Effect of substituents on the 1H-NMR chemical shifts of 3-methylene-2-substituted-1,4-pentadienes

Abstract

The principle of linear free energy relationships was applied to the 1H chemical shifts of the b-vinyl proton atoms of 3-methylene-2-substituted-1,4-pentadienes. The correlations of the proton chemical shifts with Swain and Lupton substituent parameters provide a mutually consistent picture of the electronic effects in these compounds. The overall pattern of proton chemical shifts can be largely accounted for by a model of substituent effects based on field, resonance and p polarization effects. Owing to the particular geometric arrangement of the vinyl group in 3-methylene-2-substituted-1,4-pentadienes, the b-vinyl protons HB and HC have different sensitivities to polar and resonance effects. The different sensitivities of the 1H chemical shifts to resonance effects reveals some effects not predicted by the model outlined above. Evidence is presented that demonstrates that both the 1H and 13C chemical shifts for these compounds reflect their ground-state charge densities.

Keywords

• cross-conjugated trienes
• ring substituted a-(s-cis-2-butadienyl)styrenes
• b-vinyl proton chemical shifts
• substituent effects