CN103936799B - Synthesis method of sucrose-6-acetate - Google Patents
Synthesis method of sucrose-6-acetate Download PDFInfo
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- CN103936799B CN103936799B CN201410169227.9A CN201410169227A CN103936799B CN 103936799 B CN103936799 B CN 103936799B CN 201410169227 A CN201410169227 A CN 201410169227A CN 103936799 B CN103936799 B CN 103936799B
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- acetic ester
- cane sugar
- synthetic method
- sucrose
- ester according
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- 238000001308 synthesis method Methods 0.000 title abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 57
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 13
- 229930006000 Sucrose Natural products 0.000 claims abstract description 13
- 239000005720 sucrose Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 20
- 229960004793 sucrose Drugs 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 235000013681 dietary sucrose Nutrition 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 7
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract 1
- 239000004376 Sucralose Substances 0.000 description 5
- 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 description 5
- 235000019408 sucralose Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000003765 sweetening agent Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100001234 toxic pollutant Toxicity 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 235000020824 obesity Nutrition 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Saccharide Compounds (AREA)
Abstract
The invention discloses a synthesis method of sucrose-6-acetate, which comprises the steps of mixing and dissolving sucrose and an acid-binding agent in a mixed solvent of water and dimethylformamide at 0-5 ℃; maintaining the temperature condition of 0-5 ℃, dropwise adding a dimethylformamide solution of acetic anhydride under the stirring condition, and reacting for 4-6 hours; and after the reaction is finished, distilling under reduced pressure to remove solvent water and dimethylformamide, adding a mixed solvent of acetone and methanol for recrystallization, and filtering, washing and drying to obtain the sucrose-6-acetate. According to the method, in a new reaction system, the acetic anhydride is used for directly esterifying the sucrose-6 hydroxyl, so that the use of high-price and toxic reagents is avoided, the cost is low, the method is green and environment-friendly, the reaction is carried out at a low temperature, the product quality and the yield are favorably improved, and the yield reaches 72-85%.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of preparation method of cane sugar-6-acetic ester.
Background technology
Sucralose is Sucralose again, is be that raw material is novel through the one of synthetic with sucrose, non-nutritive class intensive sweetener.1976, Britain LeslieHough taught the research group cooperated with TateLyle company and finds and synthesized Sucralose, within 1988, comes into the market.Through reaching the pharmacological evaluation of more than ten years, prove that it is definitely harmless to people, Sucralose can be used for obesity, the edible for patients such as cardiovascular diseases and diabetes, is a kind of new type functional intensive sweetener.China has had the manufacturer of more than 10 Sucralose now, what take on a certain scale only has two or three, production capacity was only broken by the situation of import in the past although can reach about 5000t, it is 600,000 Renminbi/t at present that price has also declined a lot, but cost performance, compared with other intensive sweeteners, is not preponderated.How reducing its production cost, is the research topic that another one is worth Efforts To Develop.
Cane sugar-6-acetic ester is as the important intermediate of synthesizing trichloro, but there is a lot of problem in present technique, such as the usage quantity of valuable raw material is large, the usage quantity of toxic reagent also uses the toxic raw materials such as Dibutyltin oxide as a large amount of in some traditional technologys comparatively greatly, reaction process can cause a large amount of toxic pollutants, temperature of reaction requires also higher usually, and efficiency of pcr product is not high yet.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind ofly pollutes little, that energy consumption the is low method preparing cane sugar-6-acetic ester.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A synthetic method for cane sugar-6-acetic ester, the method comprises the steps:
(1) in the mixed solvent of water and dimethyl formamide (DMF), the mixed dissolution under 0 ~ 5 DEG C of condition by sucrose and acid binding agent;
(2) maintain the temperature condition of 0 ~ 5 DEG C, under agitation condition, drip the dimethyl formamide solution of diacetyl oxide in the mixed system of step (1) after, react 4 ~ 6 hours;
(3) after reaction terminates, underpressure distillation removing aqueous solvent and dimethyl formamide, the mixed solvent adding acetone and methyl alcohol carries out recrystallization, more after filtration, washing, drying obtain product cane sugar-6-acetic ester.
In step (1), described acid binding agent is pyridine, triethylamine or diethylamine.
In step (1), the volume ratio of water and dimethyl formamide is 1:3 ~ 4, and the volume of water can dissolving saccharose completely.
