CN101555262A - Method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O - Google Patents
Method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O Download PDFInfo
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- CN101555262A CN101555262A CNA2008101035286A CN200810103528A CN101555262A CN 101555262 A CN101555262 A CN 101555262A CN A2008101035286 A CNA2008101035286 A CN A2008101035286A CN 200810103528 A CN200810103528 A CN 200810103528A CN 101555262 A CN101555262 A CN 101555262A
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- coo
- compound
- oocch
- cooch
- oso
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Abstract
The invention provides a method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O, which is shown as a formula I. The method can play an important role in carbohydrate medicine synthesis.
Description
Technical field
The present invention relates to the synthetic and Application Areas of important intermediate of the saccharide compound of biologically active.
Background technology
Natural oligosaccharides or the sugar compound that stops has good biological activity (Schmidt, R.R. aspect physiology and the pharmacology; Kinzy, W.Adv.Carbohydr.Chem.Biochem.1994,50,21-23), the concern that is subjected to is more and more closer.Up to the present, about synthesizing of saccharide compound a large amount of bibliographical informations has been arranged.In these synthesis strategies, a very important step be exactly regioselectivity remove anomeric carbon-oxygen-acyl group, then the anomeric carbon oxy-compound that obtains is converted into active reaction donor and is used for the synthetic of oligosaccharides.For this reason, there has been a lot of method reports can realize this purpose, for example, ammonia (Mikano, M.Carbohydr.Res.1989,191,150-153), benzylamine (Conchie, J.; Levvy, G.A.Methods Carbohydr.Chem 1963,2,345-347), acetic acid hydrazine (Excoffier, G.; Gagnaire, D.; Utille, J.-P.Carbohydr.Res.1975,39,368-373), stannic oxide compounds (Watanbe, K.; Itoh, K.; Araki, Y.; Ishido, Y.Carbohydr.Res.1986,154,165-176; Nudelman, A.; Herzig, J.; Gottlieb, H.E.; Keinan, E.; Sterling, J.Carbohydr.Res.1987,162,145-152), (Sambaiah, T. such as mercury compounds; Fanwick, P.E.; Cushman, M.Synthesis 2001,1450-1452).These methods or reagent costliness very, or toxicity is very big to very serious of the pollution of environment, has been run counter to the present sustainable development strategy of advocating.Consider the defective of aforesaid method, we have invented FeCl
36H
2O/ acetonitrile reaction system can obtain the anomeric carbon oxy-compound efficiently.This method is simple to operation, low price, and toxicity is low, has further reduced the pollution of chemosynthesis to environment, is applicable to large-scale industrial production, for the extensive synthetic and screening of carbohydrate medicine provides strong support.
Summary of the invention
The object of the present invention is to provide a kind of method of energy selectively removing saccharide compound anomeric carbon acyl group, and can be applicable to large-scale industrial production, can provide strong support for the extensive synthetic and screening of carbohydrate medicine.
Summary of the invention
The present invention discloses a kind of with Iron(III) chloride hexahydrate (FeCl
36H
2O) method of selectively removing saccharide compound anomeric carbon acyl group, shown in general formula I, this method plays an important role in carbohydrate medicine synthetic.
General formula I
In the general formula I:
R can be CH
3CO, C
6H
5CO, (CH
3)
3CCO, NO
2, C
13H
9CH
2OCO, CH
3SO
2, C
7H
6SO
2, C
3H
5OCO, BrC
6H
4CO, ClCH
2CO.
R
1Can be H, OH, CH
3O, C
3H
5O, C
3H
3O, C
6H
5CH
2O, CH
3OC
6H
4CH
2O, OSO
3 -, CH
3COO, C
6H
5COO, (CH
3)
3CCOO, ONO
2, BrC
6H
4COO, ClCH
2COO, CH
2COOCH
2CH
2COO, C
13H
9CH
2OCOO, C
3H
5OCOO, N
3, CH
3SO
3, C
7H
6SO
3, CH
3CONH, C
6H
5CONH, Cl
3CCH
2OCONH, Cl
3CCONH, C
8H
4O
2N, C
3H
5OCONH, F
3CCH
2OCONH, NO
2C
6H
4CONH or other sugar unit.
