CN101863940A - New aurantiamarin synthesizing technique - Google Patents
New aurantiamarin synthesizing technique Download PDFInfo
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- CN101863940A CN101863940A CN200910216057A CN200910216057A CN101863940A CN 101863940 A CN101863940 A CN 101863940A CN 200910216057 A CN200910216057 A CN 200910216057A CN 200910216057 A CN200910216057 A CN 200910216057A CN 101863940 A CN101863940 A CN 101863940A
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Abstract
A new aurantiamarin synthesizing technique relates to a method for synthesizing new aurantiamarin by using naturally abstracted naringin as raw materials. The traditional aurantiamarin synthesizing technique has the problems of low efficiency and high cost or the problems of hard condition, complex operation and long production period. The synthesizing method of the invention using naringin as raw materials comprises the steps of: a. synthesizing acetophenone-4'-beta-new flavedo glucoside and b. synthesizing new aurantiamarin. The synthesizing technique of the invention needs no hard condition, has simple operation, short period, and stable and easily controlled synthesizing condition, and is easy to separate and purify. The product yield of new aurantiamarin is equal to or more than 95% and the purity is equal to or more than 96% by using proline as an efficient catalyst for synthesizing new aurantiamarin, the production cost is low, the environmental pollution is small and the technique is suitable for industrializing production of the new aurantiamarin.
Description
Technical field
The invention belongs to the botanical drug substance synthesis technique, relating generally to a kind of botanical drug substance is the method for synthetic another the prior botanical drug substance of basic raw material, and particularly relating to a kind of is the synthetic new aurantiamarin synthesizing technique of basic raw material with the naringin.
Background technology
Neohesperidin belongs to the flavanone kind composition in the flavonoid compound, and it at first is found in the plant, distributes in bitter orange, Fructus Aurantii, the dried immature fruit of citron orange, immature shaddock usually.The neohesperidin molecular formula is C
28H
34O
15, molecular weight is 610.56, its structural formula is:
Pharmacological research shows: the flavonoid compounds such as neohesperidin in the dried immature fruit of citron orange, the Fructus Aurantii shrink the non-physiologic of rat unstriated muscle restraining effect, and can resist the spastic contraction that bariumchloride, vagusstoff cause, also has antibacterial and anti-inflammation functions in addition.Neohesperidin has better heat-resisting, and acid resistance can be used as beverage, the additive of food.The mid-90, Americanized scholar generates a kind of brand-new sweeting agent-neohesperidin dihydrochalcone with neohesperidin after high-pressure hydrogenation in the laboratory, and its sweet taste is equivalent to 1500-1800 times of sucrose.It not only sugariness be higher than sweeting agent commonly used such as asccharin, Sodium Cyclamate or aspartame, and palatability is better, mouthfeel is similar to white sugar, more valuable is, neohesperidin dihydrochalcone has good shielding bitter taste effect, be used for bitter taste tablet (or liquid preparation), correct the strong bitter taste of chemical medicine with this, thus improve tablet or liquid preparation palatability.Along with in recent years to the further investigation of neohesperidin and neohesperidin dihydrochalcone, excavate their more multivalence value and purposes, demand to neohesperidin increases rapidly, yet because can be less for the natural medicinal plant that extracts neohesperidin, the content of neohesperidin in plant is also lower, in addition neohesperidin in plant usually with the coexistence of the closely similar flavonoid compound of many structures such as Hesperidin, naringin, separate difficulty, cause the supply of neohesperidin not satisfy the demand in market far away.
