CN1800197A - Two-step method oriented synthesis of sucrose-6-higher fatty acid monoester - Google Patents
Two-step method oriented synthesis of sucrose-6-higher fatty acid monoester Download PDFInfo
- Publication number
- CN1800197A CN1800197A CN 200510200609 CN200510200609A CN1800197A CN 1800197 A CN1800197 A CN 1800197A CN 200510200609 CN200510200609 CN 200510200609 CN 200510200609 A CN200510200609 A CN 200510200609A CN 1800197 A CN1800197 A CN 1800197A
- Authority
- CN
- China
- Prior art keywords
- sucrose
- fatty acid
- higher fatty
- synthesis
- acid monoester
- 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.)
- Granted
Links
Landscapes
- Saccharide Compounds (AREA)
Abstract
The invention relates to a method for using tow-step to oriented synthesis sucrose -6-higher fatty acid monoesters. It is characterized in that the first step: using chemical synthesis method to synthesis the sucrose-6-acetate or benzoate, so that the hydroxyl of the 6 bit of the sucrose actives; the second step: it uses enzyme catalysis, higher fatty acid or methyl ester and ethyl ester and sucrose -6-acetate or benzoate to do ester exchange reaction to directional or cheesed synthesis oriented synthesis sucrose -6-higher fatty acid monoesters.
Description
Technical field
The present invention relates to a kind of two-step method oriented synthesis of sucrose-6-higher fatty acid monoester.
Background technology
Sucrose has eight hydroxyls, and each hydroxyl can both be produced the sucrose ester of different degree of substitution by the electrophilic reagent acidylate.The sucrose ester of different degree of substitution has been widely used in industries such as washing composition, food, makeup and medicine.The preparation method of sucrose fatty ester can be divided into chemical synthesis and enzyme catalysis synthesis method.In view of the chemical synthesis combined coefficient than higher, but the sucrose gamma value is difficult to control, so more and more researchers is more paid close attention to and is used enzyme and carry out optionally synthesis of sucrose higher fatty acid monoester as catalyzer, control sucrose gamma value; And common enzyme process directly utilizes sucrose and corresponding derivative of fatty acid to carry out enzymatic interesterification procedure to prepare the sucrose-fatty monoesters, and it is synthetic that the esterification position of sucrose is difficult to carry out accurate pointing.
Summary of the invention
Purpose of the present invention just provides the method that accurate pointing synthetic two-step method oriented synthesis of sucrose-6-higher fatty acid monoester is carried out at a kind of esterification position that makes sucrose.
Technical scheme of the present invention is such:
The first step: chemical synthesis synthesizing cane sugar-6-acetic ester or benzoic ether make the hydroxyl activation on 6 of the sucrose;
Second step: by enzyme catalysis, higher fatty acid or its first, ethyl ester carry out transesterification reaction orientation or selectively synthesizing sucrose-6-higher fatty acid monoester with cane sugar-6-acetic ester or benzoic ether.
Advantage of the present invention is to make the esterification position of sucrose carry out accurate pointing, realizes oriented synthesis of sucrose-6-higher fatty acid monoester.
Description of drawings
Accompanying drawing 1 is composition principle figure of the present invention.
Embodiment
Implement of the present invention:
The first step: chemical synthesis synthesizing cane sugar-6-acetic ester or benzoic ether make the hydroxyl activation on 6 of the sucrose;
Second step: by enzyme catalysis, higher fatty acid or its first, ethyl ester carry out transesterification reaction orientation or selectively synthesizing sucrose-6-higher fatty acid monoester with cane sugar-6-acetic ester or benzoic ether.
Described chemical synthesis synthesis of sucrose-6-higher fatty acid monoester is to adopt triethly orthoacetate method or Dibutyltin oxide catalysis method selectively synthesizing sucrose-6-acetic ester or benzoic ether, makes 6 hydroxyl activation of sucrose.
Behind synthesizing cane sugar-6-acetic ester or benzoic ether, to cane sugar-6-acetic ester or benzoic ether separate, behind the purifying, by enzyme catalysis, higher fatty acid or its first, ethyl ester carry out transesterification reaction orientation or selectively synthesizing sucrose-6-higher fatty acid monoester with cane sugar-6-acetic ester or benzoic ether again.
The concrete preparation example of present embodiment is:
1, cane sugar-6-acetic ester is synthetic
Method 1:
Under 20 ℃, with 1.71g (5mmol) sucrose, 12.5mLN, dinethylformamide places the there-necked flask of 50mL, adds the 20mg tosic acid then, and magnetic agitation adds the 1mL trimethyl orthoacetate again, stirring reaction 2hr.The water that adds 0.7mL, reaction 0.5hr makes sucrose alkyl 4, the open loop under the effect of water of the adjacent acylate of 6-obtains sucrose-4-acetic ester and cane sugar-6-acetic ester.Add the 0.35mL TERTIARY BUTYL AMINE, continue stirring reaction 3h, make sucrose-4-acetic ester that migration take place under alkaline condition and be converted into cane sugar-6-acetic ester.Transformation efficiency is 79.1%.
