CN114891048A - Method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose - Google Patents
Method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose Download PDFInfo
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- ribofuranose
- trioxybenzoyl
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000011973 solid acid Substances 0.000 claims abstract description 53
- 241000404883 Pisa Species 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 12
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- PYMYPHUHKUWMLA-MROZADKFSA-N aldehydo-L-ribose Chemical compound OC[C@H](O)[C@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-MROZADKFSA-N 0.000 claims abstract description 11
- NALRCAPFICWVAQ-NNXAEHONSA-N (2s,3r,4s)-2-(hydroxymethyl)-5-methoxyoxolane-3,4-diol Chemical compound COC1O[C@@H](CO)[C@H](O)[C@@H]1O NALRCAPFICWVAQ-NNXAEHONSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000006196 deacetylation Effects 0.000 claims abstract description 5
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 5
- 238000006480 benzoylation reaction Methods 0.000 claims abstract description 4
- 238000007069 methylation reaction Methods 0.000 claims abstract description 4
- 230000021736 acetylation Effects 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910021389 graphene Inorganic materials 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 11
- 239000005750 Copper hydroxide Substances 0.000 claims description 11
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 11
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- NTJBWZHVSJNKAD-UHFFFAOYSA-N triethylazanium;fluoride Chemical compound [F-].CC[NH+](CC)CC NTJBWZHVSJNKAD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- 238000004334 fluoridation Methods 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002342 ribonucleoside Substances 0.000 description 2
- ASJSAQIRZKANQN-CRCLSJGQSA-N 2-deoxy-D-ribose Chemical compound OC[C@@H](O)[C@@H](O)CC=O ASJSAQIRZKANQN-CRCLSJGQSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000005549 deoxyribonucleoside Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose, which comprises the following steps: s1: preparing a solid acid catalyst PISA/Gu-O-GN; s2: taking L-ribose as a raw material; obtaining 1-oxygen-methyl-L-ribofuranose through methylation reaction; then performing benzoylation reaction on the 1-O-methyl-L-ribofuranose to obtain 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose; s3: preparing 1-oxygen-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose by acetylation reaction in the presence of solid acid PISA/Gu-O-GN; then preparing 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose by deacetylation; s4: preparing 1-oxygen-4-fluoro-2, 3, 5-trioxybenzoyl-L-ribofuranose through fluoridation; in the acetylation process, the solid acid catalyst PISA/Gu-O-GN is added, so that the catalytic rate is improved to 95.8 percent and is improved by 20 to 50 percent compared with the catalytic rates of the existing liquid acid catalyst, solid acid catalyst and the like.
Description
Technical Field
The invention belongs to the technical field of biosugars, and particularly relates to a method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose.
Background
Deoxyribose, ribose and its derivatives, are important components of nucleic acids, as well as components of certain vitamins and coenzymes. D-ribose and derivatives thereof are widely present in natural compounds in furan type, while L-ribose, an enantiomer of D-ribose, does not exist in the nature and can be obtained only by a synthetic method generally; in recent years, the use of L-ribose and derivatives in medicine has been reported increasingly. The reason is that L-ribonucleoside has remarkable antiviral activity and lower toxicity than D-ribonucleoside, wherein 1-oxy-fluoro-2, 3, 5-trioxybenzoyl-L-ribose is an important intermediate for synthesizing deoxyribonucleoside; however, the existing process has low yield of products in each process in the preparation process, such as the production process for preparing 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose, the application number is 200810060210.4, the product is prepared by methylation-benzoyl-acetylation reaction, and the total yield of three steps is only about 60%; the catalyst is an important additive for improving the yield of biosaccharide, and the patent discloses a sulfate radical composite oxide solid acid catalyst, a preparation method thereof and a method for catalyzing xylan into furfural, wherein the application number is 201410167436.X, and the application discloses a method for adopting a solid acid catalyst-SO 4 2- /SiO 2 -Al 2 O 3 /La 3+ However, such solid acid catalysts have problems in that the specific surface area is small, reducing the catalytic activity; or the sulfur-containing group is easy to lose, the activity is quick to lose efficacy, and the repeatability is poor.
Disclosure of Invention
The invention aims to provide a method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose, and the method utilizes a high-specific-surface-area solid acid PISA/Gu-O-GN catalyst in the reaction process to improve the product yield.
