Cleavage path way and the product distribution pattern during the electrochemical perfluorination of tripropylamine

The electrochemical fluorination (ECF) of tripropylamine (TPA) was carried out in anhydrous hydrogen fluoride medium using a Simons type cell. Under optimum conditions, yield of perfluorinated product was about 51% and the selectivity of perfluorotripropylamine (PFTPA) was about 87%. Even in this process involving the well-known starting material, apart from PFTPA, about nine perfluorinated by-products were also identified. Perfluorinated products obtained were characterized by GC, 1H and 19F NMR spectra and were compared with reported values. The perfluorinated products obtained support the fission and formation of CC and CN bonds. The nature of the minor products formed also supports the involvement of cyclization and isomerization reactions during electrochemical fluorination. Suitable reaction schemes for the formation of different perfluorinated by-products were suggested based on the identified products obtained from ECF of TPA which clearly supports the free radical mechanistic pathway for this process.