CN108821949A - A kind of maliane type compound and its extracting method and purposes - Google Patents
A kind of maliane type compound and its extracting method and purposes Download PDFInfo
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- CN108821949A CN108821949A CN201810442290.3A CN201810442290A CN108821949A CN 108821949 A CN108821949 A CN 108821949A CN 201810442290 A CN201810442290 A CN 201810442290A CN 108821949 A CN108821949 A CN 108821949A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/37—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with a hydroxy group on a condensed system having three rings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/08—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing three- or four-membered rings
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Abstract
The present invention relates to methods and purposes that utility is recycled in a kind of rectifying cauldron bottom residue for having extracted fragrance from natural plants illiciumverum, specifically compound [1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene] extracting method and application thereof, the extracting method of the compound is to take Chinese anise rectifying cauldron bottom residue, through silicagel column, sephadex LH-20 sephadex column, opening ODS column, preparing thin layer etc., a series of chromatographic isolations obtain compound Isosorbide-5-Nitrae-dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene.The raffinate of bottom after octagonal rectifying can not only be made full use of using this method, moreover it is possible to there is the maliane type sesquiterpenoid of [6,6,3] tricyclic, which can be used for antibacterial candidate compound, or use as natural perfume material.
Description
Technical field
The present invention relates to a kind of from natural plants extracts the technical field of utility, specially a kind of from natural plants
Illiciumverum has extracted the method and purposes that utility is recycled in the rectifying cauldron bottom residue of fragrance.
Background technique
Chinese anise（Chinese anise）, belong to Magnoliaceae illiciumverum platymiscium, Classification system isIlliciumverum,It is commonly called as big
Expect, oceangoing ship fennel, anise, is exactly " integration of drinking and medicinal herbs " kind that China announces from 2002, research shows that Chinese anise only has
Extremely low toxicity.The provinces and regions such as Guangxi, Guangdong, Yunnan are distributed mainly in China, is the specialty spice and Chinese medicine in China, also exists
Country in Southeast Asia such as Vietnam, Pakistan etc. plants extensively.Guangxi is as octagonal source area and main producing region, existing plantation
Area and yield account for the 85% and 90% of the whole nation respectively.It can be from the fruit or branches and leaves of Chinese anise using steam distillation
Anise-oil is extracted, it is the mainstay industry of some Mountain Area Counties that fennel oil production and processing, which is also Guangxi specialty industries,.Mainstream at present
Technology be to crush illiciumverum, extract fennel oil with steam distillation, after water-oil separating, then fennel oil imported into rectifying still
It is isolated to obtain trans-anethole.Meeting volatilization in distress, liquid of vicidity are deposited on rectifying still bottom, referred to as raffinate after isolated, generally as useless
Gurry is lost, and the report studied it or utilized at present is few.
Maliane type sesquiterpenoid with [6,6,3] tricyclic belongs to more rare natural products, because of its structure
Complexity, chiral site is more, has not yet to see the synthetic method report of this type compound.Limit channel and the change of acquisition
Close object quantity.And can be obtained from waste, the cost of raw material can be made to be greatly lowered.
Summary of the invention
The purpose of the present invention is to provide one kind to extract from Chinese anise rectifying cauldron bottom residue with [6,6,3] tricyclic
The method of maliane type sesquiterpenoid, the raffinate of bottom after octagonal rectifying can not only be made full use of using this method, moreover it is possible to
There is the maliane type sesquiterpenoid of [6,6,3] tricyclic, which can be used for antibacterial candidate compound
Object, or used as natural perfume material.
It is a further object to provide the maliane types extracted from Chinese anise rectifying cauldron bottom residue
Close object in terms of prepare antibacterials application and inhibition staphylococcus aureus 01~04, staphylococcus aureus
Purposes in terms of ATCC25923.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of maliane type compound, structure are as follows：
Entitled 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (the 10)-alkene of chemistry of the compound.
