Measurement of the vicinal and geminal proton coupling constants of steroids using proton two-dimensional J spectroscopy

1980 ◽  
pp. 366 ◽  
Author(s):  
Laurance D. Hall ◽  
Jeremy K. M. Sanders ◽  
Subramaniam Sukumar
Keyword(s):  
Coupling Constants ◽  
Two Dimensional ◽  
Proton Coupling ◽  
Geminal Proton

SOLVENT EFFECTS AS AN AID IN THE ANALYSIS OF THE PROTON MAGNETIC RESONANCE SPECTRUM OF VINYL BROMIDE

1960 ◽  
Vol 38 (11) ◽  
pp. 2066-2073 ◽  
Author(s):  
T. Schaefer ◽  
W. G. Schneider
Keyword(s):  
Chemical Shift ◽  
Solvent Effects ◽  
Resonance Spectrum ◽  
Proton Magnetic Resonance Spectrum ◽  
Coupling Constants ◽  
Vinyl Bromide ◽  
Proton Coupling ◽  
Geminal Proton ◽  
Geminal Coupling ◽  
Cis And Trans

By making use of specific solvent effects it has been possible to vary the relative chemical shift between the geminal protons of vinyl bromide from about +10 cycles/sec to −4 cycles/sec (at 60 Mc/sec) and to study the resultant changes in the proton resonance spectrum in the limiting region of zero chemical shift. Of particular interest is the growth and displacement of the combination lines, which appear in the resonance signals of the proton bonded to the same carbon atom as the bromine. From the variation of the six possible lines in this region it was confirmed that the cis and trans proton coupling constants must have the same sign. The intensity distribution of the lines in the geminal proton region require the geminal coupling constant to be of opposite sign to the other two.

Hétérobicycles oxygénés. Synthèse d'alkyl-3,6,8-trioxabicyclo[3.2.1]octanes et d'alkyl-3,7,9 et -4,7,9-trioxabicyclo[4.2.1]nonanes

1978 ◽  
Vol 56 (17) ◽  
pp. 2292-2300 ◽  
Author(s):  
Pierre Calinaud ◽  
Jacques Gelas
Keyword(s):  
Double Bond ◽  
Carbon Atom ◽  
Nmr Spectra ◽  
Membered Ring ◽  
Coupling Constants ◽  
Basic Medium ◽  
Main Interest ◽  
Proton Coupling ◽  
Geminal Proton

The cyclization in a basic medium of 2 (or 4)-chloroalkyl-4 (or 2) -hydroxyalkyl-1,3-dioxolanes leads to bicyclic acetals, the 3,6,8-trioxabicyclo[3.2.1]octanes, which are useful intermediates for synthesis, yielding notably functionalized 1,4-dioxanes. The nmr spectra of these heterobicyclics were studied. The geminal proton coupling constants permit oneto distinguish between five- and six-membered rings and the determination of couplings over several bonds (4J and 5J) yields information concerning the conformation of the model bicyclics.Two isomeric series of alkylated bicyclic acetals (3,7,9- and 4,7,9-trioxabicyclo[4.2.1]nonanes) are accessible by the following routes: (a) the intramolecular addition of a 4-hydroxy-alkyl group to the ethylenic double bond on the carbon atom a to C-2 in the 1,3-dioxolanes; (b) the dechlorohydration of 2-chloromethyl-4-hydroxyalkyl-1,3-dioxolanes; (c) the dehydration of dioxolane-diols. The main interest in these heterobicyclics is to prepare a seven-membered ring and to be able to prepare functionalized 1,4-dioxepanes. [Journal translation]

Geminal Proton-Proton Coupling Constants in CH2[UNK]N-- Systems

1963 ◽  
Vol 85 (24) ◽  
pp. 4041-4042 ◽  
Author(s):  
B. L. Shapiro ◽  
S. J. Ebersole ◽  
G. J. Karabatsos ◽  
F. M. Vane ◽  
S. L. Manatt
Keyword(s):  
Coupling Constants ◽  
Proton Proton ◽  
Proton Coupling ◽  
Geminal Proton

Substituent effects on geminal proton–proton coupling constants

1970 ◽  
Vol 48 (13) ◽  
pp. 2134-2138 ◽  
Author(s):  
Y. L. Chow ◽  
S. Black ◽  
J. E. Blier ◽  
M. M. Tracey
Keyword(s):  
Carbon Tetrachloride ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
Coupling Constants ◽  
Proton Proton ◽  
Proton Coupling ◽  
Geminal Proton ◽  
Geminal Coupling ◽  
Hammett Σ Constants

The geminal coupling constants between the non-equivalent benzylic protons of a series of para- and meta-substituted N-benzyl-2-methylpiperidines were shown to be proportional to the Hammett σ constants of the substituents with ρ −1.38 in carbon tetrachloride, −1.21 in benzene, and nearly 0 in 1 N DCl solutions. The ρ values were compared with those of other series and were discussed in terms of the possible conformations involved. The chemical shifts of the benzylic protons of the piperidine derivatives did not give a good correlation with the Hammett σ constants in these solvents.

The effect of substituents on geminal proton–proton coupling constants. III

1977 ◽  
Vol 55 (14) ◽  
pp. 2642-2648 ◽  
Author(s):  
Roger N. Renaud ◽  
John W. Bovenkamp ◽  
Robert R. Fraser ◽  
Raj Capoor
Keyword(s):  
Coupling Constants ◽  
Coupling Constant ◽  
Mo Calculations ◽  
Proton Proton ◽  
Effect Of Substituents ◽  
Proton Coupling ◽  
Geminal Proton ◽  
Geminal Coupling ◽  
The Difference ◽  
Methylene Group

The effect of substituents at the 3-position in a series of N-methyl 5,6-dihydro-7H,12H-di-benzo[c,f]azocines on the geminal coupling constants of the C-12 methylene protons has been determined. The slope of the Hammett plot of 2J vs. σ has been found to be +0.20. The orientation of the methylene protons with respect to the π orbitals of the benzene ring bearing the substituent is such that no hyperconjugative effect should be present. The value of +0.20 is in contrast to a previously measured slope of −1.9 for compounds having a geometry ideal for hyperconjugative effects and substantiates the predictions of theoretical MO calculations. As a result, the reliability of this conformational dependence of ρ for use in conformational analysis has been strengthened.A comparison of the data for the azocines with those in the literature indicates the difference between the minimum and maximum effects of a phenyl substituent on a geminal coupling constant of an attached methylene group is 5.5 Hz.

Sign in / Sign up

Export Citation Format

Share Document