CN101497591B - Preparation of 6-O-sulfonyl-glycal compound - Google Patents
Preparation of 6-O-sulfonyl-glycal compound Download PDFInfo
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- CN101497591B CN101497591B CN2008100453294A CN200810045329A CN101497591B CN 101497591 B CN101497591 B CN 101497591B CN 2008100453294 A CN2008100453294 A CN 2008100453294A CN 200810045329 A CN200810045329 A CN 200810045329A CN 101497591 B CN101497591 B CN 101497591B
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- ethanoyl
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- toluenesulfonyl
- methylsulfonyl
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Abstract
The invention belongs to the technical field of organic chemistry, and discloses a method for preparing a 6-O-sulfonyl-glycal compound. The method comprises that: a 1-bromine-monosaccharide compound containing corresponding radicals is used as a raw material, is dissolved by ethyl acetate or acetone, added with a saturated aqueous solution of sodium dihydrogen phosphate and zinc powder, and stirred at the room temperature for reaction to obtain the 6-O-sulfonyl-glycal compound. The method has the advantages of easy operation, high yield, short reaction time, low cost, little 'three wastes', easy industrialization and the like.
Description
Technical field
The present invention relates to technical field of organic chemistry; specifically relate to 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal, 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal, 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal and 3, the preparation method of 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal.
Background technology
In organic compound, natural product and active polysaccharide synthetic, glycal and derivative thereof are important material, but the price height on the market, this has just limited it in breadboard application greatly.At present, the preparation method of acetylated glucal is had a lot, can retrieve more than tens kinds.But to 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal, 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal, 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal and 3; the preparation of 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal reports seldom that but the product preparation that has does not retrieve yet.Wherein a kind of method is to obtain target product from the 1-bromo-derivative, as: CarbohydrateResearch 1989,193,275-278.
Another kind of main method is to make target compound from acetylated glucal, as: Bull.Chem.Soc.Jpn.1985,58,3629-3630.
For another example: Pure App1.Chem.2005,77,145-153.
Above-mentioned several synthetic method all can obtain product, but exists different shortcomings such as step is many, productive rate is not high, complex operation.
Summary of the invention
The objective of the invention is in order to solve 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal; 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal; 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal and 3; cost height among the preparation method of 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal; shortcomings such as complex operation and productive rate are low; we provide a kind of raw material cheap; the productive rate height; simple and effective synthesizes 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal; 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal; 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal and 3, the method for 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal.
The present invention realizes in the following way:
With the 1-bromo-monose compound that contains corresponding group is starting compound, behind ethyl acetate or acetone solution, adds saturated biphosphate sodium water solution and zinc powder again, and stirring at room reaction 2～8 hours obtains 6-O-alkylsulfonyl-glycal compounds; 1-bromo-monose compound (weight, gram), zinc powder (weight, gram), saturated biphosphate sodium water solution (volume, mL), (volume, amount ratio mL) they are 1: 2～5: 5～15: 5～10 for ethyl acetate or acetone.
Preparation 3; the reaction process of 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal is as follows: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-methylsulfonyl-D-glucose dissolves with ethyl acetate (acetone); add saturated biphosphate sodium water solution and zinc powder again; stirring at room, reaction obtains 3,4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal.
Preparation 3; the reaction process of 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal is as follows: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucose dissolves with ethyl acetate (acetone); add saturated biphosphate sodium water solution and zinc powder again; stirring at room, reaction obtains 3,4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal.
Preparation 3; the reaction process of 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal is as follows: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-methylsulfonyl-D-semi-lactosi dissolves with ethyl acetate (acetone); add saturated biphosphate sodium water solution and zinc powder again; stirring at room, reaction obtains 3,4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal.
Preparation 3; the reaction process of 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal is as follows: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-p-toluenesulfonyl-D-semi-lactosi dissolves with ethyl acetate (acetone); add saturated biphosphate sodium water solution and zinc powder again; stirring at room, reaction obtains 3,4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal.
