CN1453285A - Synthesis of sucrose-6-acetate - Google Patents
Synthesis of sucrose-6-acetate Download PDFInfo
- Publication number
- CN1453285A CN1453285A CN 03126656 CN03126656A CN1453285A CN 1453285 A CN1453285 A CN 1453285A CN 03126656 CN03126656 CN 03126656 CN 03126656 A CN03126656 A CN 03126656A CN 1453285 A CN1453285 A CN 1453285A
- Authority
- CN
- China
- Prior art keywords
- acid catalyst
- solid acid
- synthetic method
- sucrose
- acetate
- 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
- 230000015572 biosynthetic process Effects 0.000 title abstract 2
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229930006000 Sucrose Natural products 0.000 claims abstract description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000005720 sucrose Substances 0.000 claims abstract description 6
- 239000011973 solid acid Substances 0.000 claims description 14
- 238000010189 synthetic method Methods 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical group [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 6
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- BAQAVOSOZGMPRM-QBMZZYIRSA-N sucralose Chemical compound O[C@@H]1[C@@H](O)[C@@H](Cl)[C@@H](CO)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 BAQAVOSOZGMPRM-QBMZZYIRSA-N 0.000 abstract description 5
- 235000019408 sucralose Nutrition 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 235000003599 food sweetener Nutrition 0.000 abstract description 3
- 239000003765 sweetening agent Substances 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 150000002148 esters Chemical group 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004376 Sucralose Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RWACICCRNCPMDT-UHFFFAOYSA-N cerium sulfuric acid Chemical compound [Ce].S(O)(O)(=O)=O RWACICCRNCPMDT-UHFFFAOYSA-N 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Saccharide Compounds (AREA)
Abstract
The present invention discloses the synthesis of sucrose-6-acetate. Sucrose material is mixed with N, N-dimethyl formamide solution, made to produce ester exchange reaction with ethyl acetate under the action of solid sulfate catalyst, which may be adsorbed on polymer carrier, to produce sucrose-6-acetate. Sucrose-6-acetate is the key intermediate for synthesizing trichlorosucrose as sweetening agent. The present invention has the advantages of simple technological process, high product purity, low production cost, etc. and is suitable for industrial production.
Description
Affiliated technical field
The present invention relates to a kind of key intermediate of synthetic sweetener Sucralose---the synthetic method of cane sugar-6-acetic ester.
Background technology
Sucralose, chemical name 4,1 ', 6 '-three chloro-4,1 ', 6 '-three deoxidation sucralose, its structural formula is:
The sugariness of Sucralose is 600 times of sucrose, is used as sweetening agent by more than 20 state approvals.
The preparation method of Sucralose has single radical protection method and full radical protection method two big classes substantially.Full radical protection method (as U.S. Pat 4801700, US4783526, US4362869 record) complex process does not have suitability for industrialized production to be worth; Usually concerning glucide, it is more more active that the hydroxyl on 6 is gone up hydroxyl than other positions, therefore, want to make other hydroxyls to react, and 6 hydroxyls remains unchanged, and just need carry out radical protection to 6 hydroxyls, and this is single basic starting point of protecting consideration.Therefore the core of single radical protection method is the preparation of cane sugar-6-acetic ester.The structural formula of cane sugar-6-acetic ester is:
The synthetic method of cane sugar-6-acetic ester mainly contains two kinds: the ethyl acetate method is (as U.S. Pat 4,889,928,5,449,772 the record) and the Dibutyltin oxide method (as U.S. Pat 5,023,329,4,950,746 records), these synthetic methods have certain advance, but also have certain limitation, as complex process, production cost height.
Summary of the invention
The object of the present invention is to provide a kind of new cane sugar-6-acetic ester synthetic method, this method technology is simple, production cost is low.
The synthetic method of a kind of cane sugar-6-acetic ester provided by the invention, this method is raw material with sucrose, add N, dinethylformamide solution, at solid acid catalyst or be adsorbed under the solid acid catalyst effect on the polymer carrier and ethyl acetate generation transesterification reaction, generate cane sugar-6-acetic ester.
