Carbon-13 nuclear magnetic resonance studies of carbocations. 5. Effect of increasing electron demand on the carbon-13 chemical shifts of 3-aryl-3-pentyl and 2-aryl-2-adamantyl carbocations. Correlation of .DELTA..delta.C+ with enhanced substituent constants .sigma.C+

1981 ◽  
Vol 46 (8) ◽  
pp. 1650-1653 ◽  
Author(s):  
David P. Kelly ◽  
Margot J. Jenkins ◽  
Robert A. Mantello
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shifts ◽  
Magnetic Resonance Studies ◽  
Substituent Constants ◽  
Electron Demand ◽  
Adamantyl Carbocations ◽  
Nuclear Magnetic

Studies of specifically fluorinated carbohydrates. Part I. Nuclear magnetic resonance studies of hexopyranosyl fluoride derivatives

1969 ◽  
Vol 47 (1) ◽  
pp. 1-17 ◽  
Author(s):  
L. D. Hall ◽  
J. F. Manville ◽  
N. S. Bhacca
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Angular Dependence ◽  
Chemical Shifts ◽  
Relative Orientation ◽  
Coupling Constants ◽  
Pyranose Ring ◽  
Spectral Parameters ◽  
Magnetic Resonance Studies ◽  
Nuclear Magnetic

A detailed study has been made of both the 1H and 19F nuclear magnetic resonance (n.m.r.) spectra of a series of hexopyranosyl fluoride derivatives. Some of the 1H spectra were measured at 220 MHz. The 1H spectral parameters define both the configuration and the conformation of each of these derivatives. Study of the 19F n.m.r. parameters revealed several stereospecific dependencies. The 19F chemical shifts depend upon, (a) the orientation of the fluorine substituent with respect to the pyranose ring and, (b) the relative orientation of other substituents attached to the ring; for acetoxy substituents, these configurational dependencies appear to be additive. The vicinal19F–1H coupling constants exhibit a marked angular dependence for which Jtrans = ca. 24 Hz whilst Jgauche = 1.0 to 1.5 Hz for [Formula: see text] and 7.5 to 12.6 Hz for [Formula: see text] The geminal19F–1H couplings depend on the orientation of the substituent at C-2; when this substituent is equatorial JF,H is ca. 53.5 Hz and when it is axial the value is ca. 49 Hz.

Studies of specifically fluorinated carbohydrates. Part II. Nuclear magnetic resonance studies of pentopyranosyl fluoride derivatives

1969 ◽  
Vol 47 (1) ◽  
pp. 19-30 ◽  
Author(s):  
L. D. Hall ◽  
J. F. Manville
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Magnetic Resonance Spectroscopy ◽  
Nuclear Magnetic Resonance Spectroscopy ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Resonance Spectroscopy ◽  
Magnetic Resonance Studies ◽  
Conformational Model ◽  
Nuclear Magnetic

Detailed studies, by 1H and 19F nuclear magnetic resonance spectroscopy, of a series of fully esterified pentopyranosyl fluorides, show that all such derivatives favor that conformer in which the fluorine substituent is axially oriented. This conclusion is supported by separate considerations of the vicinal and geminal19F–1H and 1H–1H coupling constants, of the long-range (4J) 1H–1H and 19F–1H coupling constants and of the 19F chemical shifts. The limitations of the above conformational model are discussed.

Nuclear magnetic resonance studies. III. Rotational isomerism of some C-glucosylflavonoid acetates

1965 ◽  
Vol 18 (5) ◽  
pp. 715 ◽  
Author(s):  
RA Eade ◽  
WE Hillis ◽  
DHS Horn ◽  
JJH Simes
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Steric Hindrance ◽  
Chemical Shifts ◽  
Rotational Isomerism ◽  
Bulky Substituent ◽  
Temperature Dependent ◽  
Magnetic Resonance Studies ◽  
Rotational Isomers ◽  
Nuclear Magnetic

The temperature-dependent variations in the spectra of certain C-glucosyl-flavonoid acetates are attributed to the effect of steric hindrance of bulky substituent groups of the sugar and aromatic moieties on the rate of interconversion of the two rotational isomers present. The differences in the chemical shifts of the protons of the two isomers are attributed to differences in the orientation and position of the acetyl and phenyl groups.

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