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A computational study on etherification mechanism of 4,5 - dihydroxy - 1,3 -bis (hydroxymethyl) imidazolidin - 2 - one with primary alcohols in acidic and parched condition
  • Dang Nguyen,
  • Quan Pham
Dang Nguyen
Ho Chi Minh City University of Technology
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Quan 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 primary alcohols in acidic and parched condition were investigated by using density functional theory combined with comparision and reference to results of experiment and spectral analysis. Geometry and energy of reactants, products, actived complexes and carbocation intermediate were optimized at B3LYP/6-311g(d,p) level. Energy level diagram is compatible with type of cation – molecule reaction. Reactants and products form actived complexes with H+ and water, in this state H+ is occupied by both alcohol and water or ether and water. This state has lower energy level compared to both of the following cases: H+ is only occupied by water; and H+ is only occupied by the product or reactant. Computational results indicate that the etherification reaction follows unimolecular nucleophilic substitution (SN1) mechanism; substituent group –R in primary alcohol R-CH2OH (-R = -H, -CH3, -CH2CH3, -Vinyl, -CH2NHCH3, -CH2OCH3, -CH2Cl) only affect to energy barrier of step releasing H3O+ Ec but no effect to energy barrier of activation step Ea = 12.8 kcal/mol; value of Ec is much higher than value of Ea which were verified and confirmed through experiment results.

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