CN104774227A - Chlorination method for sucrose-6-ethyl ester - Google Patents
Chlorination method for sucrose-6-ethyl ester Download PDFInfo
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- CN104774227A CN104774227A CN201510162618.2A CN201510162618A CN104774227A CN 104774227 A CN104774227 A CN 104774227A CN 201510162618 A CN201510162618 A CN 201510162618A CN 104774227 A CN104774227 A CN 104774227A
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Abstract
The invention relates to a chlorination method for sucrose-6-ethyl ester. The chlorination method comprises the following steps: (1) respectively preparing a chlorination reagent and a solution of sucrose-6-ethyl ester from a polar non-proton solvent; (2) chlorinating the sucrose-6-ethyl ester solution by a chlorination reagent solution; (3) refluxing under reduced pressure; and (4) evaporating the polar non-proton solvent by distilling, recycling, neutralizing the sucrose-6-ethyl ester solution in a distillation kettle, removing the solvent, adding water to dissolve, discoloring and crystallizing to obtain a sucrose-6-ethyl ester crude product, wherein the recycled a polar non-proton solvent is used for the chlorination reagent solution prepared in the step (1). According to the chlorination method, generated hydrogen chloride and sulfur dioxide are discharged by refluxing under reduced pressure to promote reaction to positively perform, and the final reaction temperature is reduced to 105 DEG C which is lower than the highest holding temperature in the existing chlorination technology by 10 DEG C, so that the defects generated by carbonization in the chlorination process are completely avoided; and the used polar non-proton solvent can be recycled for a next-batch chlorination reaction process, and therefore, the chlorination method is especially suitable for industrial production.
Description
Technical field
The invention belongs to technical field of food additives, be specifically related to a kind of chlorination method of sucrose-6-ethyl ester.
Background technology
The novel sweetener that Sucralose is developed at 20 century 70s by Tate & Lyle company, its sugariness is 600 times of sucrose, is one of current sweeting agent outstanding.Trichloro-cane-6-ethyl ester is the most important intermediate of single radical protection method synthesizing trichloro; it reacts obtained under suitable conditions by sucrose-6-ethyl ester with chlorination reagent, chlorination reagent used mainly contains sulfur oxychloride, pyridine, hydrochloric ether system (see United States Patent (USP) 5136031) and Vilsmeier reagent system (see United States Patent (USP) 4380476).Wherein, it is large that Vilsmeier reagent system has steric hindrance, and selectivity is strong, the advantage that yield is higher, is applicable to suitability for industrialized production.Domestic Sucralose manufacturer substantially all adopts Vilsmeier reagent system as chlorination reagent.The reaction of Vilsmeier reagent and sucrose-6-ethyl ester is shown in United States Patent (USP) 4380476 from Mufti() report since, constantly there is the patent report of improvement, such as Chinese patent CN102964397, CN101619083 etc. report improving one's methods of chlorination, but these methods all need to add a large amount of polarity when chlorination is far weaker than N, the solvent of dinethylformamide, to accelerate the sulfur dioxide gas that release reaction generates, the forward of reaction is advanced to carry out, and the solvent of these low-poles will reduce sucrose-6-ethyl ester and the solubleness of Vilsmeier reagent complex in reaction system, end reaction temperature all must be over 110 DEG C, cause a large amount of charings, and affect the yield of final trichloro-cane-6-ethyl ester.
Summary of the invention
The object of the present invention is to provide one can avoid, in chlorination process, charing occurs and technique is more simple, solvent recuperation is more convenient, and the chlorination method of the sucrose-6-ethyl ester that cost is lower, is particularly suitable for suitability for industrialized production.
