CN101270108B - Method for preparing liposoluble tea polyphenol - Google Patents
Method for preparing liposoluble tea polyphenol Download PDFInfo
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Abstract
The present invention relates to a preparation method of fat-soluble tea polyphenol and aims to expand the use of the tea polyphenol by using the water-soluble tea polyphenol as raw material to prepare the fat-soluble tea polyphenol. In the preparation method, carbon acylation is used for preparing the fat-soluble tea polyphenol. More accurately, the preparation of the fat-soluble tea polyphenol causes no loss of phenolic hydroxyl of the raw material of tea polyphenol. Thus the product has improved fat-solubility and original antioxidant properties. The product can be dissolved in oil, fat and organic solvents but can not be dissolved in water. The antioxidant free group and anti-lipid overoxidation performance are similar to the tea polyphenol. The present invention also relates to a preparation method and conditions therefore for the esterification of class formation of catechin through carbon acylation. And the fat-soluble tea polyphenol has the performances that are superior to the products of the same class in the prior art.
Description
Technical field
The present invention relates to a kind of preparation method of fat-soluble tea polyphenol, particularly, the present invention relates to prepare fat-soluble tea polyphenol with the phosphinylidyne method.
Technical background
Fat-soluble antioxidant commonly used at present mainly contains: BHA (butylated hydroxy anisole), BHT (butylated hydroxytoluene), PG (Tenox PG) and TBHQ (Tert. Butyl Hydroquinone), vitamin-E, ascorbyl palmitate, rosemary extract etc.Wherein BHA, BHT, PG, TBHQ are the chemosynthesis antioxidant, and best with the TBHQ antioxidant effect, and the chemosynthesis antioxidant has certain toxicity.Better with the rosemary extract effect in natural antioxidants.Document announcement is arranged, and in Japan, TBHQ has not allowed to be applied in the lipid antioxidant, and all uses rosemary extract.But rosemary extract costs an arm and a leg, and is difficult at home promoting the use of.Therefore existing antioxidant can not satisfy the needs of the growing grease of China, development of food industry fully.
Tea-polyphenol generally is familiar with by people as a kind of natural health care, the many pharmacological functions that have owing to its special anti-oxidant and anti peroxidation of lipid performance also have increasing report, but because tea-polyphenol tool polyphenol hydroxyl, it is the bigger material of polarity, soluble in water, be insoluble in the oil, and limited its in the lipid product application and bring into play better Human Physiology active function.
In order to increase the solubleness of tea-polyphenol in grease; there is the investigator to use carboxylesterase's esterification tea-polyphenol; separate obtaining 3-acidylate (-)-l-Epicatechol (EC) or (-)-epigallocatechin (EGC) again with polymeric amide chromatography post with the ODS chromatography column, referring to patent documentation JP 6279430 and JP 91934/93.But this method is a his-and-hers watches gallic acid catechin and gallate (EGCG) carries out the oxygen acidylate; promptly on 3 hydroxyls of EGCG, carry out fatty acid esterification; the product that obtains makes hydroxyl of 3 bit-loss of EGCG; in addition; preparation process also needs the carboxylesterase of purifying and the catechin monomers of purifying; both preparation costs are all very high, have been difficult to actual use value.
Also useful chemical method carries out the oxygen acidylate to catechin and prepares fat-soluble tea polyphenol, to increase the fat-soluble of catechin, expands its edible approach.By the prior art for preparing fat-soluble tea polyphenol is with the oxygen process for acylating; its reaction mechanism is a kind of electrophilic addition reaction; generally with fat acyl chloride as acylating agent; with the phenolic hydroxyl group effect on the catechin molecule; hydrogen atom on the phenolic hydroxyl group is replaced by acyl group; and the ester compound that obtains having R-COOR type structure; the side reaction of substituted hydroxy takes place for the hydrogenchloride that prevents to produce in the reaction process; usually use in the alkaline reagents and the hydrogenchloride that generates; in addition; for preventing that acyl chlorides from decomposing; reaction is carried out under non high temperature or room temperature usually; can need not use the EGCG and the purification of carboxylic acids lipase of purifying with mixing catechin by art methods as the feedstock production fat-soluble tea polyphenol.Compare with carboxylesterase's esterification tea-polyphenol, its preparation cost can reduce greatly, also is a kind of good method.
