CN105884738A - Microwave-assisted synthesis method for EGCG fatty acid ester - Google Patents
Microwave-assisted synthesis method for EGCG fatty acid ester Download PDFInfo
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- CN105884738A CN105884738A CN201510683671.7A CN201510683671A CN105884738A CN 105884738 A CN105884738 A CN 105884738A CN 201510683671 A CN201510683671 A CN 201510683671A CN 105884738 A CN105884738 A CN 105884738A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
- C07D311/62—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2 with oxygen atoms directly attached in position 3, e.g. anthocyanidins
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Abstract
The invention discloses a microwave-assisted synthesis method for EGCG fatty acid ester. The method comprises the steps that epigallocatechin gallate and fatty acid chloride are dissolved into an inert organic solvent according to the mole ratio of 1:(4-6); an esterifying catalyst with the quantity 2-4 times of that of the epigallocatechin gallate substance is added; microwave-assisted synthesis is conducted, and a reaction is stopped after being conducted for a period of time at a certain temperature; filtering, alkali washing, water washing, reduced pressure concentrating and recrystallizing are conducted, and then freeze drying is conducted for 4-6 h to obtain EGCG fatty acid ester. According to the microwave-assisted synthesis method for EGCG fatty acid ester, the effects which cannot be achieved by a reaction under the conventional heating condition can be achieved by utilizing the advantages of microwave-assisted synthesis, and the reaction conversion rate is increased to 84.5% from original 68%.
Description
The invention belongs to food additives synthesis field, relate to the system of the EGCG fatty acid ester of a kind of improvement
Preparation Method, a kind of method relating generally to Microwave-assisted synthesis EGCG fatty acid ester.
Background technology
Catechin is most important physiological activator in tealeaves, accounts for the 60%～80% of Tea Polyphenols total amount,
It it is the main matter composition of tea health-care function.With Epigallo-catechin gallate (EGCG) in catechin
(EGCG) content is the highest, accounts for about the 50% of catechin total amount.Due to EGCG excellent anti-oxidant,
The physiological activities such as anti-sudden change, radiation proof, antitumor, regulation is immune and delays senility, the most relevant
The research of EGCG is noticeable, but for it is applied, there is fat-soluble difference, bioavilability low, raw
Manage the problems such as instability under environment is slow with body absorption.
Based on these problems, make the molecular modification of its modification by retaining its active group, become in recent years
One of focus of EGCG research.It is to be to change the most both at home and abroad that conventional heating methods carries out molecular structure modification
The important means of material BA.But the acylated shortcomings that exists of conventional heating chemical method: region is selected
Selecting property is poor, is easily generated substantial amounts of accessory substance, and reaction conversion ratio is low, and product yield is low；Reaction rate is slow, instead
The shortcoming that should time-consumingly grow, in actual mechanical process, the reaction time is often up to 12h, but conversion ratio is only
68%, simultaneous reactions product is monosubstituted, two replacements, trisubstituted mixture, and wherein mono-substituted products is only
Account for the 52.8% of product.
Summary of the invention
The purpose of this part is summarize some aspects of embodiments of the invention and briefly introduce some relatively
Good embodiment.This part and the description of the present application make a summary and denomination of invention may be done a little simplify or
Omit to avoid making the purpose of this part, specification digest and denomination of invention to obscure, and this simplification or omission
Cannot be used for limiting the scope of the present invention.
In view of problem present in above-mentioned and/or existing synthesis EGCG fatty acid ester, it is proposed that the present invention.
Therefore, it is an object of the invention to the weak point overcoming existing conventional heating to synthesize, it is provided that a kind of with micro-
The method of ripple auxiliary synthesis EGCG fatty acid ester, synthesizes EGCG aliphatic acid under conditions of microwave radiation technology
Ester.
