A LFER Kinetic Study of The Reaction of 5‐Substituted Orotic Acids with Diazodiphenylmethane

Abstract

Linear free energy relationships (LFER) were applied to the kinetic data for the reaction of 5‐substituted orotic acids, series 1, with diazodiphenylmethane (DDM) in N,N–dimethylformamide and compared with results obtained for 2‐substituted benzoic acids, series 2. The correlation analysis of the kinetic data with σ substituent parameters was carried out using SSP (single substituent parameter) methods. From the sign and value of proportinality constant ρ, lower sensitivity to the substituent effect was obtained in series 1, 0.876, than in the series 2, 1.877. Evaluation of substituent “ortho‐effect” was performed using the Charton model, which includes the steric substituent parameter, and Fujita and Nishioka's model, which describes the total ortho‐effect as contribution of ordinary polar effect, the ortho‐steric and ortho‐polar effects. Results of correlations, obtained by using the Charton model, showed highest contribution of the polar effect, 0.861 vs. 2.101, whereas the steric effect is of lowest significance, 0.117 vs. 0.055, for series 1 and 2, respectively. Also, a low negative value of coefficient with the steric effect, –0.08, obtained from the Fujita–Nishioka model indicated low steric effect, influencing a decrease of the reaction rate in series 1. The structural and substituent effects were also studied by using the density functional theory method, and together with kinetic data, it gave a better insight into the influence of the effect of both geometry and substituent on the π−electron density shift induced reactivity of investigated acids.

Complexation of molybdenum(VI) with methyliminodiacetic acid in different water + methanol solutions

“…Specific solute-solvent interactions were subdivided into solvent Lewis-basicity interactions (hydrogen bond donor (HBD) solute/ /(hydrogen bond acceptor (HBA) solvents) and solvent Lewis acidity interactions (hydrogen bond acceptor (HBA) solute/(hydrogen bond donor (HBD) solvents). Thus, the following multiparameter equation was suggested for application in linear solvation energy relationships (LSER): [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] LSER have been used in various fields, such as, ionic liquids, solubility, thermochemistry, NMR chemical shifts, pharmaceuticals, etc. Equation (10) has been used in the correlation analysis by multiple regression of numerous reaction rates and equilibria, spectroscopic data and various other solvent dependent processes.…”