CN101029005B - Method for producing 1-acetoxy-piperonyl acetate - Google Patents
Method for producing 1-acetoxy-piperonyl acetate Download PDFInfo
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- CN101029005B CN101029005B CN2007101005784A CN200710100578A CN101029005B CN 101029005 B CN101029005 B CN 101029005B CN 2007101005784 A CN2007101005784 A CN 2007101005784A CN 200710100578 A CN200710100578 A CN 200710100578A CN 101029005 B CN101029005 B CN 101029005B
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- acetoxychavicol acetate
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Abstract
A process for preparing 1'-acetyloxy chavicol acetate from the dried rhizome of Alpina galanga Willd through supercritical CO2 extracting and molecular distillation is disclosed. It has high output rate, purity, and productivity.
Description
Technical field
The present invention relates to a kind of production method with supercritical carbon dioxide extraction and molecular distillation technique extraction separation purifying 1 '-acetoxychavicol acetate from the dry rhizome rhizome of Galanga Galangal of Zingiber Z ing iberaceae Alpinia plants Galanga Galangal Seed Al pin i a ga l anga Wil ld..
Background technology
The English 1 '-ace t oxychav i co l ace ta t e by name of 1 '-acetoxychavicol acetate, molecular formula is C
13H
14O
4, molecular weight is 234.25, structural formula is
On July 7th, 2005, Japanese Patent JP2005179201 discloses 1 '-acetoxychavicol acetate that separation obtains from the methanol extract of Rhizoma Alpiniae Galangae fruit and has had the duplicate effect of the HIV-1NL43 of inhibition in the MT-4 cell, and the MT-4 cell survival is not had influence, show the characteristics of tight security and the external migration of inhibition HIV Rev pyrenoids.Also have the research report show 1 '-acetoxychavicol acetate have antitumor (Moffa t t J, A, et a l.[J] .Carc inogenes i s, 2000,21: 2151-2157; Zheng Q etal.[J] .J Cancer Res Cl in Oncol, 2002,128: 539～546), antibacterium (Jans sen AM, [J] .p l anta Med, 1985 (6): 507～511), antimycotic (Fi cker C E, e t a l.[J] .JE thnophamaca l, 2003,85: 589～593), antiulcer agent (Mi t sui s, e t a l.[J] .Chem PhamBull, 1976,24: 2377～2382), anti-oxidant (Kubo ta K, et a l.[J] .Spec Publ R SocChem, 2001,274: 601～607), anti-inflammatory (Nakamura Y, [J] .Cancer Res, 1998,58: 4832～4839) biological activity such as, discover also that in recent years it has the tuberculosis activity.
On August 10th, 2006, Japanese Patent JP2006206541 discloses 1 '-acetoxychavicol acetate chemical synthesis process, but has the lower and problem of environmental pollution of yield.
Traditional extraction and separation technology is to extract back normal hexane-ethyl acetate extraction with methanol eddy, separate by chromatography column, method with normal hexane-eluent ethyl acetate prepares 1 '-acetoxychavicol acetate again, not only effective constituent is destroyed serious, yield and purity is low, impurity is many, technical process is complicated, production efficiency is low, and environment polluted, influence producers' safety and health, residual organic solvent constitutes a threat to the health of human body in the product.
Summary of the invention
Problem at present chemosynthesis or the existence of extraction and separation technology preparation 1 '-acetoxychavicol acetate, the invention provides a kind of yield, purity and production efficiency height, safety, health, the supercritical carbon dioxide extraction of cleaning and the production method of molecular distillation technique extraction separation purifying 1 '-acetoxychavicol acetate from the dry rhizome rhizome of Galanga Galangal of Zingiber Zingiberaceae Alpinia plants Galanga Galangal Seed Al piniagalanga Wil ld., technical scheme is as follows:
Get the dry rhizome rhizome of Galanga Galangal of Zingiber Z ingiberaceae Alpinia plants Galanga Galangal Seed Al pini a ga l anga Willd., be dried to and contain moisture less than 10%, be ground into 10～60 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 40 ℃～60 ℃, and pressure is 10Mpa～40Mpa; The separating still temperature is 40 ℃～70 ℃, and pressure is 10Mpa～20Mpa; The extraction-container temperature is 40 ℃～50 ℃, and pressure is 5Mpa～15Mpa; Flow is 5～50kg/h; The extraction time is 1～3 hour.
