CN102942599B - A kind of method of purification of sucrose-6-ethyl ester - Google Patents
A kind of method of purification of sucrose-6-ethyl ester Download PDFInfo
- Publication number
- CN102942599B CN102942599B CN201210495120.4A CN201210495120A CN102942599B CN 102942599 B CN102942599 B CN 102942599B CN 201210495120 A CN201210495120 A CN 201210495120A CN 102942599 B CN102942599 B CN 102942599B
- Authority
- CN
- China
- Prior art keywords
- sucrose
- ethyl ester
- purification
- stir
- solid
- 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.)
- Active
Links
Landscapes
- Saccharide Compounds (AREA)
Abstract
The present invention discloses a kind of method of purification of sucrose-6-ethyl ester, and its step comprises: the first step: sucrose esterifying liquid is evaporated to dry at 50-60 DEG C, so adds at 10-60 DEG C the organic solvent that sucrose esterification liquid amasss 25-50%, separates out white solid; Second step: be warmed up to 30-40 DEG C and stir the white solid dissolving above-mentioned precipitation for 1-3 hour, be then cooled to-5-5 DEG C and stir 1-3 hour, suction filtration obtains the sucrose-6-ethyl ester powder solid filter cake of white, by solid filter cake in 40-45 DEG C of oven dry.The present invention has the following advantages: the purity of the sucrose-6-ethyl ester of the white obtained is 97%-99%; This solid is preserved at Room-temperature seal, stable in properties; Its purity is high, and impurity is few, through follow-up chlorination and alcoholysis reaction, not only reduces raw material consumption, and decreases refining number of times and difficulty; Reduce cost, improve yield, shorten the production cycle, energy-saving and emission-reduction, be more suitable for suitability for industrialized production.
Description
[technical field]
The invention belongs to chemical industry and foodstuff additive field, be specially a kind of method of purification of sucrose-6-ethyl ester.
[background technology]
Sucralose is a kind of novel high sugariness non-nutritive sweetener, and its sugariness is 600 times of sucrose.It is nontoxic, safe and reliable, in human body, do not participate in metabolism, is not absorbed by the body, and is the desirable sweet taste surrogate of diabetics; And do not utilized by carious tooth germ, do not cause carious tooth.Oneself is used as sweetening agent by more than 30 state approvals at present.
The preparation of Sucralose is successfully prepared by chemosynthesis in 1976 by Tate & Lyle company of Britain the earliest, within 1988, puts goods on the market.
It is single radical protection of raw material and full radical protection method two class that Sucralose chemical synthesis process mainly contains with sucrose.Single radical protection method is Dibutyltin oxide method disclosed in ethyl ester method and US5023329, US 4950746 disclosed in US Patent No. 4889928, US5449772.Both all utilize in sucrose molecules 6 characteristics that hydroxyl is more active; acetyl or benzoyl based selective is adopted to protect 6 hydroxyls; prepare sucrose-6-second (benzene first) ester; and then obtain Sucralose-6-second (benzene first) ester with the chlorination of Vilsmier reagent selectivity, obtain Sucralose finally by alcoholysis.Full radical protection method is as US Patent No. 4; 783; 526; US4801700; US4343934; the difference of 8 hydroxyls on sterically hindered is utilized in sucrose molecules disclosed in US4362869; with the primary hydroxyl that the group selectivity ground guard space steric hindrance that volume is larger is less; then by whole for the hydroxyl of remainder acetylize; then slough protecting group under acid conditions, 4 ethanoyl are displaced to 6, three chloro positions are met the requirements; chlorination three hydroxyls again, obtain Sucralose through hydrolysis deacetylation.
Number of patent application is the synthetic method that the Chinese invention patent application of 03126655.X discloses a kind of Sucralose, it is characterized in that taking sucrose as raw material, add N, dinethylformamide solution, sulfate solid acid catalyst or under being adsorbed on polymer carrier sulfate solid katalysis with ethyl acetate generation transesterification reaction, generate sucrose-6-ethyl ester, sucrose-6-ethyl ester generates Sucralose through chlorination, alcoholysis again.
Document: " food research and development ", " ortho ester legal system is for the research of sucrose-6-ethyl ester " of 2006.Vol.27.NO.1 is reported " purity of sucrose-6-ethyl ester reaches 93.20% ".
Existing suitability for industrialized production, by the purity of the sucrose-6-ethyl ester of trimethyl orthoacetate lactate synthesis between 70-84%; Between purity 82-90% with the sucrose-6-ethyl ester having base tin catalytic esterification to synthesize.These two kinds of techniques, in esterifying liquid, impurity is more, and without purifying, the crude product impurity that direct chlorination and alcoholysis obtain is more, and particularly containing the impurity extremely similar to Sucralose character, such crude product separating impurity is quite difficult.
