CN103833495B - A kind of preparation method of plant polyphenol acylated derivatives - Google Patents
A kind of preparation method of plant polyphenol acylated derivatives Download PDFInfo
- Publication number
- CN103833495B CN103833495B CN201410039055.3A CN201410039055A CN103833495B CN 103833495 B CN103833495 B CN 103833495B CN 201410039055 A CN201410039055 A CN 201410039055A CN 103833495 B CN103833495 B CN 103833495B
- Authority
- CN
- China
- Prior art keywords
- plant polyphenol
- acylated derivatives
- preparation
- reaction
- acyl chlorides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of plant polyphenol acylated derivatives, described method is: under nitrogen protection, by plant polyphenol extract and acyl chlorides mixing, in the medium of Gemini surface active agent shown in formula I, react completely in 50 ~ 200 DEG C, obtain described plant polyphenol acylated derivatives; Simple synthetic method of the present invention, need not use an acidic catalyst, effectively can prevent material oxidation, product yield is good, yield is up to 88%, cost is low, and reaction system is reusable, is suitable for carrying out industrial operation, Gemini surface active agent can recycle, safety and stability, environmentally safe is economical and practical green technology.
Description
(1) technical field
The present invention relates to a kind of preparation method of plant polyphenol acylated derivatives, relate to a kind of method catalyzing and synthesizing plant polyphenol acylated derivatives in Gemini surface active agent system.
(2) background technology
Plant polyphenol (plantpolyphenol) is the secondary metabolite of plant, by glucose (and polyvalent alcohol) alcohol of gallic acid (or its polymkeric substance), the plant polyphenol that the polymkeric substance of Flavonol and derivative thereof and both mixing form jointly.The phenolic compound that isolation identification goes out from plant is so far more than 8000 kinds, containing the more frequently seen plants of polyphenol more than 600 kinds, in many coniferous barks, plant polyphenol content is up to 20 ~ 40%, containing higher plant polyphenol in fruit, cereal or its epidermis, form several hundred million tons of renewable resourcess in the whole world.Plant polyphenol can be combined with protein, alkaloid, polysaccharide, makes its physics, chemical conduct changes.Have the activity of reductibility and Mulberry Extract, extremely strong anti-oxidant, inhibition of enzyme activity, antibacterial, anti-mutation, anti-inflammatory, radioprotective, hypotensive isoreactivity, physiological function is remarkable.Plant polyphenol is a class renewable resources, there is amphiphilic structure and many derivative reactions activity, at the ambit such as agricultural, medicine, food, material, chemical industry, ecotope, all there is scholar to carry out fundamental research and applied research from multiple angles to plant polyphenol, make plant polyphenol constantly obtain new high value added utilization approach.In food chemistry field as foodstuff additive, particularly utilize the anti-oxidant of plant polyphenol and bacteria resistance function not only can play a part to protect food used as natural antioxidants, sanitas etc., also help the raising of food quality and nutrition.
In order to improve food storage stability, extending shelf-life, the demand of antioxidant is also obviously increased.If plant polyphenol can be applied in edible oil undoubtedly for the even consumer health's effect of being significantly improved of China's edible fat production.Therefore, molecular modification is carried out to plant polyphenol, make it to possess lipotropy again while there is anti-oxidant, biocidal property, play biological activity better and have broad application prospects.But also there is many problems in the research of effective plant polyphenol method of modifying at present; it is not quite stable that subject matter comprises the modified product performance that solvent method and emulsion process obtain; the modified product cost that molecular modification method obtains is higher; in modifying process, phenolic hydroxyl group loss is comparatively large, and the selectivity of reaction and acylation degree need research further.Especially in acylation reaction, adopting fatty acid chloride reaction, there is O-acylations and C-acylations in acyl chlorides and phenol, obtains structural similitude and the different acylate of performance.So need the number and the selectivity that are controlled acylations by the selection of reaction conditions, make the product of acquisition having fat-soluble while, still there is good oxidation-resistance.
