114541-87-6Relevant academic research and scientific papers
The fragmentation of alkoxychlorocarbenes in hydrocarbon solvents and in low temperature argon matrixes
Moss, Robert A.,Ma, Yan,Zheng, Fengmei,Sauers, Ronald R.,Bally, Thomas,Maltsev, Alexander,Toscano, John P.,Showalter, Brett M.
, p. 12280 - 12291 (2002)
Alkoxychlorocarbenes (ROCCl, R = benzyl, cyclohexyl, and 1-octyl) were generated from the corresponding diazirines in acetonitrile, dichloroethane, benzene, cyclohexane, and pentane solutions at 25°C, and the fragmentations of these carbenes were studied. A prominent product was phenacyl chloride (PhCH2CoCl), a formal rearrangement product of the carbene. In polar solvents, the two fragmentation transition states for CH3OCCl and C2H5OCCl were stabilized to the point where cis-trans isomerization, loss of CO, and concerted loss of CO + Cl all have similar activation energies. In less polar solvents, such as dichloroethane, heterolytic cleavage was probably not competitive.
