CN102731582A - Preparation method of acetyl halogenated saccharide - Google Patents
Preparation method of acetyl halogenated saccharide Download PDFInfo
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- CN102731582A CN102731582A CN2012102366371A CN201210236637A CN102731582A CN 102731582 A CN102731582 A CN 102731582A CN 2012102366371 A CN2012102366371 A CN 2012102366371A CN 201210236637 A CN201210236637 A CN 201210236637A CN 102731582 A CN102731582 A CN 102731582A
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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 the 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 the hydrolysis.Saccharide compound accounts for 3/4 in the natural biological substance, from the bacterium to the higher animal, all contains saccharide compound, so saccharide compound is called as the organic cpds that distributed in nature is the most extensive, quantity is maximum.Saccharide compound also is the earn a bare living main source of activity institute energy requirement of organism, and the energy of human picked-up about 80% is provided by carbohydrate.Saccharide compound has also obtained using widely in the medical chemistry field as the basic raw material of synthetic other compounds 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 fields such as organic medicine intermediate, tensio-active agent and additive.The ethanoyl halogeno-sugar that the monose of being protected by ethanoyl prepares becomes the research focus of biomedical sector as the important intermediate of synthetic sugar esters compounds.
In the process of preparation ethanoyl halogeno-sugar, generally adopt aceticanhydride and pyridine that monose is carried out the acetylize protection, obtain acetylize sugar; Then acetylize sugar is carried out halogenating reaction, obtain the ethanoyl halogeno-sugar.In order to guarantee making full use of of monose, adopt aceticanhydride and the excessive mode of pyridine to prepare the ethanoyl halogeno-sugar, yet, must excessive aceticanhydride and pyridine be removed in order to guarantee the purity of final product ethanoyl halogeno-sugar.Reported a kind of method for preparing the ethanoyl halogeno-sugar in the prior art; Be specially: adopt excessive aceticanhydride and excessive pyridine that monose is carried out the acetylize protection; Under 60 ~ 70 ℃, the condition of rough vacuum, distill then, excessive aceticanhydride and excessive pyridine are removed, obtain acetylize sugar; At last acetylize sugar is carried out halogenating reaction, thereby obtain the ethanoyl halogeno-sugar.But; Aforesaid method is employed in 60 ~ 70 ℃ of following distillatory methods and removes excessive aceticanhydride and pyridine; Because the distillatory temperature is higher, and then causes acetylize sugar at high temperature to be destroyed, and has influenced the productive rate of ethanoyl halogeno-sugar; The purity of the ethanoyl halogeno-sugar that obtains 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 with ethanoyl halogeno-sugar of higher yields and purity.
In view of this, the invention provides a kind of preparation method of ethanoyl halogeno-sugar, may further comprise the steps:
Monose, excessive aceticanhydride and excessive pyridine are mixed, carry out first set reaction, obtain first mix products;
In said first mix products, add entry, carry out the reaction second time, obtain second mix products;
Adopt said second mix products of organic solvent extraction, collect organic phase;
Said organic phase is washed successively and distilled, obtain acetylize sugar, said distillatory temperature is 20 ~ 30 ℃;
Said acetylize sugar and hydrogen halide solution are mixed, react for the third time, obtain the ethanoyl halogeno-sugar.
Preferably, said monose is L-arabinose, D-ribose or D-glucose.
Preferably, the temperature of said first set reaction is 20 ~ 25 ℃, and the time of said first set reaction is 20 ~ 24h.
Preferably, said organic solvent is methylene dichloride or chloroform.
Preferably, said hydrogen halide solution is the acetum of hydrogen halide.
Preferably, the mol ratio of said monose, aceticanhydride, pyridine, hydrogen halide is 1: (4 ~ 5): (0.5 ~ 0.7): (1.0 ~ 1.5).
Preferably, the said step that obtains the ethanoyl halogeno-sugar is specially:
In said acetylize sugar, add hydrogen halide solution, react for the third time, add mixed solvent, stir, filter, obtain the ethanoyl halogeno-sugar, the said time of reaction for the third time is 1 ~ 2h.
Preferably, said mixed solvent is t-butyl methyl ether and isohexane.
Preferably, the volume ratio of said t-butyl methyl ether and said isohexane is 1:1 ~ 3.
Preferably, the time of said stirring is 0.5 ~ 1.5h.