R
2Can be H, OH, CH
3O, C
3H
5O, C
3H
3O, C
6H
5CH
2O, CH
3OC
6H
4CH
2O, OSO
3 -, CH
3COO, C
6H
5COO, (CH
3)
3CCOO, ONO
2, CH
2COOCH
2CH
2COO, C
13H
9CH
2OCOO, C
3H
5OCOO, N
3, CH
3SO
3, C
7H
6SO
3, or other sugar unit.
R
3Can be H, CH
3, CH
2OH, CH
2OCH
3, CH
2OC
3H
3, CH
2OC
3H
5, CH
2OSO
3 -, COOCH
3, COOH, COONa, COOCH
2C
6H
5, COOC
3H
5, COOCH
3CH
2OOCCH
3, CH
2OOCCH
3, CH
2OOCCH
2Cl, CH
2OOCC
6H
5, CH
2OOCC
6H
4Br, CH
2OOCCH
2CH
2OOCCH
3, CH
2OOCC (CH
3)
3, CH
2OOCOCH
2C
13H
9, CH
2N
3, CH
2OC
3H
5, CH
2OCH
2C
6H
5, CH
2OCH
2C
6H
4OCH
3, CH
2OSO
2CH
3, CH
2OSO
2C
7H
6Or other sugar unit.
Method of the present invention is simple to operation, low price, and toxicity is low, has further reduced the pollution of chemosynthesis to environment, is applicable to large-scale industrial production, for the extensive synthetic and screening of carbohydrate medicine provides strong support.
Embodiment
Specific rotation records with the automatic polarimeter of Perkin-Elmer 241MC in the time of 25 ℃.
1H NMR by BrukerARX 400 at CDCl
3In record, be interior mark with tetramethylsilane.Mass spectrum adopts VG PLATFORM mass spectrograph, with ESI technology sample introduction.Thin-layer chromatography (TLC) is by HF
254Sulfuric acid methanol solution or ultraviolet (UV) detector with 30% (v/v) on the silica-gel plate detect.Column chromatography adopts 100-200 purpose silica gel, with ethyl acetate-sherwood oil (60-90 ℃) as leacheate, solution underpressure distillation the time less than 60 ℃, but below the compound that do not specify all be commercially available or the material of reference literature preparation.
Embodiment 1:
(1.0mmol) is dissolved in CH with saccharide compound 1
3Among the CN, in reaction solution, add FeCl then
36H
2O (1.0mmol), reflux is about 1 hour.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 2 (0.9mmol, 90%), and the molecular weight of mass spectroscopy compound 2 is 348.
Embodiment 2:
(1.0mmol) is dissolved in CH with saccharide compound 3
3Among the CN, in reaction solution, add FeCl then
36H
2O (1.0mmol), reflux is about 0.2 hour.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 4 (0.95mmol, 95%), and the molecular weight of mass spectroscopy compound 4 is 290.
Embodiment 3:
(1.0mmol) is dissolved in CH with saccharide compound 5
3Among the CN, in reaction solution, add FeCl then
36H
2O (2.0mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 6 (0.80mmol, 80%), and the molecular weight of mass spectroscopy compound 6 is 636.
Embodiment 4:
(1.0mmol) is dissolved in CH with saccharide compound 7
3Among the CN, in reaction solution, add FeCl then
36H
2O (2.0mmol), reflux is about 3 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 8 (0.80mmol, 80%), and the molecular weight of mass spectroscopy compound 8 is 924.
Embodiment 5:
(1.0mmol) is dissolved in CH with saccharide compound 9
3Among the CN, in reaction solution, add FeCl then
36H
2O (2.0mmol), reflux is about 3 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 10 (0.80mmol, 80%), and the molecular weight of mass spectroscopy compound 10 is 1070.
Embodiment 6:
(1.0mmol) is dissolved in CH with saccharide compound 11
3Among the CN, in reaction solution, add FeCl then
36H
2O (1.5mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 12 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 12 is 479.
Embodiment 7:
(1.0mmol) is dissolved in CH with saccharide compound 13
3Among the CN, in reaction solution, add FeCl then
36H
2O (1.5mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 14 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 14 is 572.
Embodiment 8:
(1.0mmol) is dissolved in CH with saccharide compound 15
3Among the CN, in reaction solution, add FeCl then
36H
2O (2mmol), reflux is about 3 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 16 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 16 is 1420.
