CN104761600A - Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide - Google Patents
Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide Download PDFInfo
- Publication number
- CN104761600A CN104761600A CN201510103297.9A CN201510103297A CN104761600A CN 104761600 A CN104761600 A CN 104761600A CN 201510103297 A CN201510103297 A CN 201510103297A CN 104761600 A CN104761600 A CN 104761600A
- Authority
- CN
- China
- Prior art keywords
- compound
- glucopyranose
- bromo
- tetrahydroxy
- imidazoles
- 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 *C(CC=C1NC2=O)=CC=C1C2=O Chemical compound *C(CC=C1NC2=O)=CC=C1C2=O 0.000 description 2
- CYAYKKUWALRRPA-YZYFRFPQSA-N CC(OCC([C@H](C(C1OC(C)=O)OC(C)=O)OC(C)=O)O[C@H]1Br)=O Chemical compound CC(OCC([C@H](C(C1OC(C)=O)OC(C)=O)OC(C)=O)O[C@H]1Br)=O CYAYKKUWALRRPA-YZYFRFPQSA-N 0.000 description 1
- ZJBMTVLDIAJZFV-JHJVBQTASA-N CC(OC[C@H](/C(/[C@@H](C1)OC(C)=O)=[O]/C(C)=O)O[C@H]1OC(C)=O)=O Chemical compound CC(OC[C@H](/C(/[C@@H](C1)OC(C)=O)=[O]/C(C)=O)O[C@H]1OC(C)=O)=O ZJBMTVLDIAJZFV-JHJVBQTASA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N C[n]1cncc1 Chemical compound C[n]1cncc1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- IMAXLNCKOJCLPF-NOWQFEBASA-N OCC(C[C@@H](C1)O)O[C@H]1O Chemical compound OCC(C[C@@H](C1)O)O[C@H]1O IMAXLNCKOJCLPF-NOWQFEBASA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
- C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
- C07H19/052—Imidazole radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/38—Oxygen atoms in positions 2 and 3, e.g. isatin
-
- 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)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention relates to synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide and belongs to glucopyranose chemical synthesis by multi-component reactions and uses of the glucopyranose. The synthesis includes: 1) subjecting glucose 1 that is adopted as a raw material to acetylation to obtain a compound 2; 2) performing bromination by adopting the compound 2 as a raw material to obtain a compound 3; 3) reacting the compound 3 with 1-methylimidazole to obtain a compound 4; and 4) hydrolyzing the compound 4 under alkaline conditions to obtain a target compound 5 that is the beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide. Ketone-ketone cross Aldol reactions of isatin and derivatives thereof and low-activity ketones are catalyzed by adopting the target compound 5 as an efficient catalyst to synthesize a series of 3-alkyl-3-hydroxy-2-ketone derivatives with potential medicinal value. The synthesis and the uses are advantageous in that: the low-activity ketones which cannot be catalyzed by other catalysts can react directly, thus broadening the range of reaction substrates, a method and operation are simple, reaction time is short, and the yield is high. Reactions are green, economical and efficient.
Description
Technical field
The present invention relates to a kind of many components reactive chemistry synthesizing pyran glucose and uses thereof, particularly a kind of synthesis of bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose and purposes.
Background technology
Aldol reaction and aldol reaction are most important a kind of C-C key forming reactions in modern organic synthesis.At present, the aldehyde-aldehyde undertaken by enamine intermediates, aldehyde-one Aldol reaction becomes a large pillar of modern organic synthesis chemistry.But because not activated ketone α-H activity is lower, be difficult to intermolecular ketone-one cross-aldol condensation occurs, therefore, intermolecular ketone-one cross-aldol condensation is a vitochemical significant challenge, and relevant report is considerably less.Want to obtain the 3-alkyl-3-hydroxyl-2-ketone derivatives with potential pharmaceutical use by efficient intermolecular ketone-one cross-aldol condensation, the necessary new catalyst that synthesis catalytic activity is high, selectivity is strong.