Solid acid catalyst is also referred to as Lewies acid in organic chemistry, as ferric sulfate, and cerous sulfate, zinc chloride, iron(ic) chloride, zirconium chloride is usually used in esterification, transesterification reaction, the catalyzer of aldol (ketone) condensation reaction.Industrial, also this class catalyzer is adsorbed on polymer carrier such as the silica gel sometimes, make active higher loaded catalyst.The solid acid catalyst that the present invention selects for use is vitriol or hydrosulfate solid acid catalyst, and wherein the vitriol solid acid catalyst is selected cerous sulfate, copper sulfate or titanium sulfate for use; The hydrosulfate solid acid catalyst is selected sodium pyrosulfate for use.Preferably sulfuric acid cerium of the present invention and cerous sulfate-silica gel are as above-mentioned catalyst for reaction.When making catalyzer with cerous sulfate and cerous sulfate-silica gel, the selectivity height can obtain the cane sugar-6-acetic ester of higher degree, and product yield also can be up to more than 80%.
Compare with the synthetic method of existing cane sugar-6-acetic ester, the present invention has advantages such as technology is simple, product purity is high, production cost is low, is fit to very much suitability for industrialized production.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
The preparation of loading type cerous sulfate-silica-gel catalyst
In the 100ml round-bottomed flask, add 6.2g Ce (SO
4)
24H
2O, add water 20ml dissolving after, add 230～400 purpose silica gel 4.8g again, on Rotary Evaporators, be heated to 110 ℃ of vacuum (200Pa) dry 3 hours, obtain about 9.5 gram cerous sulfate-silica gel (1: 1) catalyzer.
Embodiment 2
In the 1000ml three-necked bottle, add sucrose 50g and N, dinethylformamide (DMF) 250ml, 2g anhydrous ceric sulfate and 50ml ethyl acetate, be heated to 80 ℃ and stirring reaction 4 hours, and be chilled to 10 ℃, the filtered and recycled cerous sulfate, steam earlier the unreacted ethyl acetate at normal temperatures, decompression steams whole DMF again.Get syrup 55g, detect with HPLC, the content of cane sugar-6-acetic ester is 79.3%.
Embodiment 3
In the 1000ml three-necked bottle, add sucrose 50g and N, dinethylformamide (DMF) 250ml, cerous sulfate-silica gel (1: 1) 5g, ethyl acetate 100ml was heated to 80 ℃ and stirring reaction 4 hours, was chilled to 5 ℃, filtering recovering catalyst, steam earlier the unreacted ethyl acetate at normal temperatures, decompression steams whole DMF again, gets syrup 56g, HPLC detects, and the content of cane sugar-6-acetic ester is 85.7%.
Claims (7)
1, a kind of synthetic method of cane sugar-6-acetic ester, it is characterized in that with sucrose being raw material, add N, dinethylformamide solution, at solid acid catalyst or be adsorbed under the solid acid catalyst effect on the polymer carrier and ethyl acetate generation transesterification reaction, generate cane sugar-6-acetic ester.
2, synthetic method according to claim 1 is characterized in that described solid acid catalyst is vitriol or hydrosulfate solid acid catalyst.
3, synthetic method according to claim 2 is characterized in that described vitriol solid acid catalyst is cerous sulfate, copper sulfate or titanium sulfate.
4, synthetic method according to claim 2 is characterized in that described hydrosulfate solid acid catalyst is a sodium pyrosulfate.
5, synthetic method according to claim 1 is characterized in that described polymer carrier is a silica gel.
6, synthetic method according to claim 3 is characterized in that described vitriol solid acid catalyst is a cerous sulfate.
