Nitrosyl Chloride.

The Free Radical Photooximation of Alkanes by Nitrosyl Chloride

“…At 100" a very complex mixture is formed though these two compounds are still products. Nitrosyl chloride decomposes reversibly to chlorine and nitric oxide at a reasonable rate at these temperatures (2), as a consequence of the very weak C1-NO bond (D(C1-NO) = 38 kcal/mole). We suggest that the thermal reaction gives chlorocyclohexane and cyclohexanone oxime by the following course (Scheme 3).…”

Conjugated nitrosoalkenes

“…The latter route is possible if the carbon atom bound to the nitroso group carries a hydrogen atom (Scheme 1). 24,25 The reactions with ordinary alkenes can be classified as electrophilic substitution, and the adduct is formed in conformity with the Markovnikov rule. 24,25 The fact that nitrosyl chloride adds unexpectedly rapidly to some a,b-unsaturated carbonyl compounds 27 ± 29 might be due to preliminary coordination of the nitrosonium cation (NO + ) to the oxygen atom of the carbonyl group.…”

“…24,25 The reactions with ordinary alkenes can be classified as electrophilic substitution, and the adduct is formed in conformity with the Markovnikov rule. 24,25 The fact that nitrosyl chloride adds unexpectedly rapidly to some a,b-unsaturated carbonyl compounds 27 ± 29 might be due to preliminary coordination of the nitrosonium cation (NO + ) to the oxygen atom of the carbonyl group. Scheme 1 If there are substituents at the C=C bond of the substrate molecule, able to stabilise efficiently the carbocationic site resulting from the attack by the NO + cation, the reaction product has an ionic structure.…”

The Stereochemistry of Electrophilic Additions to Olefins and Acetylenes

“…Acetylenes also react with NOCI, but the reaction appears to be slower than that of olefins and has received very little attention (341,350). Acetylenes also react with NOCI, but the reaction appears to be slower than that of olefins and has received very little attention (341,350).…”