[summary of the invention]
The object of the invention is to the deficiency existed for the above prior art, provide that a kind of purity is high, impurity is few, raw material consumption can be reduced, reduce refining number of times and difficulty, reduce costs, improve yield, shorten the production cycle, energy-saving and emission-reduction and be more suitable for the method for purification of the sucrose-6-ethyl ester of suitability for industrialized production.
To achieve these goals, the present invention is achieved in that a kind of method of purification of sucrose-6-ethyl ester, and its step comprises:
The first step: sucrose esterifying liquid is evaporated to dry at 50-60 DEG C, so adds at 10-60 DEG C the organic solvent that sucrose esterification liquid amasss 25-50%, separates out white solid;
Second step: be warmed up to 30-40 DEG C and stir the white solid dissolving above-mentioned precipitation for 1-3 hour, is then cooled to-5-5 DEG C and stirs 1-3 hour, make crystallization complete.Suction filtration obtains the sucrose-6-ethyl ester solid filter cake of white, and by solid filter cake in 40-45 DEG C of oven dry, HPLC detects, and its purity is 97%-99%.
After separating out white solid in the described the first step, add at 28-30 DEG C the organic solvent that sucrose esterification liquid amasss 25-50%, be then warmed up to 30-40 DEG C.
The temperature range adding organic solvent in the described the first step is 20-25 DEG C.
Described organic solvent comprises organic acid solvent and alcoholic solvent, and described organic acid solvent comprises formic acid, acetic acid, propionic acid, butyric acid and valeric acid etc.; Described alcoholic solvent comprises the Organic Alcohols such as methyl alcohol, ethanol, Virahol and propyl alcohol.
Compared with prior art, the present invention has the following advantages: the sucrose-6-ethyl ester powder solid that can obtain white, and its purity is 97%-99%; This solid is preserved at Room-temperature seal, stable in properties; And its purity is high, impurity is few, through follow-up chlorination and alcoholysis reaction, not only reduce raw material consumption, and reduce refining number of times and difficulty; Reduce costs, improve yield, shorten the production cycle, energy-saving and emission-reduction, are more suitable for suitability for industrialized production.
[embodiment]
Below in conjunction with specific embodiment, explanation is described in detail to the present invention.
A method of purification for sucrose-6-ethyl ester purity, its step is as follows:
The first step: sucrose esterification hydraulic control temperature 50-60 DEG C is evaporated to dry, 10-60 DEG C adds organic acid solvent and the alcoholic solvent (or other organic solvents) that sucrose esterification liquid amasss 25-50%, produces a large amount of white solid in feed liquid.
Second step: continue to stir at 30-40 DEG C the white solid dissolving above-mentioned precipitation for 2 hours, then be cooled to-5-5 DEG C and stir 1-3 hour, suction filtration obtains the sucrose-6-ethyl ester powder solid filter cake of white, by solid filter cake in 40-45 DEG C of oven dry, HPLC detects, and its purity is 97%-99%.
Described organic solvent comprises organic acid solvent and alcoholic solvent, and described organic acid solvent comprises formic acid, acetic acid, propionic acid, butyric acid and valeric acid etc.; Described alcoholic solvent comprises the Organic Alcohols such as methyl alcohol, ethanol, Virahol and propyl alcohol.
Wherein, the preparation of sucrose esterifying liquid: drop into 50g sucrose in there-necked flask, adding weight ratio is 4-5 DMF doubly, opens and stirs.Be warming up to 50 DEG C, 50 ± 1 DEG C of insulated and stirred are dissolved for 2 hours.Be cooled to 28 DEG C, add the tosic acid of sucrose weight 1%, stir 10 minutes, add the trimethyl orthoacetate of 30g.35 ± 1 DEG C of insulation reaction 3 hours.Add sucrose weight 1.6-2.4 water doubly, stir 1.5 hours, then add the TERTIARY BUTYL AMINE of sucrose weight 8-12%, within 1.5 hours, obtain sucrose esterifying liquid in 28 DEG C ~ 40 DEG C insulation reaction.Esterifying liquid temperature control 50-60 DEG C is evaporated to dry, for subsequent use, is called " resistates after concentrated ".
Embodiment 1
Above-mentioned concentrated after resistates add 100ml Glacial acetic acid at 25-28 DEG C, stir, there is a large amount of white solid to generate, then add 100ml methyl alcohol at 25-28 DEG C, be warming up to 30-40 DEG C and stir 2 hours, be cooled to 3-5 DEG C of stirring and crystallizing 2 hours, suction filtration, obtains the sucrose-6-ethyl ester solid of white, obtains sucrose-6-ethyl ester in 40-45 DEG C of oven dry, yield 82.6%, HPLC purity 98.7%.
