Natural Abundance ¹⁷O NMR Studies on Methyl N-Arylcarbamates: Torsion Angle and Electronic Effects

Abstract

Natural abundance ¹⁷O NMR data for 14 substituted methyl N-arylcarbamates obtained in acetonitrile solution at 75°C are reported. The ¹⁷O NMR chemical shifts of hindered ortho N-arylcarbamates are shielded relative to unhindered ones; a quantitative relationship is observed between the carbonyl ¹⁷O NMR chemical shifts and molecular mechanics (MM2) predicted torsion angles. The carbonyl ¹⁷O NMR chemical shifts of meta and para substituted N-arylcarbamates are correlated with Hammett sigma constants.

Key Words:

• ¹⁷O NMR spectroscopy
• N-Arylcarbamates
• torsion angles
• electronic effects