CN103012524B - Semisynthetic method for preparing rhoifolin - Google Patents
Semisynthetic method for preparing rhoifolin Download PDFInfo
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- CN103012524B CN103012524B CN201210594260.7A CN201210594260A CN103012524B CN 103012524 B CN103012524 B CN 103012524B CN 201210594260 A CN201210594260 A CN 201210594260A CN 103012524 B CN103012524 B CN 103012524B
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- leafide
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- naringin
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Abstract
The invention discloses a semisynthetic method for preparing rhoifolin, which is characterized by comprising the following steps: mixing naringin, ethanol water solution, iodine and alkalescent salt, heating while stirring to react, and filtering or centrifugating the reaction product while the reaction product is hot, thereby obtaining the precipitate rhoifolin crude product; and washing the precipitate with water, filtering or centrifugating the water washing solution, and drying the filtered or centrifugated solid to obtain the purified rhoifolin. Compared with the prior art, the invention has the advantages of accessible raw materials and low cost, is simple to operate, and is environment-friendly.
Description
Technical field
The present invention relates to the semi-synthetic preparation method of flavonoid compound lacquer leafide, belong to organic chemistry and functional food chemical field.
Background technology
Naringin (Naringin), belong to flavanone kind composition, widely distributed at occurring in nature, especially in rutaceae, content is higher, as shaddock (Pummelo, Citrus grandis), in the pericarp of natsudaidai (Grapefruit, Citrus paradisi), bitter orange (Sourorange, Citrus aurantium) and mutation thereof and fruit (content 1 ~ 6%).Naringin aboundresources, extraction purification technology maturation, therefore on market, naringin is in liberal supply, cheap.
Apigenin (Apigenin), has another name called 4',5,7-trihydroxyflavone, be distributed widely in various fruits, vegetables, beans, tealeaves, but content is lower, and very difficult separation obtains high-purity apigenin.Apigenin has antitumor, anti-oxidant, calm, anti-inflammatory, the pharmacological effect such as hypotensive, and compare with other flavone components, apigenin has low toxicity, without features such as mutagenicities.Have certain application in fields such as food, medicine and makeup, demand is larger.Lacquer leafide is the glycoside compounds of apigenin, is also the semi-synthetic main raw material preparing apigenin at present, and lacquer leafide, by hydrolysis, is sloughed monose and prepared apigenin.
A lot of bibliographical information with the glycosides derivatives of naringenin for raw material; C ring 2 is removed using DDQ as dehydrogenating agent; 3 hydrogen atoms form double bond (Oyama; K.I.and T.Kondo; Total synthesis ofapigenin7,4'-di-O-[beta]-glucopyranoside, a component of blue flowerpigment of Salvia patens; and seven chiral analogues.Tetrahedron, 2004.60 (9): 2025-2034; Shingo Sato, et al.Total synthesis of three naturallyoccurring6,8-di-C-glycosylflavonoids:phloretin, naringenin, andapigenin bis-C-β-d-glucosides.Carbohydrate Research, 2006,341 (8): 964-970), but the dehydrogenating agent DDQ that this method uses is more expensive, and reclaim difficulty, production cost is higher.
Publication number method disclosed in the patent documentation of CN1640872A obtains lacquer leafide by naringin through dehydrogenation aromizing, then obtain apigenin by lacquer leafide hydrolysis; Another kind of approach first naringin hydrolysis is obtained naringenin, then obtains apigenin by naringenin dehydrogenation aromizing.This method two kinds of approach total recoverys are only 62.4% and 69.2% respectively, and relate to toxicity and the pungency reagent such as bromine, pyridine, methylene dichloride and acetic anhydride in preparation process, are unfavorable for that industrial production is carried out.Publication number method disclosed in the patent documentation of CN1793157A take naringin as raw material, and Isosorbide-5-Nitrae-dioxane is solvent, generates lacquer leafide in the presence of base through iodo eliminative reaction.In this method, the yield of lacquer leafide is lower, only 50-65%, and needs multistep recrystallization just to obtain the lacquer leafide of purity more than 98%, complex operation step.
Summary of the invention
The object of this invention is to provide that a kind of raw material is easy to get, cost is lower, simple to operate, the environment amenable semi-synthetic method preparing lacquer leafide.
