Terminally perfluorinated long-chain alkanethiols

Abstract

This paper describes the synthesis of a series of alkanethiols containing perfluorinated terminal segments: F(CF 2) m (CH 2) n SH, where m = 1, n = 9–15; m = 2, n = 11–14; m = 3, n = 10–13; and m = 4, n = 9–12. Fluorinated alkyl iodides of the general formula F(CF 2) m (CH 2) n I, where m = 1–4 and n = 0 or 1, were added to long-chain ω-olefins that were functionalized at the α-terminus with a thioacetate group. The reactions proceeded in good yields under free radical conditions. Reduction of the resulting secondary iodides gave long-chain alkanethioacetates with perfluoroalkyl terminal segments. These intermediates were readily transformed into the corresponding terminally perfluorinated alkanethiols by acidic deprotection. The product thiols should find use in the generation of well-defined fluorinated interfaces using the self-assembled monolayer (SAM) technique.