Conformational analysis of intramolecular bonded amino alcohols : The conformational free energies of some intramolecular OH ? N hydrogen bonds

Equilibrium positions between intramolecular OH ? N hydrogen bonded and free OH forms of some 3-piperidinols, decahydroisoquinolinols, a decahydroquinolinol, lupinine and N-methyl-3-piperidinemethanol have been determined from dilute solution IR spectral data at 33°. Conformational free energies of the H-bonds (ΔG°_OH?N, attractive) have been calculated. The results suggest a linear relationship between the apparent value of ΔG°_OH?N, as defined by the method of calculation, and the strength of the OH ? N bond expressed as Δν, within the limits of 0·5 ± 0·2kcal/mole per 100 cm^?1, from Δν 90 to 350 cm^?1. For cis-decahydroisoquinoline (N-Me or N-H) systems, a 0·4 kcal/mole difference has been calculated between the two possible ring-fused conformations, in favor of the so-called steroid form. For the corresponding cis-decahydroqumoline equilibrium, a 0·8 kcal/mole difference has been calculated, in favor of the nonsteroid form.