And the neohesperidin complex structure is difficult to synthesize by complete synthesis mode.Now generally be by behind the naringin of plant extract and its similar, transforming the preparation neohesperidin by chemical process.In the patent No. is US3375242, US3522236, the foreign patent of ES545276 and article title are " Synthesis of various fiavanone7-neohesperidosides. " (Sciences Chimiques (1966), 262 (24), 1712-14.) with " Dihydrochalcone sweeteners:preparation of neohesperidin dihydrochalcone. " (Industrial ﹠amp; Engineering Chemistry Product Research and Development (1974), 13 (2), 125-9.) document in, be after the Isovanillin (excessive 12 times) that naringin is direct and excessive greatly reacts in alkaline aqueous solution or alcoholic solution, acidifying obtains neohesperidin, be with naringin in alkaline aqueous solution, obtain after the hydrolysis phloroacetophenone-4 '-β-neohesperidoside, in alkaline aqueous solution or alcoholic solution, react the back acidifying with excessive greatly Isovanillin again and obtain neohesperidin, these methods all exist yield low, need raw material Isovanillin amount bigger, the problem that cost is high can industrial possibility because lost.The patent No. is in the foreign patent of US3947405, by using Pyrrolidine and acetate to be catalyzer, with phloroacetophenone-4 '-B-neohesperidoside and Isovanillin by 1: 1 mol ratio in dehydrated alcohol under the argon shield reaction can synthesize neohesperidin in 12 hours, this is to be suitable for industrialized production process most in the past, yet still there is following shortcoming in it: need argon shield 1.; 2. need to use dehydrated alcohol, the dehydrated alcohol of recovery to need the recycle of dry ability; 3. need to use more expensive and have the liquid Pyrrolidine of very big smell to be catalyzer; 4. the reaction times is longer; 5. yield is not too high.Because the existence of these shortcomings makes this technology have the technology strictness, complicated operation, the production cycle is longer, and therefore problems such as cost height are necessary to seek the synthetic neohesperidin of new approach.
Summary of the invention
It is simple to have the object of the present invention is to provide a kind of processing condition to require, easy to operate, with short production cycle, yield is high, new aurantiamarin synthesizing technique with low cost, it comprise a. synthesize phloroacetophenone-4 '-β-neohesperidoside, b. synthetic two steps of neohesperidin, concrete operation method is: a. phloroacetophenone-4 '-β-neohesperidoside synthetic: under agitation be dissolved in sodium hydroxide or potassium hydroxide in the tap water, be made into mass percentage concentration (w/w) and be 10～16% basic solution, under agitation condition, slowly add in this basic solution naringin then, the consumption W/V=1 of naringin and basic solution: 10～14, after stirring dissolving fully, ℃ backflow of beginning heat temperature raising to 100, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 1.5～2.5 hours, be cooled to below 30 ℃, slowly add concentrated hydrochloric acid and be neutralized to pH value 6～7, separate out yellow solid.Make solid all after the dissolving once more more than the heat temperature raising to 70 ℃, stop heating, naturally cooling leaves standstill totally 2 hours after-filtration, 60 ℃ of vacuum-drying promptly obtain yellow phloroacetophenone-4 '-β-neohesperidoside; B. neohesperidin is synthetic: with phloroacetophenone-4 '-β-neohesperidoside adds in 75～98% the ethanol, after the stirring and dissolving, add catalyzer proline(Pro) and reaction raw materials Isovanillin more respectively, wherein phloroacetophenone-4 '-β-neohesperidoside: ethanol: proline(Pro): Isovanillin (W/V/W/W)=1: (6～8): 0.24: 0.32, heat temperature raising is to refluxing, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 0.5～2 hour, be cooled to 25～30 ℃, filter, solid with massive laundering wash to solid be colourless till, 60 ℃ of vacuum-dryings promptly obtain yellow powder powder solid matter neohesperidin, yield is up to 95～98%, product purity 〉=96%.Synthetic neohesperidin of the present invention is through nuclear-magnetism (H-NMR), mass spectrum (MS), and infrared spectra (IR) and UV spectrum (UV) characterize evaluation, and consistent with the characterization data of the neohesperidin of bibliographical information, spectrogram is seen description of drawings.
The present invention is to be starting raw material with the natural plant raw material naringin, through naringin alkaline hydrolysis obtain phloroacetophenone-4 '-the B-neohesperidoside, but under proline(Pro) catalysis, react the synthetic neohesperidin of high yield again with Isovanillin, the proline(Pro) that uses among the present invention can be the L-proline(Pro), also can be the D-proline(Pro).The present invention has following advantage with respect to the past optimum process:
1. do not need protection of inert gas, synthesis condition is simple;
2. do not need the more expensive dehydrated alcohol of high purity, use the industrial spirit more than 75% to get final product, and recovered alcohol can directly directly recycle without any processing;
3. do not need to use more expensive and have the reagent of big sharp aroma, processing ease;
4. first with the effective catalyst of proline(Pro) solid reagent as synthetic neohesperidin, speed of response is fast, and is with short production cycle;
5. yield is high, reaches more than 95% low production cost.
