Fragmentation of 2,2,2-triphenylethoxychlorocarbene: evidence for ultrafast fragmentation-rearrangement in excited diazirines.
[reaction: see text] Photolysis of 3-(2,2,2-triphenylethoxy)-3-chlorodiazirine gives 2,2,2-triphenylethoxychlorocarbene which fragments with 1,2-phenyl migration and loss of CO and Cl(-) to yield the 1,1,2-triphenylethyl cation and thence 1,1,2-triphenylethene by proton loss. However, ps and fs laser flash photolysis provides evidence that up to 25% of the alkene product stems from carbocation that arises directly from excited diazirine rather than from the carbene.
Fu
Xiaolin
X
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA.
Moss
Robert A
RA
Piotrowiak
Piotr
P
Myahkostupov
Mykhaylo
M
Gould
Ian R
IR