CN104725442B - A kind of method for preparing p-nitrophenyl α D mannopyranose glycosides - Google Patents
A kind of method for preparing p-nitrophenyl α D mannopyranose glycosides Download PDFInfo
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- CN104725442B CN104725442B CN201510175516.4A CN201510175516A CN104725442B CN 104725442 B CN104725442 B CN 104725442B CN 201510175516 A CN201510175516 A CN 201510175516A CN 104725442 B CN104725442 B CN 104725442B
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- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
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- C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
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- C—CHEMISTRY; METALLURGY
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
The invention discloses a kind of method for preparing p-nitrophenyl α D mannopyranose glycosides, it is characterised in that this method includes：(1) under the conditions of coupling reaction, in the presence of a catalyst, the α D mannoses of protection are contacted with p-nitrophenol, the p-nitrophenyl α D mannosides protected；(2) the p-nitrophenyl α D mannosides of the protection obtained in step (1) are deprotected, obtain p-nitrophenyl α D mannopyranose glycosides.The preparation method of p-nitrophenyl α D mannopyranose glycosides provided by the invention has the advantages of reaction scheme is short, easy to operate, yield is higher, the reaction time is short and cost is low.
Description
Technical field
The present invention relates to a kind of method for preparing p-nitrophenyl-α-D- mannopyranose glycosides.
Background technology
P-nitrophenyl-α-D- mannopyranose glycosides has the structure shown in formula (I).
Alpha-Mannosidase can be separated from animals and plants, microorganism, be distributed mainly on endoplasmic reticulum, golgiosome, molten
Enzyme body and endochylema etc., by the folding for participating in protein glycosylation and the glycoprotein of glycoprotein glycan hydrolysis modification and new life
Folded, ripe, sorting, deliver, positioning, play the effect of its biological function.Alpha-Mannosidase is used for as useful toolenzyme
The synthesis of the enzymatic analysis and Related Oligosaccharides of high mannose oligosaccharides structure.The congenital red Hemapoiesis abnormality having now been found that
It is relevant that all with alpha-Mannosidase obstacle occurs for anaemia II types and mannosidosis.Meanwhile India scholar studies and found, closes
Two relevant with the alpha-Mannosidase and beta-N-acetylhexosaminidase gene closed in tomato, which reaches, delays tomato
Maturation, freshness date is set significantly to extend.
P-nitrophenyl-α-D- mannopyranose glycosides is the substrate of alpha-Mannosidase, as quick molecule diagnosis side
Method, using the suction of p-nitrophenol caused by spectrophotometry enzyme hydrolysis p-nitrophenyl-α-D- mannopyranose glycosides
Luminosity, confirm its enzyme activity, judge whether alpha-Mannosidase activity be raised and lowered and enzyme with the presence or absence of lack
Situations such as mistake.
Zirconium chloride is as catalyst, it was recently reported that the example of some synthesis.1996, David C.Harrowven and
Richard F.Dainty report zirconium chloride catalysis Fries rearrangement reactions, and catalytic effect is better than alchlor
(Tetrahedron Letters, 1996,37 (42), 7659-7660).2005, Habib Firouzabadi and Nasser
It is higher inconvenient for use that Iranpoor etc. reports titanium tetrachloride toxicity, and zirconium chloride it is relatively inexpensive, it is safe and easy-to-use, urge
Change efficiency high, be used successfully to epoxide deoxygenation (Tetrahedron Letters, 2005,46 (23), 4107-
4110).2008, Surendra Singh and Colm D.Duffy etc. reported zirconium chloride in one kettle way esterification and double de- second
Acylation reaction shows the catalysis characteristics (J.Org.Chem., 2008,73 (16), 6429-6432) of uniqueness.2013, Naoki
Michihata and Yuki Kaneko etc. report zirconium chloride catalysis 1,2,3,4,6- five-O- acetyl-β-D-Glucose and second
Thiol reactant, obtains ethyl -2,3,4,6- tetra--O- acetyl-β-D-1- glucosinolates (J.Org.Chem., 2013,78,
4319-4328)。
Therefore, find that a kind of new simple to operate, yield is high and what the reaction time was short prepares p-nitrophenyl-α-D- pyrans
The method of gluco-manno glucosides is significant.