Description of drawings
The nuclear magnetic spectrogram of Fig. 1, neohesperidin
The mass spectrogram of Fig. 2, neohesperidin
The infrared spectrogram of Fig. 3, neohesperidin
The ultraviolet spectrogram of Fig. 4, neohesperidin
Embodiment
The working method of the synthetic neohesperidin of this example is carried out according to following two steps:
Phloroacetophenone-4 '-β-neohesperidoside synthetic: 6.0g sodium hydroxide under agitation is dissolved in the 50mL tap water, under agitation condition, slowly add in this basic solution the 4.5g naringin then, after stirring dissolving fully, ℃ backflow of beginning heat temperature raising to 100, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 1.5 hours, be cooled to below 30 ℃, slowly add concentrated hydrochloric acid and be neutralized to pH value about 6.5, separate out yellow solid.Make solid all after the dissolving once more more than the heat temperature raising to 70 ℃, stop heating, naturally cooling leaves standstill that B filters after totally 2 hours, drain back 60 ℃ of vacuum-dryings promptly obtain the yellow phloroacetophenone-4 of 2.5g '-β-neohesperidoside, yield 68%.
Neohesperidin synthetic: with 2.0g phloroacetophenone-4 '-β-neohesperidoside adds in the ethanol of 12mL85%, after the stirring and dissolving, add 0.5g proline(Pro) and 0.6g Isovanillin more respectively, 90 ℃ of heating reflux reactions, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 1.5 hours, be cooled to below 30 ℃, B filters, solid with massive laundering wash to solid be colourless till, 60 ℃ of vacuum-dryings promptly obtain 2.4g yellow powder powder solid matter neohesperidin, and yield is 96%, and product is 96.5% through liquid chromatogram measuring purity.
The working method of the synthetic neohesperidin of this example is carried out according to following two steps:
Phloroacetophenone-4 '-β-neohesperidoside synthetic: 3.5kg sodium hydroxide under agitation is dissolved in the 30L tap water, under agitation condition, slowly add in this basic solution the 2.8kg naringin then, after stirring dissolving fully, ℃ backflow of beginning heat temperature raising to 100, from beginning the timing that refluxes, 100 ℃ of backflow stirring reactions stop heating after 2 hours, be cooled to below 30 ℃, slowly add concentrated hydrochloric acid and be neutralized to pH value about 6.5, separate out yellow solid.Make solid all after the dissolving once more more than the heat temperature raising to 70 ℃, stop heating, naturally cooling leaves standstill that B filters after totally 2 hours, drain back 60 ℃ of vacuum-dryings promptly obtain the yellow phloroacetophenone-4 of 1.6kg '-β-neohesperidoside, yield 70%.
Neohesperidin synthetic: with 1.5kg phloroacetophenone-4 '-β-neohesperidoside adds in the ethanol of 9L95%, after the stirring and dissolving, add 0.4kg proline(Pro) and 0.5kg Isovanillin more respectively, 90 ℃ of heating reflux reactions, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 2 hours, be cooled to below 30 ℃, filter, solid with massive laundering wash to solid be colourless till, 60 ℃ of vacuum-dryings promptly obtain 1.9kg yellow powder powder solid matter neohesperidin, and yield is 97%, and product purity is 96.8%.
The working method of the synthetic neohesperidin of this example is carried out according to following two steps:
Phloroacetophenone-4 '-β-neohesperidoside synthetic: 200kg sodium hydroxide under agitation is dissolved in the 1700L tap water, under agitation condition, slowly add in this basic solution the 150kg naringin then, after stirring dissolving fully, ℃ backflow of beginning heat temperature raising to 100, from beginning the timing that refluxes, 100 ℃ of backflow stirring reactions stop heating after 2 hours, be cooled to below 30 ℃, slowly add concentrated hydrochloric acid and be neutralized to pH value about 6.5, separate out yellow solid.Make solid all after the dissolving once more more than the heat temperature raising to 70 ℃, stop heating, naturally cooling leaves standstill centrifuging after totally 2 hours, drain back 60 ℃ of vacuum-dryings promptly obtain the yellow phloroacetophenone-4 of 85.5kg '-β-neohesperidoside, yield 69%.
