CN1800193A - 2-deoxidized glucose preparation method - Google Patents
2-deoxidized glucose preparation method Download PDFInfo
- Publication number
- CN1800193A CN1800193A CN 200510122912 CN200510122912A CN1800193A CN 1800193 A CN1800193 A CN 1800193A CN 200510122912 CN200510122912 CN 200510122912 CN 200510122912 A CN200510122912 A CN 200510122912A CN 1800193 A CN1800193 A CN 1800193A
- Authority
- CN
- China
- Prior art keywords
- deoxyglucose
- glucal
- add
- reaction
- preparation
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Landscapes
- Saccharide Compounds (AREA)
Abstract
The invention discloses a method for preparing for 2-deoxyglucose. The method uses D-acetylated dextroglucose and the absolute methanol to obtain the D-gluglucosan on the accelerating effect, and then it dose vacuum distillation to evaporate to dryness the methanol, it adds sulfuric acid water solution on the reacting machine to obtain the 2-deoxyglucose by hydrolyzing, it then uses normal method to do re-crystallization to the course product to obtain the 2-deoxyglucose product.
Description
One, technical field
The present invention relates to a kind of preparation method of organic compound, specifically relate to the preparation method of 2-deoxyglucose.
Two, background technology
Preparation method at present known 2-deoxyglucose has a lot; on U.S. chemical abstract (CA), can retrieve more than ten kinds; IN187908 goes on foot and obtains 2-deoxyglucose (I) through transesterify, hydrolysis two promptly from D-acetylated glucal (II):
This synthetic method is simple to operate, and cost is also lower, but has used the bigger heavy metal barium of toxicity, and second small step in the first step can be streamlined any further.
The synthetic method of latest report (PCT Int.Appl., 2004058786,15 Jul 2004) is from glucal, goes on foot through three and obtains the 2-deoxyglucose.
Though the product purity that this synthetic method obtains is higher, and is more loaded down with trivial details, cost is very high, is not suitable for scale operation and popularization.
Three, summary of the invention
The objective of the invention is to solve big, the shortcomings such as reaction process is loaded down with trivial details, cost height of toxicity that exist among the preparation method of existing 2-deoxyglucose, we provide the method for simple and effective Synthetic 2-deoxyglucose that a kind of toxicity is little, reaction process is simple, cost is low.
A kind of method for preparing the 2-deoxyglucose, its preparation process is as follows:
(1) at first in a reactor, adds D-acetylated glucal (II) and anhydrous methanol, after the stirring and dissolving, slowly add sodium Metal 99.5, generate sodium methylate, generate D-glucal (III) then under the katalysis of sodium methylate, distillation is the methyl alcohol evaporate to dryness, and is standby;
(2) in No. two reactors, add water then, add the vitriol oil, stir also cooling, in the reactor of aqueous sulfuric acid suction in No. two reactors, stir and insulation after, add the reagent neutralization, freezing, centrifugal, dry 2-deoxyglucose crude product;
(3) the crude product recrystallization is got finished product: promptly get crude product and add in another reactor, add dehydrated alcohol, heating for dissolving, the cooling, add the gac press filtration to reactor, cool off, dry 2-deoxyglucose finished product.
Its chemical equation is as follows:
In the reaction that generates D-glucal (III); D-acetylated glucal and anhydrous methanol, mole ratio be 1: 20-1: 100; with the mole ratio of sodium methylate be 1: 0.005-1: 0.05; the preferred mole ratio of D-acetylated glucal and anhydrous methanol, sodium methylate is 1: 56: 0.02; sodium methylate can be bought commercially available, but preferably existing with now doing.
In the reaction that generates 2-deoxyglucose (I); the volumetric molar concentration of the vitriol oil can be from 0.01M-2M; but temperature will be accordingly from high to low (50 ℃--5 ℃); the consumption of aqueous sulfuric acid is decided with the D-acetylated glucal; its mole ratio can be 150: 1-75: 1, and preferably mole ratio is 100: 1.
