Synthesis and pyrolysis of carbonate tosylhydrazone salts derived from vicinal glycols

✍ Scribed by Weston Thatcher Borden; Paul W. Concannon; Don I. Phillips

• Book ID: 104216197
• Publisher: Elsevier Science
• Year: 1973
• Tongue: French
• Weight: 242 KB
• Volume: 14
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)79799-1

✦ Synopsis

As a model for the synthesis of a class of theoretically interesting oleflns from the corresponding diols, 1

we undertook a study of the conversion of bicyclo[3.3.O]octanc-1, 5401 ( 1) to A l, 5 bicyclo[3. 3.0]-octene (A). '

Although a number of synthetic methods' accomplished thls transformation wltb varying degrees of success and convenience, none proved readily adaptable to olefin synthesis under conditions where the product, as it was formed, could be immediately trapped at low temperature for spectroscopic study.

3 We therefore investigated vacuum pyrolysis of the carbonate tosylhydrazone (CD-I) salt (3~) derived from tfi.

Pyrolysis of such a CTH salt would be expected to yield the 2-carbena-1, 3-dioxolane (3d), since alkoxy4 and dialkoxy' carbenes have been prepared by this method. Based on the fragmentation of the parent 2-carbena-1, 3-dioxolane,6 as well as its dithio analog, ' to ethylene, we anticipated that this reaction might provide a new method for the conversion of diols into olefins, 8 which would permit rapid low temperature product isolation.