Above-mentioned maliane type compound（1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene）, the change
Closing object is to extract to obtain from Chinese anise rectifying cauldron bottom residue, and the Chinese anise rectifying cauldron bottom residue is by rectifying
The sticky mass of rectifier bottom is fallen to afterwards, and specific extraction process operating procedure is as follows：
（1）Chinese anise rectifying cauldron bottom residue is taken, is separated through silica gel column chromatography, volume ratio hexamethylene is successively used:Ethyl acetate=1:
0,50:1,10:1,1:1 mixed solution gradient elution obtains 7 fraction A~G；
（2）Fraction F is separated through silica gel column chromatography, successively uses volume ratio hexamethylene:Ethyl acetate=1:0,50:1,25:1,10:1,
5:1,2:1,1:1 mixed solution gradient elution obtains 17 fraction F1~F17；F14 is solidifying with sephadex LH-20 glucan
Rubber column gel column chromatographic isolation, volume ratio chloroform:Methanol=1:1 mixed solution elution, obtains 2 fraction F14-1~F14-2；
（3）F14-2 successively uses vol/vol methanol through open ODS pillar layer separation:Water=30%, 50%, 70%, 90%, 100%
Mixed solution gradient elution obtains 4 fraction F14-2-1~F14-2-4；F14-2-3 is separated with silica gel column chromatography, successively uses body
Product compares hexamethylene:Ethyl acetate=10:1,8:1,6:1,4:1,2:1,1:1 mixed solution gradient elution obtains 3 fraction F14-
2-3-1~F14-2-3-3；
（4）F14-2-3-2 is through preparing TLC separation, with volume ratio chloroform:Methanol=10:1 mixed solution is solvent exhibition
It opens, obtains compound Isosorbide-5-Nitrae-dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene.
The maliane type compound extracted from Chinese anise rectifying cauldron bottom residue above, the survey of the compound structure
It is as follows to determine process：
White powder is dissolved in methanol.HR-ESI-MSm/z：259.1670 [M+Na]+ (calcd for C15H24NaO2,
259.1674).In conjunction with1H-NMR and13C-NMR speculates that the molecular formula of this compound is C15H24O2, calculating its degree of unsaturation is 4.
1H-NMR (600 MHz, CD3OD) in spectrumδ1.93 (3H, s), 1.07 (3H, s), 1.17 (3H, s), 1.04
(3H, d,J =7.1 Hz) be 4 methyl proton signal；δ4.71 (1H, d,J =4.2 Hz) andδ4.06 (1H, dd,J
=11.8,4.9 Hz) be 2 company's oxygen sp3Proton signal on hydridization carbon.13C-NMR (150 MHz, CD3OD it) combines
The spectrum discovery of DEPT-135 carbon, there are 2 sp for the compound2The quaternary carbon signal of hydridization（δ146.3,134.6）, 1 sp3Hydridization
Quaternary carbon signal（δ22.6）, the sp of 2 company's oxygen3The tertiary carbon signal of hydridization（δ75.6,74.5）, 3 sp3The secondary carbon signal of hydridization（δ
42.5,32.4,22.3）, 4 sp3The tertiary carbon signal of hydridization（δ40.6,34.6,31.5,22.3）, 4 methyl carbon signals（δ
28.6,18.9,16.1,15.7）.
?1H-1In H COSY spectrum, proton signalδ4.71 (H-2) withδ1.77 (H-3), 1.40 (H-3) proton signal phases
It closes；Proton signalδ1.77 (H-3) withδ2.56 (H-4) proton signals are related；Proton signalδ2.56 (H-4) withδ1.04(H-
3), 2.68 (H-5) proton signals are related；Proton signalδ2.68 (H-5) withδ0.59 (H-6) proton signal is related；Proton letter
Numberδ0.59 (H-6) withδ0.49 (H-7) proton signal is related；Proton signalδ0.49 (H-7) withδ2.08 (H-8), 1.68
(H-8) proton signal is related；Proton signalδ2.08 (H-8), 1.68 (H-8) respectively withδ4.06 (H-9) proton signal phases
It closes, segment A can be obtained.
In HMBC spectrum, proton signalδ1.93 (Me-12) withδ74.5 (C-2), the 134.6 long-range phases of (C-10) carbon signal
It closes；Proton signalδ4.71 (H-2) withδ134.6 (C-10), 34.6 (C-4) carbon signals are remotely related；Proton signalδ4.06
(H-9) withδ146.3 (C-1), 40.6 (C-5), 31.5 (C-7) carbon signals are remotely related, and binding fragment A can obtain segment B.HMBC
In, proton signalδ1.07 (H-15) withδ22.3 (C-6), 31.5 (C-7) carbon signals are remotely related；Proton signalδ1.17
(H-14) withδ22.3 (C-6), 31.5 (C-7) carbon signals are remotely related, crucial HMBC and1H-1H COSY signal closes
Connection such as following formula.To sum up, can release compound structure is Isosorbide-5-Nitrae-dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene.
