 " ') have Long-Range Correlation, it is determined that α-L- rhamnopyranosyloxyhies glucosides 4 " position and the 7 of galloyl " ' position is connected.
As shown in table 1, the undistorted polarization transfer of the compound strengthens during collection of illustrative plates (DEPT spectrums) shows its molecule and contains altogether
28 carbon, wherein, 1, methyl carbon, mesomethylene carbon 0, methine carbon 12, quaternary carbon 15.The Positive of the compound
FAB mass spectruies show its m/z [M+H]+And m/z [M+Na]+Correspond to 601 and 623 respectively, then it is comprehensive its1H and13C H NMR spectroscopies are illustrated
Analyse obtain the compound molecular formula be C28H24O15。
To sum up, the structure of the compound is confirmed as Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranoses
Glycosides.
Jing is retrieved, and the compound is the new quercetin derivative never reported before this.The compound is yellow without fixed
Type powder, fusing point are 169～171 DEG C, optical rotationThe compound is in uviol lamp 254nm ripples
There is uv absorption under length, it is dark green with 1% ferric chloride ethanol solution (mass percent) spraying chromogenic reaction.TLC exhibitions
Open in test, with the tert-butyl alcohol-glacial acetic acid-water volume ratio 3: 1: 1 as solvent system, the R of the compoundfIt is worth for 0.66, and with ice
When the solvent system of acetic acid-water volume ratio 6: 94 launches, the R of the compoundfIt is worth for 0.25.
1. Quercetin -3-O- of table (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides1H(400MHz)、13C NMR
(100MHz) and DEPT modal datas (MeOD)
Embodiment 3：
The antioxidant activity evaluation of Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides
1. product to be evaluated：Quercetin -3-O- (the 4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides Jing of above-mentioned preparation
After HPLC is determined, purity is 99.9%, is positive control group from α-Tocopherol and BHT.
2. experimental technique：The antioxidant activity merit rating of sample selects wide variety of removing DPPH free radicals test side
Method (DPPH free radical scavenging method), concrete operations strictly carry out (Si so that step is described in document
CL, et al, PlantaMedica, 2009,75,1165-1167).Each group experiment is independent parallel to be carried out three times, takes which average
Value is calculated.
Experimental result is as shown in table 2.As a result show, and Quercetin -3-O- (4 "-galloyl)-α-L- rhamnopyranoses
Scavenging activity IC of the glycosides to DPPH free radicals50It is worth for 6.56 μM, and positive control group α-Tocopherol and BHT removes DPPH freedom
Base activity IC50Value is respectively 6.82 and 6.88 μM.Test data announcement Quercetin -3-O- (4 "-galloyl)-α-L- pyrans
Rhamnoside is better than positive control group α-Tocopherol and BHT to the Scavenging activity of DPPH free radicals.Quercetin-the 3-O- of preparation
The antioxidant activity of (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides significantly, can be applied to food, medicine as antioxidant
Product, health product and cosmetic industry.
2. Quercetin -3-O- of table (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides, BHT and α-Tocopherol are removed
DPPH free radical ability (IC50Value, μM)
Claims (3)
1. the compound of following structural formula：
Entitled Quercetin-the 3-O- of chemistry (4 "-galloyl)-α-L- rhamnopyranosyloxyhy glucosides, its corresponding English are entitled
Quercetin-3-O-(4″-galloyl)-α-L-rhamnopyranoside。
2. the preparation method of claim 1 compound, is characterized in that comprising the steps：
(1) take the Chinese scholar tree root bark plant material of crushing, in mass ratio for 1: 1～1: 10 add concentration expressed in percentage by volumes be 40%～
60% acetonitrile solution, room temperature or heating or microwave or ultrasonic extraction 1～5 time, 1～48 hour every time, filter, and filtrate subtracts
Pressure is concentrated into the 1%～15% of original volume, obtains crude extract；
(2) water of 1～5 times of crude extract quality is added, is stirred, the n-hexane extraction of 1～5 times of addition crude extract quality 1～5 time,
Separate, remaining water layer is added into the chloroform extraction 1～5 time of 1～5 times of crude extract quality, is separated, chloroform layer concentrating under reduced pressure is obtained into chlorine
Imitative extraction phase；
(3) at least one of chloroform extraction phase Jing gel filtration chromatography and silica gel column chromatography prepare Quercetin -3-O- (4 "-do not have
Infanticide acyl group)-α-L- rhamnopyranosyloxyhy glucosides.
3. application of claim 1 compound in oxidation resistant product is prepared.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6600832B2 (en) * | 2015-12-11 | 2019-11-06 | 小林 裕司 | Methylated flavonol derivatives exhibiting fat adsorption |
| CN105859803B (en) * | 2016-05-09 | 2018-10-26 | 中国农业科学院特产研究所 | A kind of preparation method of galloyl glucose |
| CN106854223B (en) * | 2017-01-05 | 2019-03-29 | 石家庄学院 | Mustargen quercetin derivative and its preparation method and application |
| CN107312050B (en) * | 2017-08-28 | 2019-11-22 | 天津科技大学 | A kind of preparation process of galloyl flavonol glycosides in katsura tree branch |
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| CN1288896A (en) * | 1999-09-17 | 2001-03-28 | 中国人民解放军军事医学科学院毒物药物研究所 | Quercetin derivative and its medicinal use |
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| CN101103121A (en) * | 2004-12-28 | 2008-01-09 | 三得利株式会社 | Quercetin glycoside composition and method of preparing the same |
| CN102304158A (en) * | 2011-05-20 | 2012-01-04 | 中国人民解放军第二军医大学 | Acylated flavonoid glycoside compounds and application thereof in preparation of complement inhibitor medicines |
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| CN1288896A (en) * | 1999-09-17 | 2001-03-28 | 中国人民解放军军事医学科学院毒物药物研究所 | Quercetin derivative and its medicinal use |
| CN1470518A (en) * | 2003-06-26 | 2004-01-28 | 中山大学 | Method for extracting quercetin-7-0-rhamnoside |
| CN101103121A (en) * | 2004-12-28 | 2008-01-09 | 三得利株式会社 | Quercetin glycoside composition and method of preparing the same |
| CN102304158A (en) * | 2011-05-20 | 2012-01-04 | 中国人民解放军第二军医大学 | Acylated flavonoid glycoside compounds and application thereof in preparation of complement inhibitor medicines |
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