CN101624410A - Method for preparing sugar ortho ester - Google Patents
Method for preparing sugar ortho ester Download PDFInfo
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- CN101624410A CN101624410A CN200810045480A CN200810045480A CN101624410A CN 101624410 A CN101624410 A CN 101624410A CN 200810045480 A CN200810045480 A CN 200810045480A CN 200810045480 A CN200810045480 A CN 200810045480A CN 101624410 A CN101624410 A CN 101624410A
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- ethanoyl
- acid ester
- bromo
- preparation
- sodium bicarbonate
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Abstract
The invention belongs to the technical field of organic chemistry, in particular to a method for preparing sugar ortho ester. The method comprises the following steps: adding acetyl or benzoyl glycosyl bromide to a system containing alcohol or monosaccharide, sodium bicarbonate, tetrabutyl ammonium bromide, and acetonitrile or dichloromethane containing, stirring the mixture for reaction, and finally generating the sugar ortho ester. The method has the advantages of easy operation, little environmental pollution, high yield, low cost, easy industrialization and the like.
Description
Technical field
The invention belongs to technical field of organic chemistry, be specifically related to a kind of preparation method of hepatin acid ester.
Background technology
Ortho ester is a kind of very important intermediate in the organic synthesis, in carbohydrate is synthetic, and 1, the 2-ortho ester is widely used in the synthetic of oligosaccharides as saccharide donor.At present, the existing a lot of reports of the preparation method of ortho ester, wherein most widely used a kind of method is with Tetrabutyl amonium bromide/tetrabutylammonium iodide, organic bases [s-collidine, 2,6-lutidine, Et
3N, (MeO)
2CHNMe
2] as catalyzer.As:
(1)Tetrahedron，2002，58，7345。
(2)Journal?of?Organic?Chemistry，1994，59，6728。
(3)Journal?of?Natural?Products，2001，64(9)，1210。
Another kind method is with silver salt (Ag
2SO
4, Ag
2CO
3, Ag
2O etc.) and organic bases [s-collidine, EtN (Pr-i)
2] as catalyzer.As:
(4)Journal?of?Organic?Chemistry，1995，60(13)，3942。
(5)Carbohydrate?Research，1985，144(1)，137。
Also have a kind of method be with KF as catalyzer, as:
(6)Tetrahedron?Letters，2004，45，8847。
The two kinds of methods in front are because of using organic bases big for environment pollution, and have also used heavy metallic salt and benzene.Though the third method environmental pollution is less, post-reaction treatment is not only operated inconvenience and is caused the product loss bigger.
Summary of the invention
The objective of the invention is for shortcomings such as big for environment pollution and cost height among the preparation method who solves hepatin acid ester, we provide a kind of pollute little, raw material is cheap, speed of response is fast, productive rate is high, the method for simple and effective glycogen biosynthesis acid esters.
The preparation hepatin acid ester reaction process as follows: bromo sugar (ethanoyl bromo Glucopyranose, ethanoyl bromo mannopyranose, ethanoyl bromo galactopyranose, ethanoyl bromo pyrans rhamnosyl, ethanoyl-6-methylsulfonyl bromo mannopyranose, ethanoyl-6-p-toluenesulfonyl bromo mannopyranose, benzoyl bromo mannopyranose) is dissolved in the acetonitrile (or methylene dichloride), add again Tetrabutyl amonium bromide and sodium bicarbonate and alcohol (methyl alcohol, ethanol, vinylcarbinol, Virahol, propiolic alcohol, benzylalcohol) or monose with
Molecular sieve, 25～40 ℃ are stirred down, and reaction obtains hepatin acid ester.
R
1＝Ac，Bz
R
2＝Ac，Ts，Ms
R
3＝CH
3，Et，(CH
3)
2CH，H
2C＝CHCH
2，HCCCH
2，PhCH
2，sugar
Embodiment
In order further to understand summary of the invention of the present invention, characteristics and effect, enumerate following examples:
Embodiment 1: add 57mg 2,3,4 in the 10mL round-bottomed flask, 6-four-O-ethanoyl bromo Glucopyranose and 0.57mL acetonitrile add 45mg Tetrabutyl amonium bromide, 46mg sodium bicarbonate, 0.056mL methyl alcohol and 57mg again
Molecular sieve, 40 ℃ were stirred 3 hours.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4,6-three-O-ethanoyl Glucopyranose-1,2-(methyl ortho ester) 43mg, productive rate is 86%.
