A simple and efficient synthesis and dynamic NMR studies of some new podands of dithiocarbamates formed from bis(naphthyl) derivatives

The reaction of dithiocarbamate salts ( IV _{a − c} ) with bis(naphthalene chloroacetates) ( II _a,b ) and bis(naphthalene ethoxybromide) ( II _c ) in dimethylformamide (DMF) furnished corresponding podands as V _{a − i} in high to excellent yields. Three reacting ligands, ( II _a,b ) and ( II _c ), were obtained in the reaction of bis(naphthalene) ( I _a,b ) with chloroacetylchloride and 1,2‐dibromoethane. Dynamic NMR spectroscopic data of three series of podands ( V _{a − c} , V _d−f , and V _{g − i} ) are discussed, and their free energy of activation (Δ G_C^≠) at coalescence temperatures are figured out. The Δ G_C^≠ s of these podands were attributed to conformational isomerization in the range of 14.5–18.3 kcal mol⁻¹ due to rotation and resonance effects about thioamide C N bond. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:659–668, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20730