For solving above-mentioned technical problem, the present invention provides following technical scheme: a kind of Microwave-assisted synthesis
The method of EGCG fatty acid ester, it includes, by Epigallo-catechin gallate (EGCG) and fatty acid chloride
1: 4～6 it is dissolved in inert organic solvents in molar ratio；Add 2～4 times of epigallocatechin nutgalls
The esterification catalyst of the amount of acid esters material；Carry out Microwave-assisted synthesis, at a certain temperature, when reacting one section
Reaction is stopped after between；Again through filtration, alkali cleaning, washing, reduced pressure concentration, recrystallization, then freeze-drying 4～6h
Obtain EGCG fatty acid ester.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: described inertia organic reagent is in ethyl acetate or oxolane or DMF
Plant, and its volume is Epigallo-catechin gallate (EGCG) and the 100 of fatty acid chloride quality～120: 1.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: described esterification catalyst is sodium acid carbonate and/or saleratus esterification.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: described fatty acid chloride is the one in the fatty acid chloride containing 12～18 carbon atoms or any number of
Mix with arbitrary proportion.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: the frequency of described microwave reaction is 2400～2500MHz.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: described uniform temperature is 40～60 DEG C.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: described reaction a period of time is 1.5～2.5h.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: described alkali cleaning is to use saturated sodium bicarbonate solution to be removed by the palmitic acid of excess in reactant liquor.
As a kind of preferred version of the method for Microwave-assisted synthesis EGCG fatty acid ester of the present invention,
Wherein: described freeze-drying is to be placed in freeze drier by the EGCG fatty acid ester being recrystallized to give,
At subzero 40 DEG C, under the conditions of vacuum 0.01mbar, it is dried 6h.
Beneficial effects of the present invention: the method for synthesis EGCG fatty acid ester provided by the present invention utilizes micro-
The advantage of ripple auxiliary synthesis, can reach to react under normal heating conditions not available effect, reaction conversion ratio
Being risen to 84.5% by 68% before, the reaction time foreshortens to 2h, does not also have three to take in simultaneous reactions product
For the existence of product, the ratio of monosubstituted EGCG fatty acid ester also improves to 86.6%.As can be seen here, micro-
Reaction speed can be substantially accelerated in ripple auxiliary synthesis, improves reaction conversion ratio.Thus provide a kind of efficiently, quickly,
Meet the synthetic method of Green Chemistry.
Accompanying drawing explanation
Fig. 1 is EGCG palmitoylation product mass spectra analysis chart in embodiment 1；In figure, signal peak 457
For unreacted EGCG molecular ion peak, karyoplasmic ratio be the anion fragment peak of 169 be in EGCG structure
Galloyl, owing to the molecular weight of palmityl is 239, therefore EGCG molecule often replaces one
Palmityl, molecular weight will increase by 138, so in figure karyoplasmic ratio be the peak of 695 be the palm of EGCG
Acyl group one substitution product quasi-molecular ions, karyoplasmic ratio be the peak of 933 be palmityl two substitution product of EGCG
Quasi-molecular ions.
Fig. 2 is to implement the liquid chromatogram of EGCG palmitoylation product in 1, and wherein peak 1, peak 2 is main
Want EGCG mono-substituted products, account for the 86.6% of product.
Fig. 3 is the liquid chromatogram of EGCG palmitoylation product, wherein peak 1, peak 2 in comparison example 1
For main EGCG mono-substituted products, account for the 52.8% of product.
Detailed description of the invention
Understandable, below in conjunction with specification for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from
The detailed description of the invention of the present invention is described in detail by accompanying drawing.
Elaborate a lot of detail in the following description so that fully understanding the present invention, but the present invention
Other can also be used to be different from alternate manner described here implement, those skilled in the art can be not
Doing similar popularization in the case of running counter to intension of the present invention, therefore the present invention is not by following public specific embodiment
Restriction.
Secondly, " embodiment " or " embodiment " referred to herein refers to may be included in the present invention at least
Special characteristic, structure or characteristic in one implementation.Different in this manual local appearance "
In one embodiment " not refer both to same embodiment, it is not single or selective and other enforcements
The embodiment that example is mutually exclusive.
Embodiment 1:
2.2g EGCG is dissolved in 60mL ethyl acetate be placed in 100mL there-necked flask, adds 4.6g
Sodium acid carbonate, is placed in there-necked flask in microwave reactor, starts microwave reactor, sets reaction temperature
60 DEG C, be slowly added dropwise 6.8g palmitoyl chloride by constant pressure funnel, react 2h, reactant liquor through filtering,
Alkali cleaning, washing, reduced pressure concentration, recrystallization, be dried 6h, obtain 2.84g faint yellow EGCG palmitate,
The rate of recovery is 78.6%.It is 85.2% through the conversion ratio of efficient liquid phase chromatographic analysis EGCG, the most monosubstituted
EGCG palmitate accounts for the 86.6% of product.
