CN1803818A - Method for preparing acetylated glucal - Google Patents
Method for preparing acetylated glucal Download PDFInfo
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- CN1803818A CN1803818A CN 200510134952 CN200510134952A CN1803818A CN 1803818 A CN1803818 A CN 1803818A CN 200510134952 CN200510134952 CN 200510134952 CN 200510134952 A CN200510134952 A CN 200510134952A CN 1803818 A CN1803818 A CN 1803818A
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- acetylize
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- grape
- acid
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- YVECGMZCTULTIS-PBXRRBTRSA-N glucal Chemical compound OC[C@H]1OC=C[C@@H](O)[C@@H]1O YVECGMZCTULTIS-PBXRRBTRSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 10
- 239000011592 zinc chloride Substances 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 34
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- DUKURNFHYQXCJG-UHFFFAOYSA-N Lewis A pentasaccharide Natural products OC1C(O)C(O)C(C)OC1OC1C(OC2C(C(O)C(O)C(CO)O2)O)C(NC(C)=O)C(OC2C(C(OC3C(OC(O)C(O)C3O)CO)OC(CO)C2O)O)OC1CO DUKURNFHYQXCJG-UHFFFAOYSA-N 0.000 claims description 20
- 229950006780 n-acetylglucosamine Drugs 0.000 claims description 20
- 241000219095 Vitis Species 0.000 claims description 16
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 16
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 16
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 230000006837 decompression Effects 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical group CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008103 glucose Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910020667 PBr3 Inorganic materials 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 229940098779 methanesulfonic acid Drugs 0.000 abstract 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Saccharide Compounds (AREA)
Abstract
The disclosed preparation method for acetylized glucal comprises: preparing the D-acetylized glucose catalyzed by acids (HClO4, H2SO4, ZnCl2, AlCl3, p-toluenesulfonic acid and methanesulfonic acid); without separation or purification, leading directly the product into HBr or equivalent (such as PBr3 and water) to obtain and then recrystallize the coarse 1-bromoacetyl glucose with one of ethyl ether, propyl ether and isopropyl ether; adding Zn, ZnCl2, methanol and Co-ion catalyst to prepare the coarse target; recrystallizing with alcohol for the refined product. This invention saves step and reduces cost.
Description
One, technical field
The present invention relates to technical field of organic chemistry, specifically relate to the preparation method of acetylated glucal.
Two, background technology
Preparation method at present known acetylated glucal has a lot, can retrieve more than tens kinds, and also have new technology to deliver at set intervals, mainly contain two kinds of methods: a kind of substituent from the 2-position obtains target compound, as: (1) Carbohydrate Research, 23 (3), 369-77; 1972
This synthetic method is simple to operate, but raw material is somewhat expensive and rare.As: (2) Journal of CarbohydrateChemistry, 6 (2), 203-19; 1987
This synthetic method is simple to operate, but raw material is somewhat expensive and rare, and benzene is relatively more malicious, is not suitable for using in pharmaceutical production.
Another kind of substituent from the 1-position obtains target compound, and this synthetic method adopts more, as: Journal ofCarbohydrate Chemistry, 12 (4-5), 679-84; 1993
For another example: Journal of the Chemical Society, Chemical Communications, (15), 1149-50:1986
And for example: Tetrabedron L etter 41 (2000) 8645-8649
Shortcoming such as the fine product that above-mentioned several synthetic method can both obtain, but it is expensive all to exist raw material, reagent are more difficult to get or aftertreatment is more numerous.
Three, summary of the invention
The objective of the invention is shortcomings such as loaded down with trivial details for the aftertreatment that exists among the preparation method who solves acetylated glucal, that cost is high, reagent is rareer, we provide a kind of simple and effective synthetic method.
The anti-reaction process of preparation acetylated glucal (1) is as follows: in same reactor, at first D-makes glucose (II) and acetic anhydride generate D-acetyl glucose (IIi) under the katalysis of acid (perchloric acid, sulfuric acid, zinc chloride, aluminum chloride, tosic acid, methylsulfonic acid):
The D-acetyl glucose (III) that generates need not separate, purifying, directly feeds hydrogen bromide or equivalent (as phosphorus tribromide and water), obtains 1-bromo acetyl glucosamine crude product (IV), with ethers (ether, propyl ether, isopropyl ether) recrystallization, oven dry, elaboration.