In order to solve the technical problem, the technical scheme of the invention is as follows: a process for the preparation of 1-oxo-fluoro-2, 3, 5-trioxobenzoyl-L-ribose comprising the steps of:
s1: preparing a solid acid catalyst PISA/Gu-O-GN;
s2: taking L-ribose as a raw material;
obtaining 1-oxygen-methyl-L-ribofuranose through methylation reaction;
then performing benzoylation reaction on the 1-O-methyl-L-ribofuranose to obtain 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
s3: performing acetylation on the product obtained in the step S2 in the presence of solid acid PISA/Gu-O-GN to prepare 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose; in the reaction process, intermittently shaking the reaction solution by ultrasonic waves;
then preparing 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose by deacetylation;
s4: and (4) carrying out fluorination reaction on the product obtained in the step S3 to prepare the 1-oxygen-4-fluoro-2, 3, 5-trioxobenzoyl-L-ribofuranose.
Preferably, the solid acid PISA/Gu-O-GN is used in an amount of 15% by mass of 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose.
Preferably, in step S3, the acetylation reaction time is 5h-6 h.
Preferably, the preparation method of the solid acid PISA/Gu-O-GN in S1 comprises the following steps:
s11: preparing a graphene suspension; adding graphene oxide and hydrazine into a reaction kettle, performing ultrasonic dispersion, and heating to a reaction temperature for reaction to obtain a graphene precipitate; washing the precipitate, adding water again, and performing ultrasonic dispersion to obtain a graphene suspension;
s12: adding a copper hydroxide solution into the graphene suspension under the stirring condition at the temperature of 40-80 ℃, wherein the copper hydroxide is embedded into the graphene through a metal bond; filtering, washing and drying to obtain a precursor Gu-O-GN;
s13: adding the precursor into toluenesulfonic acid, filtering and drying;
s14: calcining to obtain the PISA/Gu-O-GN solid acid.
The solid acid catalyst PISA/Gu-O-GN adopts graphene suspension to mix strong copper hydroxide solution, so that a copper-based material and the graphene suspension are better fused; active sites exist on the surface of the graphene, so that metal materials can be adsorbed and grown, and after co-calcination, the graphene and copper elements are better adsorbed, so that the effective acid center number of the catalyst is increased, and the catalytic performance of the product is improved.
Preferably, the molar ratio of graphene oxide to hydrazine in S11 is 1: (1.3-1.8).
Preferably, 1 g of the precursor is mixed per 12ml to 18ml of toluenesulfonic acid in S13.
The temperature of the calcination in S14 is preferably 300-450 degrees Celsius.
In S2 of the present invention, a specific method for obtaining 1-O-methyl-L-ribofuranose by methylation reaction comprises: taking L-ribose as a raw material, mixing the L-ribose, pyridine and methanol, adding thionyl chloride, carrying out heat preservation and closed stirring reaction for 10 hours in a water bath at the temperature of 0 ℃, and carrying out reduced pressure evaporation to dryness to obtain 1-O-methyl-L-ribofuranose; the specific method for preparing 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose by benzoylation reaction comprises the following steps: and (4) dissolving the product obtained in the step (S1) in dichloromethane and pyridine, cooling in an ice water bath, dropwise adding benzoyl chloride while stirring, reacting for 2-5 h under sealed stirring, washing the reaction solution with a sodium chloride solution, taking a solvent layer, drying with anhydrous magnesium sulfate, filtering, and evaporating the solvent under reduced pressure to obtain syrup.
Preferably, the acetylation reaction in S3 is carried out to obtain 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose:
taking 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, adding solid acid PISA/Gu-O-GN, acetic acid and acetic anhydride, and carrying out heat preservation, sealing and stirring reaction for 3-5 h in a water bath at the temperature of 0 ℃;
concentrating, crystallizing, washing, filtering and drying to obtain solid 1-oxygen-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose.
