Laser flash photolysis studies of nitrogen ylides generated by the reaction of arylchlorocarbenes with substituted vinylpyridines and 1-azabuta-1,3-dienes
R. Bonneau et al., Laser flash photolysis studies of nitrogen ylides generated by the reaction of arylchlorocarbenes with substituted vinylpyridines and 1-azabuta-1,3-dienes, J PHOTOCH A, 126(1-3), 1999, pp. 31-36
Citations number
21
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
Laser Flash Photolysis of arylchlorodiazirines in isooctane/CH2Cl2 in the p
resence of substituted vinylpyridines yields substituted vinylpyridinium yl
ide (lambda = 540 nm). As the ylide decays a concomitant growth causes an a
bsorption at 330 nm, attributed to the formation of substituted indolizine.
The reaction experiences the intramolecular 1,5-cyclization of the ylide i
ntermediate. The kinetic parameters for the ylide formation and the 1,5-cyc
lization have been obtained. The activation energy for the latter process i
s reduced by 3-4 kcal mol(-1) when the vinylpyridine has a phenyl ring as a
substituent in beta-position of the ethylenic group. Laser Flash Photolysi
s of phenylchlorodiazirine in isooctane in the presence of 1-azabuta-1,3-di
ene yields azomethine ylide (lambda = 550 nm) as an intermediate. The kinet
ic parameters for the ylide formations and further intramolecular 1,5-cycli
zation to pyrrole have been determined. The results resemble those obtained
for the 1,5-cyclization of vinylpyridinium ylide. (C) 1999 Elsevier Scienc
e S.A. All rights reserved.