Study on the Degradation of the Highly Reactive Hypervalent Trifluoromethylation Iodine Reagent PhI(OAc)(CF3) |
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| Authors: | Hui Zhu Shusheng Zhang Haoyang Wang Bin Xu Yinlong Guo |
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| Institution: | 1. Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444, China;2. National Center for Organic Mass Spectrometry in Shanghai, State Key Laboratory of Organmetallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China |
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| Abstract: | Degradation of the highly reactive hypervalent trifluoromethylation iodine reagent PhI(OAc)(CF3), which can only be generated in situ with mixing PhI(OAc)2 and TMSCF3 in the presence of CsF, was studied by ESI‐MS and GC‐MS combined with 19F‐NMR. The important transient intermediate PhICF3+ was determined by ESI‐MS, and the major volatile products containing CF3 were identified with the authentic compounds by using GC‐MS, such as trifluoromethylbenzene, 2‐iodobenzotrifluoride, 3‐iodobenzotrifluoride, 4‐iodobenzotrifluoride. Meanwhile, more evidences obtained with 19F‐NMR were given for such degradation reaction. A possible rapid CF3 radical transfer reaction pathway was proposed to clarify such degradation progress based on the experimental results. Therefore, this study may be helpful in elucidating the intrinsic reactivity of PhI(OAc)(CF3) and the possible competing side reactions caused by such self‐degradation pathway. |
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| Keywords: | degradation trifluoromethylation iodine reagent mass spectrometry 19F‐NMR CF3 radical reaction |
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