The nuclear magnetic resoance spectrum signals assignment of compound is shown in Table 1：
Through overtesting, inventor's discovery maliane type compound [Isosorbide-5-Nitrae-dihydroxy -14 (10 → 1)-migration-maliane -
1 (10)-alkene] there is preferable antibacterial activity in vitro, staphylococcus aureus 01~04, golden yellow Portugal can inhibited as production
It is applied in grape coccus ATCC25923 drug, in terms of the maliane type compound can apply to preparation antibacterials.
The invention has the advantages that：
The present invention extracts from Chinese anise rectifying cauldron bottom residue and obtains 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1
(10)-alkene can not only make full use of the raffinate of bottom after octagonal rectifying, cost is greatly lowered, and extract 1 obtained,
4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene has preferable antibacterial activity in vitro, can be used for antibacterial candidate
Compound in terms of being applied to preparation antibacterials, or uses as natural perfume material, is worth development and utilization.
Detailed description of the invention
Fig. 1 is 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene1H-NMR；
Fig. 2 is 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene13C-NMR；
Fig. 3 is 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene HMBC；
Fig. 4 is 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene HSQC；
Fig. 5 is 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene HR-ESI-MS；
Fig. 6 is 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene separation process figure.
Specific embodiment
The present invention will be further described below with reference to examples.
Embodiment 1
（1）950 g of Chinese anise rectifying cauldron bottom residue is taken, is separated through silica gel column chromatography, volume ratio hexamethylene is successively used:Acetic acid second
Ester=1:0,50:1,10:1,1:1 mixed solution gradient elution obtains 7 fraction A~G；
（2）Fraction F（43.05 g）It is separated through silica gel column chromatography, successively uses volume ratio hexamethylene:Ethyl acetate=1:0,50:1,
25:1,10:1,5:1,2:1,1:1 mixed solution gradient elution obtains 17 fraction F1~F17；F14（1.61 g）With
The separation of sephadex LH-20 dextran gel column chromatography, volume ratio chloroform:Methanol=1:1 mixed solution elution, obtains 2
A fraction F14-1~F14-2；
（3）F14-2（530 mg）Through open ODS pillar layer separation, vol/vol methanol is successively used:Water=30%, 50%, 70%,
90%, 100% mixed solution gradient elution obtains 4 fraction F14-2-1~F14-2-4；F14-2-3（109 mg）Use silica gel
Pillar layer separation successively uses volume ratio hexamethylene:Ethyl acetate=10:1,8:1,6:1,4:1,2:1,1:1 mixed solution gradient
Elution, obtains 3 fraction F14-2-3-1~F14-2-3-3；
（4）F14-2-3-2（14 mg）Through preparing TLC separation, with volume ratio chloroform:Methanol=10:1 mixed solution is
Solvent expansion, obtains compound Isosorbide-5-Nitrae-dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene（6.9 mg）.
Application Example 1
Antibacterial activity in vitro experiment
Using staphylococcus aureus 01~04, staphylococcus aureus ATCC25923 is transferred to solid slope culture medium respectively
On, carry out strain inclined plane activation.Some bacterium to be measured activated are taken, are added in the test tube equipped with 10 mL physiological saline, shaking makes
It is mixed sufficiently, is obtained for trying bacteria suspension.It is accurate draw 1.0 mL this for trying bacteria suspension, be added to another and be pre-loaded with 9.0 mL
Dilution in the sterile test tube of physiological saline carries out count of bacteria with Maxwell turbidimetry, and concentration is adjusted to containing bacterium number be 107~108A/
The bacteria suspension of mL, for subsequent use.
Compound 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene that present invention extraction obtains is used
The dilution of agar plate doubling dilution, bacterium multiple spot are inoculated with instrument kind bacterium, carry out minimum inhibitory concentration（MIC）Measurement.It will experiment
Strain inoculated cultivates 18~24 h into the culture medium plate of the compound containing various concentration in 37 DEG C of incubators, and MIC value is
Minimum inhibits the drug concentration of bacterial growth.
