The unimolecular first-order thermal isomerization of isonitriles to nitriles has been investigated in a series of aryl-and alkylisonitriles. Retention of stereochemical integrity at the migrating carbon atom, lack of carbon skeleton rearrangement in the isomerization of cyclobutylisonitrile, and low sensitivity of the reaction rate to variation in para substituents in arylisonitriles, all support the view that bond breaking and bond making are essentially ...
