CN102731582B - Preparation method of acetyl halogenated saccharide - Google Patents
Preparation method of acetyl halogenated saccharide Download PDFInfo
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- CN102731582B CN102731582B CN201210236637.1A CN201210236637A CN102731582B CN 102731582 B CN102731582 B CN 102731582B CN 201210236637 A CN201210236637 A CN 201210236637A CN 102731582 B CN102731582 B CN 102731582B
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Abstract
The invention provides a preparation method of acetyl halogenated saccharide, which comprises the following steps: monosaccharide, excess acetic anhydride and excess pyridine are mixed to perform a first reaction, in order to obtain a first mixed product; the first mixed product is added with water to perform a second reaction, in order to obtain a second mixed product; the second mixed product is extracted by an organic solvent, and the organic phase is collected; the organic phase is washed by water and distilled at 20-30 degrees centigrade in sequence to obtain acetylated saccharide; the acetylated saccharide is mixed with a halogen hydride solution to perform a third reaction, in order to obtain the acetyl halogenated saccharide. In the process of preparing acetyl halogenated saccharide, excess acetic anhydride is removed by a quenching method, pyridine is removed by water washing, and the organic solvent is removed by distilling at 20-30 degrees centigrade to obtain pure acetylated saccharide, so that the high-temperature and low-vacuum distillation process of excess acetic anhydride and pyridine is avoided; the damage of intermediate products to the acetylated saccharide is reduced; and the purity and yield of the product are improved effectively.
Description
Technical field
The present invention relates to sugar compounds field, relate in particular to a kind of preparation method of ethanoyl halogeno-sugar.
Background technology
Saccharide compound is to contain the general name that can generate a compounds of poly-hydroxy aldehyde or polyhydroxyketone after poly-hydroxy aldehyde or polyhydroxyketone and hydrolysis.In natural biological substance, saccharide compound accounts for 3/4, all contains saccharide compound from bacterium to higher animal, and therefore saccharide compound is called as the organic compound that distributed in nature is the most extensive, quantity is maximum.Saccharide compound is also the sustain life main source of activity institute energy requirement of organism, and the energy about 80% of mankind's picked-up is provided by carbohydrate.Saccharide compound, as the basic raw material of synthetic other compounds, is also widely used in medical chemistry field simultaneously.
Saccharide compound can be divided into monose, oligosaccharides and polysaccharide, and monose is the simplest sugar of a class formation, is the sugar unit that can not be hydrolyzed again.The monose of ethanoyl protection is widely used in the fields such as organic medicine intermediate, tensio-active agent and additive.Ethanoyl halogeno-sugar prepared by the monose of being protected by ethanoyl, as the important intermediate of synthetic sugar esters compounds, becomes the study hotspot of biomedical sector.
Preparing in the process of ethanoyl halogeno-sugar, generally adopt aceticanhydride and pyridine that monose is carried out to acetylize protection, obtain acetylize sugar; Then acetylize sugar is carried out to halogenating reaction, obtain ethanoyl halogeno-sugar.In order to ensure making full use of of monose, excessive mode is prepared ethanoyl halogeno-sugar to adopt aceticanhydride and pyridine, but in order to ensure the purity of final product ethanoyl halogeno-sugar, excessive aceticanhydride and pyridine must be removed.In prior art, report a kind of method of preparing ethanoyl halogeno-sugar, be specially: adopt excessive aceticanhydride and excessive pyridine that monose is carried out to acetylize protection, then under 60 ~ 70 DEG C, the condition of rough vacuum, distill, excessive aceticanhydride and excessive pyridine are removed, obtain acetylize sugar; Finally acetylize sugar is carried out to halogenating reaction, thereby obtain ethanoyl halogeno-sugar.But; aforesaid method adopts the method for distillation at 60 ~ 70 DEG C to remove excessive aceticanhydride and pyridine; because the temperature of distillation is higher; and then cause acetylize sugar at high temperature destroyed; affect the productive rate of ethanoyl halogeno-sugar; the purity of the ethanoyl halogeno-sugar obtaining is 99% ~ 99.5%, and productive rate is 60 ~ 65%.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of the ethanoyl halogeno-sugar with higher yields and purity.
