CN108997465A - Epigallocatechin cupreol functional molecular, preparation method and application - Google Patents
Epigallocatechin cupreol functional molecular, preparation method and application Download PDFInfo
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- CN108997465A CN108997465A CN201810951043.6A CN201810951043A CN108997465A CN 108997465 A CN108997465 A CN 108997465A CN 201810951043 A CN201810951043 A CN 201810951043A CN 108997465 A CN108997465 A CN 108997465A
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Abstract
The invention discloses a kind of epigallocatechin cupreol functional molecular, which forms ester group by the hydroxyl of epigallocatechin and the carboxyl of sitosterol succinic acid, and epigallocatechin is connect with sitosterol.The invention also discloses preparation methods, comprising: protects epigallocatechin, is then coupled with sitosterol succinic acid, then be deprotected to obtain epigallocatechin sitosterol.Application the invention also discloses above-mentioned epigallocatechin cupreol functional molecular as antioxidant.Epigallocatechin cupreol of the invention has good antioxygenic property, there is the wider scope of application, using simple, can be used for industrialized production.
Description
Technical field
The invention belongs to functional food and healthy food field, and in particular to a kind of epigallocatechin sitosterol function
Molecule and preparation method thereof and its application.
Background technique
Sitosterol is to be present in plant a kind of natural constituents.A large amount of zooperies and human clinical data show
Phytosterol has significant meaning for reducing blood middle cholesterol content, mitigating cardiovascular disease, is a kind of important health care food
Product ingredient.But free phytosterol dissolubility in grease is poor, limits its actual use range.Phytosterol and carboxylic acid
Phytosterin ester is formed after esterification, can obviously improve its solubility.The carbon chain lengths of fatty acid and the effect of saturation degree of fatty acid
To the fusing point of phytosterin ester and fat-soluble, by selecting the type of fatty acid to form the fusing point, fat-soluble of changeable sterol ester
Etc. physical properties, be suitable for different types of product.Phytosterin ester have specific ionization phytosterol preferably it is fat-soluble and
The effect of more efficient norcholesterol, which is that one kind is ideal, to be reduced serum cholesterol, prevents and treats coronary atherosclerosis
The cardiopathic functional food ingredient of class.
Polyphenol is a kind of polyhydroxy phenol substance being widely present in plant.They are in the leaf of plant, wood, skin, shell
With have certain content in pulp, higher plant polyphenol is contained in fruit, cereal epidermis.There is polyphenol excellent antioxygen to be turned into
With this is the basis of its all physiological activity.A large amount of internal and experiment in vitro and epidemiologic data show to eat a certain amount of
Plant polyphenol have prevention and inhibiting effect to disease.Polyphenol has anti arteriosclerosis, prevention and treatment of coronary heart disease and apoplexy etc. cardiovascular
Disease and anti-inflammatory, anti-allergic effects and antivirus action.Modern medicine study proves that many diseases such as histoorgan aging etc. are all
Related with superfluous free radical, polyphenol has the function of removing free radical, and the large biological molecule induced free radical damages
To protective effect.Epigallocatechin is main ingredient in green tea polyphenols, is the characteristic resources in China.Epi-nutgall catechu
Element has excellent antioxidant activity and a variety of physiological activity.It is carried out using combination epigallocatechin and phytosterol
Modified method, the advantages of both combining while the dissolubility for improving phytosterol and epigallocatechin, have extensively
Wealthy application prospect.
Summary of the invention
The present invention provides a kind of epigallocatechin cupreol functional molecular, the fat-soluble antioxygens of the functional molecular
Change performance to greatly improve.
Invention also provides a kind of preparation method of above-mentioned cupreol functional molecular, preparation method operation letters
It is single, high income.
A kind of application the present invention also provides above-mentioned cupreol functional molecular as antioxidant.
A kind of epigallocatechin sitosterol functional molecular, shown in structure such as formula (I):
In the present invention, ester group is formed by the carboxyl of epigallocatechin and the hydroxyl of sitosterol, by epigallocatechin gallate
Theine and sitosterol are joined together to form phenols phytosterol, obtain novel epigallocatechin sitosterol function point
Son realizes the combination of sitosterol and epigallocatechin on a molecular scale, makes the functional molecular while possessing sitosterol
With the physiological activity of epigallocatechin.