Gemini surface active agent is the tensio-active agent of a class special construction with two hydrophilic radicals and two lipophilic groups, has higher better surfactivity than conventional surfactant (only having a hydrophilic radical and a lipophilic group).Gemini surface active agent is the novel surfactant of a class performance brilliance, has high surfactivity.The multiple advantages such as good water-soluble and rheological, have wide practical use.In recent years, our seminar is devoted to the research and development of green chemical industry technique always, therefore utilizes Gemini surface active agent system in the present invention, has invented a kind of novel method of synthesizing plant polyphenol acylated derivatives.The method utilizes Gemini surface active agent system both as reaction medium, again as catalyzer, simplifies operation; also the loss of the phenolic hydroxyl group of plant polyphenol can be prevented; improve the transformation efficiency of C-acylation reaction, be a Green Chemical Technology, have not yet to see report.
(3) summary of the invention
The present invention seeks to the structural performance for plant polyphenol; acidylate method is utilized to synthesize plant polyphenol acylated derivatives; expand the Application Areas of plant polyphenol; reach the utility value improving plant polyphenol; provide a kind of in Gemini surface active agent system; catalyze and synthesize the method for plant polyphenol, reach the object improving acidylate transformation efficiency and be beneficial to large-scale industrial production.
The technical solution used in the present invention is:
The invention provides a kind of preparation method of plant polyphenol acylated derivatives, described method is: under nitrogen protection, by plant polyphenol extract and acyl chlorides mixing, in the medium of Gemini surface active agent shown in formula I, react completely in 50 ~ 200 DEG C, after reaction terminates, by reaction solution petroleum ether dissolution, then use saturated common salt water washing, sherwood oil uses anhydrous sodium sulfate drying mutually, pressure reducing and steaming petroleum ether solvent, obtains described plant polyphenol acylated derivatives; Described acyl chlorides is C
6~ C
18fatty acid chloride; In described plant polyphenol extract, plant polyphenol mass content is 90%, and the quality consumption of described plant polyphenol extract is in plant polyphenol amount of substance, and described plant polyphenol is 1:15 ~ 30 with the ratio of the amount of substance that feeds intake of acyl chlorides;
Further, in described plant polyphenol extract, plant polyphenol mass content is 90%, and molecular-weight average is 1700, containing 25 phenolic hydroxyl groups.
Further, preferred described acyl chlorides is decanoyl chloride, caproyl chloride, stearyl chloride or lauroyl chloride.
Further, preferred described reaction is reacted 5 ~ 20 hours under 50 ~ 200 DEG C of conditions.
Further, the quality consumption of preferred described Gemini surface active agent and the ratio of plant polyphenol extract and acyl chlorides total mass sum are 3 ~ 10:1.
Gemini surface active agent of the present invention is ditane Gemini surface active agent, and concrete preparation method is prepared as follows with reference to " the synthesis and property research of Shuangzi face tensio-active agent, Hu Longjiang, Daqing Petroleum Institute's Master's thesis (2004) ":
1) alkylation is in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel are housed, and adds ditane and anhydrous AlC1
3, fully stir and catalyzer be uniformly dispersed, at 45-50 DEG C, drip benzene (alkene is 2:1 with the ratio of the amount of substance of ditane), time for adding controls to drip at 20-30min, then gradually temperature of reaction is risen to 70 DEG C, and remain unchanged, reaction 8h, after reaction terminates, reaction solution is adjusted to neutrality, toluene extracts, anhydrous magnesium sulfate drying, filters, concentrate to obtain alkylate, for lower step sulfonation;
2) sulfonation is in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel are housed, add the alkylate of above-mentioned acquisition, dropwise add chlorsulfonic acid under vigorous stirring, the molar ratio of alkylate and chlorsulfonic acid is 2:1, time is lh, and temperature of reaction controls at 20-25 DEG C, reacts 2 hours, place, obtain sulfonated products;
3) sulfonated products adds in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel are housed by neutralization reaction, temperature of reaction is controlled at 35 ~ 40 DEG C with water-bath, with dropping funnel, mass concentration 15% aqueous sodium hydroxide solution is slowly added, regulate pH value of reaction system to be 7 ~ 8, make sulfonic acid all generate sodium sulfonate and be Gemini surface active agent product.