In view of this, the invention provides a kind of preparation method of ethanoyl halogeno-sugar, comprise the following steps:
Monose, excessive aceticanhydride and excessive pyridine are mixed, carry out first set reaction, obtain the first mix products;
In described the first mix products, add water, react for the second time, obtain the second mix products;
The second mix products described in employing organic solvent extraction, collects organic phase;
Described organic phase is washed successively and distilled, obtain acetylize sugar, the temperature of described distillation is 20 ~ 30 DEG C;
Described acetylize sugar and hydrogen halide solution are mixed, react for the third time, obtain ethanoyl halogeno-sugar.
Preferably, described monose is L-arabinose, D-ribose or D-Glucose.
Preferably, the temperature of described first set reaction is 20 ~ 25 DEG C, and the time of described first set reaction is 20 ~ 24h.
Preferably, described organic solvent is methylene dichloride or chloroform.
Preferably, the acetum that described hydrogen halide solution is hydrogen halide.
Preferably, the mol ratio of described monose, aceticanhydride, pyridine, hydrogen halide is 1:(4 ~ 5): (0.5 ~ 0.7): (1.0 ~ 1.5).
Preferably, the step that obtains ethanoyl halogeno-sugar described in is specially:
In described acetylize sugar, add hydrogen halide solution, react for the third time, add mixed solvent, stir, filter, obtain ethanoyl halogeno-sugar, the described time of reaction is for the third time 1 ~ 2h.
Preferably, described mixed solvent is t-butyl methyl ether and isohexane.
Preferably, the volume ratio of described t-butyl methyl ether and described isohexane is 1:1 ~ 3.
Preferably, the time of described stirring is 0.5 ~ 1.5h.
The invention provides a kind of preparation method of ethanoyl halogeno-sugar, first select excessive aceticanhydride and excessive pyridine that monose is carried out to acetylize, obtain the acetylize sugar that contains aceticanhydride and pyridine; Add subsequently water to react with unreacted aceticanhydride, obtain acetic acid; Adopt organic solvent by acetylize sugar, excessive pyridine, acetic acid and the water extraction phase-splitting of generation, acetylize sugar, pyridine and the acetic acid separated are washed, to remove acetic acid and pyridine; Then by the distillation at 20 ~ 30 DEG C of low temperature of organic solvent and acetylize sugar, thereby obtain highly purified acetylize sugar; Finally acetylize sugar is reacted with hydrogen halide solution, obtain ethanoyl halogeno-sugar.The present invention, preparing in the process of ethanoyl halogeno-sugar, by adding water to react with unreacted aceticanhydride, has formed the acetic acid that dissolves in organic solvent, and aceticanhydride is removed; Then utilize the acetic acid of organic solvent extraction acetylize sugar, unreacted pyridine and generation; Because acetylize sugar is water insoluble, acetylize sugar, pyridine and the acetic acid separated are washed, thereby acetic acid and pyridine are removed, finally obtain highly purified ethanoyl halogeno-sugar.In whole process, avoid adopting pyrogenous method to remove excessive aceticanhydride and pyridine, to the destruction of intermediate product acetylize sugar, thereby improve the productive rate of ethanoyl halogeno-sugar.Experimental result shows, the purity of ethanoyl halogeno-sugar prepared by the present invention is 99.5% ~ 99.8%, and productive rate is 70% ~ 80%.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the acetyl acetylbromoglycose prepared of the embodiment of the present invention 3.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of preparation method who prepares acetylglycosyl bromide, comprise the following steps:
Monose, excessive aceticanhydride and excessive pyridine are mixed, carry out first set reaction, obtain the first mix products;
In described the first mix products, add water, react for the second time, obtain the second mix products;
The second mix products described in employing organic solvent extraction, collects organic phase;
Described organic phase is washed successively and distilled, obtain acetylize sugar, the temperature of described distillation is 20 ~ 30 DEG C;
Described acetylize sugar and hydrogen halide solution are mixed, react for the third time, obtain ethanoyl halogeno-sugar.
