CN108976273A - A kind of nutgall acyl stigmasterol functional molecular and preparation method thereof - Google Patents
A kind of nutgall acyl stigmasterol functional molecular and preparation method thereof Download PDFInfo
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- CN108976273A CN108976273A CN201810946855.1A CN201810946855A CN108976273A CN 108976273 A CN108976273 A CN 108976273A CN 201810946855 A CN201810946855 A CN 201810946855A CN 108976273 A CN108976273 A CN 108976273A
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Abstract
The invention discloses a kind of preparation method of nutgall acyl stigmasterol functional molecular, which forms ester group by the carboxyl of gallic acid and the hydroxyl of stigmasterol, and gallic acid is connect with stigmasterol.The invention also discloses preparation methods, comprising: protects gallic acid, is then coupled with stigmasterol, then be deprotected to obtain nutgall acyl stigmasterol.The invention also discloses a kind of nutgall acyl stigmasterol functional moleculars.Nutgall acyl stigmasterol 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 nutgall acyl stigmasterol functional molecular and
Preparation method.
Background technique
Phytosterol is to be present in plant a kind of natural constituents.A large amount of zooperies and human clinical data's table
Bright, it is a kind of important health care that phytosterol, which has significant meaning for reducing blood middle cholesterol content, mitigating cardiovascular disease,
Food composition.But free phytosterol dissolubility in grease is poor, limits its actual use range.Phytosterol and carboxylic
Phytosterin ester is formed after Esterification, can obviously improve its solubility.The carbon chain lengths of fatty acid and the saturation degree shadow of fatty acid
Ring the fusing point and fat-soluble, the fusing point of the changeable sterol ester of type composition by selecting fatty acid, liposoluble to phytosterin ester
Property etc. physical properties, be suitable for different types of product.Phytosterin ester has specific ionization phytosterol preferably fat-soluble
It is that preferably reduction serum cholesterol, prevention and treatment coronary artery are athero- hard for one kind with the effect of more efficient norcholesterol
Change 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.Gallic acid is the gallic important derivatives of characteristic forestry products, abundant raw material.Gallic acid has excellent
Antioxidant activity has been widely used as fat-soluble antioxidant using it as the propylgallate of raw material exploitation.Do not had using combining
The method that gallate-based and phytosterol are modified, the advantages of both combining while improving phytosterol and gallic acid
Dissolubility has broad application prospects.
The method yield that existing combination gallic acid and phytosterol are modified is lower (generally below 30%), leads
It causes product preparation cost higher, is not suitable for industrial mass production.
Summary of the invention
The present invention provides a kind of nutgall acyl stigmasterol functional molecular and preparation method thereof, the functional molecular it is fat-soluble
Antioxygenic property greatly improves.
A kind of nutgall acyl stigmasterol functional molecular, shown in structure such as formula (I):
In the present invention, ester group is formed by the carboxyl of gallic acid and the hydroxyl of stigmasterol, by gallic acid and stigmasterol
It is joined together to form phenols phytosterol, novel nutgall acyl stigmasterol functional molecular is obtained, realizes on a molecular scale
The combination of stigmasterol and gallic acid, makes the functional molecular while possessing the physiological activity of stigmasterol and gallic acid.
A kind of preparation method of nutgall acyl stigmasterol functional molecular, includes the following steps:
(1) gallic acid is protected using acid anhydrides, obtains the gallic acid of three acyl groups protection；
(2) gallic acid and stigmasterol for the three acyl groups protection that step (1) obtains carry out coupling reaction, and that is protected does not have
Infanticide acyl stigmasterol；
(3) product obtained step (2) is deprotected, and post-treated to obtain the nutgall acyl stigmasterol fat-soluble anti-
Oxidant.
Reaction process is as follows:
Wherein: R is selected from methyl, ethyl, isopropyl (or 2- propyl) etc..
The purity is high for the nutgall acyl stigmasterol functional molecular that the preparation method obtains has preferable antioxygenic property.
Gallic acid is cheap, good product performance obtained, and is easy to be absorbed.The stigmasterol is available on the market,
The mixture of sterling or various plants sterol can be used.
Preferably, in step (1), to promote rapid reaction progress that alkali can be added；Preferably, the alkali is preferably weak
One of alkali, including but not limited to potassium carbonate, triethylamine etc. are a variety of.
In step (1), acid anhydrides is acetic anhydride, propionic andydride or isobutyric anhydride.Acid anhydrides protecting group needs during the reaction
Certain stability, preferably isobutyric anhydride reduce falling off in reaction with preferable stability and wait side reactions.