EGCG palmitoylation product mass spectra is analyzed as shown in Figure 1.
In figure, signal peak 457 is unreacted EGCG molecular ion peak, and karyoplasmic ratio is the anion fragment of 169
Peak is the galloyl in EGCG structure.Owing to the molecular weight of palmityl is 239, therefore EGCG
Often replacing a palmityl in molecule, molecular weight will increase by 138, so karyoplasmic ratio is 695 in figure
Peak is the palmityl one substitution product quasi-molecular ions of EGCG, karyoplasmic ratio be the peak of 933 be the palm fibre of EGCG
Palmitic acid acyl group two substitution product quasi-molecular ions.
Fig. 2 is the liquid chromatogram of EGCG palmitoylation product in embodiment 1, wherein peak 1, and peak 2 is
Main EGCG mono-substituted products, accounts for the 86.6% of product.
Comparison example 1
2.2g EGCG is dissolved in 60mL ethyl acetate be placed in 100mL there-necked flask, adds 4.6g
Sodium acid carbonate, is placed in there-necked flask in 60 DEG C of thermostat water baths, and water bath with thermostatic control is heated, and passes through constant pressure addition
Funnel is slowly added dropwise 6.8g palmitoyl chloride, reacts 2h, after stopping reaction, reactant liquor through filtration, alkali cleaning,
Washing, reduced pressure concentration, recrystallization are dried 6h, obtain 0.96g faint yellow EGCG palmitate, reclaim
Rate is 32.8%.It is 18.6% through the conversion ratio of efficient liquid phase chromatographic analysis EGCG, the most monosubstituted EGCG
Palmitate accounts for the 52.8% of product.
Fig. 3 is the liquid chromatogram of EGCG palmitoylation product, wherein peak 1, peak 2 in comparison example 1
For main EGCG mono-substituted products, account for the 52.8% of product.
Embodiment 2:
4.6g EGCG is dissolved in 120mL oxolane be placed in 250mL there-necked flask, adds 10.2g
Sodium carbonate, is placed in there-necked flask in microwave reactor, starts microwave reactor, sets reaction temperature 60 DEG C,
It is slowly added dropwise 15.6g stearyl chloride by constant pressure funnel, reacts 2.5h, after stopping reaction, reactant liquor
Through filtration, alkali cleaning, washing, reduced pressure concentration, recrystallization, then freeze-drying 5h, obtain 5.69g yellowish
Look EGCG stearate, the rate of recovery is 76.3%.Conversion ratio through efficient liquid phase chromatographic analysis EGCG
It is 83.6%.
Embodiment 3
1.2gEGCG is dissolved in 40mL DMA be placed in 100mL there-necked flask,
Add 2.64g triethylamine, there-necked flask is placed in microwave reactor, start microwave reactor, set
Reaction temperature 50 DEG C, is slowly added dropwise 3.12g laurate acyl chlorides by constant pressure funnel, reacts 2h, stops
After reaction, reactant liquor through filtration, alkali cleaning, washing, reduced pressure concentration, recrystallization, then freeze-drying 6h,
Obtaining 1.45g faint yellow EGCG laurate, the rate of recovery is 78.8%.Through efficient liquid phase chromatographic analysis
The conversion ratio of EGCG is 86.4%.
Embodiment 4
2.3g EGCG is dissolved in 60mL DMA be placed in 100mL there-necked flask,
Add 4.45g pyridine, there-necked flask is placed in microwave reactor, start microwave reactor, set anti-
Answer temperature 60 C, be slowly added dropwise 7.4g palmitoyl chloride by constant pressure funnel, react 2.5h, stop reaction
After, reactant liquor through filtration, alkali cleaning, washing, reduced pressure concentration, recrystallization, then freeze-drying 6h, obtain
2.76g faint yellow EGCG palmitate, the rate of recovery is 76.2%.Through efficient liquid phase chromatographic analysis EGCG
Conversion ratio be 84.1%.