Consider that from the antioxidant property of product compare with other antioxidant, tea-polyphenol has stronger antioxygenation, major cause is that it has a plurality of phenolic hydroxyl groups, more hydrogen proton can be provided, accept free radical, thus the free chain reaction that the blocking-up grease causes because of autoxidation.Catechin by the esterification of oxygen acidylate after, must lose phenolic hydroxyl group with anti-oxidant activity, make the corresponding reduction of its antioxidant effect.In the fat-soluble tea polyphenol product of carboxylesterase's esterification Preparing Tea-polyphenol; because of it is enzyme reaction; it is directed esterification; only lose 3 hydroxyls (by acidylate) of EGCG; and prepare in the fat-soluble tea polyphenol process at chemical method; because of oxygen acidylate esterification reaction is not complete directed esterification; its reaction product is a kind of mixture; have monoesters; dibasic acid esters even polyester product and unreacted catechin component; and every many ester groups just make phenolic hydroxyl group of catechin molecule loss on the catechin molecule; see theoretically; its degree of esterification is high more; esterified phenolic hydroxyl group is many more, and it is also just big more that its product antioxygenation reduces degree, and the phenolic hydroxyl group that loses is again that relative reactivity is stronger.Referring to document: Catherine A.Rice-Evans, Nicholas J.Miller and George Paganga Antioxidant propertiesof phenolic compounas trends in pplant science April 1997, VoL 2, No, 4152～157.
And phosphinylidyneization to be the fatty acyl group that will introduce directly link to each other with the catechin aromatic proton, its reaction mechanism is different with the oxygen acidylate, it is a kind of nucleophilic addition.On virtue nuclear, introduce acyl group and generate arone, formation be C-C, have the ketone compounds of R-COR type structure, react and be the phosphinylidyne reaction, do not lose the phenolic hydroxyl group in the catechin molecule.
The present invention is the fat-soluble tea polyphenol by phosphinylidyne method preparation, by the fat-soluble tea polyphenol of the inventive method preparation the liposoluble performance is arranged not only, and can reduce the decline of the resistance of oxidation that catechin causes because of esterification to greatest extent.
Summary of the invention
The present invention relates to a kind of preparation method of fat-soluble tea polyphenol, its goal of the invention is with the water soluble tea polyphenol to be the feedstock production fat-soluble tea polyphenol, and with expansion tea-polyphenol purposes, the present invention prepares fat-soluble tea polyphenol with the phosphinylidyne method.More precisely, product---the fat-soluble tea polyphenol of the present invention preparation does not lose the phenolic hydroxyl group of raw material tea-polyphenol, thereby make product on the basis that increases the liposoluble performance, keep original antioxidant property, product of the present invention can be dissolved in grease and organic solvent, and water insoluble; Its antioxidant radical and anti peroxidation of lipid performance are close with tea-polyphenol.
The solution that realizes the foregoing invention purpose is:
The present invention prepares fat-soluble tea polyphenol and relates to two reactions, the i.e. phosphinylidyneization of the preparation of fat acyl chloride and tea-polyphenol.
The present invention is optimized at reactant ratio, reaction times, temperature of reaction in research fat acyl chloride preparation process.
The present invention is optimized at acylating agent ratio, catalyzer, reaction solvent ratio, temperature of reaction, reaction times etc. in research tea-polyphenol phosphinylidyne process.
The present invention has optimized the fat-soluble tea polyphenol preparation process condition, and estimates the liposoluble performance and the antioxidant property of product of the present invention with fat-soluble test, ultraviolet spectral analysis, total polyphenols content (UV mensuration), anti peroxidation of lipid, Green Tea Extract etc.