Embodiment 9:
(1.0mmol) is dissolved in CH with saccharide compound 17
3Among the CN, in reaction solution, add FeCl then
36H
2O (2mmol), reflux is about 2 hours.Reaction process is monitored with thin-layer chromatography.After having reacted, add the ethyl acetate dilution, use saturated NaHCO then
3Organic phase is collected in aqueous solution neutralization, and drying concentrates, and the column chromatography separation obtains compound 18 (0.85mmol, 85%), and the molecular weight of mass spectroscopy compound 18 is 331.
Claims (7)
1. the invention provides a kind of method of selectively removing saccharide compound anomeric carbon acyl group, the saccharide compound that is suitable for has the compound of following general formula,
General formula I
In the general formula I:
R can be CH
3CO, C
6H
5CO, (CH
3)
3CCO, NO
2, C
13H
9CH
2OCO, CH
3SO
2, C
7H
6SO
2, C
3H
5OCO, BrC
6H
4CO, ClCH
2CO.
R
1Can be H, OH, CH
3O, C
3H
5O, C
3H
3O, C
6H
5CH
2O, CH
3OC
6H
4CH
2O, OSO
3 -, CH
3COO, C
6H
5COO, (CH
3)
3CCOO, ONO
2, BrC
6H
4COO, ClCH
2COO, CH
2COOCH
2CH
2COO, C
13H
9CH
2OCOO, C
3H
5OCOO, N3, CH
3SO
3, C
7H
6SO
3, CH
3CONH, C
6H
5CONH, Cl
3CCH
2OCONH, Cl
3CCONH, C
8H
4O
2N, C
3H
5OCONH, F
3CCH
2OCONH, NO
2C
6H
4CONH or other sugar unit.
R
2Can be H, OH, CH
3O, C
3H
5O, C
3H
3O, C
6H
5CH
2O, CH
3OC
6H
4CH
2O, OSO
3 -, CH
3COO, C
6H
5COO, (CH
3)
3CCOO, ONO
2, CH
2COOCH
2CH
2COO, C
13H
9CH
2OCOO, C
3H
5OCOO, N
3, CH
3SO
3, C
7H
6SO
3, or other sugar unit.
R
3Can be H, CH
3, CH
2OH, CH
2OCH
3, CH
2OC
3H
3, CH
2OC
3H
5, CH
2OSO
3 -, COOCH
3, COOH, COONa, COOCH
2C
6H
5, COOC
3H
5, COOCH
3CH
2OOCCH
3, CH
2OOCCH
3, CH
2OOCCH
2Cl, CH
2OOCC
6H
5, CH
2OOCC
6H
4Br, CH
2OOCCH
2CH
2OOCCH
3, CH
2OOCC (CH
3)
3, CH
2OOCOCH
2C
13H
9, CH
2N
3, CH
2OC
3H
5, CH
2OCH
2C
6H
5, CH
2OCH
2C
6H
4OCH
3, CH
2OSO
2CH
3, CH
2OSO
2C
7H
6Or other sugar unit.
2. method according to claim 1 is characterized in that FeCl
36H
2The consumption of O is the 0.1-20 molar equivalent of reaction substrate.
3. method according to claim 1 is characterized in that, temperature of reaction is between 0 ℃-200 ℃.
4. method according to claim 1 is characterized in that, the reaction times is between 5 minutes-200 hours.
5. method according to claim 1 is characterized in that, can with iron trichloride (FeCl
3) form the reagent and the method for hydration mixture.
6. method according to claim 1 is characterized in that, iron trichloride (FeCl
3) with contain the solvent and the reagent of water.
7. method according to claim 1 is characterized in that, can form the reagent and the method for iron(ic) chloride.
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CNA2008101035286A CN101555262A (en) | 2008-04-08 | 2008-04-08 | Method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O |
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CNA2008101035286A CN101555262A (en) | 2008-04-08 | 2008-04-08 | Method for selectively removing carbohydrate compound anomer carbonyl by FeCl3.6H2O |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11401339B2 (en) | 2018-08-23 | 2022-08-02 | Seagen Inc. | Anti-TIGIT antibodies |
-
2008
- 2008-04-08 CN CNA2008101035286A patent/CN101555262A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11401339B2 (en) | 2018-08-23 | 2022-08-02 | Seagen Inc. | Anti-TIGIT antibodies |
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Application publication date: 20091014 |