WO2004104016A1 - Procede de preparation de 4,1',6'-trichloro-4,1',6'-tridesoxygalactosaccharose - Google Patents

Procede de preparation de 4,1',6'-trichloro-4,1',6'-tridesoxygalactosaccharose Download PDF

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Publication number
WO2004104016A1
WO2004104016A1 PCT/CN2003/000655 CN0300655W WO2004104016A1 WO 2004104016 A1 WO2004104016 A1 WO 2004104016A1 CN 0300655 W CN0300655 W CN 0300655W WO 2004104016 A1 WO2004104016 A1 WO 2004104016A1
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WIPO (PCT)
Prior art keywords
sucrose
acid catalyst
sulfate
acetate
solid acid
Prior art date
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Ceased
Application number
PCT/CN2003/000655
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English (en)
Chinese (zh)
Inventor
Sanyong Wang
Chunrong Li
Ye Li
Ganxing Cao
Wen Huang
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FOOD INDUSTRY INSTITUTE OF GUANGDONG PROVINCE
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FOOD INDUSTRY INSTITUTE OF GUANGDONG PROVINCE
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by FOOD INDUSTRY INSTITUTE OF GUANGDONG PROVINCE filed Critical FOOD INDUSTRY INSTITUTE OF GUANGDONG PROVINCE
Priority to AU2003257786A priority Critical patent/AU2003257786A1/en
Publication of WO2004104016A1 publication Critical patent/WO2004104016A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
    • C07H5/02—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to halogen

Definitions

  • the invention relates to a method for synthesizing sucralose, a food sweetener.
  • Sucralose chemical name 4, 1 ', 6'-trichloro-1, 4, 1', 6'-trideoxygalactose, its structural formula is:
  • Sucralose is 600 times sweeter than sucrose and has been approved as a food sweetener in more than 20 countries.
  • the preparation methods of sucralose are generally divided into two categories: single group protection method and full group protection method.
  • the all-group protection method (such as described in US Patents US4801700, US4783526, and US4362869) has a complicated process and has no industrial production value.
  • the hydroxyl group at the 6-position is more active than the hydroxyl group at other positions.
  • the core of the single-group protection method is the preparation of sucrose-6-acetate.
  • the structural formula of sucrose-6-acetate is:
  • sucrose-6-acetate There are two main methods for synthesizing sucrose-6-acetate: the ethyl acetate method (as described in US Patent No. 4,889,928,5,449,772) and the dibutyltin oxide method (as described in US Patent 5,023). , 329, 4, 950, 746), sucrose-6-acetate is reacted with Vilsmeier reagent to obtain sucralose-6-acetate, and finally the product sucralose is obtained by deacetylation reaction.
  • These synthetic methods have certain advancements, but also have certain limitations, such as complex processes and high production costs. Summary of the invention
  • the purpose of the present invention is to provide a new method for synthesizing sucralose.
  • the method has simple process and low production cost.
  • the invention provides a method for synthesizing sucralose, which is characterized in that sucrose is used as a raw material, an N, N-dimethylformamide solution is added, and a sulfate solid acid catalyst or a sulfate solid adsorbed on a polymer carrier is added.
  • the transesterification reaction with ethyl acetate under the action of an acid catalyst produces sucrose-6-acetate, and sucrose-6-acetate is chlorinated and alcoholylated to form sucralose.
  • sucrose molecules and ethyl acetate can selectively form sucrose-6-acetate under the action of certain catalysts, and this selectivity is above 70%, and even above 85%.
  • These catalysts are actually some solid acid catalysts, also called Lewies acids in organic chemistry. Industrially, such solid acids are sometimes adsorbed on a polymer carrier, such as silica gel.
  • These solid acid catalysts are iron sulfate, cerium sulfate, zinc chloride, aluminum chloride, zirconium chloride, and the like. In the present invention, cerium sulfate and cerium sulfate absorbed on silica gel are preferred as a catalyst for the reaction.
  • sucrose-6-acetate obtained by the present invention is usually above 80%, and it can directly react with a variety of chlorinating reagents.
  • the Dahlsmeier reagent is preferred in the present invention to produce sucralose-6-acetate.
  • the sucralose is produced by alcoholysis reaction. Sodium methoxide I methanol or sodium ethoxide I ethanol system is used for the alcoholysis reaction. The total reaction yield is above 18% (based on sucrose).
  • the present invention Compared with the existing methods for synthesizing sucralose, the present invention has the advantages of simple process, high product purity, low production cost, and the like, and is very suitable for industrial production.
  • sucralose-6-acetate 50g was dried in a vacuum, and then added to a 1000ml three-necked flask, while 400ml of anhydrous methanol was added. After heating and dissolving, 1.7ml of a 27% sodium methoxide methanol solution was added and reacted at room temperature. 5 hours, after the reaction is completed, neutralize with a weakly acidic resin to a pH of 7, and evaporate the methanol in vacuo to obtain 42.5 g of sugar. The syrup can be purified by simple purification to obtain about 39.7 g, with a purity of 99% of three. Closucrose product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Saccharide Compounds (AREA)

