Mechanistic studies of the solvolysis of alkanesulfonyl and arenesulfonyl halides

• Malcolm J. D’Souza and
• Dennis N. Kevill

Beilstein J. Org. Chem. 2022, 18, 120–132, doi:10.3762/bjoc.18.13

• . However, if one is willing to settle for a classification of the mechanism as unimolecular or bimolecular accompanied by an approximate measure of the extents of bond-making and bond-breaking at the sulfur atom involved at the transition state, one can use a linear free energy relationship (LFER) approach

• [32]. Probably the best known LFER is the Hammett equation which presents a way of correlating the behavior of reactants with a substituent present in an aromatic ring with the effect of that substituent on the acidity of benzoic acids in water at 25 °C. As one would expect as once moves away from the

• in a variety of aqueous/organic solvents at 25.0 °C and the LFER was expressed as in Equation 1, where ko is the specific rate (first-order rate coefficient) for solvolyses in the arbitrarily chosen standard solvent of 80% ethanol and 20% water (by volume) and k is the corresponding specific rate in

Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters

• Malcolm J. D’Souza,
• Matthew J. McAneny,
• Dennis N. Kevill,
• Jin Burm Kyong and
• Song Hee Choi

Beilstein J. Org. Chem. 2011, 7, 543–552, doi:10.3762/bjoc.7.62

• activation values obtained from Arrhenius plots for 1 in these five solvents are reported. The specific rates of solvolysis were analyzed using the extended Grunwald–Winstein equation. Results obtained from correlation analysis using this linear free energy relationship (LFER) reinforce our previous

Anion–π interactions influence pK_a values

• Christopher J. Cadman and
• Anna K. Croft

Beilstein J. Org. Chem. 2011, 7, 320–328, doi:10.3762/bjoc.7.42

• aromatic substitution. The pKa' values for these 1,8-disubstituted arene naphthols have been measured in acetonitrile/water (R = NO2, 8.42; R = Cl, 8.52; R = H, 8.56; R = Me 8.68; and R = OMe, 8.71) and indicate a correlation with the electronic nature of the arene substituent, as determined through LFER

• implications for a range of other systems. Keywords: anion–π; DFT; intramolecular interaction; LFER; pKa; Introduction There are numerous examples in nature of interactions involving aromatic systems and these interactions underpin many modern supramolecular binding agents, with clear applications in