Preferably, the method for preparing the 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose by deacetylation in S3 comprises the following steps: taking 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose, adding dichloromethane for dissolving, adding acetic anhydride, introducing HCL gas, keeping the temperature at-5 ℃, stirring and reacting for 4-6h in a closed manner, after the reaction is finished, adding a saturated sodium bicarbonate solution, stirring, standing, taking an extraction layer, adding imidazole and sulfuryl chloride into an extraction liquid, keeping the temperature at 25 ℃, stirring and reacting for 16-24h in a closed manner, adding a saturated sodium bicarbonate solution after the reaction is finished, stirring, and taking a solvent layer;
drying the solvent layer, filtering, concentrating, crystallizing and drying to obtain solid 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose.
Preferably, in step S4, dissolving solid 1-oxo-2, 3, 5-trioxybenzoyl- β -L-ribofuranose in ethyl acetate, adding triethylamine hydrofluoride, reacting at 80 ℃ under reflux for 18h to 25h, adding saturated sodium bicarbonate solution after the reaction is finished, and collecting the solvent layer;
concentrating under reduced pressure, crystallizing, filtering, and oven drying to obtain solid 1-O-4-fluoro-2, 3, 5-trioxybenzoyl-L-ribofuranose.
According to the technical scheme, the invention has the beneficial effects that: in the invention, in the process of preparing the intermediate product 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose through acetylation reaction, the solid acid catalyst PISA/Gu-O-GN is added, the catalytic rate is improved to 95.8 percent, and the catalytic rate is improved by 20 to 50 percent compared with the catalytic rates of the existing liquid acid catalyst, solid acid catalyst and the like; in addition, compared with the traditional solid acid, the graphene suspension is adopted as a carrier, the dispersity is good, the specific surface area of the obtained catalyst is larger than that of the product obtained by the traditional mesoporous materials such as silicon oxide and the like, and the catalysis is good; in addition, all p orbitals of the graphene are vertical to each other, so that electrons in the p orbitals can move in the whole carbon atom plane, and a metal bond exists, so that the metal bond of the graphene and copper hydroxide can be bonded with each other, the copper hydroxide is embedded into the graphene to form a precursor, and when the copper hydroxide is connected, the copper is connected with the PISA and the graphene is connected at the same time to form a stable space three-dimensional connection structure, so that the copper-based solid acid with the space three-dimensional distribution structure has a larger specific surface area, the effective acid center number of the catalyst is increased, the active sites are increased, and the catalytic activity is obviously improved.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
This example discloses a process for the preparation of 1-oxo-fluoro-2, 3, 5-trioxobenzoyl-L-ribose comprising the steps of: taking L-ribose as a raw material, mixing the L-ribose, pyridine and methanol, adding thionyl chloride, carrying out heat preservation and closed stirring reaction for 10 hours in a water bath at the temperature of 0 ℃, and carrying out reduced pressure evaporation to dryness to obtain 1-O-methyl-L-ribofuranose; dissolving 1-O-methyl-L-ribofuranose in dichloromethane and pyridine, cooling in ice water bath, dropwise adding benzoyl chloride while stirring, reacting for 4h under sealed stirring, washing the reaction solution with sodium chloride solution, collecting solvent layer, drying with anhydrous magnesium sulfate, filtering, and evaporating the solvent under reduced pressure to obtain syrup 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
taking 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, adding solid acid PISA/Gu-O-GN, acetic acid and acetic anhydride, wherein the dosage of the solid acid PISA/Gu-O-GN is 10 percent of the total amount of the 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, and carrying out heat preservation, sealing and stirring reaction for 5 hours in a water bath at the temperature of 0 ℃; intermittently oscillating the reaction solution by ultrasonic under 40W power; concentrating, crystallizing, washing, and filtering to obtain solid 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose;
taking 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose, adding dichloromethane for dissolving, adding acetic anhydride, introducing HCL gas, keeping the temperature at-5 ℃, stirring and reacting for 4-6h in a closed manner, after the reaction is finished, adding a saturated sodium bicarbonate solution, stirring, standing, taking an extraction layer, adding imidazole and sulfuryl chloride into an extraction liquid, keeping the temperature at 25 ℃, stirring and reacting for 16-24h in a closed manner, adding a saturated sodium bicarbonate solution after the reaction is finished, stirring, and taking a solvent layer; drying the solvent layer, filtering, concentrating, crystallizing and drying to obtain solid 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose; dissolving solid 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose in ethyl acetate, adding triethylamine hydrofluoride, carrying out reflux stirring reaction at 80 ℃ for 18-25 h, adding a saturated sodium bicarbonate solution after the reaction is finished, and taking a solvent layer; concentrating under reduced pressure, crystallizing, filtering, and oven drying to obtain solid 1-O-4-fluoro-2, 3, 5-trioxybenzoyl-L-ribofuranose.