Abstract

L'invention concerne un procédé de préparation de 4,1',6'-trichloro-4,1',6'-tridésoxygalactosaccharose consistant à ajouter un saccharose brut dans un N,N-diméthylformamide, à réaliser une transestérification entre le saccharose et l'éthylacétate en présence d'un catalyseur acide solide de sulfate ou d'un catalyseur acide solide de sulfate absorbé sur un support polymère, à produire du 6-acylate de saccharose, à chlorer le 6-acylate de saccharose, à opérer une réaction d'alcoolyse et à obtenir le 4,1',6'-trichloro-4,1',6'-tridésoxygalactosaccharose. L'invention se caractérise avantageusement par un procédé simple, un produit à pureté élevée et un faible coût, et convient particulièrement à une production industrielle.
PCT/CN2003/000655 2003-05-23 2003-08-11 Procede de preparation de 4,1',6'-trichloro-4,1',6'-tridesoxygalactosaccharose Ceased WO2004104016A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003257786A AU2003257786A1 (en) 2003-05-23 2003-08-11 Process for the preparation of 4, 1', 6'-trichloro-4, 1', 6'-trideoxygalactosucrose

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN03126655.X 2003-05-23
CNB03126655XA CN1176094C (zh) 2003-05-23 2003-05-23 一种三氯蔗糖的合成方法

Publications (1)

Publication Number Publication Date
WO2004104016A1 true WO2004104016A1 (fr) 2004-12-02

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2003/000655 Ceased WO2004104016A1 (fr) 2003-05-23 2003-08-11 Procede de preparation de 4,1',6'-trichloro-4,1',6'-tridesoxygalactosaccharose

Country Status (3)

Country Link
CN (1) CN1176094C (fr)
AU (1) AU2003257786A1 (fr)
WO (1) WO2004104016A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008052077A3 (fr) * 2006-10-25 2008-07-31 Mamtek Int Ltd Procédé de préparation de sucrose-6-ester par estérification en présence d'un catalyseur superacide solide
US7884203B2 (en) * 2006-03-06 2011-02-08 Jk Sucralose Inc. Method of sucralose synthesis yield
US7910727B2 (en) 2006-04-03 2011-03-22 Techno (Guangzhou) Food Ingredients Co., Ltd. Process for the preparation of sucralose
US8258291B2 (en) 2006-10-25 2012-09-04 Mamtek International Limited Process for the preparation of sucralose by the chlorination of sugar with triphosgene (BTC)
WO2016127543A1 (fr) * 2015-02-11 2016-08-18 大连民族学院 Vecteur de gène cationique de type ester de saccharose et son procédé de préparation

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1312164C (zh) * 2003-09-23 2007-04-25 李宝才 单酯法合成三氯蔗糖的方法
CN100567319C (zh) * 2006-07-12 2009-12-09 上海迪赛诺维生素有限公司 一种三氯蔗糖的结晶方法
CN100420697C (zh) 2006-08-30 2008-09-24 河北苏科瑞科技有限公司 一种制备蔗糖-6-有机酸酯的方法
CN101029062B (zh) * 2007-04-09 2011-06-15 淄博联技甜味剂有限公司 三氯蔗糖的合成工艺
GB2474311B (en) * 2009-10-12 2012-10-17 Tate & Lyle Technology Ltd Low temperature, single solvent process for the production of sucrose-6-ester
CN102002078B (zh) * 2010-11-17 2012-05-30 广西工学院 一种连续制备蔗糖-6-乙酸酯的方法
CN102816188B (zh) * 2012-08-13 2015-05-13 南通市常海食品添加剂有限公司 三氯蔗糖的生产工艺
CN104098617A (zh) * 2013-04-08 2014-10-15 南京工业大学 一种蔗糖-6-乙酸酯的制备方法
CN104387427A (zh) * 2014-10-30 2015-03-04 安徽金禾实业股份有限公司 一种三氯蔗糖的生产方法
CN105646602A (zh) * 2016-03-04 2016-06-08 李云军 一种三氯蔗糖-6-乙酸酯的脱酰方法
CN105707832A (zh) * 2016-03-07 2016-06-29 李云军 一种蔗糖素甜味剂
CN105859802B (zh) * 2016-05-14 2019-02-12 广西科技大学 一种三氯蔗糖的结晶和纯化方法
CN108997259B (zh) * 2018-08-31 2020-05-05 山东亚邦化工科技有限公司 用于合成甜味剂安赛蜜或三氯蔗糖母液脱色的工艺和装置
CN112574258A (zh) * 2020-12-02 2021-03-30 安徽金禾实业股份有限公司 一种控制三氯蔗糖酸味的方法

