CN105330704A - Preparation method of 2-deoxy-D-glucose - Google Patents
Preparation method of 2-deoxy-D-glucose Download PDFInfo
- Publication number
- CN105330704A CN105330704A CN201510780244.0A CN201510780244A CN105330704A CN 105330704 A CN105330704 A CN 105330704A CN 201510780244 A CN201510780244 A CN 201510780244A CN 105330704 A CN105330704 A CN 105330704A
- Authority
- CN
- China
- Prior art keywords
- deoxy
- compound
- preparation
- glucose
- sulfoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CNC1C=COC(*)C1* Chemical compound CNC1C=COC(*)C1* 0.000 description 2
- TXFMMJPQXAEPSW-FJXQXJEOSA-N C[C@@H]1CC(C)[Cs]CC1 Chemical compound C[C@@H]1CC(C)[Cs]CC1 TXFMMJPQXAEPSW-FJXQXJEOSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/08—Deoxysugars; Unsaturated sugars; Osones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides a preparation method of 2-deoxy-D-glucose. The preparation method includes the following steps that 1, a catalyst, sulfoxide and water are added into a compound (I), and after the materials are reacted completely, reaction liquid is filtered, concentrated and recrystallized to obtain a compound (II), wherein R indicates formyl or acetyl or propionyl or benzoyl or benzyl or dimethyl t-butyldimethylsilyl; 2, the compound (II) is subjected to deprotection and recrystallization to obtain 2-deoxy-D-glucose. According to the preparation method of 2-deoxy-D-glucose, with protected glucose syrup serving as a starting raw material, 2-deoxy-D-glucose can be obtained just through the two reaction steps of catalytic hydrolysis and deprotection. In the preparation process, reaction conditions are mild, reaction reagents are easy to obtain, the reaction yield is high, an intermediate purification method is easy to implement, the purity of the final product is high, and broad commercial application prospects are archived.
Description
Technical field
The invention belongs to drug manufacture field, especially relate to a kind of preparation method of 2-deoxy-D-glucose.
Background technology
Desoxy sugar has important biological function, 2-deoxyribosyl as the important skeleton component part of DNA, to the complete of biological heredity information and transmit there is important biological merit.Other aspects, desoxy sugar often appears among cardiac glycoside, microbiotic and cancer therapy drug. and research finds to have in the compound of obvious biological activity, the kinetic property of sugar chain portion regulating medicine, plays an important role in the identification of the transhipment of medicine, medicine and action target spot.Wherein, 2-deoxy-D-glucose is not only the composition fragment of many biologically active substances, and itself also has multiple biological activity, is widely applied to medicine, food and agriculture field.The studied discovery of 2-deoxy-D-glucose has the effect of anti-multiple virus; Meanwhile, 2-deoxy-D-glucose is also proved to be the effect having and suppress Several Kinds of Malignancy; 2-deoxy-D-glucose can be used as foodstuff additive and uses; 2-deoxy-D-glucose is also widely applied to agricultural production, and such as it can suppress the corruption of fruits and vegetables, improves effects such as producing meat poultry transformation efficiency.
Because occurring in nature 2-deoxy-D-glucose is less, the method mainly through synthesis obtains.Primary synthetic methods has following several: with D-Glucose alkene for starting raw material, utilizes mineral substance acid as catalyst catalytic hydrolysis to obtain 2-deoxy-D-glucose; Be that starting raw material synthesizes through Multi-step conversion with glucose-derivative; Be, after starting raw material and Nitromethane 99Min. react, finally obtain 2-deoxy-D-glucose through steps such as acetylize, reduction, hydrolysis with D-R.Above method reactions steps is long, and overall yield of reaction is lower, purification difficult, is difficult to commercialization.
Summary of the invention
In view of this, the present invention is intended to the preparation method proposing a kind of 2-deoxy-D-glucose, method mild condition, and yield is high, and purification process is simple, is easy to extensive preparation.