Embodiment 2: add 57mg 2,3,4 in the 10mL round-bottomed flask, 6-four-O-ethanoyl bromo Glucopyranose and 0.57mL acetonitrile add 45mg Tetrabutyl amonium bromide, 23mg sodium bicarbonate, 0.056mL methyl alcohol and 57mg again
Molecular sieve, 40 ℃ were stirred 6 hours.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4,6-three-O-ethanoyl Glucopyranose-1,2-(methyl ortho ester) 42mg, productive rate is 84%.
Embodiment 3: add 57mg 2,3,4 in the 10mL round-bottomed flask, 6-four-O-ethanoyl bromo Glucopyranose and 0.57mL acetonitrile add 13mg Tetrabutyl amonium bromide, 23mg sodium bicarbonate, 0.056mL methyl alcohol and 57mg again
Molecular sieve, 40 ℃ were stirred 6 hours.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4,6-three-O-ethanoyl Glucopyranose-1,2-(methyl ortho ester) 40mg, productive rate is 80%.
Embodiment 4: add 57mg 2,3,4 in the 10mL round-bottomed flask, 6-four-O-ethanoyl bromo Glucopyranose and 0.57mL acetonitrile add 45mg Tetrabutyl amonium bromide, 23mg sodium bicarbonate, 0.017mL methyl alcohol and 57mg again
Molecular sieve, 40 ℃ were stirred 2 hours.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4,6-three-O-ethanoyl Glucopyranose-1,2-(methyl ortho ester) 36mg, productive rate is 72%.
Embodiment 5: add 120mg 2,3,4 in the 50mL round-bottomed flask, 6-four-O-ethanoyl bromo Glucopyranose and 1.2mL methylene dichloride add 94mg Tetrabutyl amonium bromide, 98mg sodium bicarbonate, 0.118mL methyl alcohol and 120mg again
Molecular sieve, 40 ℃ were refluxed 4 hours.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4,6-three-O-ethanoyl Glucopyranose-1,2-(methyl ortho ester) 90mg, productive rate is 85%.
Embodiment 6: add 620mg 2,3,4 in the 50mL round-bottomed flask, 6-four-O-ethanoyl bromo mannopyranose and 6.2mL acetonitrile add 486mg Tetrabutyl amonium bromide, 507mg sodium bicarbonate, 0.61mL methyl alcohol and 620mg again
Molecular sieve, 40 ℃ were stirred 2 hours down.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4,6-three-O-ethanoyl mannopyranose-1,2-(methyl ortho ester) 453mg, productive rate is 83%.
Embodiment 7: add 640mg 2,3,4 in the 50mL round-bottomed flask, 6-four-O-ethanoyl bromo mannopyranose and 6.4mL acetonitrile add 502mg Tetrabutyl amonium bromide, 523mg sodium bicarbonate, 0.091mL ethanol and 640mg again
Molecular sieve, 40 ℃ were stirred 3 hours down.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1), obtain pure 3,4,6-three-O-ethanoyl mannopyranose-1,2-(ethyl ortho ester) 480mg, productive rate is 82%.
Embodiment 8: add 100mg 2,3,4 in the 10mL round-bottomed flask, 6-four-O-ethanoyl bromo galactopyranose and 1mL acetonitrile add 78mg Tetrabutyl amonium bromide, 82mg sodium bicarbonate, 0.099mL methyl alcohol and 100mg again
Molecular sieve, 40 ℃ were stirred 3 hours down.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4,6-three-O-ethanoyl galactopyranose-1,2-(methyl ortho ester) 71mg, productive rate is 81%.
