Multinuclear (1H, 13C and 15N) Magnetic Resonance Spectroscopy and Substituent Effects on N-Phenoxyethylanilines

Abstract

1 H, 13 C and 15 N NMR spectra of twenty substituted N-phenoxyethylanilines 1Ð20 were completely and unambiguously assigned using a combination of both homo- and heteronuclear (gs-COSY), 1 H detected heteronuclear one-bond (gs-HMQC) and long-range (gsHMBC) gradient-selected correlation experiments. Correlations between chemical shifts and substituent constants are analyzed separately for both phenyl rings using variable substituents para to the fixed substituent -OCH2CH2NHC6H5 (series I) and -NHCH2CH2OC6H5 (series II), respectively. The correlation coefficient for chemical shifts vs. a linear combination of inductive and resonance substituent constants is high and improves when only the six values, corresponding to each para-monosubstituted series, were used. For nitrogen chemical shifts excellent linear dependences were obtained. The results show that the ethylene chain is not able to transmit the substituent effect from one aromatic ring to the other.