Description of drawings
Fig. 1 is that the preparation fat acyl chloride uv-spectrogram that condition is not optimized (wherein locates to be fat acyl chloride about 250nm; Locate to be unreacted thionyl chloride about 280nm);
Fig. 2 is the fat acyl chloride UV scintigram for preparing behind the condition optimizing, and wherein the 280nm place has not had absorption peak;
Fig. 3 is pure thionyl chloride UV scintigram (wherein there is absorption peak at the 280nm place);
Fig. 4 is the uv-spectrogram of phosphinylidyne fat-soluble tea polyphenol and oxygen acidylate fat-soluble tea polyphenol;
Fig. 5 is the thin-layer chromatography comparison diagram of phosphinylidyne LTP, oxygen acidylate LTP and TP;
Fig. 6 is that the DPPH inhibiting rate compares;
Fig. 7 is the antioxidant property of 98 ℃ of following different times.
Specific embodiments
1. fat acyl chloride preparation:
With acylating agent, the above lipid acid of 12 carbon is reactant, and with N, dinethylformamide (DMF) is a catalyzer, synthesis under normal pressure in certain temperature range.Prepare the above fat acyl chloride of 12 carbon.Reaction must be fully.Can not contain unreacted acylating agent in the reaction solution after reaction is finished, utilize UV scanning to identify, specifically see Fig. 1, wherein locate to be fat acyl chloride about 250nm; Locate to be unreacted thionyl chloride about 280nm.
In fat acyl chloride preparation, The optimum reaction conditions is necessary, otherwise has unreacted thionyl chloride in the product, causes in the reaction of subsequent preparation fat-soluble tea polyphenol reactant fat acyl chloride dosage inaccurate, and produces more by product in the final product.
The acylating agent of described reaction is carboxylic acid, aceticanhydride, acyl chlorides such as phosphorus pentachloride, phosphorus trichloride, Phosphorus Oxychloride, thionyl chloride, and wherein best acylating agent is a thionyl chloride.
Described reactant ratio is a lipid acid: acylating agent=1: 0.5～5.0; Optimum proportion is that 1: 1.1～1.3 described temperature are between 0 ℃～80 ℃; Optimum temperature range is 12 ℃～50 ℃.
Described reaction repeatedly is meant heating-cooling and stirring gradually repeatedly in specified for temperature ranges, until reacting completely;
The described reaction times is 3～20 hours; Optimum reacting time is 5 hours～8 hours;
Described catalyzer DMF consumption is thionyl chloride: DMF=1.0: 0.007～0.1 (mol ratio).Optimum proportion is 1.0: 0.03～0.08 (mol ratio).
2. fat-soluble tea polyphenol preparation
In another reactor; earlier the fat acyl chloride that at low temperatures lewis acid or protonic acid and above-mentioned reaction is made is dissolved in the reaction solvent; make fat acyl chloride and lewis acid or protonic acid form complex compound (make fat acyl chloride discharges gradually in the reaction process, carry out acylation reaction).
Add solid catechin raw material (raw material adds too fast meeting makes the reaction fierce and overflow) more gradually, after adding, reaction is begun by lower starting temperature, slowly is warming up to temperature of reaction, reaction continues 8～9 hours, reaction finishes back (reaction system produces a large amount of solids), adds and the isopyknic band ice of reaction solution deionized water, leaves standstill, make layering, discard reaction solvent after the separation, filtered water and solid suspendible system are washed with appropriate amount of deionized water again, in filter cake, add ethyl acetate and water and hydrochloric acid, leave standstill, make layering, discard water layer, concentrate ethyl acetate layer to doing, reclaim solvent, drying promptly gets product.
Described catalyst for reaction, can be various lewis acid, such as alchlor, aluminum chloride, iron trichloride, four antimony chlorides, tantalum pentachloride, boron trifluoride, vanadium tetrachloride, tin tetrachloride, zinc dichloride, butter of antimony etc. and various protonic acids such as hydrogen fluoride, sulfuric acid, five phosphorus oxide, phosphoric acid etc., best catalyzer is aluminum chloride, iron trichloride and boron trifluoride.
The solvent that uses in the described reaction can be the lower solvent of polarity, and is wherein commonly used such as benzene, oil of mirbane, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride, ethylene dichloride, sherwood oil etc.According to reactant different choice optimum solvent as reaction solvent.Optimum solvent is oil of mirbane or benzene among the present invention.