Embodiment 9: add 400mg 2,3 in the 50mL round-bottomed flask, 4-three-O-ethanoyl bromo pyrans rhamnosyl and 4mL acetonitrile add 365mg Tetrabutyl amonium bromide, 190mg sodium bicarbonate, 0.46mL methyl alcohol and 400mg again
Molecular sieve, 40 ℃ were stirred 2 hours down.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1), obtain pure 3,4-two-O-ethanoyl pyrans rhamnosyl-1,2-(methyl ortho ester) 227mg, productive rate is 66%.
Embodiment 10: add 56mg 2,3 in the 10mL round-bottomed flask, 4-three-O-ethanoyl-6-methylsulfonyl bromo mannopyranose and 0.56mL acetonitrile adds 40mg Tetrabutyl amonium bromide, 42mg sodium bicarbonate, 0.05mL methyl alcohol and 56mg again
Molecular sieve; 40 ℃ were stirred 4 hours down; after the TLC detection reaction is complete; direct concentrating under reduced pressure; through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 3: 2), obtain pure 3,4-two-O-ethanoyl-6-methylsulfonyl mannopyranose-1; 2-(methyl ortho ester) 44mg, productive rate is 88%.
Embodiment 11: add 62mg 2,3 in the 10mL round-bottomed flask, 4-three-O-ethanoyl-6-methylsulfonyl bromo mannopyranose and 0.62mL acetonitrile adds 45mg Tetrabutyl amonium bromide, 47mg sodium bicarbonate, 0.094mL vinylcarbinol and 62mg again
Molecular sieve; 40 ℃ were stirred 3 hours down; after the TLC detection reaction is complete; direct concentrating under reduced pressure; through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1), obtain pure 3,4-two-O-ethanoyl-6-methylsulfonyl mannopyranose-1; 2-(allyl group ortho ester) 45mg, productive rate is 76%.
Embodiment 12: add 210mg 2,3 in the 10mL round-bottomed flask, 4-three-O-ethanoyl-6-p-toluenesulfonyl bromo mannopyranose and 2.1mL acetonitrile adds 129mg Tetrabutyl amonium bromide, 135mg sodium bicarbonate, 0.16mL methyl alcohol and 210mg again
Molecular sieve, 40 ℃ were stirred 4 hours down.After the TLC detection reaction was complete, direct concentrating under reduced pressure was through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1); obtain pure 3; 4-two-O-ethanoyl-6-p-toluenesulfonyl mannopyranose-1,2-(methyl ortho ester) 152mg, productive rate is 80%.
Embodiment 13: add 320mg 2,3 in the 25mL round-bottomed flask, 4-three-O-ethanoyl-6-p-toluenesulfonyl bromo mannopyranose and 3.2mL acetonitrile adds 197mg Tetrabutyl amonium bromide, 205mg sodium bicarbonate, 0.475mL Virahol and 320mg again
Molecular sieve, 40 ℃ were stirred 5 hours down.After the TLC detection reaction was complete, direct concentrating under reduced pressure was through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1); obtain pure 3; 4-two-O-ethanoyl-6-p-toluenesulfonyl mannopyranose-1,2-(sec.-propyl ortho ester) 227mg, productive rate is 74%.
Embodiment 14: add 169mg 2,3 in the 10mL round-bottomed flask, 4-three-O-ethanoyl-6-p-toluenesulfonyl bromo mannopyranose and 1.7mL acetonitrile adds 104mg Tetrabutyl amonium bromide, 109mg sodium bicarbonate, 0.334mL benzylalcohol and 169mg again
Molecular sieve, 40 ℃ were stirred 4 hours down.After the TLC detection reaction was complete, direct concentrating under reduced pressure was through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1); obtain pure 3; 4-two-O-ethanoyl-6-p-toluenesulfonyl mannopyranose-1,2-(benzyl ortho ester) 130mg, productive rate is 73%.
Embodiment 15: add 95mg 2,3 in the 5mL round-bottomed flask, 4-three-O-ethanoyl-6-p-toluenesulfonyl bromo mannopyranose and 0.95mL acetonitrile adds 59mg Tetrabutyl amonium bromide, 61mg sodium bicarbonate, 0.105mL propiolic alcohol and 95mg again
Molecular sieve, 40 ℃ were stirred 5 hours down.After the TLC detection reaction was complete, direct concentrating under reduced pressure was through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1); obtain pure 3; 4-two-O-ethanoyl-6-p-toluenesulfonyl mannopyranose-1,2-(proyl ortho ester) 64mg, productive rate is 71%.
