Photolyses of ethyl azidoformate in cyclic ethers.

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概要

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• Ethoxycarbonyl nitrene, generated by the photolysis of ethyl azidoformate (I), were inserted preferentially into the α C–H bonds of cyclic ethers. The α C–H bonds of cyclic ethers were much more reactive than the corresponding C–H bonds of hydrocarbons for the insertion of the nitrene. In addition, the reactions in cyclic ethers with an alkyl group at the α-position gave unsaturated alkoxyurethanes <I>via</I> a cleavage of the ring C–O bond. It was found that the nitrene insertion into the α C–H bonds of <I>cis</I>- and <I>trans</I>-2,5-dimethyltetrahydrofurans proceeded non-stereospecifically, while the insertion into the C–H bonds of hydrocarbons proceeded stereospecifically. The formation of the alkoxyurethanes can be explained by a mechanism in which an O–N ylide is included as an intermediate of the nitrene reaction; the non-stereospecific insertion of the nitrene give support to this 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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