CN101538260B - Isoflavone compound and prepration method and application thereof - Google Patents
Isoflavone compound and prepration method and application thereof Download PDFInfo
- Publication number
- CN101538260B CN101538260B CN2009100944089A CN200910094408A CN101538260B CN 101538260 B CN101538260 B CN 101538260B CN 2009100944089 A CN2009100944089 A CN 2009100944089A CN 200910094408 A CN200910094408 A CN 200910094408A CN 101538260 B CN101538260 B CN 101538260B
- Authority
- CN
- China
- Prior art keywords
- compound
- acetone
- silica gel
- free radical
- cigarette
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The present invention discloses an isoflavone compound with a novel structure, a preparation method and an application thereof. The compound has the structure as shown in the following formula; the present invention uses an MCI column for bleaching a papaya liquid extract, uses the silica gel column chromatography for primary separation, and then adopts the semipreparative high-performance liquid chromatography for further separation, thereby obtaining the new compound which is named as 3',4',5'-trihydroxy-5, 7-dimethoxyisoflavone. An effect test of eliminating free radicals in mainstream cigarette smoke is carried out on the compound, and the test result shows that the compound has good effect of eliminating the free radicals.
Description
Technical field
The present invention relates to a kind of tobacco additive agent, more particularly, the present invention relates to a kind of isoflavonoid of novelty.Simultaneously, the invention still further relates to the preparation method of described compound and the application aspect the free radical in removing cigarette mainstream flue gas thereof.
Background technology
Human from finding the existing so far quincentenary history of tobacco.As a kind of specialty goods, tobacco has been satisfied the needs of smoking human consumer physiology and psychology.But along with social progress and science and technology development, relevant data shows that smoking has certain influence to HUMAN HEALTH, smoking and healthy contradiction paid more and more attention.
For many years, various advanced persons' production technology is studied, used to tobacco enterprise one after another both at home and abroad, progressively reduces the objectionable constituent in the cigarette smoke, alleviates smoking to health effects.Medical science and free radical biological study show: free radical is that HUMAN HEALTH is had certain damaging effect, and also contains a certain amount of free radical in the cigarette smoke, and reducing the free radical that produces in the smoking process is effective behave of producing low-harmful cigarette.
Contain a large amount of oxidation-resistant active ingredients in the natural phant, these compositions can be by providing H
+Reduce the generation of free radical, and can interrupt the free-radical oxidn chain reaction, effectively remove the cigarette smoke free radical.BJ Tobacco Factory has just begun in cigarette to add the research that kendir reduces the flue gas free radical as far back as the beginning of the seventies, compares with the contrast cigarette, and it is about 27.4% that the tarry matters in smoke free radical reduces, and gaseous phase free radical reduces about 30.6%.Other plant in addition is as the crude extract of the dried rhizome of rehmannia, Radix Angelicae Sinensis, Spina Date Seed, glossy ganoderma, Chinese cassia tree, the bark of eucommia, matrimony vine, the red sage root, Herba Cistanches etc.; And the purification thing of many herbal medicine, as the multiple composition of shizandra berry, flavonoids of Glycyrrhiza, ginsenoside, rutin, Sang Qiansu etc., all have similar functions.But do not find relevant report so far as yet at isoflavonoid.
Summary of the invention
The object of the present invention is to provide a kind of new isoflavonoid.
Another object of the present invention provides a kind of method that extracts The compounds of this invention from cigarette additive pawpaw medicinal extract.
Further aim of the present invention provides the purposes aspect the free radical of above-claimed cpd in removing cigarette mainstream flue gas.
Purpose of the present invention is achieved by following technical proposals.
*Except as otherwise noted, the percentage ratio that is adopted among the present invention is mass percent.
A. the present invention has isolated a kind of new isoflavonoid from cigarette additive pawpaw medicinal extract, and the All new compounds formula is:
The called after 3 ', 4 ' of this compound, 5 '-trihydroxy--5,7-dimethoxy isoflavones (3 ', 4 ', 5 '-trihydroxy-5,7-dimethoxyflavone).
B. the invention provides the preparation method of described new compound, this method may further comprise the steps:
(1) pawpaw medicinal extract is decoloured with the MCI post, use the methanol-eluted fractions of pure acetone and 85%～95% respectively, acetone washes part and is mainly chlorophyll and lipid acid; Collect 90% methyl alcohol and wash part, use thick silica gel mixed sample, silica gel dress post carries out silica gel column chromatography;
(2) use chloroform: the acetone gradient elution, TLC monitoring merges identical part, and wherein, chloroform: the wash-out of acetone=1: 1 partly separates with prompt logical sequence 1,100 half preparative high-performance liquid chromatographics of peace, and the methyl alcohol with 30%～40% is moving phase, Zorbax SB-C
18Column (9.4 * 250mm, 5 μ m) semipreparative column is a stationary phase, and it is 360nm that UV-detector detects wavelength, and each sample introduction 50 μ L collect the 27.5min chromatographic peak, and the back evaporate to dryness repeatedly adds up;
(3) using pure dissolve with methanol once more, is moving phase again with methyl alcohol, separates with Sephadex LH-20 gel filtration chromatography, promptly obtains required compound.