Getting above-mentioned supercritical carbon dioxide extraction thing puts in the molecular still, input speed is 0.5～5ml/min, vacuum tightness is 5～30Mpa, Heating temperature is 80～200 ℃, cooling temperature is 2～10 ℃, rotating speed is 100～300r/min, collects distillate, promptly gets 1 '-acetoxychavicol acetate.Adopt the conventional formulation method, 1 '-acetoxychavicol acetate is made soft capsule, tablet, capsule, pill, granule, injection in medicine, use.
Adopt following method to detect beneficial effect of the present invention:
1. structural identification test: adopt the structure that ultimate analysis, ultra-violet absorption spectrum, infrared absorption spectrum, mass spectrum, nuclear magnetic resonance spectrum are resolved and conclusive evidence extraction separation of the present invention is made with extra care the compound that obtains.
2. yield calculates:
W
1Be 1 '-acetoxychavicol acetate weight.
w
2Be rhizome of Galanga Galangal medicinal material weight.
3. purity testing
Measure according to high performance liquid chromatography (an appendix VI of Chinese Pharmacopoeia version in 2005 D).
Chromatographic condition and system suitability test are weighting agent with the octadecylsilane chemically bonded silica; With methanol-water (50: 50) is moving phase; The detection wavelength is 254nm.Number of theoretical plate calculates by 1 '-acetoxychavicol acetate peak should be not less than 3000.
1 '-acetoxychavicol acetate reference substance 0.1g is got in the preparation of reference substance solution, the accurate title, decide, put in the 50ml measuring bottle, add methyl alcohol and be diluted to scale, shake up, precision is measured 0.1ml, put in the 10ml measuring bottle, add moving phase and be diluted to scale, shake up, promptly get (every 1ml contains 1 '-acetoxychavicol acetate, 20 μ g).
The about 0.1g of this product is got in the preparation of need testing solution, and accurate the title decides, and puts in the 50ml measuring bottle, adds methyl alcohol to scale, shakes up, and precision is measured 0.1ml, puts in the 10ml measuring bottle, adds moving phase and is diluted to scale, shakes up, and filters, and gets subsequent filtrate, promptly.
Accurate respectively reference substance and each the 20 μ l of need testing solution of drawing of assay method inject liquid chromatograph, measure, and calculate by external standard method, promptly.
Embodiment
Embodiment 1
Get the dry rhizome rhizome of Galanga Galangal of Zingiber Zi ng i beraceae Alpinia plants Galanga Galangal Seed Al pi n i a ga l anga Wil ld., be dried to and moisturely be divided into 4.2%, be ground into 50 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 54 ℃, and pressure is 27.5Mpa; The separating still temperature is 60 ℃, and pressure is 12.5Mpa; The extraction-container temperature is 40 ℃, and pressure is 6.5MPa; Flow is 10kg/h; The extraction time is 1.5h.Get above-mentioned supercritical carbon dioxide extraction thing and put in the molecular still, input speed is 1.5ml/min, and vacuum tightness is 15Mpa, Heating temperature is 120 ℃, and cooling temperature is 5 ℃, and rotating speed is 250r/min, collect distillate, promptly get compound 1 (1 '-acetoxychavicol acetate).Adopting the conventional formulation method that this compound (1 '-acetoxychavicol acetate) is made soft capsule, tablet, capsule, pill, granule, injection uses in medicine.
Embodiment 2
Get the dry rhizome rhizome of Galanga Galangal of Zingiber Zingiberaceae Alpinia plants Galanga Galangal Seed Alpinia galanga Wil ld., be dried to and moisturely be divided into 6.1%, be ground into 60 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 40 ℃, and pressure is 20Mpa; The separating still temperature is 45 ℃, and pressure is 10Mpa; The extraction-container temperature is 45 ℃, and pressure is 8MPa; Flow is 20kg/h; The extraction time is 1 hour.Get above-mentioned supercritical carbon dioxide extraction thing and put in the molecular still, input speed is 1ml/min, and vacuum tightness is 10Mpa, Heating temperature is 100 ℃, and cooling temperature is 3 ℃, and rotating speed is 100r/min, collect distillate, promptly get compound 2 (1 '-acetoxychavicol acetate).Adopting the conventional formulation method that this compound (1 '-acetoxychavicol acetate) is made soft capsule, tablet, capsule, pill, granule, injection uses in medicine.