Described reaction solvent consumption is 4～100ml/ gram catechin raw material, and optimum amount is 8～20ml/ gram catechin raw material.
Described reacting initial temperature is 0 ℃～25 ℃, and wherein best starting temperature is 3 ℃～8 ℃.
Described temperature of reaction is 25 ℃～100 ℃, and optimal reaction temperature is 35 ℃～45 ℃ among the present invention, and the optimum temps point is 38 ℃～40 ℃.
The described reaction times is 3 hours～24 hours, and optimum reacting time is 7 hours～10 hours.
Reactant ratio is a catechin in the described reaction: catalyzer: acylating agent=1: 1～5: 1～5, wherein optimum proportion is 1: 2～3.5: 2～3.5.
3. the performance of product of the present invention and other several fat-soluble antioxidant products relatively
1. fat-soluble test
Sample is placed chloroform, room temperature sonic oscillation 10 minutes, preparation concentration is the sample solution of 1mg/ml, in the transparence of 800nm working sample solution.The result shows (seeing Table 1), and tea-polyphenol is fat-soluble lower, and TBHQ is fat-soluble the strongest, and the liposoluble performance of phosphinylidyne fat-soluble tea polyphenol obviously is better than oxygen acidylate fat-soluble tea polyphenol and rosemary extract
Table 1: fat-soluble performance relatively
| Sample | Concentration | Transmittance % |
| Tea-polyphenol | 1mg/ml? | 38.268? |
| Oxygen acidylate fat-soluble tea polyphenol | 1mg/ml? | 79.263? |
| Phosphinylidyne fat- |
1mg/ml? | 96.053? |
| Phosphinylidyne fat- |
1mg/ml? | 98.293? |
| Rosemary extract | 1mg/ml? | 88.026? |
| TBHQ? | 1mg/ml? | 100? |
2. the UV spectrum comparative statistics observed data of phosphinylidyne fat-soluble tea polyphenol and oxygen acidylate fat-soluble tea polyphenol shows, in flavonoid compound, increases the phenolic hydroxyl group number and can make absorption peak red shift ginseng
See document 4:CATHERINE A.RICE-EVANS; NICHOLAS J.MILLER, andGEORGE PAGANGA.STRUCTURE-ANTIOXIDANT ACTIVITY RELATIONSHIPS OF FLAVONOIDS AND PHENOLIC ACIDS.Free RadicalBiology ﹠amp; Medicine, Vol.20,
No.7，pp.933-956，1996。
By accompanying drawing 4 as can be known; phosphinylidyne fat-soluble tea polyphenol and oxygen acidylate fat-soluble tea polyphenol have two absorption peaks respectively; the pairing wavelength of two peak values is respectively; phosphinylidyneization: 279.00nm and 229.50nm; oxygen acidylate: 275.50nm and 220.00nm; as seen, phosphinylidyne has divided not than the red shift of oxygen acidylate 3.5nm and 9.5nm.
3 thin layer chromatography analysis results:
The thin-layer chromatography condition:
Thin layer plate: high-efficient silica gel plate
Developping agent: chloroform, methyl alcohol, water, go upper strata fat phase
Developer: 1% Vanillin hydrochloric acid soln
As shown in Figure 5, it is the thin-layer chromatography comparison diagram of phosphinylidyne LTP, oxygen acidylate LTP and TP, wherein:
Spot indicates: 1---phosphinylidyne LTP; 2---oxygen acidylate LTP; 3---TP
Three main components of the tea-polyphenol that three of sample 3 spots are not acidylate among the thin layer figure.
The spot that equates with sample 3 spot and R f in sample 1 (phosphinylidyne LTP sample) and the sample 2 (oxygen acidylate LTP sample) is not for by the tea-polyphenol spot of oxygen acidylate; spot 4 (4 '), 5 (5 '), 6 (6 '), 7 (7 ') are acidylate spots, and are followed successively by tea-polyphenol list acidylate from the bottom to top to many acidylates composition.