In step (1), 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 gallic acid and alkali is 1:(3~6).Further preferred molar ratio is 1:
(3~5).
In step (1), the molar ratio of the gallic acid and acid anhydrides is 1:(3~6).Further preferred molar ratio is 1:
(3~5).
In step (1), catalyst can be added as needed, the catalyst is 4-dimethylaminopyridine, the catalyst
Molar ratio with gallic acid is 0.05~0.5:1.Further preferably 0.1~0.2:1.
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 1~5 hour.After step (1) fully reacting, by simple water
Wash the dry reaction raw materials that can serve as step (2).
In coupling reaction, the coupling reagent is N, N'- dicyclohexylcarbodiimide or 1- ethyl-(3- dimethyl
Aminopropyl) phosphinylidyne diimmonium salt hydrochlorate, as N preferably can be used, N'- dicyclohexylcarbodiimide coupling reagent is cheaply easy
, and there is preferable effect to the coupling reaction between phenols and phytosterol.
The preparation method of the nutgall acyl stigmasterol fat-soluble antioxidant, which is characterized in that coupling reagent is added
Mole be 0.5~5 times, preferably 0.8-2 times of gallic acid mole.The mole that stigmasterol is added is gallic acid
0.5~5 times of mole, preferably 0.5-1.0 times.
In coupling reaction, need to be added catalyst 4-dimethylaminopyridine, the mole that catalyst is added is gallic acid
0.01-0.1 times of mole, preferably 0.02-0.05.Such as tetrahydrofuran, methylene chloride in common coupling reaction solvent
In have an esterification side reaction of serious stigmasterol, the present invention pass through grope screening discovery adjustment reaction solvent be toluene or just oneself
Alkane can successfully inhibit the generation of side reaction.
In step (3), deprotecting regent is using hydrazine or to methyl benzene methanamine.The mole that deprotecting regent is added is not eat
3~6 times of sub- acid mole.
Reaction of the invention carries out at room temperature.
The present invention has the following advantages that relative to existing phytosterin ester and effect:
(1) nutgall acyl stigmasterol of the invention has good anti-oxidation function.
(2) nutgall acyl stigmasterol of the invention is cheap, is suitable for industrialized production and application.
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.
Gallic acid (170mg), isobutyric anhydride (712mg), triethylamine (455mg), 4-dimethylaminopyridine (12mg) exist
Reacted 2 hours in 0.5 milliliter of n,N-Dimethylformamide, after washing and drying obtain three isobutyryl gallic acids.By three
Isobutyryl gallic acid, stigmasterol (275mg), N, N'- dicyclohexylcarbodiimide (206mg) and 4-dimethylaminopyridine
(4mg) is stirred to react 2 hours at room temperature in toluene, and 50% hydrazine hydrate (384mg) is then added and handles 1 hour wait react knot
It is extracted with ethyl acetate after beam, nutgall acyl stigmasterol is obtained after chromatogram purification.
Structure determination data:1H NMR 7.57ppm or so shows gallic acid aromatic ring characteristic peak, IR1709cm-1Left and right is aobvious
Show that ester group characteristic absorption peak, mass spectrum show the dehydrogenation (-nization) molecular ion peak 563.42 of wherein principal component.These data demonstrate synthesis
The correctness of the structure of matter.
Embodiment 2
Gallic acid (170mg), isobutyric anhydride (712mg), triethylamine (455mg), 4-dimethylaminopyridine (12mg) exist
Reacted 2 hours in 0.5 milliliter of n,N-Dimethylformamide, after washing and drying obtain three isobutyryl gallic acids.By three
Isobutyryl gallic acid, stigmasterol (275mg), N, N'- dicyclohexylcarbodiimide (180mg) and 4-dimethylaminopyridine
(4mg) is stirred to react 2 hours at room temperature in n-hexane, and 50% hydrazine hydrate (384mg) is then added and handles 1 hour wait react
After be extracted with ethyl acetate, nutgall acyl stigmasterol is obtained after chromatogram purification.
Embodiment 3
Gallic acid (170mg), isobutyric anhydride (712mg), triethylamine (455mg), 4-dimethylaminopyridine (12mg) exist
Reacted 2 hours in 0.5 milliliter of n,N-Dimethylformamide, after washing and drying obtain three isobutyryl gallic acids.By three
Isobutyryl gallic acid, stigmasterol (300mg), N, N'- dicyclohexylcarbodiimide (206mg) and 4-dimethylaminopyridine
(2mg) is stirred to react 2 hours at room temperature in toluene, and 50% hydrazine hydrate (384mg) is then added and handles 1 hour wait react knot
It is extracted with ethyl acetate after beam, nutgall acyl stigmasterol is obtained after chromatogram purification.
