Selective esterolysis of nitrophenyl acetates in crystalline α-cyclodextrin complexes

The esterolysis ofm-nitrophenyl acetate (mNPA) andp-nitrophenyl acetate (pNPA), complexed with -cyclodextrin, was investigated in the solid state. At 117 and 140°C, the initial half-times ofmNPA esterolysis were 30 and 24 h, respectively, whereasp NPA esterolysis was undetectably slow. At 117°C, themNPA reaction proceeded to completion, and cyclodextrin acetate andm-nitrophenol products were identified. At 140°C,the initial rate was followed by a slow phase with a half-time of 130 h, evidently due to a structural change in the complex. Themeta/para selectivity of the solid-state reaction is considerably enhanced over the selectivity reported in aqueous solution.