The quality of reactivity predictions coming from alternative theoretical approaches as well as experimental reactivity constants is examined in the case of the ester aminolysis process. The aminolysis of a series of para-substituted phenyl acetates is studied. The barrier heights for the rate-determining stage of the aminolysis of 16 phenyl acetate derivatives were predicted by employing density functional theory at the B3LYP/6-31+G(d,p) level. Experimental kinetic studies were carried out for the n-butylaminolysis of seven p-substituted phenyl acetates in acetonitrile. The results show that the electrostatic potential at the carbon atom of the carbonyl reaction center provides an excellent description of reactivities with regard to both theoretical barrier heights and experimental rate constants. The performance of other reactivity indices, Mulliken and NBO atomic charges, electrophilicity index, and Hammett constants, is also assessed.
As a direct continuation of the first part of our in vitro study (Vinarov et al., Langmuir 2012, 28, 8127), here we investigate the effects of emulsifier type and concentration on the degree of triglyceride lipolysis, in the presence of bile salts. Three types of surfactants are tested as emulsifiers: anionic, nonionic, and cationic. For all systems, we observe three regions in the dependence degree of fat lipolysis, α, versus emulsifier-to-bile ratio, f(s): α is around 0.5 in Region 1 (f(s) < 0.02); α passes through a maximum close to 1 in Region 2 (0.02 < f(s) < f(TR)); α is around zero in Region 3 (f(s) > f(TR)). The threshold ratio for complete inhibition of lipolysis, f(TR), is around 0.4 for the nonionic, 1.5 for the cationic, and 7.5 for the anionic surfactants. Measurements of interfacial tensions and optical observations revealed the following: In Region 1, the emulsifier molecules are solubilized in the bile micelles, and the adsorption layer is dominated by bile molecules. In Region 2, mixed surfactant-bile micelles are formed, with high solubilization capacity for the products of triglyceride lipolysis; rapid solubilization of these products leads to complete lipolysis. In Region 3, the emulsifier molecules prevail in the adsorption layer and completely block the lipolysis.
Density functional and ab initio methods were applied in examining the possible mechanistic pathways for the reaction of methyl benzoate with ammonia. Transition state structures and energies were determined for concerted and neutral stepwise mechanisms. The theoretical results show that the two possible pathways have similar activation energies. The general base catalysis of the process was also examined. The predictions reveal that the catalytic process results in considerable energy savings and the most favorable pathway of the reaction is through a general-base-catalyzed neutral stepwise mechanism. The structure and transition vectors of the transition states indicate that the catalytic role of ammonia is realized by facilitating the proton-transfer processes. Comparison of the energetics of the aminolysis for methyl benzoate and methyl formate shows the more favorable process to be that for the aliphatic ester. The differing reactivity of the two esters is explained in terms of the electrostatic potential values at the atoms of the ester functionality.
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