The content of the invention
The technical problem to be solved in the present invention is the defects of overcoming prior art, there is provided a kind of new to prepare p-nitrophenyl
The method of base-α-D- mannopyranose glycosides, the preparation method tool of p-nitrophenyl-α-D- mannopyranose glycosides provided by the invention
There is the advantages of reaction scheme is short, easy to operate, yield is high, the reaction time is short and cost is low.
To achieve these goals, the present invention provides a kind of method for preparing p-nitrophenyl-α-D- mannopyranose glycosides,
This method includes：
(1) under the conditions of coupling reaction, in the presence of a catalyst, α-D-MANNOSE of protection and p-nitrophenol are occurred
Coupling reaction, the p-nitrophenyl-α-D- mannopyranose glycosides protected；
(2) p-nitrophenyl-α-D- mannopyranose glycosides of the protection obtained in step (1) is deprotected,
Obtain p-nitrophenyl-α-D- mannopyranose glycosides, the p-nitrophenyl-α-D- mannopyranose glycosides structure such as formula (I) institute
Show；
P-nitrophenyl-α-D- mannopyranoses the glycosides shown in formula (I) is prepared using the above method provided by the invention to have
There is the advantages of reaction scheme is short, easy to operate, yield is high, the reaction time is short and cost is low.For example, from embodiments of the invention
It can be seen that：By the catalytic action of perchloric acid with acetic anhydride acetylization reaction occurs for D-MANNOSE in the preferred case, obtains
1,2,3,4,6- five-O- acetyl group-α-D- mannopyranoses, the latter directly occur under zirconium chloride catalysis with p-nitrophenol
Coupling reaction, the coupled product protected, it is sweet that p-nitrophenyl-α-D- pyrans is further realized in the presence of sodium methoxide
Reveal the synthesis of glucosides.This method of the present invention is easy to operate, and yield is high, compensate for bromo sugar method and glycosyl tri- chloroacetimidate
The technological deficiency of method etc., it is a kind of good method for efficiently synthesizing p-nitrophenyl-α-D- mannopyranose glycosides.And use this hair
When bright method prepares the p-nitrophenyl-α-D- glucopyra mannosides shown in formula (I), coupling reaction and deprotection are anti-
The yield answered is more than 80%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of method for preparing p-nitrophenyl-α-D- mannopyranose glycosides, this method includes：
(1) under the conditions of coupling reaction, in the presence of a catalyst, α-D-MANNOSE and the p-nitrophenol of protection are connect
Touch, the p-nitrophenyl-α-D- mannopyranose glycosides protected；
(2) p-nitrophenyl-α-D- mannopyranose glycosides of the protection obtained in step (1) is deprotected,
Obtain p-nitrophenyl-α-D- mannopyranose glycosides, the p-nitrophenyl-α-D- mannopyranose glycosides structure such as formula (I) institute
Show；
When preparing the p-nitrophenyl-α-D- mannopyranose glycosides shown in formula (I) using the above method provided by the invention,
With the advantages of reaction scheme is short, easy to operate, yield is high, the reaction time is short and cost is low.
In method of the present invention, in step (1), the catalyst is zirconium chloride.
In method of the present invention, in step (1), in order to improve p-nitrophenyl-α-D- mannopyranose glycosides
Yield, the dosage mol ratio of α-D-MANNOSE of preferably described protection, p-nitrophenol and catalyst is 1: 1-6: 0.02-
0.15；More preferably 1: 3-5: 0.05-0.12.In method of the present invention, in step (1), the coupling reaction bar
Part can include：Temperature is 80-140 DEG C, preferably 100-130 DEG C.In method of the present invention, in step (1), institute
Stating coupling reaction condition can include：Pressure is 0.01-0.1MPa, preferably 0.05-0.1MPa.