Embodiment 2
Above-mentioned concentrated after resistates add 110ml Glacial acetic acid at 30-32 DEG C, stir, there is a large amount of white solid to generate, then add 150ml ethyl acetate at 30-32 DEG C, be warming up to 30-40 DEG C and stir 2 hours, be cooled to 0 DEG C of stirring and crystallizing 3 hours, suction filtration, obtains the sucrose-6-ethyl ester solid of white, obtains sucrose-6-ethyl ester in 40-45 DEG C of oven dry, yield 90.1%, HPLC purity 97.0%.
Embodiment 3
Above-mentioned concentrated after resistates add 100ml Glacial acetic acid at 20-25 DEG C, stir, there is a large amount of white solid to generate, then add 100mlDMF at 20-25 DEG C, be warming up to 30-40 DEG C and stir 2 hours, be cooled to-5--2 DEG C of stirring and crystallizing 3 hours, suction filtration, obtains the sucrose-6-ethyl ester solid of white, obtains sucrose-6-ethyl ester in 40-45 DEG C of oven dry, yield 84.1%, HPLC purity 97.6%.
Embodiment 4
Above-mentioned concentrated after resistates add 150ml Glacial acetic acid at 28-30 DEG C, stir, have a large amount of white solid to generate, then add 100ml methyl alcohol at 28-30 DEG C, be warming up to 30-40 DEG C to stir 2 hours, be cooled to 2-3 DEG C of stirring and crystallizing 3 hours, suction filtration, obtain the sucrose-6-ethyl ester solid of white, sucrose-6-ethyl ester is obtained, yield 80.6%, HPLC purity 99.1% in 40-45 DEG C of oven dry.
Embodiment 5
Above-mentioned concentrated after resistates add 100ml methyl alcohol at 10-12 DEG C, stir, 100ml Glacial acetic acid is added again at 10-12 DEG C, be warming up to 30-40 DEG C to stir 2 hours, be cooled to-1-2 DEG C of stirring and crystallizing 2.5 hours, suction filtration, obtain the sucrose-6-ethyl ester solid of white, sucrose-6-ethyl ester is obtained, yield 82.1%, HPLC purity 98.6% in 40-45 DEG C of oven dry.
Embodiment 6
Above-mentioned concentrated after resistates add 90ml formic acid at 55-60 DEG C, stir, there is a large amount of white solid to generate, then add 100ml ethanol at 55-60 DEG C, be cooled to 30-40 DEG C and stir 2 hours, be cooled to-2-0 DEG C of stirring and crystallizing again 3 hours, suction filtration, obtains the sucrose-6-ethyl ester solid of white, obtains sucrose-6-ethyl ester in 40-45 DEG C of oven dry, yield 83.3%, HPLC purity 97.5%.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention; a described example wish is as the single example of illustrating all respects of the present invention; without departing from the spirit and scope of the present invention; also comprise the various changes and modifications of functional equivalent in the scope of the invention, these changes and improvements all fall within the claimed scope of the invention.
Claims (5)
1. a method of purification for sucrose-6-ethyl ester, is characterized in that, step comprises:
The first step: be evaporated to dry at 50-60 DEG C by sucrose esterifying liquid, then adds at 10-60 DEG C the organic solvent that sucrose esterification liquid amasss 25-50%, separates out white solid;
Second step: be warmed up to 30-40 DEG C and stir the white solid dissolving above-mentioned precipitation for 1-3 hour, then be cooled to-5-5 DEG C and stir 1-3 hour, make crystallization complete, suction filtration obtains the sucrose-6-ethyl ester solid filter cake of white, by solid filter cake in 40-45 DEG C of oven dry, HPLC detects, and its purity is 97%-99%;
Described organic solvent comprises organic acid solvent and alcoholic solvent.
2. according to the method for purification of a kind of sucrose-6-ethyl ester according to claim 1, it is characterized in that, after separating out white solid in the described the first step, add at 28-30 DEG C the organic solvent that sucrose esterification liquid amasss 25-50%, and then be warmed up to 30-40 DEG C.
3. according to the method for purification of a kind of sucrose-6-ethyl ester according to claim 1, it is characterized in that, the temperature range adding organic solvent in the described the first step is 20-25 DEG C.
4. according to the method for purification of a kind of sucrose-6-ethyl ester according to claim 1, it is characterized in that, described organic acid solvent is selected from formic acid, acetic acid, propionic acid, butyric acid and valeric acid.
