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Double fragmentation in cation radicals. An example in the NADH analogues series

✍ Scribed by Agnès Anne; Sylvie Fraoua; Jacques Moiroux; Jean-Michel Savéant

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
108 KB
Volume
11
Category
Article
ISSN
0894-3230

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✦ Synopsis

The cation radical of 9-tert-butyl-N-methylacridan, generated electrochemically or photochemically, offers, in the presence of strong bases, a remarkable example of a double fragmentation. Whereas in acidic or weakly basic media the tert-butyl radical is cleaved with concomitant formation of the methylacridinium cation, the presence of a strong base triggers the cleavage of both the methyl group borne by the nitrogen atom and the tert-butyl group on C-9 leading to acridine, formaldehyde and the tert-butyl anion, even though methylacridinium cation is stable under these conditions. The origin of this unprecedented behavior resides in the prior deprotonation of the methyl group borne by the nitrogen atom which outruns the usual deprotonation at the 9-carbon because this is slowed by the steric hindrance due to the presence of the tert-butyl group.

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