For achieving the above object, the present invention adopts following technical scheme:
A chlorination method for sucrose-6-ethyl ester, concrete steps are as follows:
1. sulfur oxychloride is mixed obtained chlorination reagent solution with polar aprotic solvent, the mass ratio of sulfur oxychloride and polar aprotic solvent is 1:1 ~ 3;
Be dissolved in by sucrose-6-ethyl ester in polar aprotic solvent and obtain sucrose-6-ethyl ester solution, its concentration is 10wt% ~ 30wt%;
2. after sucrose-6-ethyl ester solution step 1. obtained is cooled to 0 DEG C ~ 20 DEG C, add the chlorination reagent solution that 1. step obtain and carry out chlorination, period keeps temperature≤20 DEG C, wherein, the mol ratio of the sulfur oxychloride in chlorination reagent solution and the sucrose-6-ethyl ester in sucrose-6-ethyl ester solution is 5 ~ 10:1;
3. after adding chlorination reagent solution, be decompressed to 2.3 ~ 26.3kPa, temperature risen to 100 DEG C ~ 105 DEG C in 0.5 ~ 4h and carry out reduced-pressure backflow and maintain this temperature reflux 1 ~ 10h, get rid of hydrogenchloride and the sulfurous gas of chlorination generation;
4. after backflow terminates, change reaction unit into water distilling apparatus and distill, the polar aprotic solvent steamed reclaims, and 1. prepares chlorination reagent solution for step; Trichloro-cane-6-ethyl ester liquid in still kettle through neutralization, desolventizing, be dissolved in water, decolour and crystallization obtains trichloro-cane-6-ethyl ester crude product.
Preferably, described polar aprotic solvent is methane amide, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or acetonitrile.
Beneficial effect of the present invention is, technical scheme of the present invention utilizes the mixing solutions of sulfur oxychloride and polar aprotic solvent as chlorination reagent and without the need to other organic solvents, sulfur oxychloride is added in the solution of the polar aprotic solvent of sucrose-6-ethyl ester between 0 DEG C ~ 20 DEG C and carries out chlorination, the hydrogenchloride utilizing the mode of reduced-pressure backflow to make to generate and sulfurous gas are discharged, promote that reaction forward is carried out, and end reaction temperature can be reduced to 105 DEG C, lower than the highest holding temperature 10 DEG C of existing chlorination technique, completely avoid in chlorination process and occur to carbonize the drawback brought, polar aprotic solvent used can reclaim, cover is used for the chlorination process of next batch, be particularly suitable for suitability for industrialized production.
Embodiment
embodiment 1
The concrete steps of chlorinated sucrose-6-ethyl ester solution are as follows:
1. 300 kilograms of (2521mol) sulfur oxychlorides are added drop-wise to the obtained chlorination reagent solution of mixing in the polar aprotic solvent DMF of 300 kilograms, the mass ratio of sulfur oxychloride and DMF is 1:1,
Be dissolved in 300 kilograms of polar aprotic solvent DMFs by double centner (260mol) sucrose-6-ethyl ester and obtain sucrose-6-ethyl ester solution, its concentration is 25wt%;
2. after sucrose-6-ethyl ester solution step 1. obtained is cooled to 0 DEG C, add step 1. obtained chlorination reagent solution carry out chlorination, period keeps temperature≤20 DEG C, wherein, the sulfur oxychloride (2521mol) in chlorination reagent solution is 9.7:1 with the mol ratio of the sucrose-6-ethyl ester (260mol) in sucrose-6-ethyl ester solution;
3. after adding chlorination reagent solution, be decompressed to 13.3kPa, temperature risen to 105 DEG C in 2h and carry out reduced-pressure backflow and maintain this temperature reflux 2h, get rid of hydrogenchloride and the sulfurous gas of chlorination generation;
Above-mentioned pressure value is the gas relative pressure recorded with conventional vacuum table, and refer to tested gaseous tension and atmospheric difference, embodiment 2 is also identical with 3.
4. after backflow terminates, change reaction unit into water distilling apparatus to distill, the polar aprotic solvent N steamed, dinethylformamide reclaims, trichloro-cane-6-ethyl ester liquid in still kettle, by ordinary method through neutralization, desolventizing, be dissolved in water, decolour and crystallization obtains trichloro-cane-6-ethyl ester crude product 95 kilograms, its purity is 92wt%, and yield is 76.4%;
The polar aprotic solvent DMF reclaimed is used further to step and 1. prepares chlorination reagent solution.