D-Glucose as occurring in nature distribution natural monosaccharide the most widely, for its understanding and effect already known by people.But never cause enough attention as its research in chemosynthesis of monose.Glucose is as the basic structural unit of polysaccharide, and not only cheap, aboundresources, itself small-molecular-weight, recyclability and the water-soluble glucose that all makes are seen as the desirable feedstock preparing organic micromolecule catalyst.
Nitrogen heterocyclic ring Cabbeen has special space and electronic structure, and be a class bipolarity isoelectronic species, as catalyzer, its avtive spot is many, and catalytic activity is high.
The sugary N-heterocyclic carbine of combination of sugar and N-heterocyclic carbine has the advantage of Cabbeen and sugar concurrently, both has higher catalytic activity, and has again stronger surfactivity, and can improve the solubleness of organic compound, and had Development volue in organic catalysis field to organic reaction.
Summary of the invention
The object of the invention is to provide a kind of sugary N-heterocyclic carbine bromo β-1-imidazoles-2,3,4, the synthesis of 6-tetrahydroxy-D-Glucopyranose and purposes, solve intermolecular ketone-one cross-aldol condensation to be difficult to occur, not easily obtain the problem with the 3-alkyl-3-hydroxyl-2-ketone derivatives of potential pharmaceutical use.
The object of the present invention is achieved like this: the synthesis of bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, comprising: 1) obtain compound 2 with glucose 1 for raw material carries out acetylize; 2) compound 3 is obtained for raw material through bromo with compound 2; 3) compound 3 and nitrogen Methylimidazole are obtained by reacting compound 4; 4) in the basic conditions compound 4 hydrolysis is obtained target compound 5, i.e. bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, concrete steps are as follows:
1) generate compound 2 with glucose 1 for raw material carries out acetylize, described compound 2 is 1,2,3,4,6-, five-ethanoyl-Glucopyranose, and its reaction formula is as follows:
In 500mL two neck round-bottomed flask, add the silicon sulfonic acid SSA of the dextrose anhydrous of 5.0mmol, the diacetyl oxide of 50.0mmol and 0.08g successively, argon shield, stirred at ambient temperature 30min, reacts completely, and directly carries out next step reaction;
2) obtain compound 3 for raw material through bromo with compound 2, described compound 3 is bromo-2,3,4, the 6-tetra--ethanoyl Glucopyranoses of 1-, and its reaction formula is as follows:
Under argon shield ice bath, in system, add the Glacial acetic acid of 20mL, pass into brand-new bromize hydrogen gas; gas reacts completely after passing into 1h, pours in frozen water by the product in system, with dichloromethane extraction; organic phase saturated sodium thiosulfate solution washing, separatory, organic phase is extremely neutral with saturated sodium bicarbonate solution washing; wash with water 2-3 time again; be separated organic phase, organic phase anhydrous sodium sulfate drying, filtering siccative; decompression is spin-dried for obtain colorless viscous shape liquid, uses V
ether: V
sherwood oil=1:1 recrystallization, obtains compound 3;
3) compound 3 and nitrogen Methylimidazole are obtained by reacting compound 4, and described compound 4 is the tetra-acetylated-D-Glucopyranose of bromo β-1-imidazoles-2,3,4,6-, and its reaction formula is as follows:
The compound 3 of 10mmol and the N-Methylimidazole of 20mmol are placed in 50mL round-bottomed flask, add 1mL acetonitrile, at room temperature stir 2h, obtain thick white shape solid, with washing with acetone, suction filtration obtains compound as white solid 4;
4) in the basic conditions compound 4 hydrolysis is obtained target product and compound 5, described compound 5 is bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, and its reaction formula is as follows:
The compound 4 of 2mmol is placed in 50mL two neck bottle, adds 10mL anhydrous methanol and 10mL anhydrous tetrahydro furan under argon shield successively, after stirring, add 0.5mmol Anhydrous potassium carbonate; React under room temperature ar gas environment to terminating, reaction process is by thin-layer chromatography (TLC) tracing detection; Suction filtration obtains light yellow liquid, pressure reducing and steaming excess of solvent, obtains pale yellow oily liquid body compound 5; Yellow oil; IR (KBr) ν: 3364,3152,1420,1364,1310,1177,1101,1074,1020cm
-1;
1h NMR (400MHz, DMSO-d
6) (δ, ppm): 3.15 (s, 1H), 3.25 (t, J=8.9Hz, 2H), 3.37 (t, J=8.8Hz, 2H), 3.42-3.51 (m, 4H), 3.71 (d, J=10.8Hz, 1H), 3.90 (s, 3H), 5.40 (d, J=8.8Hz, 1H), 7.79 (d, J=1.8Hz, 1H), 7.92 (d, J=1.9Hz, 1H), 9.45 (s, 1H);
13c NMR (100MHz, DMSO-d
6): δ 136.2,123.6,120.8,87.0,80.1,76.1,72.8,69.1,60.5,36.0; HRMS (ESI) m/z:calc.for C
10h
17n
2o
5[M-Br]
+found (expected): 245.1178 (245.1132).