The invention provides a kind of preparation method of ethanoyl halogeno-sugar, at first select for use excessive aceticanhydride and excessive pyridine that monose is carried out acetylize, obtain containing the acetylize sugar of aceticanhydride and pyridine; Add the reaction of entry and unreacted aceticanhydride subsequently, obtain acetic acid; Adopt organic solvent with acetylize sugar, excessive pyridine, the 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 organic solvent and acetylize sugar are distilled down for 20 ~ 30 ℃ at low temperature, thereby obtain highly purified acetylize sugar; With acetylize sugar and hydrogen halide solution reaction, promptly obtain the ethanoyl halogeno-sugar at last.The present invention through adding the reaction of entry and unreacted aceticanhydride, has formed the acetic acid that dissolves in organic solvent in the process of preparation ethanoyl halogeno-sugar, aceticanhydride is removed; Utilize the acetic acid of organic solvent extraction acetylize sugar, unreacted pyridine and generation then; 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, avoided adopting pyrogenous method to remove excessive aceticanhydride and pyridine, to the destruction of middle product acetylize sugar, thereby improved the productive rate of ethanoyl halogeno-sugar.Experimental result shows that the purity of the ethanoyl halogeno-sugar of the present invention's preparation is 99.5% ~ 99.8%, and productive rate is 70% ~ 80%.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the acetyl bromide of the embodiment of the invention 3 preparations for glucose.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method who prepares the ethanoyl bromo sugar, may further comprise the steps:
Monose, excessive aceticanhydride and excessive pyridine are mixed, carry out first set reaction, obtain first mix products;
In said first mix products, add entry, carry out the reaction second time, obtain second mix products;
Adopt said second mix products of organic solvent extraction, collect organic phase;
Said organic phase is washed successively and distilled, obtain acetylize sugar, said distillatory temperature is 20 ~ 30 ℃;
Said acetylize sugar and hydrogen halide solution are mixed, react for the third time, obtain the ethanoyl halogeno-sugar.
In the process of preparation ethanoyl halogeno-sugar, at first monose is carried out the acetylize protection, this step is the committed step of preparation ethanoyl halogeno-sugar.As preferred version, the present invention at first places reaction kettle with excessive aceticanhydride and excessive pyridine, opens and stirs; The temperature of control reaction kettle is 10 ~ 15 ℃; In reaction kettle, add monose then, react, obtain containing first mix products of acetylize sugar, unreacted aceticanhydride and pyridine.The temperature of said reaction is preferably 20 ~ 25 ℃, and more preferably 21 ~ 24 ℃, the time of reaction is preferably 20 ~ 24h, more preferably 21 ~ 23h.In order to guarantee sufficient reacting, the environmental optimization of above-mentioned reaction is a water-less environment, and water-content is less than 0.1%.For monose is fully reacted, as preferred version, through a plate detection reaction terminal point.
For purity and the productive rate that guarantees the ethanoyl halogeno-sugar, must excessive pyridine and aceticanhydride be removed.The present invention adopts water with excessive aceticanhydride cancellation, and the principle of said cancellation is meant that the compound with another kind of and excessive compound reaction reacts with it, thereby excessive compound is removed from system.The present invention generates acetic acid, thereby aceticanhydride is removed through adding entry and excessive aceticanhydride reaction.In the excessive aceticanhydride of cancellation, pyridine also is dissolved in the water.Said water is preferably deionized water.The process of cancellation aceticanhydride is specially: in reaction kettle, add deionized water, stir 1 ~ 2h, deionized water and aceticanhydride react, and obtain containing second mix products of acetic acid, pyridine, acetylize sugar and water.
Adopt organic solvent extraction second mix products subsequently, make organic phase and aqueous phase separation.As preferred version, the process that extracts second mix products is specially: in second mix products, add organic solvent, stir 10 ~ 20min, leave standstill 10 ~ 30min, water is separated with organic phase, collect organic phase.Contain aceticanhydride, pyridine and acetylize sugar in the said organic phase, because acetylize sugar is water insoluble, therefore with the organic phase washing, to remove acetic acid and pyridine.The preferred washed with de-ionized water organic phase twice that adopts, and add anhydrous sodium sulfate drying, to remove acetic acid and pyridine.After removing acetic acid and pyridine, organic solvent and acetylize sugar mix, and organic solvent and acetylize sugar are distilled down at 20 ~ 30 ℃, thereby obtain highly purified acetylize sugar.Above-mentioned monose is preferably L-arabinose, D-ribose or D-glucose.Above-mentioned organic solvent is preferably water-soluble very poor organic solvents such as methylene dichloride, chloroform.Can know that to sum up the present invention utilizes the reaction of water and unreacted aceticanhydride in the process of removing excessive and pyridine, formed the acetic acid that dissolves in organic solvent, and aceticanhydride is removed; Utilize the acetic acid of organic solvent extraction acetylize sugar, unreacted pyridine and generation then; 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.
