Photochemical Reactions of Arenecarbonitriles with Aliphatic Amines. 2. Effect of Amine Structure on Aminyl vs. α-Aminoalkyl Radical Formation

Frederick D Lewis*, Paul E. Correa

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

34 Scopus citations

Abstract

The photochemical reactions of 9-phenanthrenecarbonitrile with several secondary and primary amines and triethylamine have been investigated. Rate constants for fluorescence quenching by secondary and primary amines decrease with amine α-alkylation in spite of increased electron-donor ability of the more substituted amines. This trend is attributed to a steric effect on the equilibrium constant for reversible exciplex formation. The reactions of secondary and primary amines in nonpolar solvent result in selective N-H vs. α-C-H transfer from amine to arene, via a singlet exciplex. The ratio of α-C-H/N-H transfer increases with α-alkylation and increased solvent polarity and is larger for secondary vs. primary amines. The behavior of the intermediate free radical pairs is also dependent upon amine structure and solvent polarity.

Original languageEnglish (US)
Pages (from-to)194-198
Number of pages5
JournalJournal of the American Chemical Society
Volume106
Issue number1
DOIs
StatePublished - Jan 1 1984

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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