From acidylate and not acidylate composition, phosphinylidyneization and oxygen acidylate sample compare, and wherein the oxygen acidylate has more not by oxygen acidylate composition.
4. the comparison of total polyphenols content
Total polyphenols assay principle: ortho-phenolic hydroxyl generates the hyacinthine complex compound with ferrous ion in the trolamine aqueous solution.This hyacinthine complex compound has maximum absorption band at the 540nm place, and the depth of its color is directly proportional with the content of tea-polyphenol, and UV measures absorption value, and compares with the standard Progallin A, obtains polyphenol content.This measuring method is stated document: Ye Luming as follows, and the fat-soluble tea polyphenol content assaying method is inquired into, Chinese public health the 17th the 9th phase of volume of calendar year 2001: 386.
Table 2 is the result show; phosphinylidyne fat-soluble tea polyphenol (LTP) total polyphenols content is obviously greater than oxygen acidylate fat-soluble tea polyphenol (LTP); this mainly is because the oxygen acylation process of tea-polyphenol makes the part phenolic hydroxyl group esterified, so its total polyphenols content significantly is lower than the phosphinylidyne fat-soluble tea polyphenol.
Table 2. total polyphenols assay result
(annotate: " removing TP " is meant and removes the tea-polyphenol composition that has neither part nor lot in esterification reaction in the fat-soluble tea polyphenol)
| Sample number into spectrum | The sample explanation | Total |
| 1? | Phosphinylidyne fat-soluble tea polyphenol-go TP | 40.03? |
| 2? | Oxygen acidylate fat-soluble tea polyphenol-go TP | 35.14? |
5. hexichol is for the comparison of bitter taste hydrazine free radical (DPPH, content 〉=97%) inhibiting rate
Free radical is meant to have and does not match atom, atomic group or the molecule of valence electron.Because of DPPH is a kind of compound with stable not sharing electron, there be the last one to absorb at the 517nm place, its ethanolic soln is intense violet color.When free-radical scavengers existed, owing to its single electron pairing its absorption being faded away, its fading extent became quantitative relationship with the electron amount of its acceptance.Thereby available optical spectroscopy carries out quantitative analysis.Referring to following two pieces of documents: (1) Chen Jiwu, Hu Bin, Zhao Shi etc., luminous journal, the 26th the 5th phase of volume, in October, 2005: 664-668; (2) Li Hong, Zhang Yuanhu uses the resistance of oxidation that the DPPH method is measured Fructus Mali pumilae extract, Shandong Agricultural University's journal (natural science edition), the 36th the 1st phase of volume: 35～38.
Condition determination is a DPPH concentration: 300 μ mol/L; Sample concentration: 50ppm; Measure wavelength: 517nm;
From accompanying drawing 6 as can be seen, the LTP of phosphinylidyneization and oxygen acidylate is close with the TBHQ inhibiting rate.Its inhibiting rate to the DPPH free radical significantly descended after oxygen acidylate LTP removed TP, and phosphinylidyne LTP remove TP after its inhibiting rate to the DPPH free radical do not have remarkable decline.And the phosphinylidyne LTP inhibiting rate that removes TP is higher than the oxygen acidylate LTP of TP.May be because its esterification on the carbon of phenyl ring, does not have the phenolic hydroxyl group loss, so its inhibition ability significantly reduce.
6. the anti peroxidation of lipid performance relatively
With reference to GB/T5009.37-1996, measure the anti peroxidation of lipid performance.
Testing sample has phosphinylidyne LTP, oxygen acidylate LTP, rosemary extract (Salvin content 〉=60%), TBHQ and Vc cetylate.
Testing sample is dissolved in the soybean oil of no oxidation inhibitor (sample concentration is 100ppm), 98 ℃ preserve down different times (hour): 1,17.5,24.5,38,59.5,73.5,100, measure the POV value of each time period.
From accompanying drawing 7 as can be seen, the antioxidant property no significant difference of testing sample in 98 ℃ of different times.The fat-soluble antioxidant of several mensuration all has stronger antioxidant property.
