4-Acetoxytricyclo[4.1.0.02,7]Hept-4-en-3-one; synthesis and novel bond reorganization of a valence isomer of 2-acetoxytropone

✍ Scribed by Yoshikazu Sugihara; Akikazu Yamato; Ichiro Murata

• Publisher: Elsevier Science
• Year: 1981
• Tongue: French
• Weight: 234 KB
• Volume: 22
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)81878-5

✦ Synopsis

Sumnary: 4-Acetoxytricyclo[4.1.0.02y7 ]hept-4-en-3-one (S), a valence isomer of 2-acetoxytropone, was synthesized. Upon heating in pyridine at 15O"C, 3 rearranged into 1-acetoxybicyclo[3.2.O]hepta-3,6-dien-*-one (9); the mechanism of which was examined by means of deuterium labeling experTments. Recently, we have reported') the facile synthesis and properties of tricyclo[4.1.0.02'7]hept-4-en-3-one (tropovalene) (I),*) a valence isomer of tropone, and some of its derivatives. 3) Photochemical reactions of 1 in acetone gave tropone exclusively 3) suggesting the interaction between enone and bicyclobutane moieties in its excited state. Judging from the 'H-and 13C-NMR spectra of 1, some of the interaction between enone and bicyclobutane moieties appear to exist in the ground state of 1. 133) Experimental evidence support of the interaction has recently been reported by Volz et al. 4)