BROMIDE-ION CATALYZED SE1 SOLVOLYSIS OF ETHYL α-BROMOMERCURY-p-NITROPHENYLACETATE IN ETHANOL

Article abstract of DOI:10.1016/0022-328X(85)87320-4

The single product of bromide-ion catalyzed solvolysis of ethyl-α-bromomercury-p-nitrophenylacetate in ethanol is shown to be ethyl p-nitrophenylacetate.This reaction does not occur without nucleophilic assistance.Anions as well as neutral nucleophilic molecules, such as I^-, Br^-, Py and DMSO, which possess a significant affinity for mercury, can serve as the assistors.When performed in EtOD the reaction gives mainly dideuterated ethyl p-nitrophenylacetate and smaller amounts of mono- and trideuterated compounds.The occurence of dissociation of ethyl α-bromomercury-p-nitrophenylacetate producing the carbanion pNO2C6H4C(-)HCOOEt in aprotic solvents such as DME, THF, HMPT, etc., in the presence of bromide ions was demonstrated using UV spectroscopy.The reverse reaction between the carbanion and HgBr2 was also shown to be possible.These and some other data are the reasons why the reaction considered is classified as an S_E1(N) type process.