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Double fragmentation in cation radicals. An example in the NADH analogues series
Author(s) -
Anne Agnès,
Fraoua Sylvie,
Moiroux Jacques,
Savéant JeanMichel
Publication year - 1998
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(1998110)11:11<774::aid-poc40>3.0.co;2-t
Subject(s) - chemistry , steric effects , deprotonation , radical , medicinal chemistry , fragmentation (computing) , radical ion , photochemistry , nitrogen atom , carbon atom , methyl group , ion , stereochemistry , group (periodic table) , organic chemistry , ring (chemistry) , computer science , operating system
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. © 1998 John Wiley & Sons, Ltd.