tert-Butylation of Quinolinium Cations and Quinoline N-Oxides by tert-Butylmercury Halides

Glen A. Russell, Lijuan Wang, Ching-Fa Yao

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Abstract

In the presence of t-BuHgCl/KI the radical cations formed by the addition of tert-butyl radicals to C-2 of the quinolinium cation react in Me2SO by proton loss followed by one-electron oxidation (1a, R = H, Me, Cl). For the N-methyl, or N-methoxyquinolinium cations proton loss is not observed and the radical cations react by one-electron reduction (1b, R = Me, Cl; 1c, R = Me). With quinoline N-oxide and its 4-substituted derivatives the C-2 adduct radicals (1d, R = H, Me, Cl) are deprotonated by DABCO to yield after one-electron oxidation the 2-tert-butylquinoline N-oxides. The adduct radical cations formed by t-Bu addition at the C-4 of quinolinium ions 2 seldom lose the C-4 proton but react by reduction, hydration, or in the case of 2-chloroquinoline N-oxide, dimerization. The loss of the proton from the 2-adducts 1 but not from the 4-adducts 2 seems to be stereoelectronic in origin. With N-methylquinolinium cation the addition of t-Bu occurs selectively (>90%) at C-4 in contrast to the low selectivity observed in addition to quinolinium ion itself. However, with iV-methoxyquinolinium perchlorate the major reaction products (70-90%) result from the addition of t-Bu at C-2.

Original languageEnglish
Pages (from-to)5390-5395
Number of pages6
JournalJournal of Organic Chemistry
Volume60
Issue number17
DOIs
Publication statusPublished - 1995 Sep 1

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Oxides
Cations
Protons
Electrons
Ions
Oxidation
Dimerization
Reaction products
Hydration
quinoline
Derivatives

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

tert-Butylation of Quinolinium Cations and Quinoline N-Oxides by tert-Butylmercury Halides. / Russell, Glen A.; Wang, Lijuan; Yao, Ching-Fa.

In: Journal of Organic Chemistry, Vol. 60, No. 17, 01.09.1995, p. 5390-5395.

Research output: Contribution to journalArticle

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AB - In the presence of t-BuHgCl/KI the radical cations formed by the addition of tert-butyl radicals to C-2 of the quinolinium cation react in Me2SO by proton loss followed by one-electron oxidation (1a, R = H, Me, Cl). For the N-methyl, or N-methoxyquinolinium cations proton loss is not observed and the radical cations react by one-electron reduction (1b, R = Me, Cl; 1c, R = Me). With quinoline N-oxide and its 4-substituted derivatives the C-2 adduct radicals (1d, R = H, Me, Cl) are deprotonated by DABCO to yield after one-electron oxidation the 2-tert-butylquinoline N-oxides. The adduct radical cations formed by t-Bu• addition at the C-4 of quinolinium ions 2 seldom lose the C-4 proton but react by reduction, hydration, or in the case of 2-chloroquinoline N-oxide, dimerization. The loss of the proton from the 2-adducts 1 but not from the 4-adducts 2 seems to be stereoelectronic in origin. With N-methylquinolinium cation the addition of t-Bu• occurs selectively (>90%) at C-4 in contrast to the low selectivity observed in addition to quinolinium ion itself. However, with iV-methoxyquinolinium perchlorate the major reaction products (70-90%) result from the addition of t-Bu• at C-2.

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