The plant polyphenol extract that the present invention uses is published in Hua Zhong Agriculture University's journal 1998,17(3 with reference to the people such as Zhang Yan), 294. " in rapeseed cake the extracting and developing of tannin and purification " method obtains, and concrete preparation method is as follows:
With rapeseed cake dregs (market purchasing) for raw material, pulverize, with the aqueous acetone solution of volumetric concentration 70% for extraction agent, solid-liquid ratio is 1:6, temperature 30 DEG C, extracts 3 times, each extraction 10 hours, filters, united extraction liquid, extracting solution concentrating under reduced pressure, lyophilize, macroporous resin chromatographic separation, obtain plant polyphenol extract, plant polyphenol mass content 90% in described plant polyphenol extract, molecular-weight average is 1700, containing 25 phenolic hydroxyl groups.
Reaction product of the present invention utilizes infrared spectra hydroxyl group absorption peak to compare.Result display hydroxyl peak obviously weakens, and methyl and methylene peak increase, and illustrate and have carried out acylation reaction.
Compared with prior art; beneficial effect of the present invention is mainly reflected in: the present invention adopts process for acylating to synthesize plant polyphenol acylated derivatives, does not need to use an acidic catalyst, effectively can prevent the oxidation of plant polyphenol; simple synthetic method; be convenient to operation and process, product yield is good, and yield is up to 89%; cost is low; reaction system is reusable, is easy to carry out industrial operation, is a Green Chemical Technology.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
The preparation of embodiment 1 Shuangzi face tensio-active agent
1) alkylation is in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel, HCl gas access equipment are housed, and adds ditane 16.8g(0.1mol), anhydrous AlC1
313g, fully stirs and catalyzer is uniformly dispersed, at 45-50 DEG C, drip benzene 34g(0.2mol), time for adding controls to drip at 20-30min, then gradually temperature of reaction is risen to 70 DEG C, and remain unchanged, reaction 8h, after reaction terminates, is adjusted to neutrality by reaction solution, toluene extracts, anhydrous magnesium sulfate drying, filters, concentrated that alkylate is used for lower step sulfonation;
2) sulfonation is in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel are housed, add the alkylate of above-mentioned acquisition, dropwise add chlorsulfonic acid 24g(0.2mol under vigorous stirring), time for adding is lh, temperature of reaction controls at 20-25 DEG C, reacts 2 hours, after making the abundant sulfonation of alkylate, place, make the HCl of generation discharge as much as possible and obtain sulfonated products;
3) sulfonated products adds in four mouthfuls of reaction flasks that electric mixer, thermometer, reflux condensing tube, dropping funnel are housed by neutralization reaction, temperature of reaction is controlled at 35 ~ 40 DEG C with water-bath, with dropping funnel, mass concentration 15% aqueous sodium hydroxide solution is slowly added, regulate pH value of reaction system to be 7 ~ 8, make sulfonic acid all generate sodium sulfonate and be Gemini surface active agent.
Embodiment 2 plant polyphenol and decanoyl chloride react
Under nitrogen protection; by plant polyphenol extract 17 grams (containing plant polyphenol 0.01 mole) and decanoyl chloride 29 grams (0.15 mole) mixing; Gemini surface active agent 46 grams, 50 DEG C of reactions 20 hours, after reaction terminates; by reaction solution sherwood oil 100 milliliters dissolving; use 30 × 3 milliliters of saturated common salt water washings again, sherwood oil uses anhydrous sodium sulfate drying mutually, pressure reducing and steaming petroleum ether solvent; obtain White waxy plant polyphenol acylated derivatives 36 grams, yield 77%.
