Unusual reactivity of 3-chloro-1-pentafluorosulfanylpropene in nucleophilic substitution reactions
2005; Elsevier BV; Volume: 46; Issue: 28 Linguagem: Inglês
10.1016/j.tetlet.2005.05.041
ISSN1873-3581
AutoresIgor V. Trushkov, Valery K. Brel,
Tópico(s)Fluorine in Organic Chemistry
ResumoTreatment of 3-chloro-1-pentafluorosulfanylprop-1-ene 1 with KCN yielded the product of prototropic rearrangement ClCHCHCH2SF5, whereas reactions with NaN3 and KSCN gave the SN2 products. Ab initio calculations at MP2/6-311++G** level are used to explain the unusual behaviour of cyanide. It was found that proton transfers from both 1 to CN− and from HCN to the anion of 1 are exothermic. In contrast, azide and thiocyanate ions are too weakly basic to deprotonate 1.
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