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 language | English |
|---|---|
| Pages (from-to) | 1879-1891 |
| Number of pages | 13 |
| Journal | Journal of the Chemical Society, Perkin Transactions 2 |
| Issue number | 11 |
| Publication status | Published - 1992 Dec 1 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
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The mechanism of charge-transfer nitration of naphthalene. / Kim, Eun K.; Bookman, T. Michael; Kochi, Jay K.
In: Journal of the Chemical Society, Perkin Transactions 2, No. 11, 01.12.1992, p. 1879-1891.Research output: Contribution to journal › Article
TY - JOUR
T1 - The mechanism of charge-transfer nitration of naphthalene
AU - Kim, Eun K.
AU - Bookman, T. Michael
AU - Kochi, Jay K.
PY - 1992/12/1
Y1 - 1992/12/1
N2 - 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.
AB - 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.
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M3 - Article
AN - SCOPUS:37049081919
SP - 1879
EP - 1891
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
SN - 1470-1820
IS - 11
ER -