Embodiment 3 plant polyphenol and caproyl chloride react
Under nitrogen protection; by plant polyphenol extract 17 grams (containing plant polyphenol 0.01 mole) and caproyl chloride 27 grams (0.2 mole) mixing; Gemini surface active agent 132 grams, 100 DEG C of reactions 10 hours, after reaction terminates; by reaction solution sherwood oil 100 milliliters dissolving; use 30 × 3 milliliters of saturated common salt water washings again, sherwood oil uses anhydrous sodium sulfate drying mutually, pressure reducing and steaming petroleum ether solvent; obtain White waxy plant polyphenol acylated derivatives 39 grams, yield 89%.
Embodiment 4 plant polyphenol and stearyl chloride react
Under nitrogen protection; by plant polyphenol extract 17 grams (containing plant polyphenol 0.01 mole) and stearyl chloride 76 grams (0.25 mole) mixing; Gemini surface active agent 930 grams, 150 DEG C of reactions 10 hours, after reaction terminates; by reaction solution sherwood oil 100 milliliters dissolving; use 30 × 3 milliliters of saturated common salt water washings again, sherwood oil uses anhydrous sodium sulfate drying mutually, pressure reducing and steaming petroleum ether solvent; obtain White waxy plant polyphenol acylated derivatives 82 grams, yield 88%.
Embodiment 5 plant polyphenol and lauroyl chloride react
Under nitrogen protection; by plant polyphenol extract 17 grams (containing plant polyphenol 0.01 mole) and lauroyl chloride 57 grams (0.3 mole) mixing; Gemini surface active agent 370 grams, 200 DEG C of reactions 5 hours, after reaction terminates; by reaction solution sherwood oil 100 milliliters dissolving; use 30 × 3 milliliters of saturated common salt water washings again, sherwood oil uses anhydrous sodium sulfate drying mutually, pressure reducing and steaming petroleum ether solvent; obtain White waxy plant polyphenol acylated derivatives 65 grams, yield 88%.
Claims (4)
1. the preparation method of a plant polyphenol acylated derivatives, it is characterized in that described method is: under nitrogen protection, by plant polyphenol extract and acyl chlorides mixing, in the medium of Gemini surface active agent shown in formula I, react completely in 50 ~ 200 DEG C, after reaction terminates, by reaction solution petroleum ether dissolution, then use saturated common salt water washing, sherwood oil uses anhydrous sodium sulfate drying mutually, pressure reducing and steaming petroleum ether solvent, obtains described plant polyphenol acylated derivatives; Described acyl chlorides is C
6~ C
18fatty acid chloride, in described plant polyphenol extract, plant polyphenol mass content is 90%, and the quality consumption of described plant polyphenol extract is in plant polyphenol amount of substance, and described plant polyphenol is 1:15 ~ 30 with the ratio of the amount of substance that feeds intake of acyl chlorides; In described plant polyphenol extract, plant polyphenol mass content is 90%, and molecular-weight average is 1700, containing 25 phenolic hydroxyl groups;
2. the preparation method of plant polyphenol acylated derivatives as claimed in claim 1, is characterized in that described acyl chlorides is decanoyl chloride, caproyl chloride, stearyl chloride or lauroyl chloride.
3. the preparation method of plant polyphenol acylated derivatives as claimed in claim 1, is characterized in that described reaction is reacted 5 ~ 20 hours under 50 ~ 200 DEG C of conditions.