The ketone-one intersection Aldol reaction expression of described target product 5 catalysis:
R in compound 8 in general formula
1group comprises H, 5-F, 5-Cl, 5-Br, 5-CH
3, 5-CH
3o, 5,7-(CH
3)
2, 5-NO
2; R
1group comprises-C
6h
5,-CH
3;
By the Isatine derivatives 6 of 0.1mmol, 20mol% [Bmim-G ']
+[Br]
-be placed in 50mL round-bottomed flask, stir 10 minutes at adding 2mL ethanol 50 DEG C, in system, add carbonyl compound 7, described compound 7 is 3.0mmol methyl phenyl ketone or 8.0mmol acetone, continue to be stirred to and react completely, reaction process is by thin-layer chromatography (TLC) tracing detection; Excess of solvent in pressure reducing and steaming system, crude product is by column chromatography (V
sherwood oil: V
ethyl acetate=4:1-1:2.5 gradient elution) obtain purified product 8.
Bromo β-1-imidazoles-2,3,4, the purposes of 6-tetrahydroxy-D-Glucopyranose, by bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose is as catalyzer, and the ketone-one that catalysis isatin and derivative thereof and low activity ketone participate in is intersected Aldol and reacted, and synthesis has the serial 3-alkyl-3-hydroxyl-2-ketone derivatives of potential pharmaceutical use.
Beneficial effect and advantage: bromo β-1-imidazoles-2 of the present invention, 3,4, the synthetic method of 6-tetrahydroxy-D-Glucopyranose is sugary N-heterocyclic carbine bromo β-1-imidazoles-2, the synthetic method of 3,4,6-tetrahydroxy-D-Glucopyranose, the ketone-one that it can be used as catalyzer success catalysis isatin and derivative thereof and low activity ketone to participate in is intersected Aldol and is reacted, and has synthesized a series of 3-alkyl-3-hydroxyl-2-ketone derivatives with potential pharmaceutical use.
1, sugary N-heterocyclic carbine bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose has good catalytic activity to this reaction, can obtain product 8 with high yield fast, and described product 8 is 3-alkyl-3-hydroxyl-2-ketone derivatives.
2, the productive rate of reaction is general higher, demonstrates the universality of substrate.
3, not activated low activity ketone higher yields can obtain product, shows the high catalytic activity of this catalyzer.
4, reaction conditions is gentle, and simple to operate, the reaction times is short especially, and productive rate is high, and aftertreatment is easy.
5, react environmental protection, economical and efficient, has high actual application value.
