WO1999060006A1 - Method of preparation 4,1´,6´-trichloro-4,1´,6´-trideoxygalactosucrose - Google Patents
Method of preparation 4,1´,6´-trichloro-4,1´,6´-trideoxygalactosucrose Download PDFInfo
- Publication number
- WO1999060006A1 WO1999060006A1 PCT/BY1999/000001 BY9900001W WO9960006A1 WO 1999060006 A1 WO1999060006 A1 WO 1999060006A1 BY 9900001 W BY9900001 W BY 9900001W WO 9960006 A1 WO9960006 A1 WO 9960006A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sucrose
- pyridine
- reaction
- hours
- temperature
- Prior art date
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Classifications
-
- 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- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/02—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to halogen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 the method of preparation 4, 1 ', 6'- trichloro - 4, 1 ', 6'- trideoxygalactosucrose which can be used as a sugar ingredient (sweetener) of increased sweetness particularly in food and pharmaceutical industries.
- sweetening agent is a natural carbohydrate known as sucrose.
- UK patent J ⁇ ° 1543167 describes chloro- substituted derivatives of sucrose for use in food and pharmaceutical products with 4, 1 ', 6'- trichloro - 4, 1 ', 6'- trideoxygalactosucrose in this group having the most considerable degree of sweetness.
- the chemical compound described represents crystalline substance of white colour being 400- 800 times as sweet as sucrose and featuring good water solubility high stability and good taste (Food Technology, January 1989, p.60- 63). Its hydrolysis when in human organism is very slow yielding monosaccharide residues, it has no toxic effects, doesn't interact with other food products and has law energy content.
- the desired product thus prepared is of 99% purity with an overall yield of 5%. Since the abovementioned method doesn't satisfy technological requirements due to low yield of the desired product and the presence of separation stage (stage b) the aim of this invention is working out of the industrial method of preparation 4, 1 ', 6'- trichloro - 4, 1 ', 6'- trideoxygalactosucrose which doesn't have the abovementioned disadvantages.
- the target aimed has been achieved by the invention filed herein.
- a method of preparation of 4, V, 6'- trichloro - 4, 1 ', 6'- trideoxygalactosucrose with sucrose as the base material consisting in selective acetylation of sucrose in pyridine, chlorination of monoacetylated product in Vilsmeier reagent, peracylation of the chloroderivative in pyridine with the de- esterification and isolation of the disired product to follow.
- the most preferred conditions for the acetylation stage are the following: the weight of the pyridine excess being 10- times as that of sucrose, conducting the reaction at room temperature and recurring back to the pyridine process with the pyridine removed from the reaction zone by an off- distillation with freezing.
- the preferred condition for preparation of Vilsmeier reagent is the reaction of phosphorus pentachloride with dimethylformamide (DMF) at the temperature of 0- 25 °C in the absence of moisture. Chlorihation is preferably conducted at gradual addition of sucrose 6- monoacetate solution in DMF to the prepared solution of Vilsmeier reagent, the temperature being maintained below 20°C with the following heating of the reaction to 108- 1 10°C for min. 1,5 hours. Chlorination is conducted for the mixture of products received at the stage of direct acetylation without chromatographic separation of the mixture on ion- exchange resin. Peracylation is conducted by acetic anhydride in pyridine preferably at the temperature of50°C for 1,5- 2,5 hours.
- DMF dimethylformamide
- Deacylation is provided by sodium methoxide in alcohol at room temperature for min. four hours at PH 8,8- 9,0 with the following neutralization of the reaction by the ion- exchange resin in H-" .
- the total yield is 60% at 85% purity.
- Sucrose (food sugar) (HOg) is dissolved in pyridine (1100 ml) at boiling for 20 minutes The solution is cooled to room temperature and acetic anhydride added (33 ml) The reaction is maintained at room temperature for 1 hour After an ofF- distillation of pyridine in vacuum (freezing out in a trap) a syrup thus prepared consists of the mixture of nonreacted sucrose, mono- and diacetates of sucrose Nonreacted sucrose is separated by its crystallization from alcoholic solution of acetylation product According to the data of thin - layer chromatography (CHCL, MEOH- 2 1) the content of 6- acetate sucrose in the mixture is 60- 65% 125,5 g of a syrup contain 65 g of 6- 0- Ac- sucrose.
- CHCL, MEOH- 2 thin - layer chromatography
- Dimethylformamide (DMF) (490 ml) is cooled to 0°C in the reaction vessel
- phosphorus pentachloride (PCL 5 ) (344 g) is added vigorous stirring with the temperature being maintained below 20°C
- the reaction is held at 0°C for one hour
- the crystals of Vilsmeier reagent thus prepeared are filtered out and washed with DMF (2X35 ml) and ether (60 ml)
- the total yield is 260 g
- Chlorination of 6- 0 -Ac- sucrose Vilsmeier reagent is diluted with DMF (270 ml)in the reaction vessel equipped with a stirrer, a thermometer, a drying tube and a cooling both The solution is cooled to 0 C.
- sucrose acetylation products containing mainly sucrose 6- acetate after separation of nonreacted sucrose, as is described in Example 1, is chlorinated with Vilsmeier reagent prepared under conditions described in Example 1
- a suspended residue without filtering from the reaction is dissolved in dry DMF
- the suspension cooled to 0°C is added with the solution of 6- 0- Ac- sucrose and the chlorination process as well as the subsequent stages of the end product preparation are conducted under the conditions described in example 1
- the yield of 4, 1 ', 6'- trichloro - 4, 1 ', 6'- trideoxygalactosucrose is -50%
- a solid product is filtered out and dried.
