Photochemical Addition of Tertiary Amines to Stilbene. Free-Radical and Electron-Transfer Mechanisms for Amine Oxidation

Frederick D Lewis*, Tong Ing Ho, J. Thomas Simpson

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

75 Scopus citations

Abstract

Several amines of structure Me2NCH2R, where R = CH==CH2, CO2Et, C≡CCH3, and C≡CH, but not Ph, react with the singlet state of trans-stilbene in hexane solution to yield adducts of structure PhCH2CHPhCHRNMe2. In acetonitrile solutions, these adducts are accompanied by variable amounts of adducts of structure PhCH2CHPhCH2NMeCH2R. Both types of adduct are formed by cross combination of 1,2-diphenylethyl-α-aminoalkyl radical pairs. The mechanism of radical-pair formation is concluded to be solvent dependent. In nonpolar solvents, hydrogen atom transfer selectively yields a merostabilized α-aminoalkyl radical. In polar solvents, a sequential electron-transfer, proton-transfer mechanism yields both α-aminoalkyl radicals.

Original languageEnglish (US)
Pages (from-to)1924-1929
Number of pages6
JournalJournal of the American Chemical Society
Volume104
Issue number7
DOIs
StatePublished - Jan 1 1982

ASJC Scopus subject areas

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

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