After obtaining acetylize sugar,, obtain the ethanoyl halogeno-sugar with acetylize sugar and hydrogen halide solution reaction.Above-mentioned hydrogen halide solution is preferably the acetum of hydrogen halide, and said acetum provides the sour environment of hydrogen halide and the reaction of acetylize sugar, has promoted the abundant reaction of hydrogen halide and acetylize sugar.As preferred version; The step that obtains the ethanoyl halogeno-sugar is specially: the acetum that in acetylize sugar, adds hydrogen halide; Behind 20 ~ 25 ℃ of reaction 1 ~ 2h, be cooled to 0 ~ 7 ℃, add the mixed solvent of t-butyl methyl ether and isohexane, 0 ~ 7 ℃ is stirred 0.5 ~ 1.5h down; Filter, obtain the ethanoyl halogeno-sugar.The effect of the mixed solvent of above-mentioned MTBE and isohexane is that the ethanoyl halogeno-sugar is separated out, and the volume ratio of above-mentioned MTBE and isohexane is preferably 1:1 ~ 3.In the process of preparation ethanoyl haloalkane, the mol ratio of said monose, said aceticanhydride, said pyridine, said hydrogen halide is preferably 1: (4 ~ 5): (0.5 ~ 0.7): (1.0 ~ 1.5).
The present invention is in the process of preparation ethanoyl halogeno-sugar; Adopt the method for cancellation to remove excessive aceticanhydride, through washing excessive pyridine is removed again, and distilled out organic solvent at 20 ~ 30 ℃; Obtain purified acetylize sugar; Avoided high temperature and rough vacuum to distill the process of excessive aceticanhydride and pyridine, reduced destruction, thereby effectively raised product gas purity and productive rate middle product acetylize sugar.
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 reaction kettle, add 4mol aceticanhydride and 0.5mol pyridine unlatching stirring, the control temperature in the kettle is 15 ℃, in reaction kettle, adds the 1mol L-arabinose, and control reaction temperature is 20 ℃, and stirring reaction 20 hours is through a plate detection reaction terminal point.In reaction kettle, add the 5mol vaal water and stirred 1 hour, add the 10mol methylene dichloride and stir after 10 minutes, leave standstill phase-splitting in 20 minutes; Adopt the 5mol vaal water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying and filter.Organic phase is transferred in the another exsiccant reaction kettle, and in vacuum distilling below 30 ℃, it is 19% that organic phase is distilled to LOD.Adding concentration is 30% hydrogen bromide acetic acid solution in reaction kettle, and the hydrogen bromide in the hydrogen bromide acetic acid solution is 1mol, and 25 ℃ of reactions of temperature control were cooled to 0 ℃ after 1.5 hours.The mixed solution that in reaction kettle, adds 5mol t-butyl methyl ether and isohexane, 0 ℃ was stirred 1 hour, filtered and obtained solid phase prod 0.7251mol, and through bromide anion titration testing product purity 99.72%, the product yield is 72.51%.
Embodiment 2
In reaction kettle, add 5mol aceticanhydride, 0.7mol pyridine unlatching stirring, the control temperature in the kettle is 20 ℃.In reaction kettle, add the 1mol L-arabinose, control reaction temperature is 20 ℃, and stirring reaction 24 hours is through a plate detection reaction terminal point.In reaction kettle, add the 5mol vaal water and stirred 1 hour, add the 10mol methylene dichloride and stir after 10 minutes, leave standstill phase-splitting in 20 minutes.Adopt the 5mol vaal water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying and filter.Organic phase is transferred in the another exsiccant reaction kettle, and in vacuum distilling below 30 ℃, it is 15% that organic phase is distilled to LOD.Adding concentration is 30% hydrogen bromide acetic acid solution in reaction kettle, and the hydrogen bromide in the hydrogen bromide acetic acid solution is 1.16mol, and 25 ℃ of reactions of temperature control were cooled to 7 ℃ after 1.5 hours.The mixed solution that in reaction kettle, adds 5mol t-butyl methyl ether and isohexane, 0 ℃ was stirred 1 hour, filtered and obtained solid phase prod 0.75mol, and through bromide anion titration testing product purity 99.53%, the product yield is 75%.
