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Photochemical Generation and Reactivity of Naphthyl Cations: cine Substitution
Author(s) -
Slegt Micha,
Minne Floor,
Zuilhof Han,
Overkleeft Hermen S.,
Lodder Gerrit
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700338
Subject(s) - chemistry , tetrafluoroborate , singlet state , methanol , reactivity (psychology) , photochemistry , yield (engineering) , medicinal chemistry , organic chemistry , catalysis , ionic liquid , medicine , physics , alternative medicine , materials science , pathology , nuclear physics , metallurgy , excited state
Abstract The photochemical solvolyses of naphthalen‐1‐yl(phenyl)iodonium tetrafluoroborate and naphthalen‐2‐yl(phenyl)iodonium tetrafluoroborate in methanol regiospecifically yield the naphthalen‐1‐ and ‐2‐yl ethers but afford scrambled 1‐ and 2‐phenylnaphthalene Friedel–Crafts products. It is demonstrated that singlet naphthyl cations account for the formation of the naphthyl ethers, but that the cine substitution is most likely to be due to the intermediacy of triplet naphthyl cations. According to the experiments reported here, the singlet naphthyl cations are lower in energy than their triplet isomers. High‐level MO calculations for the cations in methanol support this finding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)