Observation of the keto tautomer of d-fructose in D2O using 1H NMR spectroscopy

作者: Thomas Barclay , Milena Ginic-Markovic , Martin R. Johnston , Peter Cooper , Nikolai Petrovsky

DOI: 10.1016/J.CARRES.2011.11.003

关键词:

摘要: Abstract d -Fructose was analysed by NMR spectroscopy and previously unidentified 1H resonances were assigned to the keto α-pyranose tautomers. The full assignment of shifts for various fructose tautomers enabled use in studies mutarotation (5–25 °C) tautomeric composition at equilibrium (5–50 °C). β-pyranose furanose D2O a concentration 0.18 M found have an activation energy 62.6 kJ mol−1. At (20 °C D2O) distribution β-pyranose, β-furanose, α-furanose, be 68.23%, 22.35%, 6.24%, 2.67% 0.50%, respectively. This not significantly affected varying concentrations between 0.089 0.36 M or acidification pH 3. Upon equilibrating 6 temperatures 5 50 °C there linear relationship change temperature all forms.

参考文章(39)
Klaus Bock, Christian Pedersen, Carbon-13 Nuclear Magnetic Resonance Spectroscopy of Monosaccharides Advances in Carbohydrate Chemistry and Biochemistry. ,vol. 41, pp. 27- 66 ,(1983) , 10.1016/S0065-2318(08)60055-4
Stephen J. Angyal, The composition of reducing sugars in solution Advances in Carbohydrate Chemistry and Biochemistry. ,vol. 42, pp. 15- 68 ,(1984) , 10.1016/S0065-2318(08)60122-5
Hugo E. Gottlieb, Vadim Kotlyar, Abraham Nudelman, NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities. Journal of Organic Chemistry. ,vol. 62, pp. 7512- 7515 ,(1997) , 10.1021/JO971176V
M. Cockman, D. G. Kubler, A. S. Oswald, L. Wilson, The Mutarotation of Fructose and the Invertase Hydrolysis of Sucrose Journal of Carbohydrate Chemistry. ,vol. 6, pp. 181- 201 ,(1987) , 10.1080/07328308708058870
Werner Funcke, Clemens von Sonntag, Christian Triantaphylides, DETECTION OF THE OPEN-CHAIN FORMS OF D-FRUCTOSE AND L-SORBOSE IN AQUEOUS SOLUTION BY USING 13C-N.M.R. SPECTROSCOPY Carbohydrate Research. ,vol. 75, pp. 305- 309 ,(1979) , 10.1016/S0008-6215(00)84649-2
S. J. Angyal, The Composition and Conformation of Sugars in Solution Angewandte Chemie International Edition in English. ,vol. 8, pp. 157- 166 ,(1969) , 10.1002/ANIE.196901571
Bernd Schneider, Frieder W. Lichtenthaler, Georg Steinle, Hubert Schiweck, Distribution of Furanoid and Pyranoid Tautomers of D-Fructose in Water, Dimethyl Sulfoxide, and Pyridine via 1H NMR Intensities of Anomeric Hydroxy Groups in [D6]DMSO European Journal of Organic Chemistry. ,vol. 1985, pp. 2443- 2453 ,(1985) , 10.1002/JLAC.198519851213
R. S. Shallenberger, Intrinsic chemistry of fructose Pure and Applied Chemistry. ,vol. 50, pp. 1409- 1420 ,(1978) , 10.1351/PAC197850111409
Andre´ De Bruyn, Marc Anteunis, Georges Verhegge, A 1H-n.m.r. study of D-fructose in D2O Carbohydrate Research. ,vol. 41, pp. 295- 297 ,(1975) , 10.1016/S0008-6215(00)87028-7