Neohesperidin synthetic: with 85kg phloroacetophenone-4 '-β-neohesperidoside adds in the ethanol of 620L95%, after the stirring and dissolving, add 20.4kg proline(Pro) and 27.2kg Isovanillin more respectively, 90 ℃ of heating reflux reactions, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 2 hours, be cooled to below 30 ℃, filter, solid with massive laundering wash to solid be colourless till, 60 ℃ of vacuum-dryings promptly obtain 103kg yellow powder powder solid matter neohesperidin, and yield is 95.5%, and product purity is 97%.
Claims (4)
1. new aurantiamarin synthesizing technique, it is characterized in that it comprise a. synthesize phloroacetophenone-4 '-β-neohesperidoside, b. synthetic two steps of neohesperidin, concrete operation method is: a. phloroacetophenone-4 '-β-neohesperidoside synthetic: under agitation be dissolved in sodium hydroxide or potassium hydroxide in the tap water, be made into mass percentage concentration (w/w) and be 10～16% basic solution, under agitation condition, slowly add in this basic solution naringin then, the consumption W/V=1 of naringin and basic solution: 10～14, after stirring dissolving fully, ℃ backflow of beginning heat temperature raising to 100, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 1.5～2.5 hours, be cooled to below 30 ℃, slowly add concentrated hydrochloric acid and be neutralized to pH value 6～7, separate out yellow solid.Make solid all after the dissolving once more more than the heat temperature raising to 70 ℃, stop heating, naturally cooling leaves standstill totally 2 hours after-filtration, 60 ℃ of vacuum-drying promptly obtain yellow phloroacetophenone-4 '-β-neohesperidoside; B. neohesperidin is synthetic: with phloroacetophenone-4 '-β-neohesperidoside adds in 75～98% the ethanol, after the stirring and dissolving, add catalyzer proline(Pro) and reaction raw materials Isovanillin more respectively, wherein phloroacetophenone-4 '-β-neohesperidoside: ethanol: proline(Pro): Isovanillin (W/V/W/W)=1: (6～8): 0.24: 0.32, heat temperature raising is to refluxing, from beginning the timing that refluxes, the backflow stirring reaction stops heating after 0.5～2 hour, be cooled to 25～30 ℃, filter, solid with massive laundering wash to solid be colourless till, 60 ℃ of vacuum-dryings promptly obtain yellow powder powder solid matter neohesperidin, yield is up to 95～98%, product purity 〉=96%.
2. new aurantiamarin synthesizing technique according to claim 1 is characterized in that having used proline(Pro) as a kind of catalyzer efficiently in neohesperidin synthetic.
3. new aurantiamarin synthesizing technique according to claim 1, it is characterized in that proline(Pro) can be the L-proline(Pro) described in neohesperidin synthetic, also can be the D-proline(Pro), can also be that L-proline(Pro) and D-proline(Pro) are by arbitrary proportion blended mixed type proline(Pro).
4. new aurantiamarin synthesizing technique according to claim 1, it is characterized in that described synthetic phloroacetophenone-4 '-β-neohesperidoside, be the compound that the naringin of natural extract obtains through acidifying after the alkaline hydrolysis, its structure is as follows:
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408620A (en) * | 2013-08-15 | 2013-11-27 | 西南化工研究设计院有限公司 | Neohesperidin synthesis technology |
| CN105148993A (en) * | 2015-10-20 | 2015-12-16 | 西南化工研究设计院有限公司 | Catalyst for synthesizing neohesperidin |
| CN105801636A (en) * | 2016-03-24 | 2016-07-27 | 济南诚汇双达化工有限公司 | Synthetic method for naringin dihydrochalcone |
| CN106220601A (en) * | 2016-07-20 | 2016-12-14 | 陕西嘉禾生物科技股份有限公司 | A kind of synthetic method of pinocembrin |
