N. Torimoto, T. Shingaki, T. Nagai
Oct 1, 1977
Citations
0
Influential Citations
6
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The reactions of N,N-dichloromethanesulfonamide (I) with substrates such as hydrocarbons and ethers gave the N-substituted methanesulfonamide (II) and methanesulfonamide (III) in the presence of copper. The reaction with 2-methylbutane gave the product only with a tertiary C–H bond, though the singlet nitrene which was generated from methanesulfonyl azide reacted with the primary, secondary, and tertiary C–H bonds in the ratio of 1 : 4.2 : 9.6. The reactions with the tertiary C–H bonds of cis- and trans-1,4-dimethylcyclohexanes proceeded non-stereospecifically, in contrast to those of the nitrene with them. The addition of a radical inhibitor, hydroquinone, reduced the yield of II, while it increased the yield of III. The reaction with alcohols led to a quantitative yield of III, accompanied by the corresponding aldehydes. These results suggest that the reaction proceeds not by a nitrene mechanism, but by a metal-radical mechanism.