embodiment 2:
The concrete steps of chlorinated sucrose-6-ethyl ester solution are as follows:
1. 155 kilograms of (1300mol) sulfur oxychlorides are added drop-wise to the obtained chlorination reagent solution of mixing in the polar aprotic solvent N,N-dimethylacetamide of 300 kilograms, the mass ratio of sulfur oxychloride and N,N-dimethylacetamide is 1:1.9,
Be dissolved in 500 kilograms of polar aprotic solvent N,N-dimethylacetamide by double centner (260mol) sucrose-6-ethyl ester and obtain sucrose-6-ethyl ester solution, its concentration is 16.7wt%;
2. after sucrose-6-ethyl ester solution step 1. obtained is cooled to 0 DEG C, add step 1. obtained chlorination reagent solution carry out chlorination, period keeps temperature≤20 DEG C, wherein, the sulfur oxychloride (1300mol) in chlorination reagent solution is 5:1 with the mol ratio of the sucrose-6-ethyl ester (260mol) in sucrose-6-ethyl ester solution;
3. after adding chlorination reagent solution, be decompressed to 26.3kPa, temperature risen to 100 DEG C in 1h and carry out reduced-pressure backflow and maintain this temperature reflux 4h, get rid of hydrogenchloride and the sulfurous gas of chlorination generation;
4. after backflow terminates, change reaction unit into water distilling apparatus to distill, the polar aprotic solvent N steamed, N-N,N-DIMETHYLACETAMIDE reclaims, trichloro-cane-6-ethyl ester liquid in still kettle, by ordinary method through neutralization, desolventizing, be dissolved in water, decolour and crystallization obtains trichloro-cane-6-ethyl ester crude product 90 kilograms, its purity is 93wt%, and yield is 73.2%;
The polar aprotic solvent N,N-dimethylacetamide reclaimed is used further to step and 1. prepares chlorination reagent solution.
embodiment 3:
The concrete steps of chlorinated sucrose-6-ethyl ester solution are as follows:
1. 217 kilograms of (1822mol) sulfur oxychlorides are added drop-wise to the obtained chlorination reagent solution of mixing in the polar aprotic solvent DMF of 283 kilograms, the mass ratio of sulfur oxychloride and DMF is 1:1.3,
Be dissolved in 250 kilograms of polar aprotic solvent DMFs by double centner (260mol) sucrose-6-ethyl ester and obtain sucrose-6-ethyl ester solution, its concentration is 28.6wt%;
2. after sucrose-6-ethyl ester solution step 1. obtained is cooled to 0 DEG C, add step 1. obtained chlorination reagent solution carry out chlorination, period keeps temperature≤20 DEG C, wherein, the sulfur oxychloride (1822mol) in chlorination reagent solution is 7:1 with the mol ratio of the sucrose-6-ethyl ester (260mol) in sucrose-6-ethyl ester solution;
3. after adding chlorination reagent solution, be decompressed to 2.3kPa, temperature risen to 103 DEG C in 2h and carry out reduced-pressure backflow and maintain this temperature reflux 3h, get rid of hydrogenchloride and the sulfurous gas of chlorination generation;
4. after backflow terminates, change reaction unit into water distilling apparatus to distill, the polar aprotic solvent N steamed, dinethylformamide reclaims, trichloro-cane-6-ethyl ester liquid in still kettle, by ordinary method through neutralization, desolventizing, be dissolved in water, decolour and crystallization obtains trichloro-cane-6-ethyl ester crude product 99 kilograms, its purity is 93wt%, and yield is 80.5%;
The polar aprotic solvent DMF reclaimed is used further to step and 1. prepares chlorination reagent solution.
More than display only describes principal character of the present invention and inventive point.Those skilled in the art should understand, and the present invention is not restricted to the described embodiments.Under the prerequisite not departing from inventive point and protection domain, the present invention also has various change, and these changes and improvements all will fall in the scope of protection of present invention.
Claims (2)
1. a chlorination method for sucrose-6-ethyl ester, is characterized in that, concrete steps are as follows:
1. sulfur oxychloride is mixed obtained chlorination reagent solution with polar aprotic solvent, the mass ratio of sulfur oxychloride and polar aprotic solvent is 1:1 ~ 3;
Be dissolved in by sucrose-6-ethyl ester in polar aprotic solvent and obtain sucrose-6-ethyl ester solution, its concentration is 10wt% ~ 30wt%;
2. after sucrose-6-ethyl ester solution step 1. obtained is cooled to 0 DEG C ~ 20 DEG C, add the chlorination reagent solution that 1. step obtain and carry out chlorination, period keeps temperature≤20 DEG C, wherein, the mol ratio of the sulfur oxychloride in chlorination reagent solution and the sucrose-6-ethyl ester in sucrose-6-ethyl ester solution is 5 ~ 10:1;
3. after adding chlorination reagent solution, be decompressed to 2.3 ~ 26.3kPa, temperature risen to 100 DEG C ~ 105 DEG C in 0.5 ~ 4h and carry out reduced-pressure backflow and maintain this temperature reflux 1 ~ 10h, get rid of hydrogenchloride and the sulfurous gas of chlorination generation;
4. after backflow terminates, change reaction unit into water distilling apparatus and distill, the polar aprotic solvent steamed reclaims, and 1. prepares chlorination reagent solution for step; Trichloro-cane-6-ethyl ester liquid in still kettle through neutralization, desolventizing, be dissolved in water, decolour and crystallization obtains trichloro-cane-6-ethyl ester crude product.