Wherein, preparing solid acid PISA/Gu-O-GN; the specific method comprises the following steps: graphene oxide and hydrazine are mixed according to a ratio of 1: 1.5, adding the mixture into a reaction kettle, performing ultrasonic dispersion for 2 hours, heating to 100 ℃, reacting for 4 hours to obtain graphene precipitate, washing the precipitate with absolute ethyl alcohol for three times, adding 3 times of water again, and performing ultrasonic dispersion to obtain graphene suspension; the concentration of the graphene suspension is 0.35mg/mL, and the copper hydroxide solution is added into the graphene suspension at the temperature of 40 ℃ to ensure that the molar ratio of graphene to copper element is 1: 1.6, stirring for 24h at room temperature, precipitating, filtering, washing with absolute ethyl alcohol, and drying at 120 ℃ to obtain a precursor Gu-O-GN; adding the precursor into toluenesulfonic acid, adding 12ml of toluenesulfonic acid into each gram of precursor, performing ultrasonic intermittent oscillation for 24h at room temperature under the power of 30W, wherein the ultrasonic oscillation interval time is 25min each time, drying at 150 ℃, transferring into a ceramic container, putting into a muffle furnace, and calcining for 6h at 300 ℃ to obtain the PISA/Gu-O-GN solid acid.
Example 2
The difference from example 1 is that: the dosage of the solid acid PISA/Gu-O-GN is 13 percent of the total amount of the 1-oxygen-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
example 3
The difference from example 1 is that: the dosage of the solid acid PISA/Gu-O-GN is 15 percent of the total amount of the 1-oxygen-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
example 4
The difference from example 1 is that: the dosage of the solid acid PISA/Gu-O-GN is 18 percent of the total amount of the 1-oxygen-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
example 5
The difference from example 1 is that: the dosage of the solid acid PISA/Gu-O-GN is 20 percent of the total amount of the 1-oxygen-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
example 6
The difference from example 3 is that: mixing solid acid PISA/Gu-O-GN, acetic acid and acetic anhydride in 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, and reacting in water bath at 0 deg.C under sealed condition for 3 hr;
example 7
The difference from example 3 is that: mixing solid acid PISA/Gu-O-GN, acetic acid and acetic anhydride in 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, and reacting in water bath at 0 deg.C under sealed condition for 4 hr;
example 8
The difference from example 3 is that: mixing solid acid PISA/Gu-O-GN, acetic acid and acetic anhydride in 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, and reacting in water bath at 0 deg.C under sealed condition for 6 h;
example 9
The difference from example 3 is that: mixing solid acid PISA/Gu-O-GN, acetic acid and acetic anhydride in 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, and reacting in water bath at 0 deg.C under sealed condition for 8 hr;
example 10
The difference from example 8 is that: the calcining temperature of the solid acid catalyst PISA/Gu-O-GN is 350 ℃;
example 11
The difference from example 8 is that: the calcining temperature of the solid acid catalyst PISA/Gu-O-GN is 400 ℃;
example 12
The difference from example 8 is that: the calcining temperature of the solid acid catalyst PISA/Gu-O-GN is 450 ℃;
example 13
The difference from example 11 is that: in the process of preparing the solid acid catalyst PISA/Gu-O-GN, 14ml of toluenesulfonic acid is prepared per gram of precursor;
example 14
The difference from example 11 is that: in the process of preparing the solid acid catalyst PISA/Gu-O-GN, 16ml of toluenesulfonic acid is prepared per gram of precursor;
comparative example 1
This example discloses a process for the preparation of 1-oxo-fluoro-2, 3, 5-trioxobenzoyl-L-ribose comprising the steps of: taking L-ribose as a raw material, mixing the L-ribose, pyridine and methanol, adding thionyl chloride, carrying out heat preservation and closed stirring reaction for 10 hours in a water bath at the temperature of 0 ℃, and carrying out reduced pressure evaporation to dryness to obtain 1-O-methyl-L-ribofuranose; dissolving 1-O-methyl-L-ribofuranose in dichloromethane and pyridine, cooling in ice water bath, dropwise adding benzoyl chloride while stirring, reacting for 4h under sealed stirring, washing the reaction solution with sodium chloride solution, collecting solvent layer, drying with anhydrous magnesium sulfate, filtering, and evaporating the solvent under reduced pressure to obtain syrup 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
adding acetic acid and acetic anhydride into 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, and reacting in water bath at 0 deg.C under stirring for 5 hr; concentrating, crystallizing, washing, and filtering to obtain solid 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose;