As can be seen here, the method for synthesis EGCG fatty acid ester provided by the present invention utilizes microwave radiation technology to close
The advantage become, can reach to react under normal heating conditions not available effect.Microwave can make reactant
System is uniformly acted on by microwave field, and system programming rate is fast, and homogeneous temperature and holding are stable, can substantially add
Fast response speed, improves reaction yield, improves reaction conversion ratio.Thus a kind of efficient, quick, symbol is provided
Close the synthetic method of Green Chemistry.
It should be noted that above example only in order to technical scheme to be described and unrestricted, although ginseng
According to preferred embodiment, the present invention is described in detail, it will be understood by those within the art that, can
Technical scheme is modified or equivalent, without deviating from the essence of technical solution of the present invention
God and scope, it all should be contained in the middle of scope of the presently claimed invention.
Claims (9)
1. the method for a Microwave-assisted synthesis EGCG fatty acid ester, it is characterised in that: include,
Epigallo-catechin gallate (EGCG) and fatty acid chloride 1: 4～6 is dissolved in inertia has in molar ratio
In machine solvent；
Add the esterification catalyst of the amount of 2～4 times of Epigallo-catechin gallate (EGCG) materials；
Carry out Microwave-assisted synthesis, at a certain temperature, after reaction a period of time, stop reaction；
Again through filtration, alkali cleaning, washing, reduced pressure concentration, recrystallization, then freeze-drying 4～6h obtains EGCG
Fatty acid ester.
2. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
Described inertia organic reagent is the one in ethyl acetate or oxolane or DMF, and
Its volume is Epigallo-catechin gallate (EGCG) and the 100 of fatty acid chloride quality～120: 1.
3. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
Described esterification catalyst is sodium acid carbonate and/or saleratus esterification.
4. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
Described fatty acid chloride is the one in the fatty acid chloride containing 12～18 carbon atoms or any number of with arbitrarily
Ratio mixes.
5. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
The frequency of described microwave reaction is 2400～2500MHz.
6. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
Described uniform temperature is 40～60 DEG C.
7. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
Described reaction a period of time is 1.5～2.5h.
8. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
Described alkali cleaning is to use saturated sodium bicarbonate solution to be removed by the palmitic acid of excess in reactant liquor.
9. the method for Microwave-assisted synthesis EGCG fatty acid ester as claimed in claim 1, it is characterised in that:
Described freeze-drying is to be placed in freeze drier, the EGCG fatty acid ester being recrystallized to give subzero
40 DEG C, under the conditions of vacuum 0.01mbar, it is dried 6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115777815A (en) * | 2022-11-21 | 2023-03-14 | 深圳市深宝华城科技有限公司 | High-concentration fresh scent type oolong fresh extract and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1448395A (en) * | 2003-04-03 | 2003-10-15 | 浙江大学 | Antioxidant EGCG aliphatic ester and prep. thereof |
| CN101519395A (en) * | 2008-10-16 | 2009-09-02 | 中国农业科学院茶叶研究所 | Preparation method of fully substituted acetylate of epigallocatechin-gallate (EGCG) |
| CN102382094A (en) * | 2011-11-13 | 2012-03-21 | 宜昌绿源生物技术有限公司 | Preparation method of acetylated epigallocatechin gallate |
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2015
- 2015-10-20 CN CN201510683671.7A patent/CN105884738B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1448395A (en) * | 2003-04-03 | 2003-10-15 | 浙江大学 | Antioxidant EGCG aliphatic ester and prep. thereof |
| CN101519395A (en) * | 2008-10-16 | 2009-09-02 | 中国农业科学院茶叶研究所 | Preparation method of fully substituted acetylate of epigallocatechin-gallate (EGCG) |
| CN102382094A (en) * | 2011-11-13 | 2012-03-21 | 宜昌绿源生物技术有限公司 | Preparation method of acetylated epigallocatechin gallate |
Non-Patent Citations (1)
| Title |
|---|
| SHUICHI MORI ET AL.: "Enhanced anti-influenza A virus activity of (-)-epigallocatechin-3-O-gallate fatty acid monoester derivatives:Effect of alkyl chain length", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115777815A (en) * | 2022-11-21 | 2023-03-14 | 深圳市深宝华城科技有限公司 | High-concentration fresh scent type oolong fresh extract and preparation method thereof |
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