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Acyl radical addition to benzene and related systems - a computational study

Citation

Amos, RIJ and Smith, JA and Yates, BF and Schiesser, CH, Acyl radical addition to benzene and related systems - a computational study, Tetrahedron, 66, (38) pp. 7600-7604. ISSN 0040-4020 (2011) [Refereed Article]


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DOI: doi:10.1016/j.tet.2010.07.041

Abstract

The addition of the acetyl radical to benzene, aniline, trifluoromethylbenzene and naphthalene has been investigated using DFT calculations. Addition to benzene is calculated to have an energy barrier of 63.6 kJ mol(-1) at the BHandHLYP/6-311G(d,p)+ZPE level of theory. This reaction is associated with simultaneous SOMO ->pi* and pi -> SOMO interactions with the latter interaction dominating, suggesting that acetyl reacts predominantly as an electrophilic radical in its interaction with benzene. Addition to the ortho and para positions of aniline is calculated to be slightly less favourable, while attack at the meta position is predicted to be unaffected in relation to the chemistry involving benzene. Inclusion of the electron-withdrawing substituent, trifluoromethyl, is predicted to accelerate reactions slightly at the ortho and para positions, while attack at the Cl position of naphthalene is calculated to involve a barrier of 50.3 kJ mol(-1) (BHandHLYP/6-311G(d,p)+ZPE).

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Organic Chemistry
Research Field:Organic Chemical Synthesis
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Amos, RIJ (Dr Ruth Amos)
Author:Smith, JA (Associate Professor Jason Smith)
Author:Yates, BF (Professor Brian Yates)
ID Code:72707
Year Published:2011
Web of Science® Times Cited:3
Deposited By:Chemistry
Deposited On:2011-08-30
Last Modified:2012-05-11
Downloads:1 View Download Statistics

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