taking 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose, adding dichloromethane for dissolving, adding acetic anhydride, introducing HCL gas, keeping the temperature at-5 ℃, stirring and reacting for 4-6h in a closed manner, after the reaction is finished, adding a saturated sodium bicarbonate solution, stirring, standing, taking an extraction layer, adding imidazole and sulfuryl chloride into an extraction liquid, keeping the temperature at 25 ℃, stirring and reacting for 16-24h in a closed manner, adding a saturated sodium bicarbonate solution after the reaction is finished, stirring, and taking a solvent layer; drying the solvent layer, filtering, concentrating, crystallizing and drying to obtain solid 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose; dissolving solid 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose in ethyl acetate, adding triethylamine hydrofluoride, carrying out reflux stirring reaction at 80 ℃ for 18-25 h, adding a saturated sodium bicarbonate solution after the reaction is finished, and taking a solvent layer; concentrating under reduced pressure, crystallizing, filtering, and oven drying to obtain solid 1-O-4-fluoro-2, 3, 5-trioxybenzoyl-L-ribofuranose.
Comparative example 2
The difference from comparative example 1 is: during acetylation reaction, 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose is taken, acetic acid and acetic anhydride are added, and concentrated H2SO4 is dropwise added as a catalyst for reaction under the cooling of ice-water bath and vigorous stirring;
in the embodiment, the concentrated sulfuric acid is concentrated sulfuric acid with the mass fraction of 98.3%;
comparative example 3
The difference from comparative example 2 is that: during acetylation reaction, PISA/ZrO is added into the mixture of 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, acetic acid and acetic anhydride 2 Reacting as a catalyst;
wherein, PISA/ZrO 2 The preparation method comprises the following steps:
taking ZrOCl with a certain mass 2 ·8H 2 0, dissolving in water, dropwise adding ammonia water under the stirring state, adjusting the pH value to about 9, stopping dropwise adding the ammonia water until the reaction is finished, continuously stirring the reaction solution, putting the reaction solution into a drying box, aging for 4 hours, filtering, washing, drying, grinding to obtain zirconium hydroxide powder, putting the zirconium hydroxide powder into a muffle furnace, and calcining for 5 hours at the temperature of 360 ℃ to obtain a precursor ZrO 2 ，
Adding the precursor into toluenesulfonic acid, soaking for 4h, stirring continuously by using a magnetic stirrer, evaporating to remove excessive water, and calcining in a muffle furnace at the temperature of 300 ℃ for 4h to obtain PISA/ZrO 2 A solid acid.
The specific surface area of the catalysts obtained in example 1 and comparative example 3 was measured by a specific surface area measuring instrument, and the specific data are shown in table 1.
TABLE 1 specific surface area of catalysts obtained in example 1 and comparative example 3
From table 1, it can be seen that the specific surface area of the prepared solid acid catalyst is increased by 4-5 times by using the graphene suspension as a precursor raw material, and the graphene can effectively increase the specific surface area of the catalyst;
according to the formula: the catalytic rate { (amount of 1-o-methyl-2, 3, 5-trioxobenzoyl-L-ribofuranose before reaction-amount of 1-o-acetyl-2, 3, 5-trioxobenzoyl- β -L-ribofuranose after reaction)/amount of 1-o-methyl-2, 3, 5-trioxobenzoyl-L-ribofuranose before reaction }. 100%; calculating the catalytic rates of the intermediates of comparative examples 1-3 and examples 1-14; the specific catalytic rate is shown in table 2;
TABLE 2 catalytic efficiency of intermediates obtained in comparative examples 1 to 3 and examples 1 to 14
As can be seen from the data in Table 2, the catalytic rate of the solid acid with PISA/Gu-O-GN added is improved by more than 50% compared with that of comparative example 1 without the catalyst, and is improved by more than 30% compared with comparative example 2 with the common liquid acid catalyst, concentrated sulfuric acid, and is improved by more than 20% compared with comparative example 3 with the common solid acid catalyst; the PISA/Gu-O-GN solid acid greatly improves the catalytic activity; the specific surface area of a precursor prepared from the graphene suspension is large, and in addition, active sites formed after the precursor is combined with an active substance PISA are more, specifically, all p orbitals of graphene are vertical to each other, so that electrons in the p orbitals can move in the whole carbon atom plane, and metal bonds are formed, so that the metal bonds of the graphene can be bonded with copper hydroxide, the copper hydroxide is embedded into the graphene to form the precursor, when the copper is connected, the PISA is linked to the copper, the graphene is linked to form a stable spatial and three-dimensional connecting structure, the copper-based solid acid with the spatial and three-dimensional distribution structure has a larger specific surface area, the effective acid center number of the catalyst is increased, and the active sites are more; therefore, the catalytic activity is high.