Citations (7)

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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)
US4801700A (en) * 1985-10-21 1989-01-31 Mcneilab, Inc. Process for the preparation of 1,6-dichloro-1,6-dideoxy-β-D-fructofuranosyl-4-chloro-4-deoxy-α-
US4889928A (en) * 1986-09-17 1989-12-26 Tate & Lyle Public Limited Company Sucrose alkyl 4,6-orthoacylates
US4950746A (en) * 1988-07-18 1990-08-21 Noramco, Inc. Process for synthesizing sucrose derivatives by regioselective reaction
US4980463A (en) * 1989-07-18 1990-12-25 Noramco, Inc. Sucrose-6-ester chlorination
US5023329A (en) * 1990-04-23 1991-06-11 Noramco, Inc. Sucrose-6-ester production process
US5449772A (en) * 1991-05-21 1995-09-12 Tate & Lyle Public Ltd. Co. Continuous process for the preparation of sucrose 6-esters

Patent Citations (7)

* Cited by examiner, † Cited by third party
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)
US4801700A (en) * 1985-10-21 1989-01-31 Mcneilab, Inc. Process for the preparation of 1,6-dichloro-1,6-dideoxy-β-D-fructofuranosyl-4-chloro-4-deoxy-α-
US4889928A (en) * 1986-09-17 1989-12-26 Tate & Lyle Public Limited Company Sucrose alkyl 4,6-orthoacylates
US4950746A (en) * 1988-07-18 1990-08-21 Noramco, Inc. Process for synthesizing sucrose derivatives by regioselective reaction
US4980463A (en) * 1989-07-18 1990-12-25 Noramco, Inc. Sucrose-6-ester chlorination
US5023329A (en) * 1990-04-23 1991-06-11 Noramco, Inc. Sucrose-6-ester production process
US5449772A (en) * 1991-05-21 1995-09-12 Tate & Lyle Public Ltd. Co. Continuous process for the preparation of sucrose 6-esters

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7884203B2 (en) * 2006-03-06 2011-02-08 Jk Sucralose Inc. Method of sucralose synthesis yield
US7910727B2 (en) 2006-04-03 2011-03-22 Techno (Guangzhou) Food Ingredients Co., Ltd. Process for the preparation of sucralose
US8147672B2 (en) 2006-04-03 2012-04-03 Techno Food Ingredients Co., Ltd. Process for the preparation of sucralose
WO2008052077A3 (fr) * 2006-10-25 2008-07-31 Mamtek Int Ltd Procédé de préparation de sucrose-6-ester par estérification en présence d'un catalyseur superacide solide
JP2010508286A (ja) * 2006-10-25 2010-03-18 マムテック インターナショナル リミテッド 固体の超酸触媒の存在下におけるエステル化によるスクロース−６−エステルの製造方法
US8258291B2 (en) 2006-10-25 2012-09-04 Mamtek International Limited Process for the preparation of sucralose by the chlorination of sugar with triphosgene (BTC)
WO2016127543A1 (fr) * 2015-02-11 2016-08-18 大连民族学院 Vecteur de gène cationique de type ester de saccharose et son procédé de préparation
US10279050B2 (en) 2015-02-11 2019-05-07 Dalian Nationalities University Sucrose ester based cationic gene vector and preparation method thereof

Also Published As

Publication number Publication date
CN1176094C (zh) 2004-11-17
CN1453284A (zh) 2003-11-05
AU2003257786A1 (en) 2004-12-13

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