Experimental result：1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene is to staphylococcus aureus 01
~04, the MIC value of staphylococcus aureus ATCC25923 is 26.3 μ g/mL, and the MIC value of positive control drug Amoxicillin is equal
For 2.4 μ g/mL.The result shows that 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene has preferably external resist
Bacterium activity.
Claims (5)
1. a kind of maliane type compound, which is characterized in that its structure is as follows：
Entitled 1,4- dihydroxy -14 (10 → 1)-migration-maliane -1 (the 10)-alkene of chemistry of the compound.
2. maliane type compound as described in claim 1, which is characterized in that the compound is from Chinese anise rectifying still bottom
Extraction obtains in raffinate, and concrete operation step is as follows：
（1）Chinese anise rectifying cauldron bottom residue is taken, is separated through silica gel column chromatography, volume ratio hexamethylene is successively used:Ethyl acetate=1:
0,50:1,10:1,1:1 mixed solution gradient elution obtains 7 fraction A~G；
（2）Fraction F is separated through silica gel column chromatography, successively uses volume ratio hexamethylene:Ethyl acetate=1:0,50:1,25:1,10:1,
5:1,2:1,1:1 mixed solution gradient elution obtains 17 fraction F1~F17；F14 is solidifying with sephadex LH-20 glucan
Rubber column gel column chromatographic isolation, volume ratio chloroform:Methanol=1:1 mixed solution elution, obtains 2 fraction F14-1~F14-2；
（3）F14-2 successively uses vol/vol methanol through open ODS pillar layer separation:Water=30%, 50%, 70%, 90%, 100%
Mixed solution gradient elution obtains 4 fraction F14-2-1~F14-2-4；F14-2-3 is separated with silica gel column chromatography, successively uses body
Product compares hexamethylene:Ethyl acetate=10:1,8:1,6:1,4:1,2:1,1:1 mixed solution gradient elution obtains 3 fraction F14-
2-3-1~F14-2-3-3；
（4）F14-2-3-2 is through preparing TLC separation, with volume ratio chloroform:Methanol=10:1 mixed solution is solvent exhibition
It opens, obtains compound Isosorbide-5-Nitrae-dihydroxy -14 (10 → 1)-migration-maliane -1 (10)-alkene.
3. maliane type compound as claimed in claim 2, which is characterized in that the Chinese anise rectifying cauldron bottom residue is
The sticky mass of rectifier bottom is fallen to after rectifying.
4. application of the maliane type compound as described in claim 1 in terms of preparing antibacterials.
5. maliane type compound as described in claim 1 is inhibiting staphylococcus aureus 01~04 as production, golden yellow
Application in staphylococcus A TCC25923 drug.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070117727A1 (en) * | 2005-11-23 | 2007-05-24 | International Flavors & Fragrances Inc. | Derivatives of decahydro-cycloprop[e]indene compounds and their use in perfume compositions |
| CN102031196A (en) * | 2010-12-02 | 2011-04-27 | 北京航空航天大学 | Method for extracting effective ingredients in industrial residue of Chinese anise |
| CN104628546A (en) * | 2015-02-13 | 2015-05-20 | 广西壮族自治区分析测试研究中心 | 4-hydroxyl-3-(1, 2-dimethyl-2-propylene) benzaldehyde and use |
| CN105315145A (en) * | 2015-02-13 | 2016-02-10 | 广西壮族自治区分析测试研究中心 | Method for extracting alpha and beta-unsaturated ketone from illicium verum rectifying kettle residual liquor |
-
2018
- 2018-05-10 CN CN201810442290.3A patent/CN108821949B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070117727A1 (en) * | 2005-11-23 | 2007-05-24 | International Flavors & Fragrances Inc. | Derivatives of decahydro-cycloprop[e]indene compounds and their use in perfume compositions |
| CN102031196A (en) * | 2010-12-02 | 2011-04-27 | 北京航空航天大学 | Method for extracting effective ingredients in industrial residue of Chinese anise |
| CN104628546A (en) * | 2015-02-13 | 2015-05-20 | 广西壮族自治区分析测试研究中心 | 4-hydroxyl-3-(1, 2-dimethyl-2-propylene) benzaldehyde and use |
| CN105315145A (en) * | 2015-02-13 | 2016-02-10 | 广西壮族自治区分析测试研究中心 | Method for extracting alpha and beta-unsaturated ketone from illicium verum rectifying kettle residual liquor |
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