The preparation method of the epigallocatechin sitosterol functional molecular, includes the following steps:
(1) epigallocatechin and anhydride reaction obtain the epigallocatechin of five acyl groups protection；
(2) sitosterol is reacted with succinic anhydride, obtains sitosterol succinic acid；
(3) the sitosterol succinic acid that the epigallocatechin for the five acyl groups protection that step (1) obtains and (2) obtain carries out
Coupling reaction, the epigallocatechin sitosterol protected；
(4) product for obtaining step (3) is deprotected, post-treated to obtain the epigallocatechin sitosterol rouge
Soluble antioxidant.
Reaction process is shown below:
Wherein: R is selected from methyl, ethyl, isopropyl (or 2- propyl) etc..
The purity is high for the epigallocatechin sitosterol functional molecular that the preparation method obtains has preferable anti-oxidant
Performance.Epigallocatechin is the main component in China's green tea polyphenols, and abundance, physiological activity is strong, and is easy to be inhaled
It receives.The sitosterol is available on the market, and the mixture of sterling or various plants sterol can be used.
In the present invention, the sequence that step (1) and step (2) carry out can also first carry out step (2) without limitation, then carry out
Step (1) can be selected according to actual needs.
Preferably, epigallocatechin reacts in alkaline environment with acid anhydrides in step (1).Preferably, reaction
Alkali, preferably weak base, including but not limited to one of potassium carbonate, triethylamine etc. or a variety of are added in system.Since phenolic hydroxyl group is living
Property is stronger, in mild alkaline conditions, further ensures the phenolic hydroxyl group of epigallocatechin and acid anhydrides carries out selection and reacts, in turn
Realize the selective protection to phenolic hydroxyl group.
To further increase selective yield, preferably, acid anhydrides is acetic anhydride, propionic andydride or isobutyl in step (1)
One of acid anhydrides is a variety of.Further preferably one of propionic andydride or isobutyric anhydride or a variety of.Propionic andydride is different
Butyric anhydride activity is relatively low, and selectivity is more preferable.
Step (1), in step (2), reaction dissolvent is generally esterification common organic solvent, for example can be N,
N '-dimethyl formamide, acetone etc..
In step (1), the molar ratio of epigallocatechin and acid anhydrides is 1:(5~10).Further preferred molar ratio
For 1:(5~7).
In step (1), the molar ratio of epigallocatechin and alkali is 1:(5~10).Further preferred molar ratio is
1:(5~7).
Step (1) generally carries out at room temperature, naturally it is also possible to carry out appropriate heating operation etc. according to actual needs, react
Whether the time can completely determining according to real reaction, and generally 3~8 hours.After step (1) fully reacting, by simple water
Wash the dry reaction raw materials that can serve as step (3).
In step (2), in sitosterol (or cupreol) and succinic anhydride reaction system, acid binding agent is generally added, it is common
Acid binding agent include K2CO3, triethylamine etc..
In step (2), the molar ratio of sitosterol (or cupreol) and succinic anhydride is 1:(1~5), further preferably
1:(2~4).The molar ratio of sitosterol and acid binding agent is 1:(1~5), further preferably 1:(2~3).
Step (2) generally carries out at room temperature, naturally it is also possible to carry out appropriate heating operation etc. according to actual needs, react
Time is generally 3~20 hours.
In step (3), the coupling reagent used in the coupling reaction is N, N'- dicyclohexylcarbodiimide or 1-
Ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, as N preferably can be used, N'- dicyclohexylcarbodiimide is even
Joint-trial agent is cheap and easily-available, and has preferable effect to the coupling reaction between phenols and phytosterol.
In step (3), the mole that the coupling reagent is added is 1~5 times of epigallocatechin mole, preferably
It is 1.0-2.0 times.The mole that sitosterol is added is 0.5~5 times of epigallocatechin mole, preferably 1.0-2.0
Times.
In step (3), need to be added catalyst 4-dimethylaminopyridine, the mole that catalyst is added in reaction system
For 0.01-0.1 times of epigallocatechin mole, preferably 0.02-0.08.
In step (3), the solvent of reaction is methylene chloride, toluene or tetrahydrofuran.
In step (3), deprotecting regent uses hydrazine, for example can use hydrazine hydrate.
