The synthesis of 1,2-epoxyoctane (6) and the stereo-specifically labelled mono and dideuterated derivatives (7) and (8) are described. The BF3 : etherate catalysed rearrangement of 1,2-epoxyoctanes(6), (7) and (8) in ether gave products identified as 1-ethoxy-octan-2-ol (9a), (1S, 2S)1R, 2R-1-d-1-ethoxy-octan-2-ol (10a) and (1R, 2S)1S, 2R-1,2-dideutero-1-ethoxy-octan-2-ol (11a) respectively. The BF3 : etherate catalysed rearrangement of 1,2-epoxyoctane (6) gave aldehyde (14) by selective migration (ca. 1.41 : 1) of the hydrogen atom (Hb) trans to the long chain aliphatic group.