In the reaction that generates D-glucal (III), temperature of reaction is 20 ℃-65 ℃, reaction times 24-4 hour, adopts higher temperature of reaction to shorten the reaction times accordingly.
In the reaction that generates 2-deoxyglucose (I), if adopt higher vitriolic concentration, its temperature of reaction should be below 5 ℃.
In the aftertreatment that generates D-glucal (III), the used reagent of neutralization reaction is sodium hydroxide or yellow soda ash, is preferably sodium hydroxide, and PH is controlled between 6.8～7.3, in and the time temperature can not surpass temperature of reaction.
The recrystallization of producing crude product and crude product from reaction solution all adopts conventional method, but two-step crystallization must be as cold as below-5 ℃ and keep 24 hours.
Preparation method of the present invention had both saved the process of separation of intermediates D-glucal (III), had avoided more highly toxic barium salt again, had both reduced and had produced this, had improved quality product and yield again, and its yield reaches 71.4%, and is suitable for large-scale industrial production.
Four, embodiment
Come further to understand characteristics of the present invention and effect with the following Examples:
In the 500L reactor, add 60kg D-acetylated glucal, anhydrous methanol 400L, stirring and dissolving slowly adds the 400g sodium Metal 99.5, and reacting liquid pH value is about about 10, and control reaction temperature was 25 ℃ of insulations 12 hours.Insulation finishes, and opens the vacuum pump underpressure distillation, adds entry 400kg in another 500L reactor, vitriol oil 10kg, stir logical cool brine cooling, cool the temperature to 0 ℃, the distillation of 500L reactor finishes, get the D-glucal, material vacuum in the 500L reactor is drawn in the 500L reactor of sulfuric acid water, stirs insulation 12 hours, temperature is controlled at insulation end between-2～5 ℃, the neutralization of hydro-oxidation sodium is about adjust pH to 7.0.Neutralization finishes, and adds gac 10KG, is warming up to 70 ℃ of insulations 2 hours, and insulation finishes, press filtration is to the 500L reactor, and vacuum pump is driven in vacuum distilling, heats up to stir distillation, temperature in the kettle is controlled at 70 ℃, and distillation finishes, and is cooled to 50 ℃, adds dehydrated alcohol 200L heating for dissolving.Temperature rises to boiling reflux, and insulation is to molten entirely, adds gac 5kg after molten entirely.Be incubated 1 hour, cold slightly, press filtration is to crystallization kettle, and it is freezing to feed icy salt solution in the crystallization kettle chuck, temperature control-5 ℃, freezing 24 hours, with centrifugal refrigerated material, dry 28KG2-deoxyglucose crude product.
Get crude product and put into the 500L stainless steel cauldron, add dehydrated alcohol 200L, heating for dissolving, it is transparent that solution is, about 50 ℃ of water cooling temperature.Add gac 3KG, be heated to backflow.Stop heating, cold slightly, press filtration is to crystallization kettle.Crystallization kettle chuck feeding icy salt solution is freezing, and-5 ℃, freezing 24 hours centrifugal, and oven dry gets 23KG2-deoxyglucose finished product, yield 71.4%.
Claims (6)
1, a kind of method for preparing the 2-deoxyglucose, its preparation process is as follows:
(1) at first in a reactor, adds D-acetylated glucal (II) and anhydrous methanol, after the stirring and dissolving, slowly add sodium Metal 99.5, generate sodium methylate, generate D-glucal (III) then under the katalysis of sodium methylate, distillation is the methyl alcohol evaporate to dryness, and is standby;
(2) in No. two reactors, add water then, add the vitriol oil, stir also cooling, in the reactor of aqueous sulfuric acid suction in No. two reactors, stir and insulation after, add the reagent neutralization, freezing, centrifugal, dry 2-deoxyglucose crude product;
(3) the crude product recrystallization is got finished product: promptly get crude product and add in another reactor, add dehydrated alcohol, heating for dissolving, the cooling, add the gac press filtration to reactor, cool off, dry 2-deoxyglucose finished product.