Embodiment
The synthesis of bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, comprising: 1) obtain compound 2 with glucose 1 for raw material carries out acetylize; 2) compound 3 is obtained for raw material through bromo with compound 2; 3) compound 3 and nitrogen Methylimidazole are obtained by reacting compound 4; 4) in the basic conditions compound 4 hydrolysis is obtained target compound 5, i.e. bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, concrete steps are as follows:
1) generate compound 2 with glucose 1 for raw material carries out acetylize, described compound 2 is 1,2,3,4,6-, five-ethanoyl-Glucopyranose, and its reaction formula is as follows:
In 500mL two neck round-bottomed flask, add the silicon sulfonic acid SSA of the dextrose anhydrous of 5.0mmol, the diacetyl oxide of 50.0mmol and 0.08g successively, argon shield, stirred at ambient temperature 30min, reacts completely, and directly carries out next step reaction;
2) obtain compound 3 for raw material through bromo with compound 2, described compound 3 is bromo-2,3,4, the 6-tetra--ethanoyl Glucopyranoses of 1-, and its reaction formula is as follows:
Under argon shield ice bath, in system, add the Glacial acetic acid of 20mL, pass into brand-new bromize hydrogen gas; gas reacts completely after passing into 1h, pours in frozen water by the product in system, with dichloromethane extraction; organic phase saturated sodium thiosulfate solution washing, separatory, organic phase is extremely neutral with saturated sodium bicarbonate solution washing; wash with water 2-3 time again; be separated organic phase, organic phase anhydrous sodium sulfate drying, filtering siccative; decompression is spin-dried for obtain colorless viscous shape liquid, uses V
ether: V
sherwood oil=1:1 recrystallization, obtains compound 3;
3) compound 3 and nitrogen Methylimidazole are obtained by reacting compound 4, and described compound 4 is the tetra-acetylated-D-Glucopyranose of bromo β-1-imidazoles-2,3,4,6-, and its reaction formula is as follows:
The compound 3 of 10mmol and the N-Methylimidazole of 20mmol are placed in 50mL round-bottomed flask, add 1mL acetonitrile, at room temperature stir 2h, obtain thick white shape solid, with washing with acetone, suction filtration obtains compound as white solid 4;
4) in the basic conditions compound 4 hydrolysis is obtained target product and compound 5, described compound 5 is bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, and its reaction formula is as follows:
The compound 4 of 2mmol is placed in 50mL two neck bottle, adds 10mL anhydrous methanol and 10mL anhydrous tetrahydro furan under argon shield successively, after stirring, add 0.5mmol Anhydrous potassium carbonate; React under room temperature ar gas environment to terminating, reaction process is by thin-layer chromatography (TLC) tracing detection; Suction filtration obtains light yellow liquid, pressure reducing and steaming excess of solvent, obtains pale yellow oily liquid body compound 5; Yellow oil; IR (KBr) ν: 3364,3152,1420,1364,1310,1177,1101,1074,1020cm
-1;
1h NMR (400MHz, DMSO-d
6) (δ, ppm): 3.15 (s, 1H), 3.25 (t, J=8.9Hz, 2H), 3.37 (t, J=8.8Hz, 2H), 3.42-3.51 (m, 4H), 3.71 (d, J=10.8Hz, 1H), 3.90 (s, 3H), 5.40 (d, J=8.8Hz, 1H), 7.79 (d, J=1.8Hz, 1H), 7.92 (d, J=1.9Hz, 1H), 9.45 (s, 1H);
13c NMR (100MHz, DMSO-d
6): δ 136.2,123.6,120.8,87.0,80.1,76.1,72.8,69.1,60.5,36.0; HRMS (ESI) m/z:calc.for C
10h
17n
2o
5[M-Br]
+found (expected): 245.1178 (245.1132).
The ketone-one intersection Aldol reaction expression of described target product 5 catalysis:
R in compound 8 in general formula
1group comprises H, 5-F, 5-Cl, 5-Br, 5-CH
3, 5-CH
3o, 5,7-(CH
3)
2,
5-NO
2; R
1group comprises-C
6h
5,-CH
3;
By the Isatine derivatives 6 of 0.1mmol, 20mol% [Bmim-G ']
+[Br]
-be placed in 50mL round-bottomed flask, stir 10 minutes at adding 2mL ethanol 50 DEG C, in system, add carbonyl compound 7, described compound 7 is 3.0mmol methyl phenyl ketone or 8.0mmol acetone, continue to be stirred to and react completely, reaction process is by thin-layer chromatography (TLC) tracing detection; Excess of solvent in pressure reducing and steaming system, crude product is by column chromatography (V
sherwood oil: V
ethyl acetate=4:1-1:2.5 gradient elution) obtain purified product 8.
