- Arylmethyl radicals from arylmethoxybromodiazirines
-
(Chemical Equation Presented) Photolytic decompositions of 3-arylmethoxy-3-bromodiazirines afford arylmethyl radicals by homolyses of the diazirines' excited states.
- Moss, Robert A.,Fu, Xiaolin
-
p. 3353 - 3356
(2007/10/03)
-
- A duality of mechanisms for the fragmentation of substituted benzyloxychlorocarbenes
-
Substituted benzyloxychlorocarbenes (X-PhCH2OCCl) were generated photochemically at 25 °C in dichloroethane from appropriate diazirine precursors. Fragmentations of the carbenes produced were determined by laser flash photolysis. The data (X, kfrag in s-1) were: p-Me, 2.6 × 105; p-Ph, 8.3 × 104; H, 6.0 × 104; p-Cl, 5.2 × 104; m-Cl, 1.3 × 105; p-F3C, 2.1 × 106; p-O2N, 6.3 × 106. A Hammett correlation of log kfrag versus σ+ was parabolic. The curvature was taken to imply the gradual change of the fragmentation mechanism from predominantly heterolytic for X-PhCH2CCl with electron-donating X (with developing positive charge on the benzylic carbon in the transition state) to predominantly homolytic for carbenes with electron-withdrawing X. This idea was supported by computational studies. Copyright
- Moss, Robert A.,Ma, Yan,Sauers, Ronald R.
-
p. 13968 - 13969
(2007/10/03)
-
- THE FRAGMENTATION OF BENZYLOXYCHLOROCARBENE: FORMATION OF BENZYL CATION
-
Thermolysis of 3-benzyloxy-3-chlorodiazirine in MeCN at 25 deg C affords benzyloxychlorocarbene that fragments cleanly to the benzyl cation.
- Moss, Robert A.,Wilk, Bogdan K.,Hadel, Linda M.
-
p. 1969 - 1972
(2007/10/02)
-