C. the present invention has carried out removing the effect test of free radical in the cigarette mainstream flue gas to above-claimed cpd, and compound exhibits has definite removing free radical effect,
The present invention has following outstanding advantage: (1) pawpaw is widely distributed in China, the raw material supply abundance; And compound of the present invention content in pawpaw is higher, separates easily, if industrial application, raw material obtains easily.(2) adopted conventional column chromatography and high performance liquid chromatography bonded preparation method, the compound operating process is simple, the The compounds of this invention purity height that is obtained, and suitability for industrialized production subsequently realizes easily.(3) this compound has the free radical effect in the good removing cigarette smoke, can be tobacco industry reduction cigarette smoke objectionable constituent valuable new compound or guiding compound are provided.
Description of drawings
Fig. 1 is The compounds of this invention high resolution mass spectrum (HRESIMS);
Fig. 2 be The compounds of this invention proton nmr spectra (
1H NMR);
Fig. 3 be The compounds of this invention nucleus magnetic resonance charcoal spectrum (
13C NMR);
Fig. 4 is the main HBMC relevant (→) of The compounds of this invention.
Specific implementation method
By specific embodiment given below and typically used embodiment, can further be well understood to the present invention.But they are not the qualification to protection domain of the present invention.
Embodiment 1
Used pawpaw medicinal extract is provided by all places, Yuxi, Yunnan natural product company limited.Pawpaw medicinal extract 500g decolours with the MCI post, uses the methanol-eluted fractions of pure acetone and 90% respectively, and acetone washes part and is mainly chlorophyll and lipid acid.Collect 90% methyl alcohol and wash part 100g, mix sample with thick silica gel 200g (80～100 order), 2.0kg silica gel (160～200 order) dress post carries out silica gel column chromatography, chloroform: acetone (1: 0 → 0: 1) gradient elution, the TLC monitoring merges identical part, obtain 8 part (pure chloroforms, chloroform-acetone 20: 1, chloroform-acetone 9: 1, chloroform-acetone 8: 2, chloroform-acetone 3: 2, chloroform-acetone 1: 1, chloroform-acetone 20: 1, pure acetone), wherein chloroform-acetone (1: 1) wash-out part 11.8g separates with prompt logical sequence 1,100 half preparative high-performance liquid chromatographics of peace, methyl alcohol with 35% is moving phase, Zorbax SB-C
18Column (9.4 * 250mm, 5 μ m) semipreparative column is a stationary phase, it is 360mm that UV-detector detects wavelength, each sample introduction 50 μ L collect the 27.5min chromatographic peak, and the back evaporate to dryness repeatedly adds up, use pure dissolve with methanol once more, be that mobile phase methanol is a moving phase with methyl alcohol again, separate, promptly obtain the compound of the present invention institute palpus with Sephadex LH-20 gel filtration chromatography with 35%.
Embodiment 2
The process of this embodiment is identical with embodiment 1, just adopts 85% methanol-eluted fractions, and the methyl alcohol with 30% is moving phase.
The process of this embodiment is identical with embodiment 1, just adopts 95% methanol-eluted fractions, and the methyl alcohol with 40% is moving phase.
Embodiment 4
--the structure of compound is identified
Described compound is yellow amorphous powder; UV spectrum (solvent is a methyl alcohol), λ
Max(log ε) 310 (3.67), 246 (4.18), 210 (5.79); Infrared spectra (pressing potassium bromide troche) ν
Max3384,1658,1615,1548,1508,1426,1125,1047,956,863cm
-1HRESIMS (accompanying drawing-1) shows its quasi-molecular ion peak m/z 353.0640[M+Na]
+(calcd 353.0637) determine that in conjunction with the NMR spectrum its molecular formula is C
17H
14O
7, degree of unsaturation is 10.
1H and
132 phenyl ring (the two key charcoals of 4 methynes are arranged on the phenyl ring) are arranged, 2 methoxyl group (δ in C NMR spectrum (accompanying drawing-2 and accompanying drawing-3, attribution data sees Table-1) the demonstration molecule
C56.7,56.0), 1 carbonyl (δ
C181.7), 1 two key (δ of methyne
H154.1), 1 two key season charcoal (δ
C123.1); In conjunction with this compound of documents data susceptible of proof is different cyclic ketones compounds; Further confirm that through HMBC relevant (accompanying drawing-4) C-5, C-7 position are substituted by methoxyl group, C-3 ', C-4 ', C-5 ' position are substituted by hydroxyl, and the structure of compound finally obtains confirming.Confirm that by SCIFINDER database retrieval and document inquiry this compound is a new compound.