Preparing in the process of ethanoyl halogeno-sugar, first monose is carried out to acetylize protection, this step is to prepare the committed step of ethanoyl halogeno-sugar.As preferred version, first the present invention is placed in reactor by excessive aceticanhydride and excessive pyridine, opens and stirs; the temperature of controlling reactor is 10 ~ 15 DEG C; then in reactor, add monose, react, obtain the first mix products that contains acetylize sugar, unreacted aceticanhydride and pyridine.The temperature of described reaction is preferably 20 ~ 25 DEG C, and more preferably 21 ~ 24 DEG C, the time of reaction is preferably 20 ~ 24h, more preferably 21 ~ 23h.In order to ensure sufficient reacting, the environmental optimization of above-mentioned reaction is water-less environment, and water-content is less than 0.1%.For monose is fully reacted, as preferred version, by a plate detection reaction terminal.
In order to ensure purity and the productive rate of ethanoyl halogeno-sugar, excessive pyridine and aceticanhydride must be removed.The present invention adopts water by excessive aceticanhydride cancellation, and the principle of described cancellation refers to reacts with it with the another kind of compound reacting with excessive compound, thereby excessive compound is removed from system.The present invention, by adding water to react with excessive aceticanhydride, generates acetic acid, thereby aceticanhydride is removed.In the excessive aceticanhydride of cancellation, pyridine is also dissolved in the water.Described water is preferably deionized water.The process of cancellation aceticanhydride is specially: in reactor, add deionized water, stir 1 ~ 2h, deionized water reacts with aceticanhydride, obtains the second mix products that contains acetic acid, pyridine, acetylize sugar and water.
Adopt subsequently organic solvent extraction the second mix products, make organic phase and aqueous phase separation.As preferred version, the process of extraction the second mix products is specially: in the second mix products, add organic solvent, stir 10 ~ 20min, leave standstill 10 ~ 30min, water is separated with organic phase, collect organic phase.In described organic phase, contain aceticanhydride, pyridine and acetylize sugar, because acetylize sugar is water insoluble, therefore by organic phase washing, to remove acetic acid and pyridine.Preferably adopt washed with de-ionized water organic phase twice, and add anhydrous sodium sulfate drying, to remove acetic acid and pyridine.Removing after acetic acid and pyridine, organic solvent and acetylize sugar mix, and organic solvent and acetylize sugar are distilled at 20 ~ 30 DEG C, thereby obtain highly purified acetylize sugar.Above-mentioned monose is preferably L-arabinose, D-ribose or D-Glucose.Above-mentioned organic solvent is preferably the water-soluble very poor organic solvent such as methylene dichloride, chloroform.In summary, the present invention, removing in the process of excessive and pyridine, utilizes water to react with unreacted aceticanhydride, has formed the acetic acid that dissolves in organic solvent, and aceticanhydride is removed; Then utilize the acetic acid of organic solvent extraction acetylize sugar, unreacted pyridine and generation; because acetylize sugar is water insoluble; acetylize sugar, pyridine and the acetic acid separated are washed, thereby acetic acid and pyridine are removed, finally obtain highly purified acetylize sugar.
