C-N vs. C-C bond photodissociation in N-(tert-butyldiphenylmethyl)aniline

 
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2004 (EN)
C-N vs. C-C bond photodissociation in N-(tert-butyldiphenylmethyl)aniline (EN)

Garas, S. (EN)

Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας (EL)
Garas, S. (EN)

The direct photolysis of the title aniline compound Ph-2(Me3C)C-NHPh in acetonitrile with 248 nm laser light results in the dissociation of the C-N bond giving the corresponding (tert-Bu) diphenylmethyl radical 1a(.) and the anilino radical PhNH. detectable by ns-laser flash photolysis (LFP) and ESR spectroscopy. The same radical 1a(.) is also produced from the corresponding (tert-Bu) diphenylmethyl chloride Ph-2(Me3C) C-Cl either photolytically in MeCN through C-Cl bond homolysis or pulse radiolytically in THF; the (tert-Bu) diphenylmethyl cation is also detected, however, at sorter time scales because of its high reactivity in the solvent MeCN. At higher laser pulse intensities the radical 1a(.) is reexcited by a second photon leading through electrocyclization to the 4a, 4b-dihydro-9-tert-butylfluorenyl radical (DHBF.) and finally to fluorenyl products. Product analyses of steady state photolyses using GC and GC-MS gave as principal products (tert-Bu) diphenylmethane, aniline and various 9-substituted fluorenyl derivatives, corroborating further the primary C-N bond cleavage and the formation of the radicals 1a(.) and PhNH.. Other conceivable dissociation pathways leading to the C-CMe3 or N-H bond rupture were not observed. (EN)

laser flash-photolysis (EN)

Πανεπιστήμιο Ιωαννίνων (EL)
University of Ioannina (EN)

International Journal of Photoenergy (EN)

2004

<Go to ISI>://000222779200013

Hindawi Publishing Corporation (EN)



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