Fragmentation of 2,2,2-Triphenylethoxychlorocarbene: Evidence for Ultrafast Fragmentation-Rearrangement in Excited Diazirines

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• 作者：Xiaolin Fu ; Robert A. Moss ; Piotr Piotrowiak ; Mykhaylo Myahkostupov ; Ian R. Gould
• 刊名：Organic Letters
• 出版年：2006
• 出版时间：October 12, 2006
• 年：2006
• 卷：8
• 期：21
• 页码：4807 - 4809
• 全文大小：50K
• 年卷期：v.8,no.21(October 12, 2006)
• ISSN：1523-7052

文摘

Photolysis of 3-(2,2,2-triphenylethoxy)-3-chlorodiazirine gives 2,2,2-triphenylethoxychlorocarbene which fragments with 1,2-phenyl migrationand loss of CO and Cl^- to yield the 1,1,2-triphenylethyl cation and thence 1,1,2-triphenylethene by proton loss. However, ps and fs laser flashphotolysis provides evidence that up to 25% of the alkene product stems from carbocation that arises directly from excited diazirine ratherthan from the carbene.