The synthesis of table 1. product 8
Bromo β-1-imidazoles-2,3,4, the purposes of 6-tetrahydroxy-D-Glucopyranose, by bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose is as catalyzer, and the ketone-one that catalysis isatin and derivative thereof and low activity ketone participate in is intersected Aldol and reacted, and synthesis has the serial 3-alkyl-3-hydroxyl-2-ketone derivatives of potential pharmaceutical use.
Embodiment 1: for 3-hydroxyl-3-(2-oxo-2-phenylethyl) indol-2-one (8a):
Isatin 6a (0.1mmol), target product 5 (20mol%) are placed in 50mL round-bottomed flask, add 2mL ethanol to stir 10 minutes at 50 DEG C, methyl phenyl ketone (3.0mmol methyl phenyl ketone or 8.0mmol acetone) is added in system, continue to be stirred to react completely (TLC tracking), excess of solvent in pressure reducing and steaming system, crude product is by column chromatography (V
sherwood oil: V
ethyl acetate=4:1-1:2.5 gradient elution) obtain sterling 8a.
(brs,1H),6.79-6.87(m,2H),7.14-7.18(m,1H),7.26(d,J＝7.6Hz,1H),7.49(t,J＝8.0Hz,2H),7.60-7.64(m,1H),7.87-7.89(m,2H),10.26(br s,1H)；
13C NMR(100MHz,DMSO-d
6):δ196.4,178.3,142.9,136.1,133.4,131.7,128.9,128.7,127.9,123.6,121.1,109.4,72.9,45.7.HRMS(ESI)m/z:calc.for C
16H
12NO
3[M-H]
-:266.0817；found:266.0790。
Claims (3)
1. a bromo β-1-imidazoles-2,3,4, the synthesis of 6-tetrahydroxy-D-Glucopyranose, is characterized in that: bromo β-1-imidazoles-2,3, the synthesis of 4,6-tetrahydroxy-D-Glucopyranose, comprising: 1) obtain compound 2 with glucose 1 for raw material carries out acetylize; 2) compound 3 is obtained for raw material through bromo with compound 2; 3) compound 3 and nitrogen Methylimidazole are obtained by reacting compound 4; 4) in the basic conditions compound 4 hydrolysis is obtained target compound 5, i.e. bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, concrete steps are as follows:
1) generate compound 2 with glucose 1 for raw material carries out acetylize, described compound 2 is 1,2,3,4,6-, five-ethanoyl-Glucopyranose, and its reaction formula is as follows:
In 500mL two neck round-bottomed flask, add the silicon sulfonic acid SSA of the dextrose anhydrous of 5.0mmol, the diacetyl oxide of 50.0mmol and 0.08g successively, argon shield, stirred at ambient temperature 30min, reacts completely, and directly carries out next step reaction;
2) obtain compound 3 for raw material through bromo with compound 2, described compound 3 is bromo-2,3,4, the 6-tetra--ethanoyl Glucopyranoses of 1-, and its reaction formula is as follows:
Under argon shield ice bath, in system, add the Glacial acetic acid of 20mL, pass into brand-new bromize hydrogen gas; gas reacts completely after passing into 1h, pours in frozen water by the product in system, with dichloromethane extraction; organic phase saturated sodium thiosulfate solution washing, separatory, organic phase is extremely neutral with saturated sodium bicarbonate solution washing; wash with water 2-3 time again; be separated organic phase, organic phase anhydrous sodium sulfate drying, filtering siccative; decompression is spin-dried for obtain colorless viscous shape liquid, uses V
ether: V
sherwood oil=1:1 recrystallization, obtains compound 3;
3) compound 3 and nitrogen Methylimidazole are obtained by reacting compound 4, and described compound 4 is the tetra-acetylated-D-Glucopyranose of bromo β-1-imidazoles-2,3,4,6-, and its reaction formula is as follows:
The compound 3 of 10mmol and the N-Methylimidazole of 20mmol are placed in 50mL round-bottomed flask, add 1mL acetonitrile, at room temperature stir 2h, obtain thick white shape solid, with washing with acetone, suction filtration obtains compound as white solid 4;
4) in the basic conditions compound 4 hydrolysis is obtained target product and compound 5, described compound 5 is bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, and its reaction formula is as follows:
The compound 4 of 2mmol is placed in 50mL two neck bottle, adds 10mL anhydrous methanol and 10mL anhydrous tetrahydro furan under argon shield successively, after stirring, add 0.5mmol Anhydrous potassium carbonate; React under room temperature ar gas environment to terminating, reaction process is by thin-layer chromatography (TLC) tracing detection; Suction filtration obtains light yellow liquid, pressure reducing and steaming excess of solvent, obtains pale yellow oily liquid body compound 5.