For achieving the above object, the technical solution used in the present invention is: the semi-synthetic method preparing lacquer leafide of the present invention, it is characterized in that, comprise: naringin, aqueous ethanolic solution, iodine and weakly alkaline salt are mixed also heated and stirred and react, to reaction product filtered while hot or centrifugal treating, obtain precipitate.
Further, described precipitate is washed by the present invention, then filters or centrifugal treating water lotion, then carries out drying to filtration or the centrifugal solid obtained.
Further, the present invention is when mixing naringin, aqueous ethanolic solution, iodine and weakly alkaline salt, and the proportion relation of aqueous ethanolic solution and naringin is: every milliliter of aqueous ethanolic solution is furnished with naringin 0.1 ~ 0.5 gram.
Further, the present invention is in described aqueous ethanolic solution, and the mass ratio of ethanol and water is 0.7 ~ 1 ︰ 1.
Further, the mol ratio of iodine of the present invention and naringin is 0.5 ~ 1.5 ︰ 1.
Further, the mol ratio of weakly alkaline salt of the present invention and naringin is 1 ~ 8 ︰ 1.
Further, weakly alkaline salt of the present invention is sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium-acetate or Potassium ethanoate.
Further, the temperature of reaction of the present invention is 40 ~ 80 DEG C.
Further, the time of reaction of the present invention is 12 ~ 48 hours.
Advantage of the present invention is:
(1) post-reaction treatment of the present invention is simple, is carried out by the solid of precipitation filtering or centrifugal, washing, can obtain highly purified lacquer leafide after drying, avoid purification step loaded down with trivial details in the traditional processing technology of lacquer leafide, reduce production cost after reaction terminates.
(2) in whole preparation process of the present invention, only relate to ethanol, iodine, salt, water, do not relate to high toxicity, pungency reagent and the source of heavy metal pollution such as bromine, methylene dichloride, NBS, pyridine, acetic anhydride and heavy metal, production process is safe and reliable, avoids objectionable impurities in the product residual.
(3) compare traditional technology, the inventive method adopts iodine and weakly alkaline salt to be solvent as dehydrogenating agent, ethanol water, avoids using expensive dehydrogenating agent DDQ, reduces production cost.
(4) the inventive method adopts ethanol water as reaction solvent, avoids the use of strong stimulation taste noxious solvent pyridine in the traditional processing technology of lacquer leafide, more friendly to environment.
Accompanying drawing explanation
Fig. 1 is the high-efficient liquid phase chromatogram of naringin and lacquer leafide standard substance;
Fig. 2 is the high-efficient liquid phase chromatogram of gained reaction product lacquer leafide crude product in embodiment 1;
Fig. 3 is the high-efficient liquid phase chromatogram of gained reaction product lacquer leafide crude product in embodiment 2;
Fig. 4 be in embodiment 3 gained reaction product lacquer leafide purified after high-efficient liquid phase chromatogram.
Embodiment
It is more than the structural formula of naringin.Can find out, naringin and lacquer leafide chemical structure closely similar, its difference only lacquer leafide C ring prosposition formed unsaturated link(age).For this reason, inventive concept of the present invention is: consider that C ring 3 carbon of naringin are on the α position of ortho position carbonyl, be subject to the attack of electrophilic reagent, can form double bond by first replacing the reaction eliminated afterwards.By chemical reaction, naringin is converted into lacquer leafide, avoid the lacquer leafide of natural origin or apigenin extraction yield low, the problems such as purification steps troublesome, thus reduce production cost, be suitable for industrial applications.
The invention provides a kind of be suitable for suitability for industrialized production, from the semi-synthetic novel method preparing lacquer leafide of naringin.In the traditional processing technology of lacquer leafide, using pyridine as dehydrogenating agent and reaction solvent, and pyridine toxicity is large, pungency strong, easily remains in final product, is unfavorable for that greenization is produced; And due to pyridine be the good solvent of iodine, boiling point is high, be difficult to participate in reaction iodine carry out recycling, cost is increased; In addition, reaction product needs just can obtain high-content lacquer leafide through multistep soda acid purification process, and technique is loaded down with trivial details.The inventive method adopts green solvent ethanol as reaction solvent, and iodine and weakly alkaline salt react as dehydrogenating agent, not only avoid pyridine pollution on the environment, and can be cost-saving, simplifies and produces post-processing step.The lacquer leafide production technique that the present invention relates to is environmentally friendly, and reaction product after filtration or centrifugal, washing, can obtain highly purified lacquer leafide after drying.
