CN103833810A - New preparation technology of apigenin-7-neohesperidoside - Google Patents
New preparation technology of apigenin-7-neohesperidoside Download PDFInfo
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- CN103833810A CN103833810A CN201410053352.3A CN201410053352A CN103833810A CN 103833810 A CN103833810 A CN 103833810A CN 201410053352 A CN201410053352 A CN 201410053352A CN 103833810 A CN103833810 A CN 103833810A
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- rhoifoloside
- preparation technology
- new preparation
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- naringin
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- 0 CC*(C*=*(*(CO)*(*)C(C(*)O)O)[C@@]1(C)OC1*O)N Chemical compound CC*(C*=*(*(CO)*(*)C(C(*)O)O)[C@@]1(C)OC1*O)N 0.000 description 1
Abstract
A new preparation technology of apigenin-7-neohesperidoside is disclosed. The new preparation technology comprises the following steps: reacting by dehydrogenation; concentrating under reduced pressure; depositing; filtering; concentrating; extracting; decolouring; concentrating; crystallizing; centrifugalizing; drying of the crude product; recrystallizing; and the like. The characteristic of the new preparation technology lies in that since the sustainable development of social economy, the using amount of a dehydrogenating agent is reduced to 1-5% of the amount of naringin, the optimum reaction system is selected, the utilization rate of the naringin is improved, the raw material resource is furthest utilized, the yield of synthesis intermediates of apigenin-7-neohesperidoside are substantially improved, and the manufacturing cost is greatly reduced. The new preparation technology is in accordance with the development requirements for resource-saving and environment-friendly society.
Description
Technical field
The present invention relates to a kind of new preparation technology of Rhoifoloside.
Background technology
Rhoifoloside (rhoifolin) another name: Rhoifolin.Chemical name: Apigenin-7-neohesperidoside; 7-[[2-O-(6-deoxy-alpha-L-mannopyranosyl)-beta-D-glucopyranosyl] oxy]-5-hydroxy-2-(4-hydroxyphenyl)-4H-benzopyran-4-one; 7-((2-O-(6-Deoxy-alpha-L-mannopyrano syl)-beta-D-glucopyranosyl) oxy)-5-hydroxy-2-(4-hydroxyphenyl)-4H-benzopyran-4-one; Apigenin-7-rhamnoglucoside; Molecular formula: C
27h
30o
14; Molecular weight: 578.53; CAS:17306-46-6.Structural formula is as follows:
Rhoifoloside is buff powder, derive from rutaceae Pummelo Peel (Exocarpium citrl Grandis, Pummelo Peel) prematurity or maturescent dry outer pericarp, Pteridaceae Herba Pteridis Multifidae (Pteris multifdapoir), the dry leave of Gu You section Turpinia pomifera(Roxb) D O. (Turpinia arguya Seem).Rhoifoloside has anti-oxidant, antitumor, and hypertension and fall heart rate suppresses XOD, suppresses the effect of neuraminidase, and the liver injury of triptolide induction is had to provide protection.
Because naringin content in plant is very micro-, mainly to prepare by the dehydrogenation to naringin at present, naringin is made by natural extract in mandarin orange, has very rich in natural resources in China.Take a broad view of domestic and foreign literature, flavonoid compound dehydrogenation mode roughly has three kinds: bromine dehydrogenation; Iodine dehydrogenation; The dehydrogenation of NBS/ peroxidation toluoyl.Solvent for use has pyridine, aceticanhydride, DMF etc., and take pyridine as common solvent, the effect of dehydrogenation is also better.Bromine to naringin dehydrogenation react in two steps, technique is loaded down with trivial details, complicated condition, and will use toxic reagent bromine water, cost is high.NBS/ peroxidation toluoyl dehydrogenating technology is divided into 3 steps substantially: (1) naringin acetylize is to protect all hydroxyls; (2) with oxygenant or bromizating agent, bromine (Br
2) process eight acetyl naringins, set up two keys at 2,3 and generate bromide; (3) process above-mentioned product with the dilute alcohol solution of alkali and remove hydrogen bromide and ethanoyl to remove ethanoyl or to complete simultaneously, then acidification reaction liquation goes out Rhoifoloside.
The present invention is take naringin as raw material, is dissolved in after pyridine directly with making naringin after iodine one step dehydrogenation.Product content is minimum reaches 97%, average yield 94%, greatly improved naringin yield and content, thereby effectively improved the utilization ratio of naringin and reduced production cost, this technique advanced person, stable, yield is good, content is high, production cost is well below traditional extraction technique.
Summary of the invention
The first dehydrogenation reaction: naringin is dissolved in solvent, add dehydrogenation reagent and auxiliary material, reaction at a certain temperature, detects with high performance liquid phase, obtains Rhoifoloside reaction solution after having reacted.
