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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
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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.

Peer review status:UNDER REVIEW

10 Mar 2020Submitted to International Journal of Quantum Chemistry
10 Mar 2020Assigned to Editor
10 Mar 2020Submission Checks Completed
10 Mar 2020Reviewer(s) Assigned