| CN106432386A (en) * | 2016-08-26 | 2017-02-22 | 湖南华诚生物资源股份有限公司 | Method for synthesizing neohesperidin by taking naringin as raw material |
| CN107118246A (en) * | 2016-12-28 | 2017-09-01 | 湖南鑫利生物科技有限公司 | A kind of synthesis technique of neohesperidin |
| CN107501361A (en) * | 2016-11-11 | 2017-12-22 | 湘西华方制药有限公司 | A kind of synthesis technique of the β of phloroacetophenone 4 ' neohesperidosides |
| CN109293720A (en) * | 2018-11-21 | 2019-02-01 | 湖南省农产品加工研究所 | A method of synthesis neohesperidin |
| CN109503685A (en) * | 2018-12-28 | 2019-03-22 | 成都欧康医药股份有限公司 | A method of neohesperidin is synthesized with Fructus Citri grandis extract |
| CN113559162A (en) * | 2021-08-02 | 2021-10-29 | 安徽九春堂药业有限公司 | Pharmaceutical composition for reducing blood fat and preparation method thereof |
| CN114478657A (en) * | 2022-02-18 | 2022-05-13 | 厦门大学 | Synthesis method of neohesperidin |
| CN115850225A (en) * | 2022-11-30 | 2023-03-28 | 三原润禾生物科技有限公司 | Application of hesperidin and method for semi-synthesizing chrysin by using hesperidin derivative |
| CN115850225B (en) * | 2022-11-30 | 2024-06-28 | 三原润禾生物科技有限公司 | Application of hesperidin and method for semisynthesis preparation of chrysin by using hesperidin derivative |
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2009
- 2009-10-30 CN CN200910216057.4A patent/CN101863940B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408620A (en) * | 2013-08-15 | 2013-11-27 | 西南化工研究设计院有限公司 | Neohesperidin synthesis technology |
| CN103408620B (en) * | 2013-08-15 | 2016-06-01 | 西南化工研究设计院有限公司 | The synthesis technique of a kind of neohesperidin |
| CN105148993A (en) * | 2015-10-20 | 2015-12-16 | 西南化工研究设计院有限公司 | Catalyst for synthesizing neohesperidin |
| CN105148993B (en) * | 2015-10-20 | 2017-11-28 | 西南化工研究设计院有限公司 | A kind of catalyst for being used to synthesize neohesperidin |
| CN105801636A (en) * | 2016-03-24 | 2016-07-27 | 济南诚汇双达化工有限公司 | Synthetic method for naringin dihydrochalcone |
| CN106220601A (en) * | 2016-07-20 | 2016-12-14 | 陕西嘉禾生物科技股份有限公司 | A kind of synthetic method of pinocembrin |
| CN106432386A (en) * | 2016-08-26 | 2017-02-22 | 湖南华诚生物资源股份有限公司 | Method for synthesizing neohesperidin by taking naringin as raw material |
| CN106432386B (en) * | 2016-08-26 | 2019-04-19 | 湖南华诚生物资源股份有限公司 | A method of using aurantiin as Material synthesis neohesperidin |
| CN107501361A (en) * | 2016-11-11 | 2017-12-22 | 湘西华方制药有限公司 | A kind of synthesis technique of the β of phloroacetophenone 4 ' neohesperidosides |
| CN107118246A (en) * | 2016-12-28 | 2017-09-01 | 湖南鑫利生物科技有限公司 | A kind of synthesis technique of neohesperidin |
| CN109293720A (en) * | 2018-11-21 | 2019-02-01 | 湖南省农产品加工研究所 | A method of synthesis neohesperidin |
| CN109503685A (en) * | 2018-12-28 | 2019-03-22 | 成都欧康医药股份有限公司 | A method of neohesperidin is synthesized with Fructus Citri grandis extract |
| CN113559162A (en) * | 2021-08-02 | 2021-10-29 | 安徽九春堂药业有限公司 | Pharmaceutical composition for reducing blood fat and preparation method thereof |
| CN114478657A (en) * | 2022-02-18 | 2022-05-13 | 厦门大学 | Synthesis method of neohesperidin |
| CN114478657B (en) * | 2022-02-18 | 2023-03-31 | 厦门大学 | Synthesis method of neohesperidin |
| CN115850225A (en) * | 2022-11-30 | 2023-03-28 | 三原润禾生物科技有限公司 | Application of hesperidin and method for semi-synthesizing chrysin by using hesperidin derivative |
| CN115850225B (en) * | 2022-11-30 | 2024-06-28 | 三原润禾生物科技有限公司 | Application of hesperidin and method for semisynthesis preparation of chrysin by using hesperidin derivative |
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