In same reactor, add zinc, ammonium chloride, methyl alcohol and 1-bromo acetyl glucosamine cobalt ion catalyzer, reaction generates acetylated glucal (V), uses the alcohols recrystallization, gets target compound (V).
The preparation method of the rare sugar of acetylize grape, its preparation process is as follows:
(1) at first prepares the D-acetyl glucose
In same reactor, add D-glucose, aceticanhydride and acid, stirring and dissolving, control reaction temperature generates the D-acetyl glucose under the katalysis of acid (perchloric acid, sulfuric acid, zinc chloride, aluminum chloride, tosic acid, methylsulfonic acid);
(2) secondly prepare 1-bromo acetyl glucosamine
The D-acetyl glucose that step (1) is generated need not separate, purifying, directly feed hydrogen bromide or equivalent, control reaction temperature, reaction is poured in another reactor after finishing, add chloroform, stir, add the saturated aqueous solution of sodium bicarbonate again, stir, the saturated aqueous solution that adds sodium-chlor again stirs, and transfers in the dry still, add anhydrous sodium sulphate, decompression steams chloroform, obtains 1-bromo acetyl glucosamine crude product, adds the ethers recrystallization, cooling, oven dry make 1-bromo acetyl glucosamine elaboration;
(3) prepare the rare sugared crude product of acetylize grape at last
Add methyl alcohol, zinc, sodium-chlor and cobalt ion catalyzer in the reactor of the 1-bromo acetyl glucosamine elaboration that step (2) is made, controlled temperature, decompression steams chloroform, obtains the rare sugared crude product of acetylize grape;
(4) the rare sugared crude product recrystallization of acetylize grape is got elaboration
Get the acetylated glucal crude product and add the alcohols heating for dissolving, add activated carbon, press filtration to crystallization kettle, freezing, centrifugal, dry the rare asccharin product of acetylize grape.
In the reaction that generates D-acetyl glucose (III), the mole ratio of D-glucose and acetic anhydride can be 1: 5-1: 6, and acid can be perchloric acid, sulfuric acid, zinc chloride, aluminum chloride, tosic acid, methylsulfonic acid, temperature of reaction is at 15～45 ℃.
In the reaction of 1-bromo acetyl glucosamine IV, hydrogen bromide or equivalent (as phosphorus tribromide and water) are 1: 1～1: 0.5 with the mole ratio of D-acetyl glucose, and best ratio is 1: 1, and temperature of reaction is 0 ℃～20 ℃.
In the reaction that generates acetylated glucal (V); temperature of reaction is 0 ℃～65 ℃, and in 1～4 hour reaction times, the mole ratio of zinc and ammonium chloride is 1: 1; the mole ratio of zinc and 1-bromo acetyl glucosamine (IV) is 40: 1～3: 1, and best ratio is 15: 1.
Recrystallization in the reaction all adopts icy salt solution to feed refrigerated method in the crystallization kettle chuck, but twice crystallization must be as cold as below-5 ℃ and keep 12-24 hour.
The present invention had both saved the work of separation of intermediates D-acetyl glucose (III), had adopted the reagent that is easy to get again, thereby had reduced cost, and a kind of method of the simple and effective rare sugar of synthesis of acetyl grape is provided.
Four, embodiment
In order further to understand summary of the invention of the present invention, characteristics and effect, exemplify following examples now:
Example 1: add 55kg D-glucose to the 500L reactor, aceticanhydride 200L, the perchloric acid of catalytic amount (10ml), stirring and dissolving, control reaction temperature was 15～45 ℃ of insulations 2 hours.Insulation finishes, and is chilled to below 5 ℃, feeds 7 cubic metres of hydrogen bromides, control reaction temperature was 0～10 ℃ of reaction 2 hours, and reaction finishes, and pours 2000L reactor (having in the water of 1000L) into, the chloroform that adds 200L again stirs 30min, tells chloroform, water layer with the chloroform of 100L extract again-inferior, combined chloroform adds the saturated aqueous solution of 100L sodium bicarbonate again in the chloroform, stir 30min, tell chloroform, again the saturated aqueous solution of adding 300L sodium-chlor in the chloroform, stir 30min, tell chloroform, transfer in the dry still of 500L, add the anhydrous sodium sulphate of 25KG, after 2 hours, press filtration is in the still kettle of 500L, and decompression steams chloroform, adds the ether of 100L again, stir, logical icy salt solution is chilled to-10 ℃, and is centrifugal, obtain 1-bromo acetyl glucosamine (IV) 95KG, Mp86～88 ℃.
