Abstract: Conformational preferences of alkyl substituents at various positions in the 1, 3- dithiane system have been determined by acid-catalyzed equilibration of diastereoisomeric di-and trialkyldithianes. The results are supported by evidence from nuclear magnetic resonance spectroscopy. For alkyl groups at positions 2 and 4, free-energy differences (- AGO values) between equatorial and axial locations are of the same magnitude as in ...