Thermal and Photochemistry of a Pyrene Dihydrodioxin (PDHD) and Its Radical Cation:  A Photoactivated Masking Group for ortho-Quinones

Pyrene dihydrodioxins (1 and 2) have been synthesized and shown to be effective photochemical blocking groups for pyrene-4,5-dione (3). The mechanism of quinone release proceeds through the formation of a remarkably stable radical cation. Direct evidence is provided that this radical cation is not o...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-12, Vol.126 (47), p.15324-15325
Main Authors: MACK, Eric T., CARLE, A. Björn, LIANG, J. T.-M., COYLE, W., WILSON, R. Marshall
Format: Article
Language:English
Subjects:
Cations
Chemistry
Dioxins - chemistry
DNA - chemistry
DNA - drug effects
Exact sciences and technology
Free Radicals - chemistry
General and physical chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
Pyrenes - chemistry
Quinones - chemistry
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Summary:Pyrene dihydrodioxins (1 and 2) have been synthesized and shown to be effective photochemical blocking groups for pyrene-4,5-dione (3). The mechanism of quinone release proceeds through the formation of a remarkably stable radical cation. Direct evidence is provided that this radical cation is not only thermally labile but also photochemically labile, and that both pathways lead to quinone extrusion. Once initiated with UV light, the pyrene quinone product serves as an electron-transfer photosensitizer for the further release of quinone with visible light.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0473788