The mechanism of charge-transfer nitration of naphthalene

Eun K. Kim, T. Michael Bookman, Jay K. Kochi

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Abstract

Electrophilic (thermal) and charge-transfer (photochemical) nitration of naphthalene are effectively carried out in acetonitrile with various X-substituted N-nitropyridinium salts with X = 4-MeO, H, 4-MeO2C and 2,6-Me2. Quantitative analyses indicate that both processes effect nuclear nitration to afford the same distribution of isomeric α- and β-nitronaphthalenes, together with the production of various amounts of (nitro-pyridine) adducts to naphthalene. Time-resolved (picosecond) spectroscopy identifies the naphthalene cation radical (NAPH.+) as the critical reactive intermediate in charge-transfer nitration. The subsequent disappearance of NAPH.+ occurs by its combination with NO2 to form the isomeric (α/β) Wheland intermediates, which suffer competitive deprotonation (to yield the nitronaphthalenes) and nucleophilic addition (to produce the adducts). The relevance of such a charge-transfer mechanism to naphthalene nitration via the electrophilic (thermal) process is discussed.

Original languageEnglish
Pages (from-to)1879-1891
Number of pages13
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number11
Publication statusPublished - 1992 Dec 1

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All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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