Under preferable case, in method of the present invention, in step (1), the coupling reaction can be added without
Carried out under conditions of solvent.In the present invention, in step (1), to time of the coupling reaction, there is no particular limitation, this
The time of the invention preferably coupling reaction is 0.5-5 hours, more preferably 1-3 hours.
In the present invention, in step (1), can using various conventional methods, resulting product enters afterwards to step (1)
Row post processing, the present invention do not have special requirement and restriction to this.Under preferable case, the present invention is with the following method to step
(1) product obtained by is post-processed, but the method for the present invention is not limited to this：
The reaction solution that coupling reaction obtains is washed, carries out column chromatography for separation after extraction, takes organic phase to be evaporated, tie again successively
It is brilliant and obtain the p-nitrophenyl-α-D- mannopyranose glycosides of the protection after drying.The present invention for it is described separation, dry and
The mode of recrystallization is simultaneously unrestricted.
In method of the present invention, the raw material D-MANNOSE of α-D-MANNOSE of the protection can be obtained by commercially available
To (being bought from Beijing Yi Nuokai Science and Technology Ltd.s, article No. 150600010).
In method of the present invention, preparing the method for α-D-MANNOSE of the protection includes：In acid condition,
The D-MANNOSE of structure shown in formula (II) and protective agent are reacted,
In method of the present invention, used protective agent can be conventional use of various protections in the art
Agent.In order that conversion ratio of the α-D- mannopyranoses of the protection obtained by obtaining in step (1) is higher, it is of the present invention
Protective agent include acetic anhydride, propionic andydride, butyric anhydride, pivalic acid acid anhydride, benzoyl oxide, Trichloroacetic anhydride, acrylic anhydride, chloroacetic chloride,
At least one of propionyl chloride, butyl chloride, pivaloyl chloride, chlorobenzoyl chloride, trichloro-acetic chloride, acryloyl chloride；It is preferred that the protection
Agent includes at least one of acetic anhydride and chloroacetic chloride；More preferably described protective agent is acetic anhydride.
In method of the present invention, the D-MANNOSE and protectant dosage mol ratio are preferably 1: 10-60.
Under preferable case, in method of the present invention, the formation condition of the acid condition can be a variety of, but
Be, in order to obtain α-D-MANNOSE of the higher protection of yield, and in order that the α-D-MANNOSE that must be obtained after progress
During continuous coupling reaction, coupling reaction is enabled to carry out more abundant, namely the yield of the coupled product obtained is higher, this hair
The bright preferably acid condition is formed by adding perchloric acid.
Under preferable case, in method of the present invention, the condition that the D-MANNOSE reacts with protective agent includes：Instead
It is subzero 10 DEG C to 50 DEG C above freezing to answer temperature；Preferably 0~35 DEG C.
In method of the present invention, do not have to the time for reacting the D-MANNOSE of structure shown in formula (II) with protective agent
There is special restriction, those skilled in the art can be selected according to actual conditions, can also pass through the means such as TLC, HPLC
The degree that detection reaction is carried out, when finding that the conversion ratio of raw material reaches 99% by detecting, when even more than 99%, you can to stop
Only react, under preferable case, the reaction time is 8-24 hours.The present invention is not special to the method for stopping reaction
Limit, the conventional use of various methods of those skilled in the art can be used, the present invention will not be repeated here.
In the present invention, when finding that the conversion ratio of raw material reaches 99% by detecting, when even more than 99%, can use
Obtained reaction solution is poured into appropriate frozen water and stirred rapidly, a large amount of white solids now occurs, continues to stir 1-10 hours,
Filtered, a large amount of distilled water flushings of filter cake, then separate, dry.
In the present invention, can also include being recrystallized the product obtained after above-mentioned drying, to the recrystallization
Method is not particularly limited, and the solvent used in preferably described recrystallization can be methanol and/or ethanol.
According to a kind of preferred embodiment of the present invention, in method of the present invention, the α-D- of protection are sweet
The synthesis of dew sugar can be carried out according to following reaction equation：
In method of the present invention, in step (2), preferably carry out in the basic conditions, described alkali is selected from hydrogen
At least one of sodium oxide molybdena, potassium hydroxide, lithium hydroxide, sodium methoxide, caustic alcohol, potassium tert-butoxide, sodium carbonate and potassium carbonate, most
Preferably sodium methoxide；The pH value of more preferably described alkalescence condition is 10 or so.