For achieving the above object, technical scheme of the present invention is achieved in that
A preparation method for 2-deoxy-D-glucose, comprises the following steps:
(1) in compound (I), catalyzer, sulfoxide and water is added, after reacting completely, carried out by reaction solution filtering, concentrate, obtain compound (II) after recrystallization, wherein, the general formula of compound (I), compound (II) is as follows:
Wherein, R be formyl radical, ethanoyl, propionyl, benzoyl, benzyl or dimethyl tertiary butyl silica-based in one;
(2) by after compound (II) deprotection, after recrystallization, 2-deoxy-D-glucose is obtained.
Further, in described step (1), catalyzer is acid anhydrides or muriate; Preferably, acid anhydrides is one or more in formic anhydride, diacetyl oxide, propionic anhydride, butyryl oxide, trifluoroacetic anhydride, methylsulfonic acid acid anhydride or trifluoromethanesulfanhydride anhydride; Preferably, muriate is one or more in thionyl chloride, phosphorus oxychloride, phosphorus trichloride, Acetyl Chloride 98Min., oxalyl chloride, Benzoyl chloride, p-methyl benzene sulfonic chloride, methylsulfonyl chloride, cyanuric chloride or chlorosuccinimide.
Further, in described step (1), sulfoxide is the one in alkyl sulfoxide, thiazolinyl sulfoxide, alkynyl sulfoxide or phenylsulfone.
Further, in described step (1), sulfoxide is dimethyl sulfoxide (DMSO).
Further, the temperature of reaction of described step (1) is-20 DEG C-180 DEG C, and the reaction times is 1-72 hour; Preferably, temperature of reaction is 10 DEG C-40 DEG C, and the reaction times is 1-5 hour.
Further, the solvent that re-crystallization step uses in described step (1) is methyl alcohol, one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, DMF, dimethyl sulfoxide (DMSO), toluene, methylene dichloride, chloroform, acetonitrile, dioxane, tetrahydrofuran (THF), ether or methyl tertiary butyl ether.
Further, in described step (1), the concentration of compound (I) is 0.01-3mol/L; Preferably, the concentration of compound (I) is 0.1-0.5mol/L; Preferably, the concentration of compound (I) is 0.25mol/L.
Further, the preparation method of the middle compound (I) of described step (1): D-Glucose alkene is protected, obtains compound (I); Wherein, protecting group be formyl radical, ethanoyl, propionyl, benzoyl, benzyl or dimethyl tertiary butyl silica-based in one.
Further, in described step (1), the mol ratio of compound (I), catalyzer, sulfoxide, water is 1:(0.01-3): (0.03-9): (1-50); Preferably, the mol ratio of compound (I), catalyzer, sulfoxide, water is 1:(0.1-0.5): (0.5-0.8): (1-5).
Further, the solvent that re-crystallization step uses in described step (2) is methyl alcohol, one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, DMF, dimethyl sulfoxide (DMSO), toluene, methylene dichloride, chloroform, acetonitrile, dioxane, tetrahydrofuran (THF), ether or methyl tertiary butyl ether.
Reaction principle of the present invention is:
Relative to prior art, the preparation method of 2-deoxy-D-glucose of the present invention has following advantage:
The preparation method of 2-deoxy-D-glucose of the present invention is with the glucose thin malt sugar of protection for starting raw material, and through catalytic hydrolysis, deprotection, only 2 Walk reactions, just can obtain 2-deoxy-D-glucose.In preparation process, reaction conditions is gentle, and reaction reagent is easy to get, and reaction yield is high, and purification of intermediate method is simple, and the finished product purity is high, has wide commercial application prospect.
Embodiment
Technical spirit of the present invention and invention advantage fully can be understood in order to make the public; applicant will describe in detail the specific embodiment of the present invention below; but applicant is not the restriction to technical scheme to the description of embodiment, any changing in the form rather than substance according to the present invention's design all should be considered as protection scope of the present invention.
