Restricted Internal Rotation in 1-Arylhydantoins, 3-Arylhydantoins, and 3-Aryl-2-Thiohydantoins: Reversal of the Effective Sizes of Methyl and Chlorine

Abstract

In 1-arylhydantoins an o-methyl group is effectively larger than an o-chloro substituent in restricting rotation about the aryl-C—N bond, whereas in 3-arylhydantoins and 3-aryl-2-thiohydantoins the reverse order of sizes is observed. This difference is attributed to repulsion between the chlorine atom and a carbonyl oxygen atom in the torsional transition state of the 3-aryl compounds.