Antioxidant activity test: DPPH free radical inhibitory effect progress antioxygenic property measurement (test method bibliography:
Food Chemistry 163 (2014) 171-177), using concentration 1.0mM wherein reference material have the stigmasterol before not being transformed,
BHA (butylated hydroxy anisole), BHT (2,6 di tert butyl 4 methyl phenol).DPPH inhibiting rate test result is as follows table institute
Show.
DPPH inhibiting rate antioxidant activity test result
| Stigmasterol | Nutgall acyl stigmasterol | BHA | BHT |
| 4% | 91% | 70% | 41% |
As seen from the above table, the work for the unmodified preceding stigmasterol that the antioxidant activity of nutgall acyl stigmasterol is far longer than
Property, and it is significantly higher than the antioxidant activity of BHA, BHT.
Claims (10)
1. a kind of preparation method of nutgall acyl stigmasterol functional molecular, which is characterized in that including following preparation step:
(1) gallic acid is protected using acid anhydrides, obtains the gallic acid of three acyl groups protection；
(2) gallic acid and stigmasterol for the three acyl groups protection that step (1) obtains carry out coupling reaction, the galla turcica protected
Acyl stigmasterol；
(3) product for obtaining step (2) is deprotected, post-treated to obtain the nutgall acyl stigmasterol functional molecular, knot
Shown in structure such as formula (I):
2. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 1, which is characterized in that step (1)
In, the molar ratio of gallic acid and acid anhydrides is 1:(3~6).
3. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 1, which is characterized in that step (1)
In, acid anhydrides is acetic anhydride, propionic andydride or isobutyric anhydride.
4. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 1, which is characterized in that step (1)
In, in coupling reaction, coupling reagent N, N'- dicyclohexylcarbodiimide or 1- ethyl-(3- dimethylaminopropyl) carbon
Acyl diimmonium salt hydrochlorate.
5. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 4, which is characterized in that coupling reagent
The mole of addition is 1~5 times of gallic acid mole.
6. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 1, which is characterized in that the beans steroid
The mole that alcohol is added is 0.5~5 times of gallic acid mole.
7. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 1, which is characterized in that coupling reaction
In need to be added catalyst 4-dimethylaminopyridine, the mole that catalyst is added is the 0.01-0.5 of gallic acid mole
Times.
8. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 1, which is characterized in that coupling reaction
Solvent be toluene or n-hexane.
9. the preparation method of nutgall acyl stigmasterol functional molecular according to claim 1, which is characterized in that step (3)
In, deprotecting regent is using hydrazine or to methyl benzene methanamine.
10. a kind of nutgall acyl stigmasterol functional molecular, which is characterized in that structure is shown below:
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318905A (en) * | 2008-07-15 | 2008-12-10 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing gallic acid terpene alcohol ester with auxiliary supersonic wave |
| CN103304617A (en) * | 2013-06-04 | 2013-09-18 | 浙江大学 | Phenols-phytosterol functional molecule and preparation method for same |
| CN104672291A (en) * | 2015-01-30 | 2015-06-03 | 江南大学 | Preparation method of gallate phytosterol ester |
| CN106565808A (en) * | 2016-10-21 | 2017-04-19 | 浙江大学 | Beta-sitosterol type catechinic acid liposolubility antioxidant and preparation method thereof |
-
2018
- 2018-08-20 CN CN201810946855.1A patent/CN108976273A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318905A (en) * | 2008-07-15 | 2008-12-10 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing gallic acid terpene alcohol ester with auxiliary supersonic wave |
| CN103304617A (en) * | 2013-06-04 | 2013-09-18 | 浙江大学 | Phenols-phytosterol functional molecule and preparation method for same |
| CN104672291A (en) * | 2015-01-30 | 2015-06-03 | 江南大学 | Preparation method of gallate phytosterol ester |
| CN106565808A (en) * | 2016-10-21 | 2017-04-19 | 浙江大学 | Beta-sitosterol type catechinic acid liposolubility antioxidant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| IKURO ABE，ET AL.: "Potent and Selective Inhibition of Squalene Epoxidase by Synthetic Galloy Esters", 《BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS》 * |
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