Embodiment 1
A preparation method for 2-deoxy-D-glucose, comprises the following steps:
(1) at room temperature, to compound (III) (272.3g, cyanuric chloride (36.9g is added in acetonitrile (4L) solution 1.0mol), 0.2mol), dimethyl sulfoxide (DMSO) (46.8g, 0.6mol) with water (54g, 3mol).Stirring at room temperature is after 3.5 hours, by reacting liquid filtering, and filtrate reduced in volume.Crude product uses ether (500mL) recrystallization to obtain compound (IV) (267.6g, white solid), yield 92%.Hydrogen nuclear magnetic resonance spectrum: (600MHz, CDCl
3) δ 5.54 – 5.35 (m, 8H), 5.08 – 4.95 (m, 6H), 4.37 – 4.19 (m, 10H), 4.13 (t, J=13.3Hz, 5H), 3.69 (d, J=6.9Hz, 1H), 3.49 (s, 1H), 3.04 (s, 4H), 2.42 (dd, J=11.9,4.1Hz, 1H), 2.32 – 2.27 (m, 4H), 2.14 – 2.00 (m, 45H), 1.88 – 1.73 (m, 5H).
(2) by compound (IV) (200g, 0.69mol) be dissolved in anhydrous methanol (1.38L), add freshly prepd sodium methylate (3.7g, 0.069mol) stirring at room temperature 6h afterwards, adds acidic ion exchange resin Dowex-50 (20g).After stirring at room temperature 1h, filter, filtrate reduced in volume.Mixture (the mol ratio 1:1 of propyl carbinol, the methyl alcohol) recrystallization of crude product propyl carbinol, methyl alcohol obtains 2-deoxy-D-glucose 100g, yield 88%.Hydrogen nuclear magnetic resonance spectrum: (400MHz, CD
3oD) δ 5.26 (d, J=2.6,1H), 3.90 (m, 1H), 3.80 (m, 1H), 3.68 (m, 1H), 3.64 (m, 1H), 3.26 (m, 1H), 2.05 (dd, J=5.0,12.8,1H), 1.62 (dt, J=2.6,12.8,1H).
Chemical equation is as follows:
Embodiment 2
A preparation method for 2-deoxy-D-glucose, comprises the following steps:
(1) at room temperature, to compound (V) (416.5g, cyanuric chloride (36.9g is added successively in acetonitrile (4L) solution 1.0mol), 0.2mol), dimethyl sulfoxide (DMSO) (46.8g, 0.6mol) with water (54g, 3mol).Stirring at room temperature is after 3.5 hours, by reacting liquid filtering, and filtrate reduced in volume.Crude product ether (500mL) recrystallization obtains compound (VI) (412.8g, white solid), yield 95%.Hydrogen nuclear magnetic resonance spectrum: (600MHz, CDCl
3) δ 7.36 – 7.24 (m, 65H), 7.17 (d, J=6.0Hz, 10H), 5.38 (s, 4H), 4.88 (t, J=11.0Hz, 5H), 4.70 – 4.60 (m, 10H), 4.57 (dd, J=12.1, 6.5Hz, 6H), 4.51 (dd, J=12.1, 4.6Hz, 10H), 4.04 (dt, J=7.7, 7.0Hz, 9H), 3.76 – 3.61 (m, 10H), 3.61 – 3.54 (m, 1H), 3.46 – 3.41 (m, 4H), 3.43 (dd, J=14.9, 9.0Hz, 2H) .), 3.28 (s, 4H), 2.28 (dd, J=12.9, 4.4Hz, 5H), 1.67 (t, J=12.1Hz, 4H), 1.55 (dd, J=21.9, 11.8Hz, 1H).
(2) compound (VI) (300g, 0.69mol) is dissolved in anhydrous methanol (1.38L), adds the Pd/C (15g) of 5% at 100 psi, stirring at room temperature 12h.Then filter, filtrate reduced in volume.Mixture (the mol ratio 1:1 of propyl carbinol, the methyl alcohol) recrystallization of crude product propyl carbinol, methyl alcohol obtains 2-deoxy-D-glucose 113g, yield 91%.Hydrogen nuclear magnetic resonance spectrum: (400MHz, CD
3oD) δ 5.26 (d, J=2.6,1H), 3.90 (m, 1H), 3.80 (m, 1H), 3.68 (m, 1H), 3.64 (m, 1H), 3.26 (m, 1H), 2.05 (dd, J=5.0,12.8,1H), 1.62 (dt, J=2.6,12.8,1H).