In-1000L reactor, add methyl alcohol 500kg, zinc 200KG, ammonium chloride 243KG, 1-bromo acetyl glucosamine 95KG and cobalt ion catalyzer (20g); 30 ℃～35 ℃ reactions of temperature control 1 hour; press filtration is in the still kettle of 1000L; decompression steams methyl alcohol; add the chloroform of 200L and the water of 300L again; stir; tell chloroform; with anhydrous sodium sulphate 20KG drying; after 2 hours, press filtration is in the still kettle of 500L, and decompression steams chloroform; get acetylated glucal (IV), add dehydrated alcohol 100L heating for dissolving.Temperature rises to boiling reflux, and insulation is to molten entirely.The complete molten gac 5kg that adds.Be incubated 1 hour, cold slightly, press filtration is to crystallization kettle.It is freezing to feed icy salt solution in the crystallization kettle chuck, temperature control-5 ℃, freezing 24 hours.Centrifugal refrigerated material, dry 60KG acetylated glucal (V), yield 72.2%.
Example 2: add 55kg D-glucose to the 500L reactor, aceticanhydride 200L, the zinc chloride of catalytic amount (50g), stirring and dissolving, control reaction temperature was 15～45 ℃ of insulations 2 hours.Insulation finishes, and is chilled to below 5 ℃, feeds 7 cubic metres of hydrogen bromides, control reaction temperature was 0～10 ℃ of reaction 2 hours, and reaction finishes, and pours 2000L reactor (having in the water of 1000L) into, the chloroform that adds 200L again stirs 30min, tells chloroform, water layer extracts once with the chloroform of 100L again, and combined chloroform adds the saturated aqueous solution of 100L sodium bicarbonate again in the chloroform, stir 30min, tell chloroform, again the saturated aqueous solution of adding 300L sodium-chlor in the chloroform, stir 30min, tell chloroform, transfer in the dry still of 500L, add the anhydrous sodium sulphate of 25KG, after 2 hours, press filtration is in the still kettle of 500L, and decompression steams chloroform, adds the isopropyl ether of 80L again, stir, logical icy salt solution is chilled to-10 ℃, and is centrifugal, obtain 1-bromo acetyl glucosamine (IV) 95KG, Mp86～88 ℃.
Prepare the method for acetylated glucal with example 1 from 1-bromo acetyl glucosamine
Example 3: add 55kg D-glucose to the 500L reactor, aceticanhydride 200L, the tosic acid 15ml of catalytic amount, stirring and dissolving, control reaction temperature was 15～45 ℃ of insulations 2 hours.Insulation finishes, and is chilled to below 5 ℃, adds the 90KG phosphorus tribromide, add the water that adds 18KG again, control reaction temperature was 0～10 ℃ of reaction 2 hours, and reaction finishes, pour 2000L reactor (having in the water of 1000L) into, add the chloroform of 200L again, stir 30min, tell chloroform, water layer extracts once combined chloroform again with the chloroform of 100L, add the saturated aqueous solution of 100L sodium bicarbonate again in the chloroform, stir 30min, tell chloroform, add the saturated aqueous solution of 300L sodium-chlor again in the chloroform, stir 30min, tell chloroform, transfer in the dry still of 500L, add the anhydrous sodium sulphate of 25KG, after 2 hours, press filtration is in the still kettle of 500L, decompression steams chloroform, the propyl ether that adds 120L again stirs, logical icy salt solution, be chilled to-10 ℃, centrifugal, obtain 1-bromo acetyl glucosamine (IV) 95KG, Mp86～88 ℃.