Embodiment one
Claim palmitinic acid 104 grams (0.4mol), put (band stirring, charging opening, prolong) in the 250ml three-necked bottle, add 36ml (0.49mol) sulfur oxychloride again.Lifting temperature repeatedly between 20 ℃～50 ℃, stirring reaction does not produce about about 5～8 times lifting temperature repeatedly to there being bubble simultaneously.About about 7 hours of reaction times, the cooling back adds 1.2mlDMF (0.0156mol), be warming up to 50 ℃ more gradually, reaction is to there not being HCL bubble (about about 2 hours), cooling afterreaction liquid is clear solution, and there is not solid, through UV scanning (400nm～200nm), no sulfur oxychloride absorption peak about 280nm.
Get 160ml oil of mirbane and put (band stirring in the 500ml three-necked bottle, charging opening, the condensation drying tube) adds aluminum chloride 8.05 grams (0.061mol) and above-mentioned reaction while stirring successively and make palmityl chloride 18.88ml (0.061mol) to dissolving fully, again under condition of ice bath, add catechin powder raw material 10 gram (raw material adds too fast meeting makes the reaction fierce and overflow) gradually, after adding, reaction is by 5 ℃ of beginnings, be warming up to 45 ℃ of temperature of reaction gradually, the fierce degree of temperature rise rate visual response and decide sustained reaction 10 hours, reaction finishes back (reactant is tied to form and produces a large amount of solids), add with the band of reaction solution equivalent and ice deionized water 160ml, leave standstill, make layering, the isolated for disposal reaction solvent, filtered water and solid suspendible system with the appropriate amount of deionized water washing, add ethyl acetate 500ml again in filter cake, deionized water 200ml and hydrochloric acid 20ml, leave standstill, make layering, discard water layer, ethyl acetate layer washes with water once again, concentrate ethyl acetate layer to doing, reclaim solvent, drying promptly gets product.Other devices and precaution are combined to reaction by phosphinylidyne and are carried out.
Embodiment two
Claim palmitinic acid 104 grams (0.4mol), put (band stirring, charging opening, prolong) in the 250ml three-necked bottle, add 38.2ml (0.52mol) sulfur oxychloride again.Lifting temperature repeatedly between 20 ℃～50 ℃, stirring reaction does not produce about about 5～8 times lifting temperature repeatedly to there being bubble simultaneously.In about about 5 hours of reaction times, the cooling back adds 1.6mlDMF (0.021mol), is warming up to 50 ℃ more gradually, reaction is to there not being bubble (about about 2 hours), cooling afterreaction liquid is clear solution, and does not have solid, through UV scanning (the no sulfur oxychloride absorption peak about 280nm of 400nm～200nm).
Get 180ml oil of mirbane and put (band stirring in the 500ml three-necked bottle, charging opening, the condensation drying tube) adds aluminum chloride 9.71 grams (0.074mol) and above-mentioned reaction while stirring successively and make palmityl chloride 22.89ml (0.074mol) to dissolving fully, again under condition of ice bath, add catechin powder raw material 10 gram (raw material adds too fast meeting makes the reaction fierce and overflow) gradually, after adding, reaction is by 5 ℃ of beginnings, be warming up to 40 ℃ of temperature of reaction gradually, the fierce degree of temperature rise rate visual response and decide sustained reaction l0 hour, reaction finishes back (reactant is tied to form and produces a large amount of solids), add with the band of reaction solution equivalent and ice deionized water, leave standstill, make layering, the isolated for disposal reaction solvent, filtered water and solid suspendible system with the appropriate amount of deionized water washing, add ethyl acetate 500ml again in filter cake, deionized water 200ml and hydrochloric acid 20ml, leave standstill, make layering, discard water layer, ethyl acetate layer washes with water once again, concentrate ethyl acetate layer to doing, reclaim solvent, drying promptly gets product.