Chemical equation is as follows:
Embodiment 3
A preparation method for 2-deoxy-D-glucose, comprises the following steps:
(1) at room temperature, to compound (VII) (458.4g, cyanuric chloride (36.9g is added successively in acetonitrile (4L) solution 1.0mol), 0.2mol), dimethyl sulfoxide (DMSO) (46.8g, 0.6mol) with water (54g, 3mol).Stirring at room temperature is after 3.5 hours, by reacting liquid filtering, and filtrate reduced in volume.Crude product ether (500mL) recrystallization obtains compound (VIII) (395.5g, white solid), yield 83%.Hydrogen nuclear magnetic resonance spectrum: (600MHz, CDCl
3) δ 8.04 (t, J=9.7Hz, 46H), 7.96 (dt, J=13.7, 6.9Hz, 92H), 7.57 – 7.47 (m, 69H), 7.38 (ddd, J=13.0, 11.4, 6.7Hz, 138H), 5.85 – 5.77 (m, 20H), 5.64 (t, J=9.7Hz, 20H), 5.59 (t, J=9.7Hz, 3H), 5.54 (s, 20H), 5.47 – 5.39 (m, 3H), 5.17 – 5.12 (m, 3H), 4.62 (ddd, J=10.8, 9.9, 2.7Hz, 43H), 4.44 (ddd, J=15.9, 11.9, 4.5Hz, 23H), 4.08 – 4.02 (m, 3H), 3.56 – 3.37 (m, 23H), 2.67 (dd, J=11.9, 4.4Hz, 3H), 2.55 (dd, J=12.8, 5.1Hz, 20H), 2.00 (t, J=11.9Hz, 20H), 1.93 (t, J=10.8Hz, 3H).
(2) by compound (VIII) (328.8g, 0.69mol) be dissolved in anhydrous methanol (1.38L), add freshly prepd sodium methylate (3.7g, 0.069mol) stirring at room temperature 6h afterwards, adds acidic ion exchange resin Dowex-50 (20g).After stirring at room temperature 1h, filter, filtrate reduced in volume.Mixture (the mol ratio 1:1 of propyl carbinol, the methyl alcohol) recrystallization of crude product propyl carbinol, methyl alcohol obtains 2-deoxy-D-glucose 92.2g, yield 81%.Hydrogen nuclear magnetic resonance spectrum: (400MHz, CD
3oD) δ 5.26 (d, J=2.6,1H), 3.90 (m, 1H), 3.80 (m, 1H), 3.68 (m, 1H), 3.64 (m, 1H), 3.26 (m, 1H), 2.05 (dd, J=5.0,12.8,1H), 1.62 (dt, J=2.6,12.8,1H).
Chemical equation is as follows:
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for 2-deoxy-D-glucose, is characterized in that: comprise the following steps:
(1) in compound (I), catalyzer, sulfoxide and water is added, after reacting completely, carried out by reaction solution filtering, concentrate, obtain compound (II) after recrystallization, wherein, the general formula of compound (I), compound (II) is as follows:
Wherein, R be formyl radical, ethanoyl, propionyl, benzoyl, benzyl or dimethyl tertiary butyl silica-based in one;
(2) by after compound (II) deprotection, after recrystallization, 2-deoxy-D-glucose is obtained.
2. the preparation method of 2-deoxy-D-glucose according to claim 1, is characterized in that: in described step (1), catalyzer is acid anhydrides or muriate; Preferably, acid anhydrides is one or more in formic anhydride, diacetyl oxide, propionic anhydride, butyryl oxide, trifluoroacetic anhydride, methylsulfonic acid acid anhydride or trifluoromethanesulfanhydride anhydride; Preferably, muriate is one or more in thionyl chloride, phosphorus oxychloride, phosphorus trichloride, Acetyl Chloride 98Min., oxalyl chloride, Benzoyl chloride, p-methyl benzene sulfonic chloride, methylsulfonyl chloride, cyanuric chloride or chlorosuccinimide.