The invention provides a kind of simple and effective preparation 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal, 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal, 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal and 3, the method for 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal.Advantage of the present invention is: simple to operate, productive rate is high, the reaction times is short, cost is low, the three wastes are few, environmental pollution is little, is easy to industrialization.
Embodiment
In order further to understand summary of the invention of the present invention, characteristics and effect, enumerate following examples:
Example 1: with 0.25g 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-methylsulfonyl-D-glucose 1.25mL acetic acid ethyl dissolution; add saturated biphosphate sodium water solution of 1.25mL and 0.5g zinc powder again; stirred 2 hours under the room temperature, after the TLC detection reaction is complete, reaction solution ethyl acetate extraction 3 times; merge organic phase; water washing 3 times, saturated sodium bicarbonate aqueous solution washing 2 times, saturated brine washing 1 time; anhydrous sodium sulfate drying; concentrating under reduced pressure through the silicagel column purifying, gets 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal 0.155g, productive rate is 90%.
Example 2: with 1.0g 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-methylsulfonyl-D-glucose 8mL acetone solution; add saturated biphosphate sodium water solution of 10mL and 3.5g zinc powder again; stirred 5 hours under the room temperature, after the TLC detection reaction is complete, reaction solution ethyl acetate extraction 3 times; merge organic phase; water washing 3 times, saturated sodium bicarbonate aqueous solution washing 2 times, saturated brine washing 1 time; anhydrous sodium sulfate drying; concentrating under reduced pressure through the silicagel column purifying, gets 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal 0.588g, productive rate is 85%.
Example 3: with 3.46g 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucose 17.5mL acetic acid ethyl dissolution; add saturated biphosphate sodium water solution of 35mL and 7.0g zinc powder again; stirred 5 hours under the room temperature, after the TLC detection reaction is complete, reaction solution ethyl acetate extraction 3 times; merge organic phase; water washing 3 times, saturated sodium bicarbonate aqueous solution washing 2 times, saturated brine washing 1 time; anhydrous sodium sulfate drying; concentrating under reduced pressure through the silicagel column purifying, gets 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal 1.91g, productive rate is 75%.
Example 4: with 1.0g 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucose 5mL acetone solution; add saturated biphosphate sodium water solution of 10mL and 2.0g zinc powder again; stirred 3 hours under the room temperature, after the TLC detection reaction is complete, reaction solution ethyl acetate extraction 3 times; merge organic phase; water washing 3 times, saturated sodium bicarbonate aqueous solution washing 2 times, saturated brine washing 1 time; anhydrous sodium sulfate drying; concentrating under reduced pressure through the silicagel column purifying, gets 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal 0.609g, productive rate is 83%.
Example 5: with 0.15g 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-p-toluenesulfonyl-D-semi-lactosi 1.5mL acetic acid ethyl dissolution; add saturated biphosphate sodium water solution of 2.25mL and 0.75g zinc powder again; stirred 3 hours under the room temperature, after the TLC detection reaction is complete, reaction solution ethyl acetate extraction 3 times; merge organic phase; water washing 3 times, saturated sodium bicarbonate aqueous solution washing 2 times, saturated brine washing 1 time; anhydrous sodium sulfate drying; concentrating under reduced pressure through the silicagel column purifying, gets 3; 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal 0.088g, productive rate is 80%.
Example 6: with 0.35g 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-methylsulfonyl-D-semi-lactosi 1.8mL acetic acid ethyl dissolution; add saturated biphosphate sodium water solution of 3.5mL and 0.7g zinc powder again; stirred 8 hours under the room temperature, after the TLC detection reaction is complete, reaction solution ethyl acetate extraction 3 times; merge organic phase; water washing 3 times, saturated sodium bicarbonate aqueous solution washing 2 times, saturated brine washing 1 time; anhydrous sodium sulfate drying; concentrating under reduced pressure through the silicagel column purifying, gets 3; 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal 0.221g, productive rate is 92%.
