O-17 NMR Substituent Chemical Shift (SCS) values on the carbonyl and methoxy oxygens in methyl 2,6-dimethyl-4-X-benzoates 2’ have been measured in acetonitrile-d3 and compared with those of the 2,6-unsubstituted methyl 4-X-benzoates 2, the former exhibiting very little sensitivity to the effect of 4-substituents and not appearing to be related to π-electron density changes in such sterically hindered systems. Conversely C-13 NMR SCS values of the methoxy carbon of the ester function in either 2 and 2’, although modest in size, exhibit a very good dual substituent parameter (DSP) correlation with the polar and resonance effect of 4-substituents and are therefore effective indicators of local π-electron densities. Moreover, C-13 NMR SCS values of the methoxy carbon of 2’ exhibit an excellent linear correlation with those of 2,6-unsubstituted benzoates 2. Once more this agrees with our previous conclusion that the resonance interaction between the aromatic ring and the ester group is essentially related to a π-polarization effect, not involving charge-transfer between the two moieties and therefore not sensitive to steric hindrance to their coplanarity.
O-17 vs C-13 NMR chemical shifts as effective indicators of pi-electron density distribution in hindered methyl benzoates
MUSIO, Roberta;
2009-01-01
Abstract
O-17 NMR Substituent Chemical Shift (SCS) values on the carbonyl and methoxy oxygens in methyl 2,6-dimethyl-4-X-benzoates 2’ have been measured in acetonitrile-d3 and compared with those of the 2,6-unsubstituted methyl 4-X-benzoates 2, the former exhibiting very little sensitivity to the effect of 4-substituents and not appearing to be related to π-electron density changes in such sterically hindered systems. Conversely C-13 NMR SCS values of the methoxy carbon of the ester function in either 2 and 2’, although modest in size, exhibit a very good dual substituent parameter (DSP) correlation with the polar and resonance effect of 4-substituents and are therefore effective indicators of local π-electron densities. Moreover, C-13 NMR SCS values of the methoxy carbon of 2’ exhibit an excellent linear correlation with those of 2,6-unsubstituted benzoates 2. Once more this agrees with our previous conclusion that the resonance interaction between the aromatic ring and the ester group is essentially related to a π-polarization effect, not involving charge-transfer between the two moieties and therefore not sensitive to steric hindrance to their coplanarity.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