The semi-synthetic preparation method preparing lacquer leafide of the present invention comprises as follows:
Reaction formula I
Take naringin as raw material, aqueous ethanolic solution is as reaction solvent, and iodine and weakly alkaline salt are as dehydrogenating agent, and the reaction that heated and stirred is carried out as reaction formula I generates lacquer leafide.After reaction terminates, by the solid filtering or centrifugal of separating out in reaction process, lacquer leafide crude product can be obtained.
If the lacquer leafide crude product obtained is added water washing, after filtration or centrifugal, drying can obtain highly purified lacquer leafide.
In the methods of the invention, the proportion relation of preferred naringin quality and aqueous ethanolic solution volume is that every milliliter of aqueous ethanolic solution is furnished with naringin 0.1 ~ 0.5 gram; The consumption of preferred iodine is 0.5 ~ 1.5 times of naringin mole number; The mole number of preferred weakly alkaline salt is 1 ~ 8 times of the mole number of naringin; In the reaction preparing lacquer leafide crude product, preferable reaction temperature is 40 ~ 80 DEG C, and the preferred reaction time is 12-48 hour; The preferred sodium carbonate of weakly alkaline salt, salt of wormwood, sodium bicarbonate, saleratus, sodium-acetate or Potassium ethanoate.
In the examples below, the detection method of use is high performance liquid chromatography.Chromatographic condition: Shimadzu LC-10AT high performance liquid chromatograph, workstation is that Zhejiang University's intelligence reaches N2000, and detector is Shimadzu SPD-10A UV-detector, and chromatographic column is Diamonsil C
18reversed-phase column (4.6 × 250mm, 5 μ), moving phase is Jia Chun ︰ Yi Jing ︰ water=20 ︰ 15 ︰ 65(volume ratio), determined wavelength 280nm, column temperature is room temperature.As shown in Figure 1, under this chromatographic condition, the chromatographic peak of naringin and lacquer leafide all reaches baseline separation.Further, under this chromatographic condition, in following embodiment, the content of lacquer leafide and the equal usable floor area normalization method of the transformation efficiency of naringin calculate.
The preparation method of lacquer leafide in the present invention is further illustrated below by specific embodiment.Unless otherwise indicated, the percentage ratio that the present invention uses refers to mass percent.
Embodiment 1
(1) take naringin (purity is 98%) 0.017mol, add sodium acetate, anhydrous 0.135mol, iodine 0.017mol, 70% ethanol 25mL, be heated to 55 DEG C of reactions.After reaction carries out 24 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product.This crude product is through high-performance liquid chromatogram determination, and the content of lacquer leafide is 43.3%; Relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 74.7%.
As shown in Figure 2, from high performance liquid chromatography spectrogram, the reaction of the present embodiment is thorough, and the transformation efficiency of naringin is 99%.When non-drying and dehydrating and water-washing desalting, the relative content of lacquer leafide is lower, is lacquer leafide crude product.
Embodiment 2
(1) take naringin (purity is 98%) 0.017mol, add sodium acetate, anhydrous 0.017mol, iodine 0.0085mol, 100% ethanol 20mL, be heated to 55 DEG C of reactions.After reaction carries out 48 hours, terminate reaction.Centrifugal reaction solution obtains lacquer leafide crude product.Lacquer leafide crude product is carried out drying, obtains lacquer leafide crude product 8.7g.Through high-performance liquid chromatogram determination, in the present embodiment gained lacquer leafide crude product, the content of lacquer leafide is 86.7%; Relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 76.9%.
Visible on high performance liquid chromatography spectrogram as shown in Figure 3, the reaction of the present embodiment is comparatively thorough, and the transformation efficiency of naringin is 97%.
Embodiment 3
(1) take naringin (purity is 98%) 0.017mol, add sodium acetate, anhydrous 0.017mol, iodine 0.017mol, 70% ethanol 25mL, be heated to 80 DEG C of reactions.After reaction carries out 24 hours, terminate reaction.Filtering reacting liquid obtains lacquer leafide crude product.
(2) in lacquer leafide crude product, add 100mL water to carry out washing, filtering, then add in gained solid 50mL water carry out washing, filter, dry, obtain lacquer leafide sterling 7.6g.