5. according to the method for purification of a kind of sucrose-6-ethyl ester according to claim 1, it is characterized in that, described alcoholic solvent is selected from methyl alcohol, ethanol, Virahol and propyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210495120.4A CN102942599B (en) | 2012-11-28 | 2012-11-28 | A kind of method of purification of sucrose-6-ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210495120.4A CN102942599B (en) | 2012-11-28 | 2012-11-28 | A kind of method of purification of sucrose-6-ethyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102942599A CN102942599A (en) | 2013-02-27 |
| CN102942599B true CN102942599B (en) | 2015-08-26 |
Family
ID=47725610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210495120.4A Active CN102942599B (en) | 2012-11-28 | 2012-11-28 | A kind of method of purification of sucrose-6-ethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942599B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749440B (en) * | 2016-12-07 | 2019-07-02 | 广西科技大学 | A kind of method for crystallising by sucrose and ortho-acetate synthesizing cane sugar-6-acetic ester |
| CN109593107A (en) * | 2018-12-10 | 2019-04-09 | 安徽金禾实业股份有限公司 | A kind of method of purification of cane sugar-6-acetic ester |
| CN111592574A (en) * | 2020-05-22 | 2020-08-28 | 安徽金禾实业股份有限公司 | Industrial refining method of sucrose-6-acetate |
| CN113214330A (en) * | 2021-05-13 | 2021-08-06 | 安徽金禾化学材料研究所有限公司 | Purification and chlorination process of sucrose-6-ethyl ester |
| CN114437146B (en) * | 2022-01-10 | 2023-12-08 | 福州大学 | Production process of sucralose-6-acetate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4362869A (en) * | 1907-12-02 | 1982-12-07 | Talres Development (N.A.) N.V. | Process for the preparation of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose |
| US4889928A (en) * | 1986-09-17 | 1989-12-26 | Tate & Lyle Public Limited Company | Sucrose alkyl 4,6-orthoacylates |
| CN101293902A (en) * | 2007-04-25 | 2008-10-29 | 吉安市新琪安科技有限公司 | Process for synthesizing sucrose-6- ethyl ester |
-
2012
- 2012-11-28 CN CN201210495120.4A patent/CN102942599B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4362869A (en) * | 1907-12-02 | 1982-12-07 | Talres Development (N.A.) N.V. | Process for the preparation of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose |
| US4889928A (en) * | 1986-09-17 | 1989-12-26 | Tate & Lyle Public Limited Company | Sucrose alkyl 4,6-orthoacylates |
| CN101293902A (en) * | 2007-04-25 | 2008-10-29 | 吉安市新琪安科技有限公司 | Process for synthesizing sucrose-6- ethyl ester |
Non-Patent Citations (2)
| Title |
|---|
| 原酸酯法制备蔗糖-6-乙酸酯的研究;陆正清，等;《食品研究与开发》;20060228;第127卷(第01期);20-22 * |
| 蔗糖-6-乙酯的制备及提纯;林富荣，等;《化学试剂》;20101130;第32卷(第11期);1054-1056 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102942599A (en) | 2013-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102942599B (en) | A kind of method of purification of sucrose-6-ethyl ester | |
| CN101245085B (en) | Technique for synthesizing and purifying sucrose trichloride | |
| CN102827891B (en) | Method for preparing steviol by carrying out catalytic hydrolysis on stevioside by beta-glucosidase | |
| CN102181494A (en) | Synthesis of sucrose-6-fatty acid ester through selective catalysis of immobilized aspergillus oryzae lipase | |
| CN1176094C (en) | Synthesis of trichlorosucrose | |
| CN101735123A (en) | Method for synthesizing valnemulin hydrochloride | |
| CN102558559A (en) | Method of synthetizing small molecule hydroxyl silicone oil through using continuation method | |
| CN109180627B (en) | Semi-synthesis method of diosmetin | |
| CN100395251C (en) | Sucralose synthesis method | |
| CN110669082B (en) | Purification and separation method of N-acetyl-D-glucosamine | |
| CN104672291B (en) | A kind of preparation method of gallic acid plant sterol ester | |
| CN103554196A (en) | Crystallization method of sucrose-6-acetate | |
| CN101302244B (en) | Production process of betulinic acid | |
| CN103709209B (en) | The preparation method of isopropyl-β-D-thiogalactoside | |
| CN104725443B (en) | A kind of method that rebaudioside A is purified by Reaction Separation | |
| CN104086608A (en) | High-efficiency synthesis method of natural product glucan pentasaccharide | |
| CN101792780B (en) | Separation method of D-glucuronic acid gamma-lactone | |
| CN110483316B (en) | Asymmetric synthesis method of L-carnitine | |
| CN103709210B (en) | The preparation technology of isopropyl-β-D-thiogalactoside | |
| CN102618593B (en) | Method for preparing scutellarin by using Aspergillus niger AS 3.795 for hydrolyzing scutellarin-7-O-glucuronide | |
| CN103012524B (en) | Semisynthetic method for preparing rhoifolin | |
| CN102863511B (en) | Neotame preparation method | |
| CN102942602B (en) | The preparation method of o-nitrophenyl galactoside | |
| CN105732547A (en) | Preparation method of dehydrated andrographolide diacid half ester basic salt | |
| CN115677806B (en) | Acetylspiramycin and synthesis method thereof |
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 |