Embodiment 16: add 500mg 2,3,4 in the 25mL round-bottomed flask, 6-four-O-benzoyl bromo mannopyranose and 5mL acetonitrile add 147mg Tetrabutyl amonium bromide, 127mg sodium bicarbonate, 0.31mL methyl alcohol and 500mg again
Molecular sieve, 40 ℃ were stirred 4 hours down.The TLC detection reaction fully after, direct concentrating under reduced pressure, through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 4: 1), obtain pure 3,4,6-three-O-phenylacetyl mannopyranose-1,2-(methyl ortho ester) 407mg, productive rate is 88%.
Embodiment 17: add 316mg 2 in the 25mL round-bottomed flask; 3,4,6-four-O-ethanoyl bromo mannopyranose, 100mg 1:2; 3:4-two--and O-isopropylidene-α-D-galactopyranose and 3mL acetonitrile add 124mg Tetrabutyl amonium bromide, 129mg sodium bicarbonate and 300mg again
Molecular sieve stirred 18 hours under the room temperature.After the TLC detection reaction is complete; direct concentrating under reduced pressure; through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1); obtain pure 3; 4,6-three-O-ethanoyl-D-mannopyranose-1,2-(1:2; 3:4-two-O-isopropylidene-α-D-galactopyranose base ortho ester) 204mg, productive rate is 90%.
Embodiment 18: add 488mg 2 in the 25mL round-bottomed flask; 3; 4-three-O-ethanoyl-bromo pyrans rhamnosyl, 180mg 1:2,3:4-two-O-isopropylidene-α-D-galactopyranose and 5.4mL adds 223mg Tetrabutyl amonium bromide, 232mg sodium bicarbonate and 540mg again
Molecular sieve stirred 15 hours under the room temperature.After the TLC detection reaction is complete; direct concentrating under reduced pressure; through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 5: 2); obtain pure 3; 4-two-O-ethanoyl-L-pyrans rhamnosyl-1; 2-(1:2,3:4-two-O-isopropylidene-α-D-galactopyranose base ortho ester) 280mg, productive rate is 76%.
Embodiment 19: add 215mg 2 in the 10mL round-bottomed flask; 3,4,6-four-O-ethanoyl bromo Glucopyranose, 68mg 1:2; 3:4-two-O-isopropylidene-α-D-galactopyranose and 2mL acetonitrile add 84mg Tetrabutyl amonium bromide, 88mg sodium bicarbonate and 200mg again
Molecular sieve stirred 16 hours under the room temperature.After the TLC detection reaction is complete; direct concentrating under reduced pressure; through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1); obtain pure 3; 4,6-three-O-ethanoyl-D-Glucopyranose-1,2-(1:2; 3:4-two-O-isopropylidene-α-D-galactopyranose base ortho ester) 120mg, productive rate is 78%.
Embodiment 20: add 266mg 2,3,4 in the 25mL round-bottomed flask; 6-four-O-ethanoyl bromo mannopyranose, 150mg methyl-2; 3,4-three-O-benzyl-alpha-D-glucoside and 4.5mL acetonitrile add 104mg Tetrabutyl amonium bromide, 108mg sodium bicarbonate and 450mg again
Molecular sieve stirred 18 hours under the room temperature.After the TLC detection reaction is complete; direct concentrating under reduced pressure; through purification by silica gel column chromatography (eluent is petrol ether/ethyl acetate 2: 1); obtain pure 3,4,6-three-O-ethanoyl-D-mannopyranose-1; 2-(methyl-2; 3,4-three-O-benzyl-alpha-D-glucoside base ortho ester) 205mg, productive rate is 80%.
Top embodiment can make the present invention of those skilled in the art complete understanding, but does not limit the present invention in any way.
Claims (9)
1. the preparation method of a hepatin acid ester is characterized in that: the ethanoyl bromo sugar is dissolved in acetonitrile or the methylene dichloride, adds Tetrabutyl amonium bromide and sodium bicarbonate and pure and mild 4 again
Molecular sieve, 40 ℃ of following stirring reactions obtain hepatin acid ester, separate the pure product of hepatin acid ester that obtain through purification by silica gel column chromatography.