2. the synthesis of one according to claim 1 sugary N-heterocyclic carbine bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose, is characterized in that: the ketone-one intersection Aldol reaction expression of described target product 5 catalysis:
R in compound 8 in general formula
1group comprises H, 5-F, 5-Cl, 5-Br, 5-CH
3, 5-CH
3o, 5,7-(CH
3)
2, 5-NO
2; R
1group comprises-C
6h
5,-CH
3;
By the Isatine derivatives 6 of 0.1mmol, 20mol% [Bmim-G ']
+[Br]
-be placed in 50mL round-bottomed flask, stir 10 minutes at adding 2mL ethanol 50 DEG C, in system, add carbonyl compound 7, described compound 7 is 3.0mmol methyl phenyl ketone or 8.0mmol acetone, continue to be stirred to and react completely, reaction process is by thin-layer chromatography (TLC) tracing detection; Excess of solvent in pressure reducing and steaming system, crude product is by column chromatography (V
sherwood oil: V
ethyl acetate=4:1-1:2.5 gradient elution) obtain purified product 8.
3. one according to claim 1 sugary N-heterocyclic carbine bromo β-1-imidazoles-2,3,4, the purposes of 6-tetrahydroxy-D-Glucopyranose, it is characterized in that: bromo β-1-imidazoles-2,3,4, the purposes of 6-tetrahydroxy-D-Glucopyranose, by bromo β-1-imidazoles-2,3,4,6-tetrahydroxy-D-Glucopyranose is as catalyzer, and the ketone-one that catalysis isatin and derivative thereof and low activity ketone participate in is intersected Aldol and reacted, and synthesis has the serial 3-alkyl-3-hydroxyl-2-ketone derivatives of potential pharmaceutical use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510103297.9A CN104761600B (en) | 2015-03-09 | 2015-03-09 | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510103297.9A CN104761600B (en) | 2015-03-09 | 2015-03-09 | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104761600A true CN104761600A (en) | 2015-07-08 |
| CN104761600B CN104761600B (en) | 2017-04-26 |
Family
ID=53643734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510103297.9A Active CN104761600B (en) | 2015-03-09 | 2015-03-09 | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104761600B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586558A (en) * | 2018-07-02 | 2018-09-28 | 赣南师范大学 | Carbohydrate alkyl bond connects imidazole type N-heterocyclic carbine palladium complex and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617657A (en) * | 2012-02-22 | 2012-08-01 | 徐州师范大学 | Method and reaction device for synthesizing 1-bromo-2,3,4,6-tetra-acetyl glucopyranose |
-
2015
- 2015-03-09 CN CN201510103297.9A patent/CN104761600B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617657A (en) * | 2012-02-22 | 2012-08-01 | 徐州师范大学 | Method and reaction device for synthesizing 1-bromo-2,3,4,6-tetra-acetyl glucopyranose |
Non-Patent Citations (4)
| Title |
|---|
| BENJAMIN K. KEITZ, ET AL.,: "Ruthenium Olefin Metathesis Catalysts Bearing Carbohydrate-Based N-Heterocyclic Carbenes.", 《ORGANOMETALLICS》 * |
| FRIEDERIKE TEWES, ET AL.,: "Carbohydrate-containing N-heterocyclic carbene complexes.", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| TAKANORI NISHIOKA, ET AL.,: "Sugar-Incorporated N-Heterocyclic Carbene Complexes.", 《ORGANOMETALLICS》 * |