- the yield is 60 g of pentaacetate 4, 1', 6'- trichloro - 4, 1 ', 6'- trideoxygalactosucrose which is deacetylated according to the method described in Example 2
- the yield of 4, 1 ', 6'- trichloro - 4, 1', 6'- trideoxygalactosucrose is 60%
- Chlorination is conducted using the mixture of sucrose selective vacetylation products derived according to the method described in Example 1, without separation of nonreacted sucrose
- the chlorination process and other stages of end product preparation are conducted according to the methods described in Example 2
- the yield of 4, 1', 6'- trichloro - 4, 1', 6'- trideoxygalactosucrose is 48 %
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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
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99900192A EP1076661A1 (en) | 1998-05-15 | 1999-01-04 | Method of preparation of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose |
AU18648/99A AU1864899A (en) | 1998-05-15 | 1999-01-04 | Method of preparation 4,1,6-trichloro-4,1,6-trideoxygalactosucrose |
UA2000127166A UA58595C2 (en) | 1998-05-15 | 1999-04-01 | process for preparation OF 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BY19980472 | 1998-05-15 | ||
BY19980472 | 1998-05-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999060006A1 true WO1999060006A1 (en) | 1999-11-25 |
Family
ID=4083724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/BY1999/000001 WO1999060006A1 (en) | 1998-05-15 | 1999-01-04 | Method of preparation 4,1´,6´-trichloro-4,1´,6´-trideoxygalactosucrose |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1076661A1 (en) |
AU (1) | AU1864899A (en) |
RU (1) | RU2217435C2 (en) |
UA (1) | UA58595C2 (en) |
WO (1) | WO1999060006A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1905838A1 (en) * | 2006-09-29 | 2008-04-02 | DSMIP Assets B.V. | Enzymatic regioselective 6-acylation of sucrose |
WO2008084498A1 (en) * | 2007-01-08 | 2008-07-17 | V. B. Medicare Pvt. Ltd. | Decolorization of process streams by chemical oxidation in the manufacture of trichlorogalactosucrose |
WO2008096928A1 (en) * | 2007-02-07 | 2008-08-14 | Ilshin Chemical Co., Ltd | Method of producing sucralose |
EP2094873A2 (en) * | 2006-10-25 | 2009-09-02 | Mamtek International Limited | Process for the preparation of sucralose by the chlorination of sugar with triphosgene (btc) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1543167A (en) * | 1976-01-08 | 1979-03-28 | Tate & Lyle Ltd | Sweeteners |
GB2079749A (en) * | 1980-07-08 | 1982-01-27 | Tate & Lyle Ltd | Process for the preparation of 4,1',6'-trichloro-4,1',6'- trideoxygalactosucrose |
EP0356304A2 (en) * | 1988-08-10 | 1990-02-28 | Eridania Beghin-Say | Process for the preparation of 4,1',6'-trichloro-4,1',6'-tridesoxy-galactosaccharose |
EP0409549A2 (en) * | 1989-07-18 | 1991-01-23 | Noramco, Inc. | Improved sucrose-6-ester chlorination |
-
1999
- 1999-01-04 EP EP99900192A patent/EP1076661A1/en not_active Withdrawn
- 1999-01-04 RU RU2000131192/04A patent/RU2217435C2/en not_active IP Right Cessation
- 1999-01-04 WO PCT/BY1999/000001 patent/WO1999060006A1/en not_active Application Discontinuation
- 1999-01-04 AU AU18648/99A patent/AU1864899A/en not_active Abandoned
- 1999-04-01 UA UA2000127166A patent/UA58595C2/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1543167A (en) * | 1976-01-08 | 1979-03-28 | Tate & Lyle Ltd | Sweeteners |
GB2079749A (en) * | 1980-07-08 | 1982-01-27 | Tate & Lyle Ltd | Process for the preparation of 4,1',6'-trichloro-4,1',6'- trideoxygalactosucrose |
EP0356304A2 (en) * | 1988-08-10 | 1990-02-28 | Eridania Beghin-Say | Process for the preparation of 4,1',6'-trichloro-4,1',6'-tridesoxy-galactosaccharose |
EP0409549A2 (en) * | 1989-07-18 | 1991-01-23 | Noramco, Inc. | Improved sucrose-6-ester chlorination |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1905838A1 (en) * | 2006-09-29 | 2008-04-02 | DSMIP Assets B.V. | Enzymatic regioselective 6-acylation of sucrose |
EP2094873A2 (en) * | 2006-10-25 | 2009-09-02 | Mamtek International Limited | Process for the preparation of sucralose by the chlorination of sugar with triphosgene (btc) |
EP2094873A4 (en) * | 2006-10-25 | 2009-11-25 | Mamtek Int Ltd | Process for the preparation of sucralose by the chlorination of sugar with triphosgene (btc) |
WO2008084498A1 (en) * | 2007-01-08 | 2008-07-17 | V. B. Medicare Pvt. Ltd. | Decolorization of process streams by chemical oxidation in the manufacture of trichlorogalactosucrose |
WO2008096928A1 (en) * | 2007-02-07 | 2008-08-14 | Ilshin Chemical Co., Ltd | Method of producing sucralose |
Also Published As
Publication number | Publication date |
---|---|
EP1076661A1 (en) | 2001-02-21 |
RU2217435C2 (en) | 2003-11-27 |
UA58595C2 (en) | 2003-08-15 |
AU1864899A (en) | 1999-12-06 |
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