2. the chlorination method of sucrose-6-ethyl ester as claimed in claim 1, it is characterized in that, described polar aprotic solvent is methane amide, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or acetonitrile.
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| CN201510162618.2A CN104774227A (en) | 2015-04-08 | 2015-04-08 | Chlorination method for sucrose-6-ethyl ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734755A (en) * | 2018-12-28 | 2019-05-10 | 山东三和维信生物科技有限公司 | A kind of Sucralose crystallization processes |
| CN111548376A (en) * | 2020-05-27 | 2020-08-18 | 万华化学集团股份有限公司 | Method for preparing sucralose-6-ethyl ester |
| CN113698443A (en) * | 2021-08-17 | 2021-11-26 | 安徽金禾实业股份有限公司 | Method for preparing sucralose by purifying dichlorosucrose-6-ethyl ester from sucralose wastewater |
| CN114106065A (en) * | 2021-12-20 | 2022-03-01 | 安徽金禾实业股份有限公司 | Method for directly preparing sucralose by sucralose chlorination liquid |
Citations (3)
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| WO2008052076A2 (en) * | 2006-10-25 | 2008-05-02 | Mamtek International Limited | Process for the preparation of sucralose by the chlorination of sugar with triphosgene (btc) |
| CN101270136A (en) * | 2007-03-22 | 2008-09-24 | 常州市牛塘化工厂有限公司 | Process for preparing sucrose trichloride-6-ester |
| US20120184729A1 (en) * | 2011-01-19 | 2012-07-19 | Liang Hengbo | Method for preparing sucralose with high yield |
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2015
- 2015-04-08 CN CN201510162618.2A patent/CN104774227A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008052076A2 (en) * | 2006-10-25 | 2008-05-02 | Mamtek International Limited | Process for the preparation of sucralose by the chlorination of sugar with triphosgene (btc) |
| CN101270136A (en) * | 2007-03-22 | 2008-09-24 | 常州市牛塘化工厂有限公司 | Process for preparing sucrose trichloride-6-ester |
| US20120184729A1 (en) * | 2011-01-19 | 2012-07-19 | Liang Hengbo | Method for preparing sucralose with high yield |
Non-Patent Citations (1)
| Title |
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| 冷一欣 等: "蔗糖-6-乙酯制备三氯蔗糖的工艺", 《常州大学学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734755A (en) * | 2018-12-28 | 2019-05-10 | 山东三和维信生物科技有限公司 | A kind of Sucralose crystallization processes |
| CN111548376A (en) * | 2020-05-27 | 2020-08-18 | 万华化学集团股份有限公司 | Method for preparing sucralose-6-ethyl ester |
| CN111548376B (en) * | 2020-05-27 | 2021-06-29 | 万华化学集团股份有限公司 | Method for preparing sucralose-6-ethyl ester |
| CN113698443A (en) * | 2021-08-17 | 2021-11-26 | 安徽金禾实业股份有限公司 | Method for preparing sucralose by purifying dichlorosucrose-6-ethyl ester from sucralose wastewater |
| CN114106065A (en) * | 2021-12-20 | 2022-03-01 | 安徽金禾实业股份有限公司 | Method for directly preparing sucralose by sucralose chlorination liquid |
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Effective date of registration: 20170621 Address after: 226111, 15, Daqing Road, Qinglong Chemical Industrial Park, Haimen Development Zone, Jiangsu, Nantong Applicant after: Nantong Changhai Food Additive Co., Ltd. Address before: 213163, 51, Yan Zheng Road, Niu Tong Town, Wujin District, Jiangsu, Changzhou Applicant before: Changzhou Niutang Chemical Industry Co., Ltd. |
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Application publication date: 20150715 |