| Popis: |
The reaction of 1-halocyclopropyl sulfides with sodium alkanethiolates in protic or aprotic solvents leads to high yields of cyclopropyl sulfides, in which halogen has been replaced by hydrogen. The complementary oxidized product is, in most cases, the thioketone or thioaldehyde derived from the alkanethiolate. The reduction is unaffected by radical scavengers or by oneelectron donors. Reaction kinetics indicate that the reduction proceeds via the 1-(alkylthio)cyclopropyl cation. A mechanism is discussed (Scheme 9) in which this ambident cation is attacked by thiolate on sulfur. In the intermediary sulfonium ylid an intramolecular hydrogen shift leads to the observed products. |