Obtaining after acetylize sugar, acetylize sugar is being reacted with hydrogen halide solution, obtaining ethanoyl halogeno-sugar.Above-mentioned hydrogen halide solution is preferably the acetum of hydrogen halide, and sour environment that described acetum provides hydrogen halide and acetylize sugar to react has promoted fully reacting of hydrogen halide and acetylize sugar.As preferred version; the step that obtains ethanoyl halogeno-sugar is specially: to the acetum that adds hydrogen halide in acetylize sugar; after 20 ~ 25 DEG C of reaction 1 ~ 2h, be cooled to 0 ~ 7 DEG C; add the mixed solvent of t-butyl methyl ether and isohexane; at 0 ~ 7 DEG C, stir 0.5 ~ 1.5h; filter, obtain ethanoyl halogeno-sugar.The effect of the mixed solvent of above-mentioned methyl tertiary butyl ether and isohexane is that ethanoyl halogeno-sugar is separated out, and the volume ratio of above-mentioned methyl tertiary butyl ether and isohexane is preferably 1:1 ~ 3.Preparing in the process of ethanoyl haloalkane, the mol ratio of described monose, described aceticanhydride, described pyridine, described hydrogen halide is preferably 1:(4 ~ 5): (0.5 ~ 0.7): (1.0 ~ 1.5).
The present invention is preparing in the process of ethanoyl halogeno-sugar; adopt the method for cancellation to remove excessive aceticanhydride; by washing, excessive pyridine is removed again; and distill out organic solvent at 20 ~ 30 DEG C; obtain pure acetylize sugar; avoid high temperature and rough vacuum to distill the process of excessive aceticanhydride and pyridine, reduced the destruction to intermediate product acetylize sugar, thereby effectively raised purity and the productive rate of product.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of ethanoyl halogeno-sugar provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
In reactor, add 4mol aceticanhydride and 0.5mol pyridine to open stirring, controlling temperature in the kettle is 15 DEG C, in reactor, adds 1mol L-arabinose, and controlling temperature of reaction is 20 DEG C, and stirring reaction 20 hours, by a plate detection reaction terminal.In reactor, add 5mol deionized water to stir 1 hour, add 10mol methylene dichloride to stir after 10 minutes, leave standstill phase-splitting in 20 minutes; Adopt 5mol deionized water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying to filter.Organic phase is transferred in the dry reactor of another, vacuum distilling below 30 DEG C, it is 19% that organic phase is distilled to LOD.Be 30% hydrogen bromide acetic acid solution to adding concentration in reactor, the hydrogen bromide in hydrogen bromide acetic acid solution is 1mol, and 25 DEG C of reactions of temperature control were cooled to 0 DEG C after 1.5 hours.To the mixed solution that adds 5mol t-butyl methyl ether and isohexane in reactor, 0 DEG C is stirred 1 hour, filters and obtains solid phase prod 0.7251mol, and by bromide anion titration testing product purity 99.72%, product yield is 72.51%.
Embodiment 2
In reactor, add 5mol aceticanhydride, 0.7mol pyridine to open stirring, controlling temperature in the kettle is 20 DEG C.In reactor, add 1mol L-arabinose, controlling temperature of reaction is 20 DEG C, and stirring reaction 24 hours, by a plate detection reaction terminal.In reactor, add 5mol deionized water to stir 1 hour, add 10mol methylene dichloride to stir after 10 minutes, leave standstill phase-splitting in 20 minutes.Adopt 5mol deionized water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying to filter.Organic phase is transferred in the dry reactor of another, vacuum distilling below 30 DEG C, it is 15% that organic phase is distilled to LOD.Be 30% hydrogen bromide acetic acid solution to adding concentration in reactor, the hydrogen bromide in hydrogen bromide acetic acid solution is 1.16mol, and 25 DEG C of reactions of temperature control were cooled to 7 DEG C after 1.5 hours.To the mixed solution that adds 5mol t-butyl methyl ether and isohexane in reactor, 0 DEG C is stirred 1 hour, filters and obtains solid phase prod 0.75mol, and by bromide anion titration testing product purity 99.53%, product yield is 75%.
