Photochemistry of N-Acetyl-, N-Trifluoroacetyl-, N- Mesyl-, and N-Tosyldibenzothiophene Sulfilimines

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• 作者：Vasumathi Desikan ; Yonglin Liu ; John P. Toscano ; William S. Jenks
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：June 20, 2008
• 年：2008
• 卷：73
• 期：12
• 页码：4398 - 4414
• 全文大小：916K
• 年卷期：v.73,no.12(June 20, 2008)
• ISSN：1520-6904

文摘

Time-resolved infrared (TRIR) spectroscopy, product studies, and computational methods were applied to the photolysis of sulfilimines derived from dibenzothiophene that were expected to release acetylnitrene, trifluoroacetylnitrene, mesylnitrene, and tosylnitrene. All three methods provided results for acetylnitrene consistent with literature precedent and analogous experiments with the benzoylnitrene precursor, i.e., that the ground-state multiplicity is singlet. In contrast, product studies clearly indicate triplet reactivity for trifluoroacetylnitrene, though TRIR experiments were more ambiguous. Product studies suggest that these sulfilimines are superior sources for sulfonylnitrenes, which have triplet grounds states, to the corresponding azides, and computational studies shed light on the electronic structure of the nitrenes.