In step (1), the mol ratio of sucrose and acid binding agent is 1:1 ~ 3, preferred 1:2 ~ 3.
In step (2), the mol ratio of sucrose and diacetyl oxide is 1:1 ~ 2.
In step (2), in the dimethyl formamide solution of diacetyl oxide, the concentration of diacetyl oxide is 1 ~ 2mol/L.
In step (2), stirring velocity maintains 400 ~ 600 revs/min.
In step (2), the time for adding of the dimethyl formamide solution of diacetyl oxide is 0.5 ~ 1 hour.
In step (3), the mixed solvent of acetone and methyl alcohol, the volume ratio of acetone and methyl alcohol is 2:1.
In step (3), recrystallization temperature is-5 ~ 0 DEG C.
In step (3), wash conditions is for adopting washing with acetone.
Beneficial effect: there is a lot of problem in present technique, such as the usage quantity of valuable raw material is large, the usage quantity of toxic reagent is also larger, the Dibutyltin oxide etc. such as, used in traditional technology, reaction process can cause a large amount of toxic pollutants, temperature of reaction requires also higher usually, and carbonization phenomenon is relatively more serious, and efficiency of pcr product is not high yet.Present invention process is with diacetyl oxide direct esterification sucrose-6-hydroxyl in new reaction system, and cost is low, avoids the use of valency height toxic reagent, environmental protection, has again relatively high productive rate simultaneously.The transformation efficiency that the present invention prepares sucrose-6-ethyl ester reaches 72%-85%.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1:
20ml deionized water is added, 60mlDMF, 3.62ml pyridine (0.045mol) in 250ml round-bottomed flask, and 5.13g sucrose (0.015mol), mechanical stirring, is cooled to 0 ~ 5 DEG C in cold well, keep 1 hour, after temperature-stable, 2.84ml diacetyl oxide (0.03mol) is blended in 15mlDMF solvent and is dripped by constant pressure funnel, time for adding is continuously 40 minutes, 400 revs/min are stirred in during reaction, temperature continues to maintain 0 ~ 5 DEG C, react after 4 hours and terminate reaction, then by water most of in reaction solution and DMF solvent evaporate to dryness,-5 ~ 0 DEG C, the mixture (volume ratio of acetone and methyl alcohol is 2:1) adding acetone and methyl alcohol at low temperatures carries out recrystallization, use washing with acetone after filtration, finally in vacuum drying oven, carry out drying treatment, obtain white crystal, find it is target molecular weight 429.13 through mass spectrometric detection, prove that it is cane sugar-6-acetic ester, output is 4.2g, transformation efficiency is 73%.
Embodiment 2:
18ml deionized water is added, 72mlDMF, 3.0ml (0.037mol) pyridine (0.037mol) in 250ml round-bottomed flask, and 4.5g (0.013mol) sucrose, mechanical stirring is cooled to 0 ~ 5 DEG C in cold well, keep 0.5 hour, after temperature-stable, 2.36ml (0.025mol) diacetyl oxide is blended in 20mlDMF solvent and is dripped by constant pressure funnel, time for adding is continuously 30 minutes, 500 revs/min are stirred in during reaction, temperature continues to maintain 0 ~ 5 DEG C, react after 5 hours and terminate reaction, then by water most of in reaction solution and DMF solvent evaporate to dryness, add acetone methanol solution (2:1)-5 ~ 0 DEG C at low temperatures and carry out recrystallization, use washing with acetone after filtration, finally in vacuum drying oven, carry out drying treatment, obtain white crystal, target molecular weight 429.13 is proved through mass spectrometric detection, cane sugar-6-acetic ester can be determined that it is, output is 3.9g, transformation efficiency is 78.1%
Embodiment 3:
30ml deionized water is added, 70mlDMF, 5.8ml (0.041mol) triethylamine in 250ml round-bottomed flask, and 6g (0.0175mol) sucrose, mechanical stirring, is cooled to 0 ~ 5 DEG C in cold well; Keep 1 hour, after temperature-stable, 3.21ml (0.034mol) diacetyl oxide is blended in 20mlDMF solvent and is dripped by constant pressure funnel, time for adding is continuously 60 minutes, 600 revs/min are stirred in during reaction, temperature continues to maintain 0 ~ 5 DEG C, react 6 hours, then by water most of in reaction solution and DMF solvent evaporate to dryness, add acetone methyl alcohol (2:1) at low temperatures and carry out recrystallization at-5 ~ 0 DEG C, use washing with acetone after filtration, finally in vacuum drying oven, carry out drying treatment.Prove target molecular weight 429.13 through mass spectrometric detection, can determine that it is cane sugar-6-acetic ester, output is 5.23g output is 5.23g.Transformation efficiency is 77.8%.