Its chemical equation is as follows:
2, the preparation method of 2-deoxyglucose according to claim 1; it is characterized in that generating in the reaction of D-glucal (III) in step (1); D-acetylated glucal (II) is 1 with the mole ratio of anhydrous methanol: 20-1: 100; with the mole ratio of sodium methylate be 1: 0.005-1: 0.05, D-acetylated glucal II and anhydrous methanol, the preferred mole ratio of sodium methylate are 1: 56-0.02.
3, the preparation method of 2-deoxyglucose according to claim 1 is characterized in that generating in D-glucal (III) reaction in step (1), and temperature of reaction is 20 ℃-65 ℃, reaction times 24-4 hour.
4, the preparation method of 2-deoxyglucose according to claim 1; it is characterized in that generating in the reaction of 2-deoxyglucose (I) in step (2); the volumetric molar concentration of the vitriol oil is 0.01M-2M; temperature of reaction is 50 ℃～-5 ℃; the mole ratio of the consumption of aqueous sulfuric acid and D-acetylated glucal is 150: 1-75: 1, and preferred mole ratio is 100: 1.
5, the preparation method of 2-deoxyglucose according to claim 1 is characterized in that the neutralization reagent described in the step (2) is sodium hydroxide or yellow soda ash, is preferably sodium hydroxide, regulates PH between 6.8-7.3.
6, the preparation method of 2-deoxyglucose according to claim 1, the recrystallization temperature that it is characterized in that the 2-deoxyglucose crude product described in the step (3) is below-5 ℃, and keeps 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101229127A CN100362009C (en) | 2005-12-07 | 2005-12-07 | 2-deoxidized glucose preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101229127A CN100362009C (en) | 2005-12-07 | 2005-12-07 | 2-deoxidized glucose preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1800193A true CN1800193A (en) | 2006-07-12 |
| CN100362009C CN100362009C (en) | 2008-01-16 |
Family
ID=36810437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101229127A Expired - Fee Related CN100362009C (en) | 2005-12-07 | 2005-12-07 | 2-deoxidized glucose preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100362009C (en) |
Cited By (7)
| 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 |
| CN102180914A (en) * | 2011-04-06 | 2011-09-14 | 华东师范大学 | Preparation method of 2-deoxidizing-D-glucose |
| CN102924540A (en) * | 2012-10-22 | 2013-02-13 | 山东鲁抗舍里乐药业有限公司 | Preparation method of 2-deoxy-D-glucose |
| CN102993242A (en) * | 2012-12-05 | 2013-03-27 | 国家海洋局第三海洋研究所 | Preparation process of marine organism source 2-deoxyglucose |
| CN103694279A (en) * | 2013-12-23 | 2014-04-02 | 江西苏克尔新材料有限公司 | Preparation method of 2-deoxy-L-ribose |
| CN105330704A (en) * | 2015-11-13 | 2016-02-17 | 天津现代职业技术学院 | Preparation method of 2-deoxy-D-glucose |
| CN115745934A (en) * | 2022-12-06 | 2023-03-07 | 北京瑞博奥医药科技有限公司 | Preparation method of 1-deuterated-2-deoxy-D-glucose |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6353095B1 (en) * | 1991-09-20 | 2002-03-05 | The Scripps Research Institute | Ketoaldonic acids having formed stereogenic centers of R configuration: methods and compositions |
-
2005
- 2005-12-07 CN CNB2005101229127A patent/CN100362009C/en not_active Expired - Fee Related
Cited By (10)
| 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 |
| CN102180914A (en) * | 2011-04-06 | 2011-09-14 | 华东师范大学 | Preparation method of 2-deoxidizing-D-glucose |
| CN102924540A (en) * | 2012-10-22 | 2013-02-13 | 山东鲁抗舍里乐药业有限公司 | Preparation method of 2-deoxy-D-glucose |