Comparing example 3 with example 6 to example 9, it can be seen that the reaction time is prolonged from 3h to 8h, the catalytic rate of 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose is increased continuously, the catalytic rate is increased linearly within 3h to 5h, and then the catalytic rate is increased slowly, which indicates that the optimal reaction time is 5h to 6 h;
as can be seen from the comparison of examples 1 to 5, as the ratio of the solid acid PISA/Gu-O-GN to the total amount of 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose increases, the catalytic rate of the product increases and then levels; the solid acid PISA/Gu-O-GN is proved to be a factor which is no longer limited on the catalytic rate of the product when the dosage of the solid acid PISA/Gu-O-GN exceeds 15 percent of the total amount of 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, so that the catalytic rate of the product is high and the economic benefit is maximum under the condition when the dosage of the solid acid PISA/Gu-O-GN is 15 percent of the total amount of 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
comparing example 8, example 10 to example 12, it is known that when the calcination temperature of the catalyst is low, the catalytic activity of the catalyst is low because the bonding ability of PISA is weak and the active sites that the catalyst can form are small, and when the calcination temperature of the catalyst is too high, this causes decomposition of the active components in the catalyst, resulting in reduction of the amount of active components effective in the catalyst, and thus the optimum calcination temperature of the present invention is about 400 ℃.
It can be seen from comparison of example 11 and examples 13 to 14 that the catalytic rate of the product gradually increases with the increase of the amount of tosylate per gram of precursor, i.e. the increase of the loading amount of PISA, but when the amount of tosylate per gram of precursor is 14ml, the catalytic rate of the product does not significantly increase, and the catalytic rate of 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose increases and then becomes flat because the excessive tosylate cannot be sufficiently attached to the precursor with the increase of the amount of tosylate, so that the catalytic activity of the solid acid PISA/Gu-O-GN does not increase, and therefore the amount of tosylate per gram of precursor is 14ml, which is the optimal ratio of the precursor to the tosylate.
Claims (9)
1. A method for preparing 1-oxygen-fluoro-2, 3, 5-trioxybenzoyl-L-ribose is characterized by comprising the following steps:
s1: preparing a solid acid catalyst PISA/Gu-O-GN;
s2: taking L-ribose as a raw material;
obtaining 1-oxygen-methyl-L-ribofuranose through methylation reaction;
then performing benzoylation reaction on the 1-O-methyl-L-ribofuranose to obtain 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose;
s3: performing acetylation on the product obtained in the step S2 in the presence of solid acid PISA/Gu-O-GN to prepare 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose; in the reaction process, intermittently shaking the reaction solution by ultrasonic waves;
then preparing 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose by deacetylation;
s4: and (4) carrying out fluorination reaction on the product obtained in the step S3 to prepare the 1-oxygen-4-fluoro-2, 3, 5-trioxobenzoyl-L-ribofuranose.
2. The process for preparing 1-O-fluoro-2, 3, 5-trioxobenzoyl-L-ribose according to claim 1, wherein the solid acid PISA/Gu-O-GN is used in an amount of 15% by mass based on 1-O-methyl-2, 3, 5-trioxobenzoyl-L-ribofuranose.
3. The process for producing 1-oxo-fluoro-2, 3, 5-trioxobenzoyl-L-ribose according to claim 1, wherein the acetylation reaction time is 5 to 6 hours in step S3.
