Kinetic and mechanistic study on the thermal reactivity of stabilized phosphorus ylides, part 3: [(Acetyl)(arylcarbamoyl)methylene]triphenylphosphoranes and [(alkoxycarbonyl) (arylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

A series of five [(acetyt)(arylcarbabmoyl)methylene]triphenyl-phosphoranes 1a-e and their thiocarbarnoyl analogues 2a-e, [(alkoxycarbonyl)(arylcarbamoyl)methylene]triphenylphosphoranes 3a-e and their thiocarbarnoyl analogues 4a-e were prepared and fully characterized. All ylides are found under conditions of flash vacuum pyrolysis to fragment giving arylisocyanate or isothiocyanate and acetyl ylides or alkoxy ylides which undergo thermal extrusion of Ph3PO. A kinetic study shows that these reactions are unimolecular and are of first-order nature with no significant substituent effect. The thiocarbarnoyl ylides 2 react from 4.6 to 42 times faster than their carbamoyl ylides 1, while the thiocarbarnoyl ylides 4 react from 6.6 to 20.9 times faster than their carbamoyl ylides 3. (c) 2006 Wiley Periodicals, Inc.