ISSN:
0030-4921
Keywords:
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The analysis of the ABKX spectra of thirteen compounds of the series RC(H-K)(F-X)C(H-A)(H-B)X gave the four vicinal proton-proton and fluorine-proton coupling constants. These coupling constants of conformationally mobile structures were used (i) to calculate the populations of the rotational states of the —CHF—CH2— bond, (ii) to calculate the vicinal trans proton-proton J(HH)t and gauche and trans fluorine-proton coupling constants J(FH)g and J(FH)t and (iii) to give the unambiguous assignment of protons H-A and H-B. The dependence of the gauche and trans coupling constants with substituent electronegativity is explored. The results extend known correlations towards smaller electronegativity values. More quantitatively, the results and those in the literature, excluding those where deformations of torsional or bond angles occur, give a good fit of the data: a linear fit for J(HH)t = 15.0-0.77 Σ(ΔE), an exponential fit for J(FH)g = 15.35 exp [-0.266 Σ (ΔE)] and a linear fit for J(FH)t = 65.75 - 7.52 Σ (ΔE), where Σ (ΔE) is the sum of the electronegativity difference between hydrogen and the six atoms or groups on the CH—CF fragment.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/omr.1270210605