Prepare the method for acetylated glucal with example 1 from 1-bromo acetyl glucosamine
Claims (5)
1, the preparation method of the rare sugar of acetylize grape, its preparation process is as follows:
(1) at first prepares the D-acetyl glucose
In same reactor, add D-glucose, aceticanhydride and acid (in perchloric acid, sulfuric acid, zinc chloride, aluminum chloride, tosic acid and the methylsulfonic acid a kind of), stirring and dissolving, control reaction temperature, generation D-acetyl glucose under the katalysis of acid;
(2) secondly prepare 1-bromo acetyl glucosamine
After the D-acetyl glucose insulation end with step (1) generation, cooling, feed hydrogen bromide or equivalent, control reaction temperature, reaction is poured in another reactor after finishing, and adds chloroform, stir, the saturated aqueous solution that adds sodium bicarbonate again stirs, and adds the saturated aqueous solution of sodium-chlor again, stir, transfer in the dry still, add anhydrous sodium sulphate, decompression steams chloroform, obtain 1-bromo acetyl glucosamine crude product, with a kind of recrystallization in ether, propyl ether and the isopropyl ether, cooling, oven dry make 1-bromo acetyl glucosamine elaboration;
(3) prepare the rare sugared crude product of acetylize grape at last
Add methyl alcohol, zinc, sodium-chlor and cobalt ion catalyzer in the reactor of the 1-bromo acetyl glucosamine crude product that step (2) is made, controlled temperature, decompression steams chloroform, obtains the rare sugared crude product of acetylize grape;
(4) the rare sugared crude product recrystallization of acetylize grape is got elaboration
Get the acetylated glucal crude product and add the alcohols heating for dissolving, add activated carbon, press filtration to crystallization kettle, freezing, centrifugal, dry the rare asccharin product of acetylize grape.
2, the preparation method of the rare sugar of acetylize grape according to claim 1; it is characterized in that the mole ratio of D-acetyl glucose and acetic anhydride is 1 in step (1): 5-1: 6; described acid is perchloric acid, sulfuric acid, zinc chloride, aluminum chloride, tosic acid and methylsulfonic acid; in the reaction that generates the D-acetyl glucose, its temperature of reaction is 15-45 ℃.
3, the preparation method of the rare sugar of acetylize grape according to claim 1 is characterized in that in step (2), described equivalent is phosphorus tribromide and water; The mole ratio of hydrogen bromide or equivalent and D-acetyl glucose is 1: 1-1: 0.5, and in the reaction that generates 1-bromo acetyl glucosamine, its temperature of reaction is 0-20 ℃.
4, the preparation method of the rare sugar of acetylize grape according to claim 1 is characterized in that the mole ratio of zinc and ammonium chloride is 1: 1 in step (3), and the mole ratio of zinc and 1-bromo acetyl glucosamine is 40: 1-3: 1, be preferably 15: 1; In the reaction that generates the rare sugared crude product of acetylize grape, its temperature of reaction is 0 ℃-65 ℃, and the reaction times is 1-4 hour.
5, the preparation method of the rare sugar of acetylize grape according to claim 1 is characterized in that in step (2) and (4) recrystallization is icy salt solution to be fed in the crystallization kettle chuck freezing, and temperature control remained on 12-24 hour below-5 ℃.
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| CNB2005101349523A CN100357305C (en) | 2005-12-30 | 2005-12-30 | Method for preparing acetylated glucal |
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| CNB2005101349523A CN100357305C (en) | 2005-12-30 | 2005-12-30 | Method for preparing acetylated glucal |
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| CN100357305C CN100357305C (en) | 2007-12-26 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100579973C (en) * | 2007-02-13 | 2010-01-13 | 中国科学院成都生物研究所 | Process for producing glucal |
| CN101935313A (en) * | 2010-09-15 | 2011-01-05 | 山西农业大学 | Method for ultrasonically synthesizing glycal |
| CN101289439B (en) * | 2007-04-16 | 2011-04-06 | 中国科学院成都生物研究所 | Process for preparing arabglycal |
