Pyrolysis of the Tosylhydrazone Sodium Salts of Two Bicyclic Lactones

Article abstract of DOI:10.1021/jo00341a020

Lactone tosylhydrazone sodium salt 17a was prepared from lactone 10 by way of thionolactone 14.The tert-butyl homologue 17b was available by way of hydroxy nitrile 5.Pyrolysis of these salts led to enol ethers 18a,b and the ring-contracted ketones 19a,b.Together with earlier work, our results suggest that biradical 3 is probably an intermediate in conversion of alkoxycarbene 2 to ketone 4 and that the activation energy for this biradical coupling is ca. 2-3 kcal/mol.