| CN102924540B (en) * | 2012-10-22 | 2015-12-16 | 山东鲁抗舍里乐药业有限公司 | A kind of preparation method of 2-deoxy-D-glucose |
| CN102993242A (en) * | 2012-12-05 | 2013-03-27 | 国家海洋局第三海洋研究所 | Preparation process of marine organism source 2-deoxyglucose |
| CN103694279A (en) * | 2013-12-23 | 2014-04-02 | 江西苏克尔新材料有限公司 | Preparation method of 2-deoxy-L-ribose |
| CN103694279B (en) * | 2013-12-23 | 2015-12-02 | 江西苏克尔新材料有限公司 | A kind of method preparing 2-deoxidation-L-ribose |
| CN105330704A (en) * | 2015-11-13 | 2016-02-17 | 天津现代职业技术学院 | Preparation method of 2-deoxy-D-glucose |
| CN105330704B (en) * | 2015-11-13 | 2019-05-10 | 天津现代职业技术学院 | The preparation method of 2-deoxy-D-glucose |
| CN115745934A (en) * | 2022-12-06 | 2023-03-07 | 北京瑞博奥医药科技有限公司 | Preparation method of 1-deuterated-2-deoxy-D-glucose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100362009C (en) | 2008-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100362009C (en) | 2-deoxidized glucose preparation method | |
| CN100999516B (en) | Purifying process of glycolide | |
| CN1803818A (en) | Method for preparing acetylated glucal | |
| CN100348603C (en) | Process for synthesis of hydroxy ethidene diphosphoric acid | |
| CN101880248A (en) | Synthetic reaction of calcium dobesilate hydrate | |
| CN105037139A (en) | Preparation method for 2-phenylpropionic acid | |
| CN101979713A (en) | Method for electrolytic synthesis of parahydroxybenzaldehyde | |
| CN107673985A (en) | A kind of high yield N, the preparation technology of N DMAAs | |
| CN101781264B (en) | Production method of 1-methyl-5-mercapto-1,2,3,4-tetrazole | |
| CN112479938B (en) | Preparation method of N-cyclohexyl-2-aminoethanesulfonic acid | |
| CN110862413A (en) | Glyphosate synthesis process and device | |
| CN101381297B (en) | Method for separating caprylic acid from mixture of caprylic acid and capric acid | |
| CN101712615A (en) | Method for preparing crystal glyoxylic acid | |
| CN1209329C (en) | Method for producing double pentaerythritol | |
| CN106380441B (en) | Synthetic method of fexofenadine intermediate | |
| CN101402576A (en) | Method for producing bi(2-hydroxyethyl)imino-tri(hydroxymethyl)methyl hydride | |
| CN1907973A (en) | Process for preparing 2,3-cyclopentene pyridine | |
| CN1418883A (en) | Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid | |
| CN101565369B (en) | Method for preparing 3-bromine-5-trifluoromethylbenzoic acid | |
| CN1927808A (en) | Method of preparing 2,2-dimethyl-1-hydroxypropionic acid by chemical oxidization | |
| CN112062688B (en) | Preparation method of N, N-diethyl acetamide | |
| CN111269083B (en) | Synthesis method of guerbet acid | |
| CN109400468B (en) | Preparation method of L-dibenzoyl dimethyl tartrate | |
| CN1687096A (en) | Method for synthesizing fatty ester of maltose | |
| CN101434529A (en) | Chemical synthesis formula and process of veratone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081128 Address after: No. 8, phoenix garden, Longfeng garden, Longjiang District, Gulou District, Jiangsu, Nanjing 501, China Patentee after: Zhu Shuhan Address before: Room 1602, Tian An International Building, No. 122, Zhongshan South Road, Nanjing, Jiangsu Patentee before: Jiangsu Hanfa Trade Development Co., Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: ZHU SHUHAN Free format text: FORMER OWNER: JIANGSU HANFA TRADE DEVELOPMENT CO., LTD. Effective date: 20081128 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080116 Termination date: 20111207 |