2. the preparation method of a hepatin acid ester also can be: the benzoyl bromo sugar is dissolved in acetonitrile or the methylene dichloride, adds Tetrabutyl amonium bromide and sodium bicarbonate and pure and mild 4 again
Molecular sieve, 40 ℃ of following stirring reactions obtain hepatin acid ester, separate the pure product of benzoyl mannopyranose ortho ester that obtain through purification by silica gel column chromatography.
3. the preparation method of a hepatin acid ester also can be: ethanoyl bromo sugar and monose are dissolved in acetonitrile or the methylene dichloride, add Tetrabutyl amonium bromide and sodium bicarbonate and 4 again
Molecular sieve, stirring reaction under the room temperature obtains hepatin acid ester, separates the pure product of hepatin acid ester that obtain monose through purification by silica gel column chromatography.
4. the preparation method of a kind of hepatin acid ester according to claim 1, it is characterized in that: described ethanoyl bromo sugar is ethanoyl bromo Glucopyranose or ethanoyl bromo mannopyranose or ethanoyl bromo galactopyranose or ethanoyl bromo pyrans rhamnosyl or ethanoyl-6-methylsulfonyl bromo mannopyranose or ethanoyl-6-p-toluenesulfonyl bromo mannopyranose; Alcohol is: methyl alcohol, ethanol, vinylcarbinol, Virahol, propiolic alcohol or benzylalcohol.
5. the preparation method of a kind of hepatin acid ester according to claim 1, it is characterized in that: described alcohol is methyl alcohol or ethanol or vinylcarbinol or Virahol or propiolic alcohol or benzylalcohol.
6. the preparation method of a kind of hepatin acid ester according to claim 1 is characterized in that: the mol ratio of ethanoyl bromo sugar, Tetrabutyl amonium bromide, sodium bicarbonate, alcohol is 1: 0.3～1: 2～4: 3～10, ethanoyl bromo sugar, 4
The quality g volume mL ratio of molecular sieve, acetonitrile or methylene dichloride is 1: 1: 10, and 40 ℃ were reacted 2～6 hours down.
7. the preparation method of a kind of hepatin acid ester according to claim 2 is characterized in that: the mol ratio of benzoyl bromo sugar, Tetrabutyl amonium bromide, sodium bicarbonate, alcohol is 1: 0.3～1: 2～4: 3～10, benzoyl bromo sugar, 4
The quality g volume mL of molecular sieve, acetonitrile or methylene dichloride was than 1: 1: 10, and 40 ℃ were reacted 3～5 hours down.
8. the preparation method of a kind of hepatin acid ester according to claim 3, it is characterized in that: described monose is 1:2,3:4-two-O-isopropylidene-α-D-galactopyranose or methyl-2,3,4-three-O-benzyl-alpha-D-glucoside.
9. the preparation method of a kind of hepatin acid ester according to claim 3, it is characterized in that: the mol ratio of ethanoyl bromo sugar, monose, Tetrabutyl amonium bromide, sodium bicarbonate is 1.5～2: 1: 0.6～1: 2～4, ethanoyl bromo sugar, 4
The quality g volume mL of molecular sieve, acetonitrile methylene dichloride reacted under the room temperature 15～18 hours than 1: 3: 30.
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|---|---|---|---|
| CN2008100454808A CN101624410B (en) | 2008-07-07 | 2008-07-07 | Method for preparing sugar ortho ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105878212A (en) * | 2016-05-27 | 2016-08-24 | 四川大学 | Double-cell and microenvironment-sensitive anti-tumor drug-loaded nanocapsule and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105878212A (en) * | 2016-05-27 | 2016-08-24 | 四川大学 | Double-cell and microenvironment-sensitive anti-tumor drug-loaded nanocapsule and preparation method |
| CN105878212B (en) * | 2016-05-27 | 2018-06-15 | 四川大学 | A kind of antitumor medicament-carried nano capsule and preparation method of d cell microenvironment sensitivity |
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