MECHANISMUS DER PROTONKATALYSIERTEN GASPHASENDEHYDRATISIERUNG VON FURFURYLALKOHOL

Article abstract of DOI:10.1016/0040-4020(82)80141-5

The gas phase proton catalysed water elimination of tetrahydrofurfuryl alcohol (1) gives exclusively the ring-enlarged oxonium-ion 12.There is no experimental indication for the generation of 11 via a <1.2>-hydrogen migration.From the analysis of appropriately 13C-labelled precursors in combination with collisional activation mass spectrometry the mechanism for the ring-enlargement has been derived, clearly indicating that the oxygen/carbon bond is cleaved.A comparison of the experimental results with computational investigation (ab initio molecular orbital calculations at the 4-31G level) suggests that free tetrahydrofurfuryl cation 7 is not generated in the gas phase solvolysis.The elimination of H2O from the protonated molecule of 1 is a process characterised by anchimeric assistance of the ether oxygen 15.