Embodiment 3
In reactor, add 5mol aceticanhydride, 0.7mol pyridine to open stirring, controlling temperature in the kettle is 20 DEG C.In reactor, add 1mol D-Glucose, controlling temperature of reaction is 20 DEG C, and stirring reaction 24 hours, by a plate detection reaction terminal.In reactor, add 5mol deionized water to stir 1 hour, add 10mol methylene dichloride to stir after 10 minutes, leave standstill phase-splitting in 20 minutes.Adopt 5mol deionized water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying to filter.Organic phase is transferred in the dry reactor of another, vacuum distilling below 30 DEG C, it is 15% that organic phase is distilled to LOD.Be 30% hydrogen bromide acetic acid solution to adding concentration in reactor, the hydrogen bromide in hydrogen bromide acetic acid solution is 1.5mol, and 25 DEG C of reactions of temperature control were cooled to 7 DEG C after 1.5 hours.To the mixed solution that adds 5mol t-butyl methyl ether and isohexane in reactor, 0 DEG C is stirred 1 hour, filters and obtains solid phase prod 0.78mol, and by bromide anion titration testing product purity 99.53%, product yield is 78%.Fig. 1 is the nucleus magnetic hydrogen spectrum figure of acetyl acetylbromoglycose, and hence one can see that, and acetyl acetylbromoglycose can be prepared.
Embodiment 4
In reactor, add 4mol aceticanhydride, 0.5mol pyridine to open stirring, controlling temperature in the kettle is 20 DEG C.In reactor, add 1mol D-ribose, controlling temperature of reaction is 20 DEG C, and stirring reaction 24 hours, by a plate detection reaction terminal.In reactor, add 5mol deionized water to stir 1 hour, add 10mol methylene dichloride to stir after 10 minutes, leave standstill phase-splitting in 20 minutes.Adopt 5mol deionized water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying to filter.Organic phase is transferred in the dry reactor of another, 30 DEG C of following vacuum distillings, it is 15% that organic phase is distilled to LOD.Be 30% hydrogen bromide acetic acid solution to adding concentration in reactor, the hydrogen bromide in hydrogen bromide acetic acid solution is 1.5mol, and 25 DEG C of reactions of temperature control were cooled to 7 DEG C after 1.5 hours.To the mixed solution that adds 5mol t-butyl methyl ether and isohexane in reactor, 0 DEG C is stirred 1 hour, filters and obtains solid phase prod 0.76mol, and by bromide anion titration testing product purity 99.53%, product yield is 76%.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (6)
1. a preparation method for ethanoyl halogeno-sugar, is characterized in that, comprises the following steps:
Excessive aceticanhydride and excessive pyridine are placed in to reactor, open and stir, the temperature of controlling reactor is 10～15 DEG C, then in reactor, adds monose, carry out first set reaction, obtain the first mix products that contains acetylize sugar, unreacted aceticanhydride and pyridine; The temperature of described first set reaction is 20～25 DEG C, and the time of described first set reaction is 20～24h;
In described the first mix products, add water, react for the second time, obtain the second mix products;
The second mix products described in employing organic solvent extraction, collects organic phase;
Described organic phase is washed successively and distilled, obtain acetylize sugar, the temperature of described distillation is 20～30 DEG C;
In described acetylize sugar, add hydrogen halide solution, react for the third time, add mixed solvent, stir, filter, obtain ethanoyl halogeno-sugar, the described time of reaction is for the third time 1～2h; Described mixed solvent is t-butyl methyl ether and isohexane;
The mol ratio of described monose, aceticanhydride, pyridine, hydrogen halide is 1:(4～5): (0.5～0.7): (1.0～1.5).
2. preparation method according to claim 1, is characterized in that, described monose is L-arabinose, D-ribose or D-Glucose.
3. preparation method according to claim 1, is characterized in that, described organic solvent is methylene dichloride or chloroform.
4. preparation method according to claim 1, is characterized in that, the acetum that described hydrogen halide solution is hydrogen halide.
5. preparation method according to claim 1, is characterized in that, the volume ratio of described t-butyl methyl ether and described isohexane is 1:1～3.
6. preparation method according to claim 1, is characterized in that, the time of described stirring is 0.5～1.5h.
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