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A Thermodynamic And Kinetic Characterization Of The Solvent Dependence Of The Saddle-Crown Equilibrium Of Cyclotriveratrylene (Ctv) Oxime, David C. French, Marlon R. Lutz Jr., Chichi Lu, Matthias Zeller, Daniel Becker

Daniel P. Becker

The equilibration of the saddle conformer of cyclotriveratrylene (CTV) oxime to the corresponding crown conformer was followed by (1)H NMR in five separate solvents, and kinetic and thermodynamic parameters were determined from the NMR data. The oxime saddle conformers of 3 are favored in CDCl(3) (K(eq) = [saddle]/[crown] = 1.4), whereas the CTV oxime crown conformer 3a is favored in three more polar solvents studied (DMSO-d(6), acetonitrile-d(3), acetone-d(6)). Surprisingly, the CTV oxime crown conformer is also slightly favored in the nonpolar solvent 1,4-dioxane-d(8). These behaviors are discussed in terms of hydrogen bonding, entropy, and possible host-guest considerations. An X-ray crystal …