The second concentrating under reduced pressure: Rhoifoloside reaction solution is under reduced pressure concentrated, reclaims solvent, obtains Rhoifoloside enriched material.
The 3rd precipitation, filter: in Rhoifoloside enriched material, add large water gaging, fully stir, heating, precipitation, press filtration, collects water liquid.
The 4th is concentrated, extraction: above-mentioned water liquid concentrating under reduced pressure, concentrated solution extracts with extraction agent, obtains Rhoifoloside extraction liquid.
The 5th decolouring, concentrated: in Rhoifoloside extraction liquid, add a certain amount of activated carbon decolorizing, filter and remove gac, filtrate decompression is concentrated, obtains Rhoifoloside concentrated solution.
The 6th crystallization, centrifugal: the crystallization at low temperatures of Rhoifoloside concentrated solution, centrifugal crystallisate, obtains Rhoifoloside fine work, dry under the Rhoifoloside filter cake vacuum after centrifugal, obtains dry Rhoifoloside fine work.
Septuple crystallization: dried crude product Rhoifoloside, with solvent heating for dissolving, filters, and filtrate is concentrated, and crystallization is centrifugal, obtains fine work Rhoifoloside.
Embodiment
In reactor, suction 300.0kg pyridine, slowly adds naringin 50.0kg, and then adds iodine 1.0kg, and auxiliary material 3.0kg is heated to 100 ℃ under stirring, at this temperature, react 1～10h.Sample thief detects the content of naringin, and when the content of naringin is lower than 0.5% time, reaction finishes, and obtains Rhoifoloside reaction solution.Reaction solution is at 70～90 ℃, and vacuum tightness reclaims pyridine solvent under-(0.01～0.05) Mpa, obtains paste Rhoifoloside enriched material.In paste Rhoifoloside enriched material, add 1200kg purified water, fully stir, be heated to 40～60 ℃, insulation 30～60min, press filtration, obtains the Rhoifoloside aqueous solution.The Rhoifoloside aqueous solution is concentrated into proportion 1.05 under-(0.01～0.05) Mpa, with equal-volume ethyl acetate extraction extraction 3～5 times, collect acetic acid ethyl acetate extract, add the gac of 5% (w/v) 30min that decolours at 60 ℃, filter, filtrate is concentrated into proportion 1.10,10 ℃ of following crystallizations, centrifugal, dry, obtain Rhoifoloside crude product.
Seal reactor mouth, by the 400.0kg methyl alcohol of accurate-metering, with vacuum suction reactor, slowly added 40.0kg Rhoifoloside crude product, and then add gac 3.0kg, under stirring, be heated to 70 ± 2 ℃, backflow 1h.Dissolving material is pressed into strainer by pipeline, receive filtrate from dissolving post, close material feeding valve, open solvent recuperation valve on concentration tank, open vacuum valve, open concentration tank and upload hot steam valve, at-(0.06～0.08) Mpa, concentrating under reduced pressure under 50 ℃ ± 2 ℃ conditions, is concentrated into 1/2 o'clock of original volume, stop concentrating, be pressed into crystallizer.Close crystallizer material inlet valve, open crystallizer cooling water valve, ON cycle water pump, in the time that temperature of charge is down to below 30 ℃, opens crystallizer and stirs, and makes material stirring crystallization 12～16h.Pour the gradation of advantages of good crystallization material into whizzer centrifugal, will after centrifugal good material metage metering, hand over dry post dry.Refining Rhoifoloside wet product after centrifugal is transferred in drying machine ,-(0.06～0.08) MPa, dry 2.5h under 40～60 ℃ of conditions of temperature.Dried refining Rhoifoloside is pulverized with pulverizer, after having pulverized, comminuting matter is handed over through-station application sampling to detect.Determine mixed batch batch, joined total mixed machine, mixed with the rotating speed rotation 30min of 2r/min.Material is divided in polyethylene packaging bag, adjusts every packed amount at 25.0 ± 0.1kg between internal packing, and sampling detects, and pricks sealing, overlaps the 2nd layer of packing bag, pricks sealing, then transfers between outer packaging outsourcing, labeling warehouse-in from transmitting window.
Claims (8)
1. a new preparation technology for Rhoifoloside, is characterized in that, take naringin as raw material, the method is successively through following steps:
(1) dehydrogenation reaction: naringin adds dehydrogenation reagent and auxiliary material after dissolving in solvent, reaction at a certain temperature, detects with high performance liquid phase, obtains Rhoifoloside reaction solution after having reacted.
(2) concentrating under reduced pressure: Rhoifoloside reaction solution is under reduced pressure concentrated, obtains Rhoifoloside enriched material.