In step (4), the mole that deprotecting regent is added is 5~10 times of epigallocatechin mole.
Reaction of the invention can carry out at room temperature.
The present invention has the following advantages that relative to existing phytosterin ester and effect:
(1) epigallocatechin sitosterol of the invention has good anti-oxidation function.
(2) epigallocatechin sitosterol preparation efficiency of the invention is high, and method is simple, answers suitable for industrialized production
With.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
Epigallocatechin (61.2mg, 0.2mmol) is dissolved in N, and propionic andydride is added dropwise in N '-dimethyl formamide (5ml)
(166.1 microlitres, 1.2mmol), triethylamine (166.1 microlitres, 1.2mmol) into mixed liquor, react about 4 hours, after water
It washes and is dried to obtain five propiono epigallocatechins.Sitosterol (104.0mg, 0.25mmol), K2CO3(69.1mg,
0.5mmol), succinic anhydride (125.1mg, 0.75mmol) is dissolved in N, and in N '-dimethyl formamide (3ml) solvent, reaction 10 is small
When, after washing and drying obtain sitosterol succinic acid.By five propiono epigallocatechins, sitosterol succinic acid, N, N'-
Dicyclohexylcarbodiimide (49.0mg) and 4-dimethylaminopyridine (2.0mg) are stirred to react 2 hours in methylene chloride, then
50% hydrazine hydrate (60mg) is added and handles 1 hour to be extracted with ethyl acetate after reaction, table is obtained after chromatogram purification
Nutgall catechin sitosterol (yield: 84%, purity 90%).
Structure determination data: nuclear magnetic data shows the characteristic peak of 5-8ppm catechin and the characteristic peak of 1-4ppm sitosterol,
IR 1714cm-1Left and right display ester group characteristic absorption peak, mass spectrum is shown plus sodium molecule quasi-molecular ions 826.52.These data demonstrate
The correctness of synthetic structure.
Embodiment 2
Epigallocatechin (61.2mg, 0.2mmol) is dissolved in N, and propionic andydride is added dropwise in N '-dimethyl formamide (5ml)
(166.1 microlitres, 1.2mmol), triethylamine (166.1 microlitres, 1.2mmol) into mixed liquor, react about 4 hours, after water
It washes and is dried to obtain five propiono epigallocatechins.Sitosterol (83.4mg, 0.2mmol), K2CO3(69.1mg, 0.5mmol),
Succinic anhydride (125.1mg, 0.75mmol) is dissolved in N, in N '-dimethyl formamide (3ml) solvent, reacts 10 hours, after
Washing and drying obtains sitosterol succinic acid.By five propiono epigallocatechins, sitosterol succinic acid, 1- ethyl-(3- diformazan
Base aminopropyl) that 2 are stirred to react in toluene is small for phosphinylidyne diimmonium salt hydrochlorate (46.0mg) and 4-dimethylaminopyridine (2.0mg)
When, 50% hydrazine hydrate (60mg) is then added and handles 1 hour to be extracted with ethyl acetate after reaction, after chromatogram purification
Obtain epigallocatechin sitosterol (yield: 82%, purity 90%).Structure determination data consistent with Example 1.
Embodiment 3
Epigallocatechin (61.2mg, 0.2mmol) is dissolved in N, and propionic andydride is added dropwise in N '-dimethyl formamide (5ml)
(166.1 microlitres, 1.2mmol), triethylamine (166.1 microlitres, 1.2mmol) into mixed liquor, react about 4 hours, after water
It washes and is dried to obtain five propiono epigallocatechins.Sitosterol (104.1mg, 0.25mmol), K2CO3(69.1mg,
0.5mmol), succinic anhydride (125.1mg, 0.75mmol) is dissolved in N, and in N '-dimethyl formamide (3ml) solvent, reaction 10 is small
When, after washing and drying obtain sitosterol succinic acid.By five propiono epigallocatechins, sitosterol succinic acid, 1- second
Base-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (46.0mg) and 4-dimethylaminopyridine (2.0mg) are in tetrahydro furan
It is stirred to react in muttering 2 hours, 50% hydrazine hydrate (60mg) is then added and handles 1 hour to be extracted after reaction with ethyl acetate
It takes, epigallocatechin sitosterol (yield: 84%, purity 90%) is obtained after chromatogram purification.Structure determination data are the same as real
Apply example 1.
