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Acyl radical addition to benzene and related systems - a computational study
journal contribution
posted on 2023-05-17, 07:56 authored by Amos, RIJ, Jason SmithJason Smith, Brian YatesBrian Yates, Schiesser, CHThe 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).
History
Publication title
TetrahedronVolume
66Issue
38Pagination
7600-7604ISSN
0040-4020Department/School
School of Natural SciencesPublisher
Pergamon-Elsevier Science LtdPlace of publication
Oxford, EnglandRights statement
The definitive version is available at http://www.sciencedirect.comRepository Status
- Restricted