Embodiment three
Claim palmitinic acid 104 grams (0.4mol), put (band stirring, charging opening, prolong) in the 250ml three-necked bottle, add 32.3ml (0.44mol) sulfur oxychloride again.Lifting temperature repeatedly between 20 ℃～50 ℃, stirring reaction does not produce about about 5～8 times lifting temperature repeatedly to there being bubble simultaneously.About about 10 hours of reaction times, the cooling back adds 2.6mlDMF (0.035mol), be warming up to 50 ℃ more gradually, reaction is to there not being HCL bubble (about about 3 hours), cooling afterreaction liquid is clear solution, and there is not solid, through UV scanning (the no sulfur oxychloride absorption peak about 280nm of 400nm～200nm).
Get 200ml oil of mirbane and put (band stirring in the 500ml three-necked bottle, charging opening, the condensation drying tube) adding aluminum chloride 12.9 grams (0.098mol) and above-mentioned reaction while stirring successively makes to such an extent that palmityl chloride 30.3ml (0.098mol) extremely dissolves fully, again under condition of ice bath, add catechin powder raw material 10 gram (raw material adds too fast meeting makes the reaction fierce and overflow) gradually, after adding, reaction is by 5 ℃ of beginnings, be warming up to 35 ℃ of temperature of reaction gradually, the fierce degree of temperature rise rate visual response and decide sustained reaction 15 hours, reaction finishes back (reactant is tied to form and produces a large amount of solids), add with the band of reaction solution equivalent and ice deionized water, leave standstill, make layering, the isolated for disposal reaction solvent, filtered water and solid suspendible system with the appropriate amount of deionized water washing, add ethyl acetate 500ml again in filter cake, deionized water 200ml and hydrochloric acid 20ml, leave standstill, make layering, discard water layer, ethyl acetate layer washes with water once again, concentrate ethyl acetate layer to doing, reclaim solvent, drying promptly gets product.
Claims (7)
1. the preparation method of a fat-soluble tea polyphenol is characterized in that, comprises following steps:
A, under starting temperature, lewis acid or bronsted acid catalyst and fatty acylating agent are dissolved in reaction solvent, form complex compound;
B, in the product that step a obtains, add tea-polyphenol gradually, the fatty acyl group that makes described fatty acylating agent directly with described tea-polyphenol in the aromatic nucleus of catechin carry out nucleophilic addition, generate arone;
The starting temperature of described nucleophilic addition is 3～8 ℃, and temperature of reaction is 35～45 ℃, and the reaction times is 7～10 hours; Described fatty acylating agent is the above fat acyl chlorides of 12 carbon;
Described lewis acid is selected from alchlor, aluminum chloride, iron trichloride.
2. preparation method according to claim 1 is characterized in that, described protonic acid is hydrogen fluoride, sulfuric acid or phosphoric acid.
3. preparation method according to claim 1 is characterized in that described solvent is selected from benzene, oil of mirbane, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride, ethylene dichloride or sherwood oil.
4. preparation method according to claim 1 is characterized in that, the consumption of described solvent is 4～100ml/ gram catechin raw material.
5. preparation method according to claim 4 is characterized in that, the consumption of described solvent is 8～20ml/ gram catechin raw material.
6. preparation method according to claim 1 is characterized in that, the reactant molar ratio of described nucleophilic addition is a catechin: catalyzer: acylating agent=1: 1～5: 1～5.
7. preparation method according to claim 6 is characterized in that, the reactant molar ratio of described nucleophilic addition is a catechin: catalyzer: acylating agent=1: 2～3.5: 2～3.5.
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| 旷英姿等.脂溶性茶多酚的制备与表征.食品科技 7.2005,(7),53-56. * |
| 王巧娥等.脂溶性茶多酚的合成及其抗油脂自动氧化特性的研究.天然产物研究与开发13 4.2001,13(4),12-15. |
| 王巧娥等.脂溶性茶多酚的合成及其抗油脂自动氧化特性的研究.天然产物研究与开发13 4.2001,13(4),12-15. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103005007A (en) * | 2012-12-25 | 2013-04-03 | 浙江大学 | Fat-soluble antioxidant of bamboo leaves and preparation method thereof |
| CN103005007B (en) * | 2012-12-25 | 2015-07-29 | 浙江大学 | Fat-soluble AOB and preparation method thereof |
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| CN101270108A (en) | 2008-09-24 |
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