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 A theoretical study on etherification of 4,5-dihydroxy-1,3-bis (hydroxymethyl) imidazolidin-2-one with the primary alcohols and the hydroxyl groups of cellulose chain (n=1-2) in acidic condition            
  • Dang T. Nguyen,
  • Quan T. Pham
Dang T. Nguyen
Ho Chi Minh City University of Technology

Corresponding Author:thuongdang85@yahoo.com

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Quan T. Pham
Ho Chi Minh City University of Technology
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Abstract

Etherification mechanism of 4,5-dihydroxy-1,3-bis (hydroxymethyl) imidazolidin-2-one (DMDHEU) with the primary alcohols and the –OH hydroxyl groups of cellulose chain (n=1-2) in acidic condition were investigated by using density functional theory (DFT) method and a two-layer ONIOM approach. Geometry and energy of reactants, products, intermediate complexes, carbocation intermediate, and transition states were optimized at B3LYP/6-311g(d,p) level and ONIOM (B3LYP/6-311g(d,p):PM3MM) level. Computational results indicate that the etherification adheres to unimolecular nucleophilic substitution (SN1) mechanism; the reactant and product can form the activated complexes with H+ ions in which H+ ions are occupied by the O-atom of C=O group in the reactant complex and the product complex. Potential energy surface (PES) of the reaction has the triple-well shape. Effect of substituent R in primary alcohol R-CH2OH (R = H, CH3, CH2CH3, CH2OCH3, CH2F) and cellulose chain on the reactivity is significant. The energy barrier of H+ ions releasing step is much higher than those of the activation steps. The calculational data is in the good agreement with the experimental data in the literature.
10 Mar 2020Submitted to International Journal of Quantum Chemistry
10 Mar 2020Assigned to Editor
10 Mar 2020Submission Checks Completed
10 Mar 2020Reviewer(s) Assigned