C-Transacylation, intramolecular

C-transacylation, intramolecular W agne r-Meerwein rearrangement Walden inversion... 

Poly phosphoric acid Intramolecular C-transacylation Benzanthrones from benzofluorenones 761. O... 

Imidazole-based Ylides (Table 8, entry 36) Polymer-bound acyl imidazolinium species display special reactivity. They can be deprotonated at their C-atom to form azolium yhdes, which can be trapped with benzaldehyde. Intramolecular transacylation involving the polymer-bound carboxyl group ensues to give the a-acyloxy methyl imidazole [487] (Scheme 136). 

The Fries rearrangement of phenyl acetate (PA) over solid-acid catalysts was first studied in a fixed bed reactor at 400 °C by Pouilloux et al. [9,10]. o- and p-Hydro-xyacetophenone (o- and p-HAP), p-acetoxyacetophenone (p-AXAP), and phenol (P) were the main reaction products. Fluorinated alumina and H-FAU zeolites afforded approximately the same product distribution, o-HAP being highly favored over the para isomer. The reaction scheme proposed was that PA dissociates into phenol (P) and ketene and that o-HAP results partly from an intramolecular rearrangement of PA and partly from transacylation (Eq. 2) whereas p-HAP results from the latter reaction only [10]. 

C.H. Johnson, T.J. Athersuch, I.D. Wilson, L. Iddon, X. Meng, A.V. Stachulski, et aL, Kinetic and J-resolved statistical total correlation NMR spectroscopy approaches to structural information recovery in complex reacting mixtures apphcation to acyl gju-curonide intramolecular transacylation reactions. Anal. Chem. 80 (2008) 4886. 

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