Table-1 compound
1H and
13C NMR data
Embodiment 5
--with the free radical in the removing cigarette smoke of this compound
1. the leaf group of cigarette is the leaf group (upper tobacco leaf is 20%, and the middle part tobacco leaf is 40%, and lower tobacco leaf is 30%, expanded cut stem 5%, tobacco sheet 5%) of Yunnan brand cigarette.Adopt cellulose acetate mouth rod, the cigarette plug paper Gas permeability is 4500CU; The cigarette tissue grammes per square metre is 50g/m
2, Gas permeability is 80CU, yew paper Gas permeability is 200CU.The weight that the finished cigarettes cigarette props up is 0.93+0.02g, and circumference is 24.5mm, and length is 84mm (wherein mouth rod length is 25mm).
2. test compound is with adding in the cigarette-filter tow, and every cigarette addition is 0.5～5.0mg, and is contrast with the cigarette that does not add test compound.
Cigarette captures with sampling tube with 44mm cambridge filter capture, gas phase part with RM200 type 20 duct automatic smoking machine smokings under standard conditions, main flume granule phase substance; Grain phase free radical with the benzole soln that contains 0.05mol/LN-tertiary butyl-α-phenyl nitrogen cave be extraction agent from the cambridge filter stripping, and washing cambridge filter, constant volume gets a phase free radical test fluid.Gaseous phase free radical free radical sampling tube, benzole soln with 0.05mol/LN-tertiary butyl-α-phenyl nitrogen cave is the absorption agent collection, the gaseous phase free radical sampling tube is taken out in the intact back of cigarette smoking, divide the outside and sampling tube inwall of pipe in 3 flushing ventilations with a small amount of absorption agent simultaneously, merge absorption liquid and washings, get the gaseous phase free radical sample liquid.
Measure free radical with EPR spectrometer, ESR analyzes experiment condition: central magnetic field=3.385T, sweeps wide=0.500T, microwave frequency=1.5GHz, sweep time=2min, scanning times=5, magnification=10
3～10
5(adjusting) according to peak height, amount of samples 20 μ L; Variation according to calculated by peak area gas phase in the ESR collection of illustrative plates and grain phase free radical quantity.
3. experimental result shows: carry out 5 experiments, with to compare in the same old way, the cigarette gaseous phase free radical reduced rate that adds this compound is 22-28%, and grain phase free radical reduced rate is between 18.5-26.7%, and this compound has definite removing effect to the free radical in the cigarette mainstream flue gas.
Claims (3)
1. isoflavonoid with following structural formula:
2. the preparation method of the described compound of claim 1 is characterized in that: this method adopts following steps:
(1) pawpaw medicinal extract is decoloured with the MCI post, use the methanol-eluted fractions of pure acetone and 85%～95% respectively, acetone washes part and is mainly chlorophyll and lipid acid; Collect 90% methyl alcohol and wash part, use thick silica gel mixed sample, silica gel dress post carries out silica gel column chromatography;
(2) use chloroform: the acetone gradient elution, TLC monitoring merges identical part, and wherein, chloroform: the wash-out of acetone=1: 1 partly separates with prompt logical sequence 1,100 half preparative high-performance liquid chromatographics of peace, and the methyl alcohol with 30%～40% is moving phase, Zorbax SB-C
18Semipreparative column is a stationary phase, and it is 360nm that UV-detector detects wavelength, and each sample introduction 50 μ L collect the 27.5min chromatographic peak, and the back evaporate to dryness repeatedly adds up;
(3) use pure dissolve with methanol once more, again with
Moving phase is separated with Sephadex LH-20 gel filtration chromatography, promptly obtains required compound.