Antioxidant activity test: DPPH free radical inhibitory effect progress antioxygenic property measurement (test method bibliography:
Food Chemistry 163 (2014) 171-177), wherein reference material has the sitosterol before not being transformed, BHA (butylhydroxy fennel
Fragrant ether), BHT (2,6 di tert butyl 4 methyl phenol).Test result is as follows by inhibiting rate IC50 shown in table 1.
Table 1:DPPH inhibiting rate IC50 antioxidant activity test result
| Sitosterol | Epigallocatechin sitosterol | BHA | BHT |
| Unrestraint activity | 19μM | 230μM | 256μM |
By the test result of table 1 it is found that the antioxidant activity of epigallocatechin sitosterol is apparently higher than other controls
Product.
Claims (10)
1. a kind of epigallocatechin cupreol functional molecular, which is characterized in that shown in structure such as formula (I):
2. a kind of preparation method of epigallocatechin cupreol functional molecular as described in claim 1, which is characterized in that
Include the following steps:
(1) phenolic hydroxyl group and anhydride reaction in epigallocatechin obtain the epigallocatechin of five acyl groups protection；
(2) sitosterol is reacted with succinic anhydride, obtains sitosterol succinic acid；
(3) the sitosterol succinic acid that the epigallocatechin for the five acyl groups protection that step (1) obtains and step (2) obtain carries out
Coupling reaction, the epigallocatechin sitosterol protected；
(4) product for obtaining step (3) is deprotected, post-treated to obtain the epigallocatechin cupreol function
Molecule.
3. the preparation method of epigallocatechin cupreol functional molecular according to claim 2, which is characterized in that
In step (1), the acid anhydrides is selected from propionic andydride or isobutyric anhydride.
4. the preparation method of epigallocatechin cupreol functional molecular according to claim 2, which is characterized in that
Step (1) carries out under alkaline condition, and alkali used is potassium carbonate or triethylamine.
5. the preparation method of epigallocatechin cupreol functional molecular according to claim 2, which is characterized in that
In step (1), the molar ratio of epigallocatechin and acid anhydrides is 1:(5~10).
6. the preparation method of epigallocatechin cupreol functional molecular according to claim 2, which is characterized in that
The coupling reagent that the coupling reaction uses is N, N'- dicyclohexylcarbodiimide or 1- ethyl-(3- dimethylamino third
Base) phosphinylidyne diimmonium salt hydrochlorate.
7. the preparation method of epigallocatechin cupreol functional molecular according to claim 6, which is characterized in that
The mole that coupling reagent is added is 1~5 times of epigallocatechin mole；The mole that sitosterol is added is that table is not eaten
0.5~5 times of sub- catechin mole.
8. the preparation method of epigallocatechin cupreol functional molecular according to claim 2, which is characterized in that
Need to be added catalyst 4-dimethylaminopyridine in the coupling reaction, the mole that catalyst is added is epigallocatechin
0.01-0.5 times of mole.
9. the preparation method of epigallocatechin cupreol functional molecular according to claim 2, which is characterized in that
Deprotecting regent uses hydrazine.
10. application of the epigallocatechin cupreol functional molecular as antioxidant described in a kind of claim 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565808A (en) * | 2016-10-21 | 2017-04-19 | 浙江大学 | Beta-sitosterol type catechinic acid liposolubility antioxidant and preparation method thereof |
| US20170151271A1 (en) * | 2013-03-15 | 2017-06-01 | Suzanne Janine Paxton-Pierson | Novel Androgen Effectors |
| CN107973835A (en) * | 2016-10-21 | 2018-05-01 | 浙江大学 | Natural mixed phytosterin catechin, preparation method and application |
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2018
- 2018-08-20 CN CN201810951043.6A patent/CN108997465A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170151271A1 (en) * | 2013-03-15 | 2017-06-01 | Suzanne Janine Paxton-Pierson | Novel Androgen Effectors |
| CN106565808A (en) * | 2016-10-21 | 2017-04-19 | 浙江大学 | Beta-sitosterol type catechinic acid liposolubility antioxidant and preparation method thereof |
| CN107973835A (en) * | 2016-10-21 | 2018-05-01 | 浙江大学 | Natural mixed phytosterin catechin, preparation method and application |
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