| 杨志才等，: "手性NHC中间体1-(2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖基)咪唑的合成及核磁共振研究.", 《化工中间体》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586558A (en) * | 2018-07-02 | 2018-09-28 | 赣南师范大学 | Carbohydrate alkyl bond connects imidazole type N-heterocyclic carbine palladium complex and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104761600B (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102276673B (en) | Preparation method of 2-deoxy-beta-D-glucopyranosyl triazole compound | |
| CN101417972A (en) | 3-methylene-indol-2-one derivates and preparation method thereof | |
| CN103304393B (en) | A kind of synthetic method of benzil analog derivative | |
| Nakayama et al. | Asymmetric Morita–Baylis–Hillman reactions of 2-cyclohexen-1-one catalyzed by chiral biaryl-based bis (thiourea) organocatalysts | |
| CN104876971B (en) | Based on Co（Ⅱ）Metal organic frame and preparation method and application | |
| CN102432485B (en) | Alpha,beta-diamino acid derivative and synthetic method and application thereof | |
| CN106518663B (en) | A kind of preparation method of alpha-acyloxy ketone compound | |
| CN104892614A (en) | Synthesis method of 6H-isoindolo[2, 1-alpha]indol-6-one derivative | |
| CN102391154B (en) | Alpha-hydroxyl-beta-aminoketone derivatives, synthetic method and application thereof | |
| Turks et al. | Novel 3-C-aminomethyl-hexofuranose-derived thioureas and their testing in asymmetric catalysis | |
| CN104761600A (en) | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide | |
| CN110590751B (en) | Preparation method of 5-maleimide chromone compound | |
| CN103551193B (en) | N2 replaces 1,2,3-triazoles part/Cu(I) composite catalyst and Synthesis and application thereof | |
| CN103553889B (en) | A kind of synthetic method of paradol | |
| CN104761601A (en) | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrasulfo-D-glucopyranose hydrosulfate | |
| CN105732648A (en) | Nitrogen heterocyclic ring compound of pyrrolofuran and synthetic method | |
| CN101906445B (en) | Synthesis method of 2H-1-benzopyran-2-ketone derivatives | |
| CN104909970A (en) | Novel catalytic method for Meyer-Schuster rearrangement | |
| Andreu et al. | Inhibition of imidazolidinone intermediate formation in the aldol reactions catalyzed by zinc–prolinamide complexes | |
| CN106380469A (en) | Synthesis method of 1-aromatic carbonyl-2-aryl-3-ester imidazolone compounds | |
| CN108191736B (en) | 2, 3-disubstituted indole derivatives and preparation method thereof | |
| CN105017189B (en) | A kind of synthetic method of fused rings ketone compounds | |
| CN103113291A (en) | Synthesis method of 3-position alkenyl pyridine derivatives | |
| CN109053543A (en) | A kind of preparation method of cis- 3- alkoxy -1- methylene isoindole derivatives | |
| CN103130702A (en) | Method for synthesizing 3-substituted indole and 2,3-disubstituted indole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191224 Address after: 334221 new hillock town, Shangrao, Jiangxi, Dexing Patentee after: Jiangxi Dexing PARCHN Sodium VC Co., Ltd. Address before: 221116 Key Laboratory of No. 101 Shanghai Road, Copper Mt. New District, Jiangsu, Xuzhou 106 Patentee before: Jiangsu Normal University |
|
| TR01 | Transfer of patent right |