4. the preparation method of plant polyphenol acylated derivatives as claimed in claim 1, is characterized in that the quality consumption of described Gemini surface active agent and the ratio of plant polyphenol extract and acyl chlorides total mass sum are 3 ~ 10:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410039055.3A CN103833495B (en) | 2014-01-26 | 2014-01-26 | A kind of preparation method of plant polyphenol acylated derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410039055.3A CN103833495B (en) | 2014-01-26 | 2014-01-26 | A kind of preparation method of plant polyphenol acylated derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103833495A CN103833495A (en) | 2014-06-04 |
| CN103833495B true CN103833495B (en) | 2016-04-13 |
Family
ID=50797439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410039055.3A Expired - Fee Related CN103833495B (en) | 2014-01-26 | 2014-01-26 | A kind of preparation method of plant polyphenol acylated derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103833495B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106983720A (en) * | 2017-05-19 | 2017-07-28 | 浙江工业大学 | A kind of reverse micelle includes the preparation method of insulin system |
-
2014
- 2014-01-26 CN CN201410039055.3A patent/CN103833495B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103833495A (en) | 2014-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475448B (en) | Green synthesis of high-content carvacrol capable of replacing natural origanum | |
| CN102659652B (en) | Solid phase extraction method for extracting total astaxanthin from haematococcus pluvialis | |
| Khoo et al. | Bioprocessing of Chaetoceros calcitrans for the recovery of fucoxanthin using CO2-based alkyl carbamate ionic liquids | |
| CN106434784B (en) | A kind of ionic liquid is the method that the enzyme process of reaction medium prepares fat-soluble tea polyphenol | |
| CN101148631A (en) | Method for preparing lycopene-enriched vegetable oil | |
| CN103936643A (en) | Method for extraction and separation of xanthophyll and flavones in marigold | |
| CN104370680A (en) | Method for extracting lycopene from tomatoes | |
| CN103319389A (en) | Method for preparing food-grade lutein crystal from marigold extract | |
| JP2010254687A (en) | Method for isolating carotenoid from plant source | |
| CN103833495B (en) | A kind of preparation method of plant polyphenol acylated derivatives | |
| CN104513844A (en) | Lipase catalysis method for synthesis of astaxanthin succinate | |
| CN104672291A (en) | Preparation method of gallate phytosterol ester | |
| CN101130512A (en) | Method for producing xanthophyll | |
| CN103833496B (en) | A kind of preparation method of plant polyphenol esterified derivative | |
| CN104710393A (en) | Pretreatment ethanol extraction method of dihydroquercetin in larix gmelini wood powder | |
| CN104478974B (en) | A kind of 20, the synthetic method of 23-dipiperidino-5-O-mycamino syl-tylono lide | |
| CN103709021B (en) | Vanillin extraction method | |
| KR102409067B1 (en) | Method for extracting fucoidan from saccharina japonica | |
| CN105125664A (en) | Blackberry anthocyanidin extracting method, blackberry anthocyanidin extract and application of blackberry anthocyanidin extract | |
| CN102887848A (en) | Method for preparing lutein crystals from marigold ointment by catalytic saponification | |
| CN103804460A (en) | Preparation method of tea saponin myristinate surfactant and product thereof | |
| JP5937450B2 (en) | Hyaluronidase inhibitor | |
| CN103772451B (en) | Astacin derivative and preparation method thereof | |
| CN105399653A (en) | Industrialization method for preparing zeaxanthine from marigold oil resin in one step | |
| CN106922679A (en) | The formamide of azophenlyene 1 transforms application of the compound 15 1 in Sclerotinia sclerotiorum is suppressed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180322 Address after: 313000 Zhejiang Province, Huzhou city Wuxing District Road No. 1188 district headquarters free port B building 14 Building 1403 room Patentee after: Zhejiang creation Intellectual Property Service Co., Ltd. Address before: 310014 Hangzhou city in the lower reaches of the city of Zhejiang Wang Road, No. 18 Patentee before: Zhejiang University of Technology |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180525 Address after: 226532 Jiangsu, Nantong, Rugao, Changjiang town (Rugao port) Fine Chemical Industrial Park Pujiang Road No. 6 Patentee after: Rugao Zhongchang Chemical Co., Ltd. Address before: 313000 1403, room 14, B building, free port, 1188 headquarters, Wuxing District, Huzhou, Zhejiang. Patentee before: Zhejiang creation Intellectual Property Service Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20200126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |