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ID 30877
file
creator
Ishihara, Chizuko
NDC
Chemistry
abstract
The thermal denitrogenation rates (k) of a series of 7,7-dimethoxy-1,4-diaryl-2,3-diazabicyclo[2.2.1] hept-2-ene derivatives 2 with a variety of aryl groups (p-CNC6H4, C6H5, p-MeC6H4, p-MeOC6H4) were determined to investigate the denitrogenation mechanism. A linear correlation (r=0.988) between the relative rate-constant (log k(rel)) of the denitrogenation reaction and Arnold's sigma(.)(alpha) parameter for benzylic-type radical-stabilization was observed. However, the relative rate-constant was not correlated with the substituent effect on the lifetime of the resulting singlet diradicals DR2. These results indicate that the rate-determining step of denitrogenation of 7,7-dimethoxy-2,3-diazabicyclo[2.2.1] hept-2-ene derivatives involves stepwise C-N bond cleavage.
journal title
Australian Journal of Chemistry
volume
Volume 63
issue
Issue 12
start page
1615
end page
1618
date of issued
2010-12-06
publisher
Csiro Publishing
issn
0004-9425
ncid
publisher doi
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
author
rights
Copyright (c) 2010 CSIRO
relation url
department
Graduate School of Science