3. the preparation method of 2-deoxy-D-glucose according to claim 1, is characterized in that: in described step (1), sulfoxide is the one in alkyl sulfoxide, thiazolinyl sulfoxide, alkynyl sulfoxide or phenylsulfone.
4. the preparation method of 2-deoxy-D-glucose according to claim 3, is characterized in that: in described step (1), sulfoxide is dimethyl sulfoxide (DMSO).
5. the preparation method of 2-deoxy-D-glucose according to claim 1, is characterized in that: the temperature of reaction of described step (1) is-20 DEG C-180 DEG C, and the reaction times is 1-72 hour; Preferably, temperature of reaction is 10 DEG C-40 DEG C, and the reaction times is 1-5 hour.
6. the preparation method of 2-deoxy-D-glucose according to claim 1, it is characterized in that: the solvent that re-crystallization step uses in described step (1) is methyl alcohol, one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, DMF, dimethyl sulfoxide (DMSO), toluene, methylene dichloride, chloroform, acetonitrile, dioxane, tetrahydrofuran (THF), ether or methyl tertiary butyl ether.
7. the preparation method of 2-deoxy-D-glucose according to claim 1, is characterized in that: in described step (1), the concentration of compound (I) is 0.01-3mol/L; Preferably, the concentration of compound (I) is 0.1-0.5mol/L; Preferably, the concentration of compound (I) is 0.25mol/L.
8. the preparation method of 2-deoxy-D-glucose according to claim 1, is characterized in that: the preparation method of compound (I) in described step (1): protected by D-Glucose alkene, obtain compound (I); Wherein, protecting group be formyl radical, ethanoyl, propionyl, benzoyl, benzyl or dimethyl tertiary butyl silica-based in one.
9. the preparation method of the 2-deoxy-D-glucose according to any one of claim 1-8, is characterized in that: in described step (1), the mol ratio of compound (I), catalyzer, sulfoxide, water is 1:(0.01-3): (0.03-9): (1-50); Preferably, the mol ratio of compound (I), catalyzer, sulfoxide, water is 1:(0.1-0.5): (0.5-0.8): (1-5).
10. the preparation method of 2-deoxy-D-glucose according to claim 9, it is characterized in that: the solvent that re-crystallization step uses in described step (2) is methyl alcohol, one or more in ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, DMF, dimethyl sulfoxide (DMSO), toluene, methylene dichloride, chloroform, acetonitrile, dioxane, tetrahydrofuran (THF), ether or methyl tertiary butyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510780244.0A CN105330704B (en) | 2015-11-13 | 2015-11-13 | The preparation method of 2-deoxy-D-glucose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510780244.0A CN105330704B (en) | 2015-11-13 | 2015-11-13 | The preparation method of 2-deoxy-D-glucose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105330704A true CN105330704A (en) | 2016-02-17 |
| CN105330704B CN105330704B (en) | 2019-05-10 |
Family
ID=55281492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510780244.0A Expired - Fee Related CN105330704B (en) | 2015-11-13 | 2015-11-13 | The preparation method of 2-deoxy-D-glucose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105330704B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955044A (en) * | 2017-11-13 | 2018-04-24 | 天津现代职业技术学院 | A kind of preparation method of 2-deoxy-D-glucose |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800193A (en) * | 2005-12-07 | 2006-07-12 | 江苏汉发贸易发展有限公司 | 2-deoxidized glucose preparation method |
| WO2008069440A1 (en) * | 2006-12-06 | 2008-06-12 | Samchully Pharm. Co., Ltd. | The preparation method of 2-de0xy-l-rib0se |
| CN102924540A (en) * | 2012-10-22 | 2013-02-13 | 山东鲁抗舍里乐药业有限公司 | Preparation method of 2-deoxy-D-glucose |