Claims (5)
1. the preparation method of 6-O-alkylsulfonyl-glycal compounds, it is characterized in that: with 1-bromo-α-D-monose compound is raw material, behind ethyl acetate or acetone solution, add saturated biphosphate sodium water solution and zinc powder again, stirring at room reaction 2～8 hours obtains 6-O-alkylsulfonyl-glycal compounds;
Wherein, described 6-O-alkylsulfonyl-glycal compounds is: 3,4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal, 3,4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal, 3,4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal or 3,4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal;
Described 1-bromo-α-D-monose compound is: 1-bromo-2,3,4-three-O-ethanoyl-6-O-methylsulfonyl-alpha-D-glucose, 1-bromo-2,3,4-three-O-ethanoyl-6-O-methylsulfonyl-α-D-semi-lactosi, 1-bromo-2,3,4-three-O-ethanoyl-6-O-p-toluenesulfonyl-alpha-D-glucose, 1-bromo-2,3,4-three-O-ethanoyl-6-O-p-toluenesulfonyl-α-D-semi-lactosi;
The mass volume ratio of used 1-bromo-α-D-monose compound g, zinc powder g, saturated biphosphate sodium water solution mL, ethyl acetate or acetone mL is 1: 2～5: 5～15: 5～10.
2. the preparation method of 6-O-alkylsulfonyl according to claim 1-glycal compounds; it is characterized in that: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-methylsulfonyl-alpha-D-glucose is a raw material; through ethyl acetate or acetone solution, add saturated biphosphate sodium water solution and zinc powder again, stir under the room temperature; reaction obtains having 3 of following structure, 4-two-O-ethanoyl-6-O-methylsulfonyl-D-glucal:
3. the preparation method of 6-O-alkylsulfonyl according to claim 1-glycal compounds; it is characterized in that: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-p-toluenesulfonyl-alpha-D-glucose is a raw material; with ethyl acetate or acetone solution, add saturated biphosphate sodium water solution and zinc powder again, stir under the room temperature; reaction obtains having 3 of following structure, 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-glucal:
4. the preparation method of 6-O-alkylsulfonyl according to claim 1-glycal compounds; it is characterized in that: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-methylsulfonyl-α-D-semi-lactosi is a raw material; with ethyl acetate or acetone solution, add saturated biphosphate sodium water solution and zinc powder again, stir under the room temperature; reaction obtains having 3 of following structure, 4-two-O-ethanoyl-6-O-methylsulfonyl-D-gala glycal:
5. the preparation method of 6-O-alkylsulfonyl according to claim 1-glycal compounds; it is characterized in that: with 1-bromo-2; 3; 4-three-O-ethanoyl-6-O-p-toluenesulfonyl-α-D-semi-lactosi is a raw material; with ethyl acetate or acetone solution, add saturated biphosphate sodium water solution and zinc powder again, stir under the room temperature; reaction obtains having 3 of following structure, 4-two-O-ethanoyl-6-O-p-toluenesulfonyl-D-gala glycal:
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1803818A (en) * | 2005-12-30 | 2006-07-19 | 江苏汉发贸易发展有限公司 | Method for preparing acetylated glucal |
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| CN1803818A (en) * | 2005-12-30 | 2006-07-19 | 江苏汉发贸易发展有限公司 | Method for preparing acetylated glucal |
Non-Patent Citations (5)
| Title |
|---|
| ,et al..A convenient route to 6-functionalized derivatives of D-glucal.《Carbohydrate Research》.1989,第193卷275-278. |
| an Miljković |
| Duš |
| Dušan Miljković,et al..A convenient route to 6-functionalized derivatives of D-glucal.《Carbohydrate Research》.1989,第193卷275-278. * |
| Perali Ramu Sridhar,et al..Chemistry of tetrathiomolybdate and tetraselenotungstate: Applications in carbohydrate chemistry.《Pure Appl. Chem.》.2005,第77卷(第1期),145-153. * |
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