In method of the present invention, in step (2), be preferably deprotected used in solvent be sodium methoxide and
The mixed solution of methanol, and both volume ratios are 5-20: 100.The present invention carries out the remove-insurance preferably under conditions of stirring
Shield, the present invention is for the speed of stirring and unrestricted.The reaction temperature of the deprotection is preferably 0-50 DEG C, more preferably room
Temperature；The reaction time of the deprotection is preferably 4-12 hours.
In method of the present invention, in step (2), preferably fitted in rear added into reaction solution of deprotection completion
The nertralizer of amount neutralizes to reaction solution.The preferably nertralizer of the invention can be acetic acid, hydrochloric acid and cation exchange tree
At least one of fat.The nertralizer is cationic ion-exchange resin in the case of more preferably.
According to the present invention a kind of preferred embodiment, in method of the present invention, in step (1),
The reaction can be carried out according to following reaction equation：
According to the present invention a kind of preferred embodiment, in method of the present invention, in step (2),
The reaction can be carried out according to following reaction equation：
The present invention will be described in detail by way of examples below.In case of no particular description, implement below
Various reagents used are all from commercially available in example；Used water is the homemade deionized water in laboratory.
Preparation example 1
421mmol acetic anhydrides are added into 100mL three neck round bottom flask, the high chlorine of 0.13mL is added after 30min is stirred at 0 DEG C
Acid (it is purchased from Aladdin, article No. P112027-500mL, similarly hereinafter).D-MANNOSE (27.8mmol) is added in three-necked flask, after
Continuous reaction 12h, then reaction solution is poured into trash ice water and stirred rapidly, a large amount of white solids now occurs, continue stir about
5h, is filtered, and filter cake is rinsed with a large amount of water, is then dried.With methanol, (w/v of residue and methanol is after drying
1: 30) recrystallized, obtain white powder 9.60g, yield 88.5%.
Using nuclear magnetic resonance (BRUKER companies of Switzerland, model BRUKER-400MHz NMRs, similarly hereinafter), optically-active
(Henan Gongyi Ying Yu gives Hua Yi for instrument (company of PE companies of the U.S., the type polarimeters of model Model 341, similarly hereinafter) and melting point apparatus
Device factory, model X-4 numerical monitor micro melting point apparatus, similarly hereinafter) characterize, confirm as target product.
Preparation example 2
421mmol acetic anhydrides are added into 100mL three neck round bottom flask, are added after stirring 30min at subzero 10 DEG C
0.13mL perchloric acid.D-MANNOSE (27.8mmol) is added in three-necked flask, continues to react 12h, then pours into reaction solution
Stir in trash ice water and rapidly, a large amount of white solids now occur, continue stir about 5h, filter, filter cake is rinsed with a large amount of water, so
After be dried.Recrystallized with methanol (w/v of residue and methanol is 1: 30 after drying), obtain white powder
Last 9.35g, yield 86.2%.
Embodiment 1
(1) at 120 DEG C, 1 obtained by preparation example 1,2,3,4,6- five-O- second are sequentially added into 100mL round-bottomed flasks
Acyl-alpha-D-MANNOSE (12.82mmol), p-nitrophenol (51.28mmol) and zirconium chloride (1.03mmol), are decompressed to
0.08MPa, stirring melt, and after 1.3h, TLC detection reactions are complete.Take above-mentioned reaction solution directly carry out column chromatography (V (petroleum ether):
V (ethyl acetate)=3: 1) separation.Obtain 4.93g p-nitrophenyls -2,3,4,6- tetra--O- acetyl group-α-D- mannopyranoses
Glycosides, yield 81.9%.1H-NMR, optically-active and fusing point have been carried out to product to characterize, and confirm as target product.