| CN101497591B (en) * | 2008-02-01 | 2011-04-13 | 中国科学院成都生物研究所 | Preparation of 6-O-sulfonyl-glycal compound |
| CN101747304B (en) * | 2008-11-28 | 2012-01-04 | 中国科学院成都生物研究所 | Method for preparing glycal |
| CN102397270A (en) * | 2010-09-17 | 2012-04-04 | 苏州天人合生物技术有限公司 | Application of glucal and glucal derivative in preparation of drugs |
| US20130005954A1 (en) * | 2011-06-28 | 2013-01-03 | Apicore, Llc | Process for preparing heparinoids and intermediates useful in the synthesis thereof |
| CN103142626A (en) * | 2010-07-21 | 2013-06-12 | 苏州天人合生物技术有限公司 | Application of triacetyl glucal in preparation of antitumor drug |
| CN103142627A (en) * | 2010-07-21 | 2013-06-12 | 苏州天人合生物技术有限公司 | Application of triacetyl glucal in preparation of antiviral drug |
| CN103288789A (en) * | 2013-06-04 | 2013-09-11 | 华东师范大学 | Preparation method of fully-acylated glycal |
| CN103951720A (en) * | 2014-04-29 | 2014-07-30 | 河南孟成生物药业股份有限公司 | Super maduramicin and synthesis method thereof |
| CN102115483B (en) * | 2009-12-30 | 2014-12-17 | 苏州天人合生物技术有限公司 | Halogenated dideoxy sugar derivative, preparation method and application thereof |
| CN112321541A (en) * | 2020-12-08 | 2021-02-05 | 南京先之达医药科技有限公司 | Synthesis method of hydroxypropyl tetrahydrofuran |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324798A (en) * | 2000-05-24 | 2001-12-05 | 中国科学院生态环境研究中心 | Synthesis of mannitose-glucose tetrasaccharide repeated unit with anti-tumor activity |
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2005
- 2005-12-30 CN CNB2005101349523A patent/CN100357305C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100579973C (en) * | 2007-02-13 | 2010-01-13 | 中国科学院成都生物研究所 | Process for producing glucal |
| CN101289439B (en) * | 2007-04-16 | 2011-04-06 | 中国科学院成都生物研究所 | Process for preparing arabglycal |
| CN101497591B (en) * | 2008-02-01 | 2011-04-13 | 中国科学院成都生物研究所 | Preparation of 6-O-sulfonyl-glycal compound |
| CN101747304B (en) * | 2008-11-28 | 2012-01-04 | 中国科学院成都生物研究所 | Method for preparing glycal |
| CN102115483B (en) * | 2009-12-30 | 2014-12-17 | 苏州天人合生物技术有限公司 | Halogenated dideoxy sugar derivative, preparation method and application thereof |
| CN103142627A (en) * | 2010-07-21 | 2013-06-12 | 苏州天人合生物技术有限公司 | Application of triacetyl glucal in preparation of antiviral drug |
| CN103142626A (en) * | 2010-07-21 | 2013-06-12 | 苏州天人合生物技术有限公司 | Application of triacetyl glucal in preparation of antitumor drug |
| CN103142626B (en) * | 2010-07-21 | 2014-08-20 | 苏州天人合生物技术有限公司 | Application of triacetyl glucal in preparation of antitumor drug |
| CN103142627B (en) * | 2010-07-21 | 2014-08-20 | 苏州天人合生物技术有限公司 | Application of triacetyl glucal in preparation of antiviral drug |
| CN101935313B (en) * | 2010-09-15 | 2011-12-28 | 山西农业大学 | Method for ultrasonically synthesizing glycal |
| CN101935313A (en) * | 2010-09-15 | 2011-01-05 | 山西农业大学 | Method for ultrasonically synthesizing glycal |
| CN102397270A (en) * | 2010-09-17 | 2012-04-04 | 苏州天人合生物技术有限公司 | Application of glucal and glucal derivative in preparation of drugs |
| CN102397270B (en) * | 2010-09-17 | 2014-02-05 | 苏州天人合生物技术有限公司 | Application of glucal and glucal derivative in preparation of drugs |
| US20140336369A1 (en) * | 2011-06-28 | 2014-11-13 | Apicore Us Llc | Process for preparing heparinoids and intermediates useful in the synthesis thereof |
| US20130005954A1 (en) * | 2011-06-28 | 2013-01-03 | Apicore, Llc | Process for preparing heparinoids and intermediates useful in the synthesis thereof |
| CN103288789A (en) * | 2013-06-04 | 2013-09-11 | 华东师范大学 | Preparation method of fully-acylated glycal |
| CN103288789B (en) * | 2013-06-04 | 2016-01-20 | 华东师范大学 | A kind of preparation method of full acidylate thin malt sugar |
| CN103951720A (en) * | 2014-04-29 | 2014-07-30 | 河南孟成生物药业股份有限公司 | Super maduramicin and synthesis method thereof |
| CN103951720B (en) * | 2014-04-29 | 2016-01-20 | 河南孟成生物药业股份有限公司 | Super Maduramicin and synthetic method thereof |
| CN112321541A (en) * | 2020-12-08 | 2021-02-05 | 南京先之达医药科技有限公司 | Synthesis method of hydroxypropyl tetrahydrofuran |
| CN112321541B (en) * | 2020-12-08 | 2023-03-28 | 南京先达医药科技有限公司 | Synthesis method of hydroxypropyl tetrahydropyrane triol |
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