Method 2:
In the there-necked flask of taking back stream device and water trap, add 20g (0.0584mol) sucrose, 14.5g (0.0584mol) Dibutyltin oxide and 100mL solvent, be heated to 1100C, backflow 7hr.Reactant is cooled to 100C, under nitrogen protection.Add 5.5mL (0.0584mol) diacetyl oxide, reaction mixture rises to room temperature react 2hr under 100C after, stirs 24hr.Less water is joined in the above-mentioned reaction mixture,, contain Dibutyltin oxide and extraction agent in the upper solution, remove extraction agent under reduced pressure, the oily matter that obtains is added drop-wise in the NaOH solution, produce the Dibutyltin oxide precipitation of white with the extraction of extraction agents such as hexanaphthene.Under optimum reaction condition, the Dibutyltin oxide rate of recovery can reach 98%.Contain cane sugar-6-acetic ester and solvent in lower floor's solution, solvent is removed in decompression, can obtain the melicera cane sugar-6-acetic ester of yellowish brown, through column chromatography separate white solid, productive rate 70%.
2, the separation of cane sugar-6-acetic ester, purifying
Reaction product is removed through the decompression rotary evaporation and is desolvated, and gets a faint yellow syrupy shape magma.With wet method upper prop behind a small amount of eluent dissolving saccharose-thick product of 6-acetic ester.Automatically collect instrument with computer and collect elutriant, flow velocity is 0.03mL/min, and every collection 10mL elutriant is identified with thin-layer chromatography, and component that will be identical with the Rf value of cane sugar-6-acetic ester merges, and removes solvent then under reduced pressure.The gained dope is moved in the beaker, place in the moisture eliminator, after for some time, have crystal and separate out.After supernatant liquid and crystal separation, crystal promptly gets purer cane sugar-6-acetic ester through vacuum-drying 24h.[pillar specification: post height (dress sorbent material height) 25cm, column diameter 2.5cm; The sorbent material silica gel G activates 24h in 110 ℃ of baking ovens, adopt wet method dress post, and pillar should be adorned directly as far as possible, fills evenly, and the bubble in the post is caught up with to the greatest extent.Elutriant is V (chloroform): V (methyl alcohol): V (glacial acetic acid): V (water)=70: 28: 2: 2]].
3, sucrose-6-higher fatty acid monoester is synthetic
In the single port reaction flask of 10mL, add 30.7mg (0.08mmol) cane sugar-6-acetic ester, 2mL solvent (mixed solvent of tertiary amyl alcohol/DMSO=4/1 (V/V)) and 100mg molecular sieve, add 100mgNovozyme435 or other enzymes after being preheated to 50 ℃, 30min again vibrates in the constant-temperature shaking culture case, the Laurate ethyl that adds 1-5 times of cane sugar-6-acetic ester amount then, soft-ethyl ester, Stearic ethyl stearate, ethyl oleate, ethyl linoleate or ethyl linolenate, put in the constant-temperature shaking culture case and reacted 24-48 hour, rotating speed is 200rpm, and temperature of reaction is about 50 ℃.Reaction conversion ratio is 40-80%.Timing sampling is analyzed with thin-layer chromatography, high performance liquid chromatography.Separation detection adopts tlc or high performance liquid chromatography, and actual conditions is as follows: chromatographic silica gel (G) thin plate (glass chip, 2.5 * 7.5cm).Developping agent is: chloroform: methyl alcohol: glacial acetic acid: water=70: 28: 2: 2 (V/V/V/V), sulfuric acid charing colour developing.High performance liquid chromatography detects and adopts Tianjin, island LC-10AT type high performance liquid chromatograph to carry out.High performance liquid chromatography groundwork index or parameter are: the LC-10AT high-pressure delivery pump, VP-ODS (250 * 4.6mm) chromatographic columns, the CTO-10AS column oven, the RID-10A differential refraction detector, Weil-McLain dragon data processing station, column temperature is 40 ℃, flow is 1.0mL/min, sample size is 20ul, moving phase: methyl alcohol: water=80: 20 (V/V).
Claims (4)
1. two-step method oriented synthesis of sucrose-6-higher fatty acid monoester is characterized in that:
The first step: chemical synthesis synthesizing cane sugar-6-acetic ester or benzoic ether make the hydroxyl activation on 6 of the sucrose;
Second step: by enzyme catalysis, higher fatty acid or its first, ethyl ester carry out transesterification reaction orientation or selectively synthesizing sucrose-6-higher fatty acid monoester with cane sugar-6-acetic ester or benzoic ether.
2. two-step method oriented synthesis of sucrose-6-higher fatty acid monoester according to claim 1, it is characterized in that described chemical synthesis synthesis of sucrose-6-higher fatty acid monoester is to adopt triethly orthoacetate method selectively synthesizing sucrose-6-acetic ester or benzoic ether, make 6 hydroxyl activation of sucrose.
