The Free Radical Photooximation of Alkanes by Nitrosyl Chloride

Abstract

The mechanism of the photooximation of alkanes with nitrosyl chloride has been reinvestigated. The lack of initiation of the reaction with free radical initiators suggests that a free radical chain pathway is not involved. Nevertheless, the relative reactivities of hydrocarbons of different structure and the deuterium isotope effect are very similar to those obtained in chlorinations with elemental chlorine, and in particular, primary and tertiary hydrogens are not inert to photooximation as has been previously supposed. A probable reaction mechanism involves hydrogen abstraction from the substrate by atomic chlorine in a free radical non-chain process. This hydrogen abstraction step is shown not to be significantly reversible.

Free Radical Bromination of Saturated Hydrocarbons using Bromine and Mercuric Oxide

“…analysis on SE30 or diisodecyl phthalate (DIDP) columns. The reactions were carried out in at least triplicate, and the reactivities were evaluated as described previously (31). From the results obtained (Table 4) were calculated the data ofTables 5 and 6 pertaining to the HgOIBr, reagent.…”

Relative reactivates in free radical systems. An organic chemistry experiment

“…R-+ SOsCls -RC1 + SOsCl-SO,Cl' + RH -S02 + HCI + R-The chlorine atom has been shown to be the abstracting radical when N-chlorosuccinimide is used as a chlorinating agent (3). With N-chlorosuccinimide, unlike sulfuryl chloride, the thermal initiator reacts with molecular chlorine to form a chlorine atom which then starts the chain reaction.…”