4. The method for preparing 1-O-fluoro-2, 3, 5-trioxobenzoyl-L-ribose according to claim 1, wherein the method for preparing solid acid PISA/Gu-O-GN in S1 comprises the following steps:
s11: preparing a graphene suspension; adding graphene oxide and hydrazine into a reaction kettle, performing ultrasonic dispersion, and heating to a reaction temperature for reaction to obtain a graphene precipitate; washing the precipitate, adding water again, and performing ultrasonic dispersion to obtain a graphene suspension;
s12: adding a copper hydroxide solution into the graphene suspension under the stirring condition at the temperature of 40-80 ℃, wherein the copper hydroxide is embedded into the graphene through a metal bond; filtering, washing and drying to obtain a precursor Gu-O-GN;
s13: adding the precursor into toluenesulfonic acid, filtering and drying;
s14: calcining to obtain the PISA/Gu-O-GN solid acid.
5. The process for producing 1-oxo-fluoro-2, 3, 5-trioxobenzoyl-L-ribose according to claim 1, wherein the calcination temperature in S14 is 400 ℃.
6. The process for producing 1-oxo-fluoro-2, 3, 5-trioxobenzoyl-L-ribose according to claim 1, wherein 1 g of the precursor is mixed with 14ml of toluenesulfonic acid in S13.
7. The process for preparing 1-O-fluoro-2, 3, 5-trioxobenzoyl-L-ribose according to claim 1, wherein acetylation reaction in S3 is carried out to obtain 1-O-acetyl-2, 3, 5-trioxobenzoyl- β -L-ribofuranose:
taking 1-O-methyl-2, 3, 5-trioxybenzoyl-L-ribofuranose, adding solid acid PISA/Gu-O-GN, acetic acid and acetic anhydride, and carrying out heat preservation, sealing and stirring reaction for 3-5 h in a water bath at the temperature of 0 ℃;
concentrating, crystallizing, washing, filtering and drying to obtain solid 1-oxygen-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose.
8. The process for producing 1-oxo-fluoro-2, 3, 5-trioxobenzoyl-L-ribose according to claim 1, wherein the process for producing 1-oxo-2, 3, 5-trioxobenzoyl- β -L-ribofuranose by deacetylation at S3 comprises: taking 1-O-acetyl-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose, adding dichloromethane for dissolving, adding acetic anhydride, introducing HCL gas, keeping the temperature at-5 ℃, stirring and reacting for 4-6h in a closed manner, after the reaction is finished, adding a saturated sodium bicarbonate solution, stirring, standing, taking an extraction layer, adding imidazole and sulfuryl chloride into an extraction liquid, keeping the temperature at 25 ℃, stirring and reacting for 16-24h in a closed manner, adding a saturated sodium bicarbonate solution after the reaction is finished, stirring, and taking a solvent layer;
drying the solvent layer, filtering, concentrating, crystallizing and drying to obtain solid 1-oxygen-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose.
9. The method for preparing 1-O-fluoro-2, 3, 5-trioxybenzoyl-L-ribose according to claim 1, wherein in step S4, the solid 1-O-2, 3, 5-trioxybenzoyl-beta-L-ribofuranose is dissolved in ethyl acetate, triethylamine hydrofluoride is added, the mixture is stirred and reacted at 80 ℃ for 18 to 25 hours under reflux, and after the reaction is finished, a saturated sodium bicarbonate solution is added to take out a solvent layer;
concentrating under reduced pressure, crystallizing, filtering, and oven drying to obtain solid 1-O-4-fluoro-2, 3, 5-trioxybenzoyl-L-ribofuranose.
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| WO2009058800A2 (en) * | 2007-10-29 | 2009-05-07 | President And Fellows Of Harvard College | Synthesis of nucleosides |
| CN108440286A (en) * | 2018-04-18 | 2018-08-24 | 肖锦 | A kind of method for preparing acetylsalicylic acid |
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| CN101274950A (en) * | 2008-03-31 | 2008-10-01 | 葛建利 | Production process for preparing 1-oxy-acetyl-2,3,5-3-benzoyl-beta-Lribofuranose |
| CN108440286A (en) * | 2018-04-18 | 2018-08-24 | 肖锦 | A kind of method for preparing acetylsalicylic acid |
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