Embodiment 3
Get the dry rhizome rhizome of Galanga Galangal of Zingiber Zingiberaceae Alpinia plants Galanga Galangal Seed Al pinia galanga Wil ld., be dried to and moisturely be divided into 5.2%, be ground into 40 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 45 ℃, and pressure is 30Mpa; The separating still temperature is 55 ℃, and pressure is 16Mpa; The extraction-container temperature is 45 ℃, and pressure is 15MPa; Flow is 30kg/h; The extraction time is 2 hours.Get above-mentioned supercritical carbon dioxide extraction thing and put in the molecular still, input speed is 0.5ml/min, and vacuum tightness is 5Mpa, Heating temperature is 80 ℃, and cooling temperature is 6 ℃, and rotating speed is 200r/mi n, collect distillate, promptly get compound 3 (1 '-acetoxychavicol acetate).Adopting the conventional formulation method that this compound (1 '-acetoxychavicol acetate) is made soft capsule, tablet, capsule, pill, granule, injection uses in medicine.
Embodiment 4
Get the dry rhizome rhizome of Galanga Galangal of Zingiber Zi ng iberaceae Alpinia plants Galanga Galangal Seed Al pi ni a ga l anga Wil ld., be dried to and moisturely be divided into 5.5%, be ground into 30 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 50 ℃, and pressure is 25Mpa; The separating still temperature is 44 ℃, and pressure is 18Mpa; The extraction-container temperature is 48 ℃, and pressure is 5MPa; Flow is 40kg/h; The extraction time is 3 hours.Get above-mentioned supercritical carbon dioxide extraction thing and put in the molecular still, input speed is 2.0ml/min, and vacuum tightness is 20Mpa, Heating temperature is 150 ℃, and cooling temperature is 8 ℃, and rotating speed is 150r/min, collect distillate, promptly get compound 4 (1 '-acetoxychavicol acetate).Adopting the conventional formulation method that this compound (1 '-acetoxychavicol acetate) is made soft capsule, tablet, capsule, pill, granule, injection uses in medicine.
Embodiment 5
Get the dry rhizome rhizome of Galanga Galangal of Zingiber Zing iberaceae Alpinia plants Galanga Galangal Seed Al p inia ga langa Willd., be dried to and moisturely be divided into 4.3%, be ground into 20 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 55 ℃, and pressure is 40Mpa; The separating still temperature is 68 ℃, and pressure is 15Mpa; The extraction-container temperature is 45 ℃, and pressure is 12MPa; Flow is 50kg/h; The extraction time is 2.5 hours.Get above-mentioned supercritical carbon dioxide extraction thing and put in the molecular still, input speed is 3.5ml/min, and vacuum tightness is 25Mpa, Heating temperature is 160 ℃, and cooling temperature is 4 ℃, and rotating speed is 200r/min, collect distillate, promptly get compound 5 (1 '-acetoxychavicol acetate).Adopting the conventional formulation method that this compound (1 '-acetoxychavicol acetate) is made soft capsule, tablet, capsule, pill, granule, injection uses in medicine.
Embodiment 6
Get the dry rhizome rhizome of Galanga Galangal of Zingiber Z i ng i beraceae Alpinia plants Galanga Galangal Seed Al p in i a gal anga Wi l ld., be dried to and moisturely be divided into 4.9%, be ground into 55 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 49 ℃, and pressure is 23Mpa; The separating still temperature is 66 ℃, and pressure is 11Mpa; The extraction-container temperature is 43 ℃, and pressure is 8MPa; Flow is 5kg/h; The extraction time is 3 hours.Get above-mentioned supercritical carbon dioxide extraction thing and put in the molecular still, input speed is 4.5ml/mi n, and vacuum tightness is 28Mpa, Heating temperature is 115 ℃, and cooling temperature is 2 ℃, and rotating speed is 180r/min, collect distillate, promptly get compound 6 (1 '-acetoxychavicol acetate).Adopting the conventional formulation method that this compound (1 '-acetoxychavicol acetate) is made soft capsule, tablet, capsule, pill, granule, injection uses in medicine.
The beneficial effect that the present invention obtains:
1. structural identification test: the compound of getting above 6 embodiment preparation carries out the structural identification test, and the result is as follows:
1. ultimate analysis
Instrument model: German EAS Vario ELIII
Theoretical value: C%:66.67%, H:5.98%.