| CN103910767A (en) * | 2013-01-06 | 2014-07-09 | 路梦洋 | Preparation method of 2-deoxy-D-glucose |
| CN103951714A (en) * | 2014-04-03 | 2014-07-30 | 马玉 | Preparation method of 2-deoxy-D-glucose |
-
2015
- 2015-11-13 CN CN201510780244.0A patent/CN105330704B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800193A (en) * | 2005-12-07 | 2006-07-12 | 江苏汉发贸易发展有限公司 | 2-deoxidized glucose preparation method |
| WO2008069440A1 (en) * | 2006-12-06 | 2008-06-12 | Samchully Pharm. Co., Ltd. | The preparation method of 2-de0xy-l-rib0se |
| CN102924540A (en) * | 2012-10-22 | 2013-02-13 | 山东鲁抗舍里乐药业有限公司 | Preparation method of 2-deoxy-D-glucose |
| CN103910767A (en) * | 2013-01-06 | 2014-07-09 | 路梦洋 | Preparation method of 2-deoxy-D-glucose |
| CN103951714A (en) * | 2014-04-03 | 2014-07-30 | 马玉 | Preparation method of 2-deoxy-D-glucose |
Non-Patent Citations (1)
| Title |
|---|
| 徐淑周，等: "2-脱氧-D-葡萄糖的合成", 《应用化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955044A (en) * | 2017-11-13 | 2018-04-24 | 天津现代职业技术学院 | A kind of preparation method of 2-deoxy-D-glucose |
| CN107955044B (en) * | 2017-11-13 | 2021-04-30 | 天津现代职业技术学院 | Preparation method of 2-deoxy-D-glucose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105330704B (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106810426B (en) | Method for synthesizing cannabidiol | |
| US10221155B2 (en) | Method for preparing Alectinib | |
| CN102417491A (en) | Method for preparing cabazitaxel by taking 10-deacetylate-baccatin III as raw material | |
| CN105218621A (en) | One class dehydroabietic acid Benzimidazole Schiff base class Hete rocyclic derivatives with anti-tumor activity and its preparation method and application | |
| CN107629001B (en) | Synthesis method of anticancer drug lenvatinib | |
| CN102199180B (en) | Preparation method of capectabine | |
| CN102180914A (en) | Preparation method of 2-deoxidizing-D-glucose | |
| CN103145636B (en) | 1,4-diacyl-3,6-diphenyl-1,4-dihydrotetrazine compound as well as preparation method and application thereof | |
| CN1332929C (en) | One-pot-method for preparing caffeic acid ester derivants | |
| CN105330704A (en) | Preparation method of 2-deoxy-D-glucose | |
| CN101973993A (en) | Method for preparing 2-[imidazo[1,2-a]pyridine-3-yl]acetic acid | |
| CN103588765A (en) | Synthesis method for azilsartan medoxomil or salt thereof, intermediate of azilsartan medoxomil or salt thereof and synthesis method for intermediate | |
| CN103342707B (en) | For the preparation of the preparation method of A Sainaping intermediate | |
| CN101845066A (en) | Synthetic method of capecitabine intermediate 5-deoxy-D-ribofuranose | |
| CN106674281B (en) | A kind of Rosuvastatin midbody compound, preparation method and its usage | |
| CN101696187B (en) | Synthesizing method of N-substituent-1,2,3,6-tetrahydropyridine | |
| CN103288693A (en) | Method for preparing 1-thiol pyrene and intermediate compound thereof | |
| CN104109182A (en) | Preparation method of gemcitabine hydrochloride | |
| CN103193679B (en) | The preparation method of rivastigmine intermediate (R)-N-ethyl-N-methylamino formic acid-3-(1-hydroxyethyl) phenyl ester | |
| CN108203396B (en) | Synthesis of enkephalinase inhibitor | |
| CN106397416B (en) | A kind of preparation method of Tegafur | |
| CN108558818B (en) | Preparation method of methoxymethyl alkenyl compound | |
| CN116082111B (en) | Method for synthesizing 1, 2-triarylethane | |
| CN103435586B (en) | Containing the polyamine derivative and its preparation method and application of flavones structure | |
| CN109422783A (en) | A kind of method of chemical synthesis rhodioside |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190510 Termination date: 20201113 |