Quantitative First-Principles Kinetic Modeling of the Aza-Michael Addition to Acrylates in Polar Aprotic Solvents
作者： Gilles B. Desmet , Dagmar R. D’hooge , Pinar Sinem Omurtag , Pieter Espeel , Guy B. Marin
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摘要: This work presents a detailed computational study and kinetic analysis of the aza-Michael addition primary secondary amines to acrylates in an aprotic solvent. Accurate rate coefficients for all elementary steps various competing mechanisms are calculated using ONIOM-based approach which full system is with M06-2X/6-311+G(d,p) core CBS-QB3 corrected solvation COSMO-RS. Diffusional contributions taken into account coupled encounter pair model diffusion based on molecular dynamics simulations. The thermodynamic parameters forward reverse reactions fed microkinetic giving excellent agreement experimental data obtained GC analysis. Rate reveals that amines, ethyl acrylate occurs preferentially according 1,2-addition mechanism, consisting pseudoequilibrated fo...
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