Correlation of Rates of Solvolysis of Diphenylacetyl Chloride Using Extended Grunwald–Winstein Equation

Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates

“…KSIE data are few ( Table 3 , References [ 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 ]), although there is an additional value of 1.25 for (Pr i O) 2 POCl in k water / k D2O [ 64 ]. (PhO) 2 POCl shows approximately constant values of log k 3 and KSIE of 3 , consistent with third order kinetics and general base catalysis by a second water molecule [ 61 ]; Hartree-Fock and DFT levels calculations [ 65 ] for (RO) 2 POX (R = H or Me, X = F or Cl) supported this proposal [ 65 ].…”

“…Other substrates show low and usually positive slopes, due to small changes in log k 3 , and hence a poor correlation with Y . The largest positive slope is 0.28 for Ph 2 PSCl, but the data refer only to 95%–50% acetone-water [ 63 ]. Emphasising the importance of nucleophilic attack, it is usually stated that the hydrolyses are bimolecular [ 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 ]; it is now suggested that additional KSIE data would confirm the role of catalysis by a second solvent molecule.…”

“… a Refers to k water / k D2O ; b Refers to k MeOH / k MeOD ; c Reference [ 56 ]; d Data from Reference [ 57 ] at 10 °C; e Reference [ 58 ]; f Shallow-U-shaped plot; g Reference [ 59 ]; h Reference [ 60 ]; i At 50 °C; j Reference [ 61 ]; k Very shallow U-shaped plot, with all values of log k 3 within the narrow range −4.8 to −5.26; l At 5 °C; m Reference [ 62 ]; n Values of log k 3 vary within a very narrow range (−2.87 to −2.97); o Data from Reference [ 63 ] at 55 °C. …”