(3) precipitation, filter: in Rhoifoloside enriched material, add large water gaging, fully stir, heating, precipitation, press filtration, collects water liquid.
(4) concentrated, extraction: with extraction agent extraction, obtain Rhoifoloside extraction liquid after above-mentioned water liquid is concentrated.
(5) decolouring, concentrated: Rhoifoloside extraction liquid adds activated carbon decolorizing, to filter, filtrate decompression is concentrated, obtains Rhoifoloside concentrated solution.
(6) crystallization, centrifugal, dry: crystallization under Rhoifoloside concentrated solution low temperature, crystallisate is centrifugal, obtains Rhoifoloside crude product, and the Rhoifoloside filter cake drying under reduced pressure after centrifugal, obtains dry Rhoifoloside crude product
(7) recrystallization: dried crude product Rhoifoloside, with solvent heating for dissolving, filters, and filtrate is concentrated, and crystallization is centrifugal, obtains fine work Rhoifoloside.
2. the new preparation technology of a kind of Rhoifoloside as claimed in claim 1, is characterized in that, in step (1), dehydrogenation reaction solvent is water, methyl alcohol, ethanol, acetone, pyridine, dimethyl formamide, quinoline, in morpholine any one, any two kinds or any three kinds mix with arbitrary proportion; Dehydrogenating agent is iodine; Auxiliary material is sodium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide.
3. the new preparation technology of a kind of Rhoifoloside as claimed in claim 1, is characterized in that, in step (1), the consumption of iodine is 1～5% of naringin amount; Solvent load is 5～8 times of naringin amount; Temperature of reaction is at 70～100 ℃; Supplementary product consumption is 5～10% of naringin amount.
4. the new preparation technology of a kind of Rhoifoloside as claimed in claim 1, is characterized in that, in step (2), enriched material proportion is 1.05～1.20.
5. the new preparation technology of a kind of Rhoifoloside as claimed in claim 1, is characterized in that, in step (3), in Rhoifoloside enriched material, adds 10～15 times of (w/w) water, fully stir, be heated to 50～80 ℃, insulation 30～60min, press filtration.
6. the new preparation technology of a kind of Rhoifoloside as claimed in claim 1, is characterized in that, in step (4), concentrated solution proportion is 1.05～1.10; Extraction agent is ethyl acetate, in propyl carbinol any one, any two kinds mix with arbitrary proportion.
7. the new preparation technology of a kind of Rhoifoloside as claimed in claim 1, is characterized in that, in step (5), enriched material proportion is 1.05～1.20.
8. the new preparation technology of a kind of Rhoifoloside as claimed in claim 1, is characterized in that, in step (7), solvent for use is water, methyl alcohol, ethanol, acetone, propyl carbinol, in ethyl acetate any one, any two kinds or any three kinds mix with arbitrary proportion; Enriched material proportion is 1.05～1.20.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2740950C2 (en) * | 1977-09-10 | 1987-10-22 | Merck Patent Gmbh, 6100 Darmstadt, De | |
| CN1640872A (en) * | 2004-01-14 | 2005-07-20 | 南京莱尔生物化工有限公司 | Novel semi-synthetic versulin preparing process |
| CN1793157A (en) * | 2005-12-31 | 2006-06-28 | 浙江大学 | Process for synthesizing lacquer leafide |
| CN102391337A (en) * | 2011-10-10 | 2012-03-28 | 南京泽朗医药科技有限公司 | Method for extracting rhoifolin from turpinia formosana leaves |
| CN103012524A (en) * | 2012-12-31 | 2013-04-03 | 浙江大学 | Semisynthetic method for preparing rhoifolin |
-
2014
- 2014-02-12 CN CN201410053352.3A patent/CN103833810A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2740950C2 (en) * | 1977-09-10 | 1987-10-22 | Merck Patent Gmbh, 6100 Darmstadt, De | |
| CN1640872A (en) * | 2004-01-14 | 2005-07-20 | 南京莱尔生物化工有限公司 | Novel semi-synthetic versulin preparing process |
| CN1793157A (en) * | 2005-12-31 | 2006-06-28 | 浙江大学 | Process for synthesizing lacquer leafide |
| CN102391337A (en) * | 2011-10-10 | 2012-03-28 | 南京泽朗医药科技有限公司 | Method for extracting rhoifolin from turpinia formosana leaves |
| CN103012524A (en) * | 2012-12-31 | 2013-04-03 | 浙江大学 | Semisynthetic method for preparing rhoifolin |
Non-Patent Citations (1)
| Title |
|---|
| HANS-WALTER VOIGTLANDER，等: "Eine einfache Methode zur Oberfiihrung von Flavanonen in Flavone", 《ARCH. PHARM.》 * |
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Application publication date: 20140604 |