(2) at room temperature, p-nitrophenyl -2,3 made from step (1), 4,6- tetra--O- second are added to 100mL round-bottomed flasks
Acyl-alpha-D- mannopyranoses glycosides (10.51mmol) and 40mL absolute methanols, be added dropwise 10% (percentage by weight) sodium methoxide/
Methanol solution, regulation pH value are 10 or so, and stirring reaction 5h, TLC detection reaction is complete, add appropriate resin cation regulation pH
Be worth for 7, filtering, and filtrate concentrated, column chromatography (V (ethyl acetate): V (methanol)=10: 1) separation, obtain p-nitrophenyl-
α-D- mannopyranose glycosides 2.63g, yield 83.1%.1H-NMR, optically-active and fusing point have been carried out to product to characterize, and confirm as mesh
Mark product.
Embodiment 2
(1) at 100 DEG C, 1 obtained by preparation example 1,2,3,4,6- five-O- second are sequentially added into 100mL round-bottomed flasks
Acyl-alpha-D-MANNOSE (12.82mmol), p-nitrophenol (51.28mmol) and zirconium chloride (1.03mmol), are decompressed to
0.1MPa, stirring melt, and after 1.8h, TLC detection reactions take above-mentioned reaction solution directly to carry out column chromatography (V (petroleum ether): V completely
(ethyl acetate)=3: 1) separation.Obtain 4.89g p-nitrophenyls -2,3,4,6- tetra--O- acetyl group-α-D- mannopyranoses
Glycosides, yield 81.3%.1H-NMR, optically-active and fusing point have been carried out to product to characterize, and confirm as target product.
(2) at room temperature, the p-nitrophenyl -2,3 obtained to the addition of 100mL round-bottomed flasks using step (1), 4,6- tetra- -
O- acetyl group-α-D- mannopyranoses glycosides (10.51mmol) and 40mL absolute methanols, the methanol of 10% (percentage by weight) is added dropwise
Sodium/methanol solution, regulation pH value are 10 or so, and stirring reaction 5h, TLC detection reaction is complete, adds appropriate resin cation and adjusts
It is 7 to save pH value, filtering, and filtrate is concentrated, and column chromatography (V (ethyl acetate): V (methanol)=10: 1) separation, is obtained to nitro
Phenyl-α-D- mannopyranose glycosides 2.64g, yield 83.4%.Carry out 1H-NMR, optically-active and fusing point to product to characterize, really
Think target product.
Embodiment 3
(1) at 80 DEG C, 1 obtained by preparation example 1,2,3,4,6- five-O- acetyl are sequentially added into 100mL round-bottomed flasks
Base-α-D-MANNOSE (12.82mmol), p-nitrophenol (51.28mmol) and zirconium chloride (1.03mmol), are decompressed to
0.08MPa, stirring melt, and after 1.3h, TLC detection reactions are complete.Take above-mentioned reaction solution directly carry out column chromatography (V (petroleum ether):
V (ethyl acetate)=3: 1) separation.Obtain 4.82g p-nitrophenyls -2,3,4,6- tetra--O- acetyl group-α-D- mannopyranoses
Glycosides, yield 80.1%.1H-NMR, optically-active and fusing point have been carried out to product to characterize, and confirm as target product.
(2) at room temperature, the p-nitrophenyl -2,3 obtained to the addition of 100mL round-bottomed flasks using step (1), 4,6- tetra- -
O- acetyl group-α-D- mannopyranoses glycosides (10.51mmol) and 40mL absolute methanols, the methanol of 10% (percentage by weight) is added dropwise
Sodium/methanol solution, regulation pH value are 10 or so, and stirring reaction 5h, TLC detection reaction is complete, adds appropriate resin cation and adjusts
It is 7 to save pH value, filtering, and filtrate is concentrated, and column chromatography (V (ethyl acetate): V (methanol)=10: 1) separation, is obtained to nitro
Phenyl-α-D- mannopyranose glycosides 2.57g, yield 81.2%.Carry out 1H-NMR, optically-active and fusing point to product to characterize, really
Think target product.