Claims (10)
1. a synthetic method for cane sugar-6-acetic ester, is characterized in that, the method comprises the steps:
(1) in the mixed solvent of water and dimethyl formamide, the mixed dissolution under 0 ~ 5 DEG C of condition by sucrose and acid binding agent;
(2) maintain the temperature condition of 0 ~ 5 DEG C, under agitation condition, drip the dimethyl formamide solution of diacetyl oxide in the mixed system of step (1) after, react 4 ~ 6 hours;
(3) after reaction terminates, underpressure distillation removing aqueous solvent and dimethyl formamide, the mixed solvent adding acetone and methyl alcohol carries out recrystallization, more after filtration, washing, drying obtain product cane sugar-6-acetic ester.
2. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (1), described acid binding agent is pyridine, triethylamine or diethylamine.
3. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (1), the volume ratio of water and dimethyl formamide is 1:3 ~ 4, and the volume of water can dissolving saccharose completely.
4. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (1), the mol ratio of sucrose and acid binding agent is 1:1 ~ 3.
5. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (2), the mol ratio of sucrose and diacetyl oxide is 1:1 ~ 2.
6. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (2), in the dimethyl formamide solution of diacetyl oxide, the concentration of diacetyl oxide is 1 ~ 2mol/L.
7. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (2), stirring velocity maintains 400 ~ 600 revs/min.
8. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (2), the time for adding of the dimethyl formamide solution of diacetyl oxide is 0.5 ~ 1 hour.
9. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (3), recrystallization temperature is-5 ~ 0 DEG C.
10. the synthetic method of cane sugar-6-acetic ester according to claim 1, is characterized in that, in step (3), wash conditions is for adopting washing with acetone.
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| CN201410169227.9A CN103936799B (en) | 2014-04-24 | 2014-04-24 | Synthesis method of sucrose-6-acetate |
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| CN201410169227.9A CN103936799B (en) | 2014-04-24 | 2014-04-24 | Synthesis method of sucrose-6-acetate |
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| CN103936799B true CN103936799B (en) | 2016-04-20 |
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| CN106946956B (en) * | 2017-03-16 | 2020-06-09 | 浙江新和成股份有限公司 | Recrystallization method and application of sucrose-6-acetate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380476A (en) * | 1980-07-08 | 1983-04-19 | Talres Development (N.A.) N.V. | Process for the preparation of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose (TGS) |
| US5023329A (en) * | 1990-04-23 | 1991-06-11 | Noramco, Inc. | Sucrose-6-ester production process |
| CN101029062A (en) * | 2007-04-09 | 2007-09-05 | 淄博联技甜味剂有限公司 | Synthesis of trichloio-sugar |
| CN101693729A (en) * | 2009-10-09 | 2010-04-14 | 李松伦 | Synthesis method of sucrose-6-acetate |
-
2014
- 2014-04-24 CN CN201410169227.9A patent/CN103936799B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4380476A (en) * | 1980-07-08 | 1983-04-19 | Talres Development (N.A.) N.V. | Process for the preparation of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose (TGS) |
| US5023329A (en) * | 1990-04-23 | 1991-06-11 | Noramco, Inc. | Sucrose-6-ester production process |
| CN101029062A (en) * | 2007-04-09 | 2007-09-05 | 淄博联技甜味剂有限公司 | Synthesis of trichloio-sugar |
| CN101693729A (en) * | 2009-10-09 | 2010-04-14 | 李松伦 | Synthesis method of sucrose-6-acetate |
Non-Patent Citations (3)
| Title |
|---|
| Feng-wu liu et al..A facile approach to anhydrogalactosucrose derivatives from chlorinated sucrose.《Carbohydrate research》.2004,第339卷第2651-2656页. * |
| 郑建仙等.单基团保护法制备三氯蔗糖的研究.《食品与发酵工业》.2001,第27卷(第9期),第1页1.2.1. * |
| 黄东雨等.三氯蔗糖合成技术的研究进展.《中国调味品》.2011,第36卷(第2期),第89-92页. * |
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