Known through high-performance liquid chromatogram determination, in the present embodiment products therefrom lacquer leafide sterling, the content of lacquer leafide is 96.3%; Relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 73.6%.
Visible on high performance liquid chromatography spectrogram as shown in Figure 4, the present embodiment reaction is comparatively thorough, and the transformation efficiency of naringin is 97.3%.It can thus be appreciated that reaction product is after washing and drying step, and the content of lacquer leafide significantly increases.
Embodiment 4
(1) take naringin (purity is 98%) 0.017mol, add sodium acetate, anhydrous 0.05molg, iodine 0.026mol, 70% ethanol 100mL, be heated to 40 DEG C of reactions.After reaction carries out 12 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product.
(2) add in lacquer leafide crude product 100mL water carry out washing, centrifugal, then add in gained solid 100mL water carry out washing, centrifugal, dry, obtain lacquer leafide 7.6g.Through high-performance liquid chromatogram determination, in the present embodiment, the lacquer leafide content of gained is 96.6%, and relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 74.8%.
Embodiment 5
(1) take naringin (purity is 98%) 0.017mol, add saleratus 0.017mol, iodine 0.026mol, 85% ethanol 50mL, be heated to 55 DEG C of reactions.After reaction carries out 24 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product.
(2) in lacquer leafide crude product, add 100mL water to carry out washing, filtering, then add in gained solid 50mL water carry out washing, centrifugal, dry, obtain lacquer leafide 7.3g.Through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 98.7%, and relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 73.5%.
Embodiment 6
(1) take naringin (purity is 98%) 0.017mol, add saleratus 0.068mol, iodine 0.026mol, 85% ethanol 50mL, be heated to 55 DEG C of reactions.After reaction carries out 24 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product.
(2) in lacquer leafide crude product, add 100mL water to carry out washing, filtering, then add in gained solid 50mL water carry out washing, filter, dry, obtain lacquer leafide 7.6g.Through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 97.3%, and relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 75.5%.
Embodiment 7
(1) take naringin (purity is 98%) 0.017mol, add salt of wormwood 0.017mol, iodine 0.0085mol, 95% ethanol 50mL, be heated to 55 DEG C of reactions.After reaction carries out 48 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product.
(2) in lacquer leafide crude product, add 100mL water to carry out washing, filtering, add in gained solid again 50mL water carry out washing, filter, dry, obtain lacquer leafide 6.1g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 97.7%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 58.4%.
Embodiment 8
(1) take naringin (purity is 98%) 0.017mol, add salt of wormwood 0.136mol, iodine 0.0085mol, 95% ethanol 50mL, be heated to 55 DEG C of reactions.After reaction carries out 48 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product.
(2) in lacquer leafide crude product, add 100mL water to carry out washing, filtering, add in gained solid again 50mL water carry out washing, filter, dry, obtain lacquer leafide 7.1g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 96.7%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 70.1%.
Embodiment 9
(1) take naringin (purity is 98%) 0.017mol, add salt of wormwood 0.068mol, iodine 0.017mol, 95% ethanol 50mL, be heated to 75 DEG C of reactions.After reaction carries out 48 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product.
(2) in lacquer leafide crude product, add 100mL water to carry out washing, filtering, add in gained solid again 50mL water carry out washing, filter, dry, obtain lacquer leafide 7.6g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 97.5%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 75.6%.
Embodiment 10
(1) take naringin (purity is 98%) 0.017mol, add Potassium ethanoate 0.068mol, iodine 0.026mol, dehydrated alcohol 100mL, be heated to 75 DEG C of reactions.After reaction carries out 12 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product;
(2) in lacquer leafide crude product, add 100mL water to carry out washing, filtering, add in gained solid again 50mL water carry out washing, filter, dry, obtain lacquer leafide 8.4g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 98.1%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 84.1%.
Embodiment 11
(1) take naringin (purity is 98%) 0.085mol, add sodium bicarbonate 0.17mol, iodine 0.043mol, 85% ethanol 400mL, be heated to 75 DEG C of reactions.After reaction carries out 36 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product;
(2) in lacquer leafide crude product, add 500mL water to carry out washing, filtering, add in gained solid again 500mL water carry out washing, filter, dry, obtain lacquer leafide 40.6g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 97.2%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 80.5%.