Detected value: 1) C%:66.83%, H%:6.01%
2)C％：66.74％，H％：6.15％
2. ultra-violet absorption spectrum
Instrument model: the UV-3400 of HIT
Detected value:
220.15nm:n the absorption peak that → π * transition produces is the uv-absorbing of ester group.
259.25nm: the absorption peak that π → π * transition produces is the absorption of phenyl ring.
3. infrared absorption spectrum
Instrument model: the NEXUS670 of U.S. Buddhist nun's high-tensile strength company
Detected value:
2941cm
-1C-H?s?t，1746cm
-1C＝O?s?t，1639cm
-1C＝C?s?t，
1231cm
-1CO-O?s?t?as，1201cm
-1O-C-C?s?t?a?s。
4. mass spectrum
Instrument model: the VARIAN of U.S. Varian company 2200
Detected value:
Obtain the fragment ion of following nucleo plasmic relation: 231,189,172,147,131.Wherein 231 is molions, sloughs nucleo plasmic relation and is 42 ethanoyl ion and obtain 189 fragment ion; It is that 59 acetate ion obtains 172 fragment ion that molion 231 is sloughed nucleo plasmic relation; It is that 42 ethanoyl ion obtains 147 fragment ion that molion 231 is sloughed 2 nucleo plasmic relations; It is that 16 oxonium ion obtains 131 fragment ion that 147 fragment ion is sloughed nucleo plasmic relation.
5. nuclear magnetic resonance spectrum
Instrument model: the AVANCE-400 of Switzerland Bruker company
Detected value:
1H-NMR(400MHz，CDCl
3)：7.396～7.372，7.112～7.091，6.301～6.284，6.063～6.016，5.432～5.314，2.306，2.287。
13C-NMR(400MHz，CDCl
3)：169.011,169.894,150.203,136.587,136.432，128.115,120.987,116.843，75.421，20.969，21.154。
Integration analysis: above test-results conclusive evidence the present invention extraction separation purified compound from the dry rhizome rhizome of Galanga Galangal of Zingiber Zingiberaceae Alpinia plants Galanga Galangal Seed Alpinia galanga Wil ld. is 1 '-acetoxychavicol acetate, and its molecular formula is C
13H
14O
4, molecular weight is 234.25, structural formula is
2.1 refining yield of '-acetoxychavicol acetate extraction separation and purity detecting result: 1 '-acetoxychavicol acetate of getting above 6 embodiment preparation detects, and the results are shown in Table.
Table 1 '-refining yield of acetoxychavicol acetate extraction separation and purity detecting result
Claims (1)
1. 1 '-acetoxychavicol acetate production method, it is characterized in that it is that water intaking divides and to be dried to less than 10% and to be ground into the Zingiber Zingiberaceae Alpinia plants Galanga Galangal Seed Alpinia galanga Willd. rhizome rhizome of Galanga Galangal of 10～60 order fine powders, put in the supercritical carbon dioxide extraction device, the extraction kettle temperature is 40 ℃～60 ℃, and pressure is 10Mpa～40Mpa; The separating still temperature is 40 ℃～70 ℃, and pressure is 10Mpa～20Mpa; The extraction-container temperature is 40 ℃～50 ℃, and pressure is 5Mpa～15Mpa; Flow is 5～50kg/h; The extraction time is 1～3 hour; Getting above-mentioned supercritical carbon dioxide extraction thing puts in the molecular still, input speed is 0.5～5ml/min, vacuum tightness is 5～30Mpa, Heating temperature is 80～200 ℃, cooling temperature is 2～10 ℃, rotating speed is 100～300r/min, collects distillate, makes English 1 '-acetoxychavicol acetate by name, molecular formula is C
13H
14O
4, molecular weight is 234.25, structural formula is
1 '-acetoxychavicol acetate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101005784A CN101029005B (en) | 2007-04-11 | 2007-04-11 | Method for producing 1-acetoxy-piperonyl acetate |
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| CN2007101005784A CN101029005B (en) | 2007-04-11 | 2007-04-11 | Method for producing 1-acetoxy-piperonyl acetate |
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| CN101029005B true CN101029005B (en) | 2010-08-11 |
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| CN104058963B (en) * | 2014-06-30 | 2016-05-11 | 苏州派腾生物医药科技有限公司 | A kind of method of extracting ACA from the ginger of the Huashan |
| CN117337188A (en) * | 2021-05-21 | 2024-01-02 | 三得利控股株式会社 | Method for preparing rhizoma Alpiniae Officinarum extract containing 1' -acetoxychavicol acetate |
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