A 4 K matrix ESR study of the rearrangement and fragmentation of molecular radical cations of alkyl formates and acetates: Direct evidence for a McLafferty rearrangement

✍ Scribed by Hachizo Muto; Kazumi Toriyama; Keichi Nunome; Machio Iwasaki

• Publisher: Elsevier Science
• Year: 1984
• Tongue: English
• Weight: 376 KB
• Volume: 105
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(84)85663-8

✦ Synopsis

A 4 K matrix ESR study shows that the molecular radrcal cations of isopropyl formate and acetate, produced radio-IyticaJly in halocarbon matrices at 4-2 I(, undergo spontaneous rearrangement due to a selective intramolecular hydrogen shift from the tertiary C-H bond in the isopropyl group to the carbonyl oxygen atom giving RC*(OH)Or?(CH3)2. where R = H orCH3. The radical cation of tert-butyl acetate undergoes further fragmentation at the ester C-O bond following a similar rearrangemenr to give an isobutene radical cation in CFCJ3 _