3. two-step method oriented synthesis of sucrose-6-higher fatty acid monoester according to claim 1, it is characterized in that described chemical synthesis synthesis of sucrose-6-higher fatty acid monoester is to adopt Dibutyltin oxide catalysis method selectively synthesizing sucrose-6-acetic ester or benzoic ether, make 6 hydroxyl activation of sucrose.
4. two-step method oriented synthesis of sucrose-6-higher fatty acid monoester according to claim 1, it is characterized in that behind synthesizing cane sugar-6-acetic ester or benzoic ether, to cane sugar-6-acetic ester or benzoic ether separate, behind the purifying, by enzyme catalysis, higher fatty acid or its first, ethyl ester carry out transesterification reaction orientation or selectively synthesizing sucrose-6-higher fatty acid monoester with cane sugar-6-acetic ester or benzoic ether again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005102006094A CN100451026C (en) | 2005-10-14 | 2005-10-14 | Two-step method oriented synthesis of sucrose-6-higher fatty acid monoester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005102006094A CN100451026C (en) | 2005-10-14 | 2005-10-14 | Two-step method oriented synthesis of sucrose-6-higher fatty acid monoester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1800197A true CN1800197A (en) | 2006-07-12 |
| CN100451026C CN100451026C (en) | 2009-01-14 |
Family
ID=36810441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005102006094A Expired - Fee Related CN100451026C (en) | 2005-10-14 | 2005-10-14 | Two-step method oriented synthesis of sucrose-6-higher fatty acid monoester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100451026C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796145A (en) * | 2012-06-19 | 2012-11-28 | 天津北方食品有限公司 | Preparation method of sucrose-6-benzoate |
-
2005
- 2005-10-14 CN CNB2005102006094A patent/CN100451026C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796145A (en) * | 2012-06-19 | 2012-11-28 | 天津北方食品有限公司 | Preparation method of sucrose-6-benzoate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100451026C (en) | 2009-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105294874B (en) | A kind of method for efficiently separating Black Ganoderma immunocompetence polysaccharide | |
| CN103667402B (en) | A kind of lipase-catalyzed online synthesis 6 " method of-O-lauroyl-naringin ester | |
| CN101124988A (en) | Method for extracting refined cordycepin and cordyceps polysaccharide from Cordyceps militaris | |
| CN105859906B (en) | With immunocompetent sunset abelmoschus stem or bark leaf polyose acetylation modification product of raising and preparation method thereof | |
| CN107475330A (en) | A kind of method of lipase-catalyzed online synthesis N (5 glucose ester valeryl) metoprolol | |
| CN103923150A (en) | Stevenleaf and preparation method thereof | |
| CN107384992A (en) | A kind of method of lipase-catalyzed online synthesis 5 '-O- lauroyl -5-methyl-uridin | |
| CN107384991A (en) | A kind of method of 5 '-O- ethene adipyl uridines of lipase-catalyzed online synthesis | |
| CN101880305A (en) | Preparation method of ginsenoside metabolin M1 fatty acid ester compound | |
| CN100451026C (en) | Two-step method oriented synthesis of sucrose-6-higher fatty acid monoester | |
| CN107456472A (en) | A kind of preparation method of rare ginsenoside | |
| CN107988277A (en) | A kind of method of lipase-catalyzed online synthesis S- benzyl palmitic acid thioesters | |
| CN107488690A (en) | A kind of method of lipase-catalyzed online synthesis N (5 glucose ester valeryl) mexiletine | |
| CN103667393B (en) | A kind of lipase-catalyzed online synthesis 6 " method of-O-palmityl-neohesperidin dihydrochalcone ester | |
| CN113896755A (en) | Synthesis method of 2-deoxyglycoside and application thereof in pharmacy | |
| CN104673862A (en) | Methodfor synthesizing prunin from naringin in presence of alpha-L-rhamnosidase | |
| CN101921305B (en) | Method for preparing ginsenoside metabolite M1 fatty acid monoester compound | |
| CN109942663B (en) | Method for preparing cycloastragenol by using diphasic acid hydrolysis | |
| CN113786641B (en) | Subcritical composite solvent extraction separation method for various components in flaxseed meal | |
| CN104497058B (en) | The method that the biomolecule of fluorine loaded by carrier is synthesized using polytetrafluoroethylparticle particle | |
| CN101152624B (en) | Alcoholic hydroxyl group hydrophily color spectrum stationary phase and method for preparing the same | |
| CN1179967C (en) | Preparation method of high purity soyabean lecithin | |
| CN111995653A (en) | Preparation method of phytosterol/stanol ferulic acid ester | |
| CN1273213C (en) | Highlyerformance liquid phase chromatogram fixed phase, method for making same and use thereof | |
| CN1624472A (en) | Preparing linkage type polysaccharide chiral fixed phase by free radical copoly merization method |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20060712 Assignee: Liuzhou Gaotong Food Chemicals Co., Ltd. Assignor: Guangxi University of Technology Contract record no.: 2009450000042 Denomination of invention: Two-step method oriented synthesis of sucrose-6-higher fatty acid monoester Granted publication date: 20090114 License type: Exclusive License Record date: 20090708 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090114 Termination date: 20151014 |
|
| EXPY | Termination of patent right or utility model |