Embodiment 12
(1) take naringin (purity is 98%) 0.17mol, add sodium carbonate 1.02mol, iodine 0.255mol, 80% ethanol 1000mL, be heated to 45 DEG C of reactions.After reaction carries out 12 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product;
(2) in lacquer leafide crude product, add 1000mL water to carry out washing, filtering, add in gained solid again 1000mL water carry out washing, filter, dry, obtain lacquer leafide 86.4g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 98.5%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 86.8%.
Embodiment 13
(1) take naringin (purity is 98%) 0.017mol, add Potassium ethanoate 0.136mol, iodine 0.012mol, dehydrated alcohol 100mL, be heated to 75 DEG C of reactions.After reaction carries out 12 hours, terminate reaction.Filtered while hot reaction solution obtains lacquer leafide crude product;
(2) add in lacquer leafide crude product 100mL water carry out washing, centrifugal, add in gained solid again 50mL water carry out washing, filter, dry, obtain lacquer leafide 7.9g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 98.1%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 79.1%.
Embodiment 14
(1) take naringin (purity is 98%) 1.7mol, add sodium carbonate 8.5mol, iodine 0.85mol, 85% ethanol 5000mL, be heated to 75 DEG C of reactions.After reaction carries out 24 hours, terminate reaction.Centrifugal reaction solution obtains lacquer leafide crude product;
(2) in lacquer leafide crude product, add 1000mL water to carry out washing, filtering, add in gained solid again 1000mL water carry out washing, filter, dry, obtain lacquer leafide 768.7g, through high-performance liquid chromatogram determination, in the present embodiment, the content of gained lacquer leafide is 96.4%, relative to the quality of the naringin in feeding intake, the yield of lacquer leafide is 75.6%.
Claims (9)
1. the semi-synthetic method preparing lacquer leafide, is characterized in that, comprising: naringin, aqueous ethanolic solution, iodine and weakly alkaline salt are mixed also heated and stirred and react, to reaction product filtered while hot or centrifugal treating, obtain precipitate.
2. the semi-synthetic method preparing lacquer leafide according to claim 1, is characterized in that: washed by described precipitate, then filters or centrifugal treating water lotion, then carries out drying to filtration or the centrifugal solid obtained.
3. method according to claim 1 and 2, is characterized in that: when naringin, aqueous ethanolic solution, iodine and weakly alkaline salt being mixed, the proportion relation of aqueous ethanolic solution and naringin is: every milliliter of aqueous ethanolic solution is furnished with naringin 0.1 ~ 0.5 gram.
4. method according to claim 1 and 2, is characterized in that: in described aqueous ethanolic solution, and the mass ratio of ethanol and water is 0.7 ~ 1 ︰ 1.
5. method according to claim 1 and 2, is characterized in that: the mol ratio of described iodine and naringin is 0.5 ~ 1.5 ︰ 1.
6. method according to claim 1 and 2, is characterized in that: the mol ratio of described weakly alkaline salt and naringin is 1 ~ 8 ︰ 1.
7. method according to claim 1 and 2, is characterized in that: described weakly alkaline salt is sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium-acetate or Potassium ethanoate.
8. method according to claim 1 and 2, is characterized in that: the temperature of described reaction is 40 ~ 80 DEG C.
9. method according to claim 1 and 2, is characterized in that: the time of described reaction is 12 ~ 48 hours.
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| CN103833810A (en) * | 2014-02-12 | 2014-06-04 | 李玉山 | New preparation technology of apigenin-7-neohesperidoside |
| CN113583063A (en) * | 2021-08-18 | 2021-11-02 | 陕西嘉禾生物科技股份有限公司 | Method for synthesizing cosmosiin by using naringin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| FR2782518A1 (en) * | 1998-08-19 | 2000-02-25 | Innokem Sarl | Preparation of vasotropic diosmin from hesperidin by anhydrous reaction with iodine and pyridine with solid mineral base |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| Jérôme Quintin,等.."Synthesis and anti-tubulin evaluation of chromone-based analogues of combretastatins".《Tetrahedron》.2006,第62卷4038–4051. * |
| Jidan Liu,等.."Semisynthesis of apigenin and acacetin-7-O-b-D-glycosides from naringin and their cytotoxic activities".《Carbohydrate Research》.2012,第357卷41-46. * |
| 冯宣,等.."迪奥明合成工艺的改进".《第四军医大学学报》.2008,第29卷(第21期),1947. * |
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