From above example 1-3 result can be seen that using method provided by the invention prepare formula (I) shown in nitre
Base phenyl-α-D- mannopyranose glycosides has reaction scheme is short, easy to operate, reaction time is short and cost is low (need not use
Solvent, i.e. solvent-free reaction) the advantages of, and the p-nitrophenyl-α-D- pyrroles shown in using the method preparation formula (I) of the present invention
Mutter mannoside when, the yield of coupling reaction and deprotection reaction is more than 80%.Also, by contrasting the He of preparation example 1
The result of preparation example 2 can be seen that preparation example 1 can reach higher yield by regularization condition.By comparative example 1, in fact
The result for applying example 2 and embodiment 3 can be seen that embodiment 1 and enable to coupling reaction by adjusting the condition of coupling reaction
Yield is apparently higher than embodiment 2 and the result of embodiment 3.The preferred embodiment of the present invention described in detail above, still, this
Invention is not limited to the detail in above-mentioned embodiment, can be to the present invention's in the range of the technology design of the present invention
Technical scheme carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (9)
- A kind of 1. method for preparing p-nitrophenyl-α-D- mannopyranose glycosides, it is characterised in that this method includes：(1) under the conditions of coupling reaction, in the presence of a catalyst, α-D-MANNOSE of protection is contacted with p-nitrophenol, obtained To the p-nitrophenyl-α-D- mannopyranose glycosides of protection, the catalyst is zirconium chloride, the α-D- sweet dews of the protection The dosage mol ratio of sugar, p-nitrophenol and catalyst is 1: 1-6: 0.02-0.15, and the coupling reaction condition includes：Temperature For 80-140 DEG C；Pressure is 0.01-0.1MPa；(2) p-nitrophenyl-α-D- mannopyranose glycosides of the protection obtained in step (1) is deprotected, obtained P-nitrophenyl-α-D- mannopyranose glycosides, shown in the p-nitrophenyl-α-D- mannopyranose glycosides structure such as formula (I)；
- 2. according to the method for claim 1, wherein, in step (1), the coupling reaction condition includes：Temperature is 100-130℃；Pressure is 0.05-0.1MPa.
- 3. according to the method for claim 2, wherein, the coupling reaction is carried out under conditions of solvent is added without.
- 4. according to the method for claim 1, wherein, preparing the method for α-D-MANNOSE of the protection includes：In acidity Under catalytic condition, by structure be formula (II) shown in D-MANNOSE reacted with protective agent, the protective agent including acetic anhydride, Propionic andydride, butyric anhydride, pivalic acid acid anhydride, benzoyl oxide, Trichloroacetic anhydride, acrylic anhydride, chloroacetic chloride, propionyl chloride, butyl chloride, spy penta At least one of acyl chlorides, chlorobenzoyl chloride, trichloro-acetic chloride, acryloyl chloride；
- 5. according to the method for claim 4, wherein, the protective agent includes at least one of acetic anhydride and chloroacetic chloride.
- 6. the method according to claim 4 or 5, wherein, the D-MANNOSE is 1: 10- with protectant dosage mol ratio 60。
- 7. the method according to claim 4 or 5, wherein, the acidic catalysis conditions are reached by adding perchloric acid.
- 8. according to the method for claim 5, wherein, the condition that the D-MANNOSE reacts with protective agent includes：Reaction temperature Spend for subzero 10 DEG C to 50 DEG C above freezing.
- 9. according to the method for claim 8, wherein the condition that the D-MANNOSE reacts with protective agent includes：Reaction temperature For 0-35 DEG C.
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Non-Patent Citations (3)
| Title |
|---|
| Introduction of alkali labile groups at glycosidic centres in various sugars and study of their rates of hydrolysis;M. Hamid-Ul-Qadir;《Pak. J. Sci. Ind. Res.》;19910831;第34卷(第7-8期);第282-287页 * |
| Zirconium(IV) chloride-catalyzed synthesis of 1,2-trans-l-thioglycopyranosides;Marie-Odile Contour，等;《Carbohydrate Research》;19891231;第193卷;第283-287页 * |
| 对硝基苯基-α-D-吡喃木糖苷的合成;曾森，等;《化学试剂》;20131231;第35卷(第7期);第599-900页 * |
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