7, synthetic method according to claim 2 is characterized in that the described vitriol that is adsorbed on the polymer carrier is cerous sulfate-silica gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031266568A CN1176095C (en) | 2003-05-23 | 2003-05-23 | Synthesis of sucrose-6-acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031266568A CN1176095C (en) | 2003-05-23 | 2003-05-23 | Synthesis of sucrose-6-acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1453285A true CN1453285A (en) | 2003-11-05 |
| CN1176095C CN1176095C (en) | 2004-11-17 |
Family
ID=29260330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031266568A Expired - Lifetime CN1176095C (en) | 2003-05-23 | 2003-05-23 | Synthesis of sucrose-6-acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1176095C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007053947A1 (en) | 2007-04-25 | 2008-10-30 | Shenzhen New Trend Industrial Development Co., Ltd., Shenzhen | Process for the synthesis of sucrose-6-acetic acid ester |
| CN100436467C (en) * | 2007-04-18 | 2008-11-26 | 江苏强盛化工有限公司 | Preparation method of saccharose-6-acetic acid esters |
| CN100480252C (en) * | 2006-10-13 | 2009-04-22 | 恩滋药业(南京)有限公司 | Sucrose derivative and preparing method thereofr, and method for synthesizing trichloro sucrose utilizing same |
| CN101886100A (en) * | 2010-07-12 | 2010-11-17 | 江南大学 | A method for enzymatically preparing sucrose-6-acetate |
| CN104356175A (en) * | 2014-11-24 | 2015-02-18 | 苏州乔纳森新材料科技有限公司 | Method for preparing sucralose-6-acetate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420697C (en) * | 2006-08-30 | 2008-09-24 | 河北苏科瑞科技有限公司 | Method of preparing trichloro sucrose-6-organic acid ester |
-
2003
- 2003-05-23 CN CNB031266568A patent/CN1176095C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100480252C (en) * | 2006-10-13 | 2009-04-22 | 恩滋药业(南京)有限公司 | Sucrose derivative and preparing method thereofr, and method for synthesizing trichloro sucrose utilizing same |
| CN100436467C (en) * | 2007-04-18 | 2008-11-26 | 江苏强盛化工有限公司 | Preparation method of saccharose-6-acetic acid esters |
| DE102007053947A1 (en) | 2007-04-25 | 2008-10-30 | Shenzhen New Trend Industrial Development Co., Ltd., Shenzhen | Process for the synthesis of sucrose-6-acetic acid ester |
| CN101293902B (en) * | 2007-04-25 | 2011-05-11 | 吉安市新琪安科技有限公司 | Process for synthesizing sucrose-6- ethyl ester |
| US8609834B2 (en) | 2007-04-25 | 2013-12-17 | Shenzhen New Trend Industrial Development Co. Ltd. | Method for synthesizing sucrose-6-acetic ester |
| CN101886100A (en) * | 2010-07-12 | 2010-11-17 | 江南大学 | A method for enzymatically preparing sucrose-6-acetate |
| CN101886100B (en) * | 2010-07-12 | 2012-08-08 | 江南大学 | Method for preparing sucrose-6-acetic ester by enzymatic method |
| CN104356175A (en) * | 2014-11-24 | 2015-02-18 | 苏州乔纳森新材料科技有限公司 | Method for preparing sucralose-6-acetate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1176095C (en) | 2004-11-17 |
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| ASS | Succession or assignment of patent right |
Owner name: GUANGDONG GUANG YE QING YI FOOD TECHNOLOGY CO., L Free format text: FORMER OWNER: GUANGDONG PROV. INST. OF FOOD INDUSTRY Effective date: 20080118 |
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| TR01 | Transfer of patent right |
Effective date of registration: 20080118 Address after: Guangzhou, Guangdong Province, Panyu District City, South Village, new base village industrial zone, 303 Jin Xin Avenue Patentee after: GUANGDONG GUANGYE QINGYI FOOD TECHNOLOGY CO.,LTD. Address before: No. 146, Xingang East Road, Guangdong, Guangzhou Patentee before: Guangdong Food Industry Institute Co.,Ltd. |
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Granted publication date: 20041117 |
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