3. the application in the free radical of the described isoflavonoid of claim 1 in removing cigarette smoke.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100944089A CN101538260B (en) | 2009-04-28 | 2009-04-28 | Isoflavone compound and prepration method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100944089A CN101538260B (en) | 2009-04-28 | 2009-04-28 | Isoflavone compound and prepration method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101538260A CN101538260A (en) | 2009-09-23 |
| CN101538260B true CN101538260B (en) | 2011-07-20 |
Family
ID=41121673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100944089A Expired - Fee Related CN101538260B (en) | 2009-04-28 | 2009-04-28 | Isoflavone compound and prepration method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101538260B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653532B (en) * | 2012-04-24 | 2015-02-18 | 云南烟草科学研究院 | Lignans compound in aromatic tobacco and preparation method and application of lignans compound |
| CN104829580B (en) * | 2015-04-11 | 2017-11-24 | 云南中烟工业有限责任公司 | Isoflavonoid contained by tobacco and its preparation method and application |
| CN107129480B (en) * | 2017-06-02 | 2019-08-09 | 云南中烟工业有限责任公司 | A kind of new isoflavone compound and the preparation method and application thereof in pueraria lobata |
| CN107373745B (en) * | 2017-07-28 | 2020-04-03 | 云南中烟工业有限责任公司 | Additive for preventing tobacco feed liquid from being corrupted and deteriorated and application thereof |
| CN107700278B (en) * | 2017-08-31 | 2019-12-13 | 云南中烟工业有限责任公司 | Cigarette paper additive with effects of returning sweet and moistening throat and application thereof |
| CN107476130B (en) * | 2017-08-31 | 2019-10-11 | 云南中烟工业有限责任公司 | A kind of cigarette paper additive with moistening throat and clearing lung type resolving sputum and its application |
| CN107903234B (en) * | 2017-10-18 | 2020-08-25 | 云南中烟工业有限责任公司 | Isoflavone compound extracted from pawpaw as well as preparation method and application thereof |
| CN107759554B (en) * | 2017-10-18 | 2020-08-25 | 云南中烟工业有限责任公司 | Hydroxypropyl isoflavone compound and preparation method and application thereof |
| CN109953367B (en) * | 2019-03-22 | 2022-08-02 | 内蒙古昆明卷烟有限责任公司 | Cistanche extracting solution and preparation method, composition and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142530A (en) * | 1996-05-03 | 1997-02-12 | 云南省烟草工业研究所 | Tobacco improving agent, preparation and application thereof |
-
2009
- 2009-04-28 CN CN2009100944089A patent/CN101538260B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142530A (en) * | 1996-05-03 | 1997-02-12 | 云南省烟草工业研究所 | Tobacco improving agent, preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李雪梅.酸木瓜浓缩提取物的制备及其在卷烟加料中的应用.《烟草科技/烟草工艺》.2000,(第2期),4-5. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101538260A (en) | 2009-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101538260B (en) | Isoflavone compound and prepration method and application thereof | |
| CN107337586A (en) | A kind of method of extraction purification cannabidiol in fiber crops from the Chinese | |
| CN104945360B (en) | Preparation method and application of phenylpropanoid compound in tobacco | |
| CN103524472B (en) | Phenolic compound, and preparation method and application thereof | |
| CN102304114B (en) | Flavanone compound and application thereof | |
| CN105348192B (en) | Isoquinoline alkaloids bases compound of antiviral activity and preparation method thereof in a kind of wing pod Cassia tora | |
| CN103554077B (en) | Chromone compound as well as preparation method and application thereof | |
| CN101550083B (en) | Benzo compounds in tobacco, preparation method and uses thereof | |
| CN104926772B (en) | Novel flavonoid compound as well as preparation method and uses thereof | |
| CN106883243A (en) | It is a kind of with the isobenzofuran class compound and its tobacco purposes of removing free radical effect in the root of kudzu vine | |
| CN105175233B (en) | A kind of sesquiterpenoids and preparation method and application | |
| CN101982467A (en) | Lignans compounds contained in Schisandra chinensis, and preparation method and application thereof | |
| CN104974122A (en) | Coumarin compound originated from tobacco, and preparation method and application thereof | |
| CN105884588B (en) | One kind drop sesquiterpenoids and preparation method and application | |
| CN104387361B (en) | A kind of Isocoumarin compounds and its production and use | |
| CN101973883B (en) | Phenolic compound in tobaccos and preparation method and application thereof | |
| CN108033984B (en) | Caffeic acid glucoside compound, preparation method and application thereof | |
| CN110526890A (en) | A method of dihydromyricetin is isolated and purified and identified from vine tea tissue | |
| CN106008219A (en) | Sesquiterpenoid compound, preparation method of sesquiterpenoid compound and application of sesquiterpenoid compound to preparation of anti-rotavirus medicines | |
| CN107778275B (en) | Isoflavone compound extracted from rose waste residue and preparation method and application thereof | |
| CN102351818A (en) | Coumarone phenylpropanoids compound contained in tobacco root stalk, its preparation method and its application | |
| CN107987112B (en) | Preparation method of afzelin derivative | |
| CN110526891A (en) | A method of texifolin is isolated and purified and identified from vine tea tissue | |
| CN103739661A (en) | Method for extracting pennogenin from paris polyphylla | |
| CN107400107A (en) | A kind of flavone compound in rose waste residue and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110720 Termination date: 20120428 |