C-N vs. C-C Bond Photodissociation in N-(tert-butyldiphenylmethyl)aniline
The direct photolysis of the title aniline compound Ph2(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 sp...
Saved in:
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2004-01-01
|
| Series: | International Journal of Photoenergy |
| Online Access: | http://dx.doi.org/10.1155/S1110662X04000303 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | The direct photolysis of the title aniline compound Ph2(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
Ph2(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. |
|---|---|
| ISSN: | 1110-662X |