Collect. Czech. Chem. Commun. 1989, 54, 2399-2407

Chemometrical analysis of substituent effects on 13C and 15N NMR chemical shifts in 1-aroyl-3-substituted thioureas

Oldřich Pytelaa, Josef Jirmanb and Antonín Lyčkab

a Department of Organic Chemistry, Institute of Chemical Technology, 532 10 Pardubice
b Research Institute of Organic Syntheses, 532 18 Pardubice-Rybitví


The methods of conjugated deviations and regression analysis have been used to study the substituent effects on 13C and 15N NMR chemical shifts of 12 derivatives of 1-aroyl-3-phenylthiourea and 1-aroyl-3-methylthiourea. The 13C NMR chemical shifts can be described by two latent variables, one univocally correlated with the Hammett substituent constants (r = 0.993) and the other reflecting the increased shielding of the nuclei due to overlap of the adjacent bond electrons as a consequence of electron-donor or electron-acceptor character of the substituents.This effect is less pronounced with the 15N nuclei. Application of dual substituent constants σR, σF with the additional constant σα describing the polarization has failed in giving sufficiently close correlations and explanation of the substituent effect found.