The decomposition of N,N-dichlorourethane by copper: A comparison with the photolysis of ethyl azidoformate.

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概要

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• The reactions of <I>N</I>,<I>N</I>-dichlorourethane (<B>1</B>) with substrates, such as hydrocarbons and ethers, gave <I>N</I>-substituted urethanes (<B>3</B>) and urethane (<B>4</B>) in the presence of copper or copper(I) chloride. The reactions with aromatic hydrocarbons and cyclic ethers possessing an alkyl group at the α-position, however, gave no azepine and no alkoxyurethane respectively, in contrast to those of ethoxycarbonylnitrene generated from the azide. The reactions with the tertiary C–H bonds of <I>cis</I>- and <I>trans</I>-1,4-dimethylcyclohexanes proceeded non-stereospecifically, contrary to those of the nitrene. The reactions with alcohols led to high yields of <B>4</B>, accompanied by the corresponding aldehydes, but afforded no O–H insertion product. The addition of a radical inhibitor, nitrobenzene, reduced the yield of <B>3</B>, while it had no appreciable effect on the yield of <B>4</B>. Furthermore, the reactions of <I>N</I>-chlorourethane with hydrocarbons also gave <B>3</B> and <B>4</B>. These results suggest that the reaction of <B>1</B> with substrates proceeds not by a nitrene mechanism, but by a metal-radical mechanism.

• 公益社団法人 日本化学会の論文

著者

• Shingaki Tadao

  College of General Education, Osaka University

• Nagai Toshikazu

  College of General Education, Osaka University

• Torimoto Noboru

  Science Education Institute of Osaka Prefecture

関連論文

• Photolyses of S,S-dimethyl-N-(ethoxycarbonyl)sulfimide in hydrocarbons and in oxygen compounds.
• Copper-initiated decomposition of N,N-dichloromethanesulfonamide.
• The decomposition of N,N-dichlorourethane by copper: A comparison with the photolysis of ethyl azidoformate.
• Photolysis of ethyl azidoformate in ethers and in alcohols.
• Photolyses of ethyl azidoformate in cyclic ethers.
• On the behavior of sulfonyl imide as a reactive intermediate. The reaction with enamines.

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