Embodiment 3
In reaction kettle, add 5mol aceticanhydride, 0.7mol pyridine unlatching stirring, the control temperature in the kettle is 20 ℃.In reaction kettle, add 1mol D-glucose, control reaction temperature is 20 ℃, and stirring reaction 24 hours is through a plate detection reaction terminal point.In reaction kettle, add the 5mol vaal water and stirred 1 hour, add the 10mol methylene dichloride and stir after 10 minutes, leave standstill phase-splitting in 20 minutes.Adopt the 5mol vaal water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying and filter.Organic phase is transferred in the another exsiccant reaction kettle, and in vacuum distilling below 30 ℃, it is 15% that organic phase is distilled to LOD.Adding concentration is 30% hydrogen bromide acetic acid solution in reaction kettle, and the hydrogen bromide in the hydrogen bromide acetic acid solution is 1.5mol, and 25 ℃ of reactions of temperature control were cooled to 7 ℃ after 1.5 hours.The mixed solution that in reaction kettle, adds 5mol t-butyl methyl ether and isohexane, 0 ℃ was stirred 1 hour, filtered and obtained solid phase prod 0.78mol, and through bromide anion titration testing product purity 99.53%, the product yield is 78%.Fig. 1 is the nucleus magnetic hydrogen spectrum figure of acetyl bromide for glucose, and hence one can see that, and acetyl bromide can prepare for glucose.
Embodiment 4
In reaction kettle, add 4mol aceticanhydride, 0.5mol pyridine unlatching stirring, the control temperature in the kettle is 20 ℃.In reaction kettle, add 1mol D-ribose, control reaction temperature is 20 ℃, and stirring reaction 24 hours is through a plate detection reaction terminal point.In reaction kettle, add the 5mol vaal water and stirred 1 hour, add the 10mol methylene dichloride and stir after 10 minutes, leave standstill phase-splitting in 20 minutes.Adopt the 5mol vaal water to clean organic phase twice, in organic phase, add anhydrous sodium sulfate drying and filter.Organic phase is transferred in the another exsiccant reaction kettle, vacuum distilling below 30 ℃, it is 15% that organic phase is distilled to LOD.Adding concentration is 30% hydrogen bromide acetic acid solution in reaction kettle, and the hydrogen bromide in the hydrogen bromide acetic acid solution is 1.5mol, and 25 ℃ of reactions of temperature control were cooled to 7 ℃ after 1.5 hours.The mixed solution that in reaction kettle, adds 5mol t-butyl methyl ether and isohexane, 0 ℃ was stirred 1 hour, filtered and obtained solid phase prod 0.76mol, and through bromide anion titration testing product purity 99.53%, the product yield is 76%.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of an ethanoyl halogeno-sugar is characterized in that, may further comprise the steps:
Monose, excessive aceticanhydride and excessive pyridine are mixed, carry out first set reaction, obtain first mix products;
In said first mix products, add entry, carry out the reaction second time, obtain second mix products;
Adopt said second mix products of organic solvent extraction, collect organic phase;
Said organic phase is washed successively and distilled, obtain acetylize sugar, said distillatory temperature is 20 ~ 30 ℃;
Said acetylize sugar and hydrogen halide solution are mixed, react for the third time, obtain the ethanoyl halogeno-sugar.
2. preparation method according to claim 1 is characterized in that, said monose is L-arabinose, D-ribose or D-glucose.
3. preparation method according to claim 1 is characterized in that, the temperature of said first set reaction is 20 ~ 25 ℃, and the time of said first set reaction is 20 ~ 24h.
4. preparation method according to claim 1 is characterized in that, said organic solvent is methylene dichloride or chloroform.
5. preparation method according to claim 1 is characterized in that, said hydrogen halide solution is the acetum of hydrogen halide.
6. preparation method according to claim 1 is characterized in that, the mol ratio of said monose, aceticanhydride, pyridine, hydrogen halide is 1: (4 ~ 5): (0.5 ~ 0.7): (1.0 ~ 1.5).
7. preparation method according to claim 1 is characterized in that, the said step that obtains the ethanoyl halogeno-sugar is specially:
In said acetylize sugar, add hydrogen halide solution, react for the third time, add mixed solvent, stir, filter, obtain the ethanoyl halogeno-sugar, the said time of reaction for the third time is 1 ~ 2h.
8. preparation method according to claim 7 is characterized in that, said mixed solvent is t-butyl methyl ether and isohexane.
9. preparation method according to claim 8 is characterized in that, the volume ratio of said t-butyl methyl ether and said isohexane is 1:1 ~ 3.
10. preparation method according to claim 7 is characterized in that, the time of said stirring is 0.5 ~ 1.5h.
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| CN102942598A (en) * | 2012-11-28 | 2013-02-27 | 济南圣泉唐和唐生物科技有限公司 | Post-treatment method for acetyl sugar halogenating reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101875675A (en) * | 2010-06-11 | 2010-11-03 | 江苏惠利隆塑业集团有限公司 | Preparation method of some glucoside |
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| CN101875675A (en) * | 2010-06-11 | 2010-11-03 | 江苏惠利隆塑业集团有限公司 | Preparation method of some glucoside |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102942598A (en) * | 2012-11-28 | 2013-02-27 | 济南圣泉唐和唐生物科技有限公司 | Post-treatment method for acetyl sugar halogenating reaction |
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