412025-81-1Relevant articles and documents
Hydrolysis of substituted α-nitrostilbenes: Dissection of rate coefficients for individual steps in the four-step mechanism. Estimates of intrinsic rate constants and transition-state imbalances
Bernasconi, Claude F.,Fassberg, Julianne
, p. 514 - 522 (2007/10/02)
A kinetic study of the hydrolysis of substituted α-nitrostilbenes (NS-Z with Z = 4-Me, H, 4-Br, 3-NO2, and 4-NO2) in 50% Me2SO-50% water (v/v) at 20 °C is reported. The mechanism consists of four steps: nucleophilic addition to NS-Z of water (k1H2O) and OH- (k1OH) to form PhCH(OH)C(Ar)NO2- (TOH-); carbon protonation of TOH- by water (k2H2O), H3O+ (k2H), and buffer acids (k2BH) to form PhCH(OH)CH(Ar)NO2 (TOH0); rapid oxygen deprotonation of TOH0 (KaOH) to form PhCH(O-)CH(Ar)NO2 (TO-); collapse of TO- (k4) into benzaldehyde and arylnitromethane anion. The aci-form of TOH0, PhCH(OH)CH(Ar)NO2H (TOH,aci0), can also be generated as a transient by reaction of TOH- with strong acid. A combination of kinetic experiments involving the reaction of the olefin with water and OH-, the reaction of TOH- with acid, and the reaction of independently synthesized TOH0 with base allowed the dissection of the rate coefficients of most of the individual steps. From the substituent dependence of these rate coefficients, it is concluded that water and OH- addition to NS-Z (k1H2O and k1OH) as well as the collapse of TO- to benzaldehyde and ArCH=NO2- (k4) is characterized by substantial transition-state imbalances, reminiscent of the imbalance observed in the deprotonation of ArCH2NO2. It is also shown that the intrinsic rate constants for the k1OH and k4 steps are low compared to those for the corresponding steps in the hydrolysis of other olefins of the type PhCH=CXY (XY = (H, NO2), (CO)2C6H4, (COO)2C(CHj)2, and (CN)2). This again parallels the behavior in the deprotonation of ArCH2NO2.
