Synthesis of (3, 6-dihydro-2H-pyran-2-yl)phosphonate derivatives and investigation of catalyst effect on frontier molecular orbitals using DFT method. (1st September 2016)

• Record Type: Journal Article
• Authors: Hossain, Md. Shakhawoat; Polat Cakir, Sidika; Altınbaş Özpınar, Gül; Nadeem, Said; Demir, Ayhan S.
• Is Part Of: Phosphorus, sulfur, and silicon and the related elements. Volume 191:Number 9(2016)
• Page Start: 1262
• Page End: 1267
• Publication Date: 2016-09-01
• Subjects: Aroyl phosphonate -- cycloaddition reaction -- 2, 3-dimethyl 1, 3-butadiene -- B97D -- frontier molecular orbital; Sulfur compounds -- Periodicals; Organosulfur compounds -- Periodicals; Phosphorus compounds -- Periodicals; Organophosphorus compounds -- Periodicals; Silicon compounds -- Periodicals; Organosilicon compounds -- Periodicals; 546
• DOI: 10.1080/10426507.2016.1166502
• Languages: English
• ISSNs: 1042-6507

Abstract

GRAPHICAL ABSTRACT: ABSTRACT: Hetero Diels-Alder (HDA) reactions between 2, 3-dimethyl-1, 3-butadiene and diethyl ester of aroyl phosphonates catalyzed by AlCl3 to afford (3, 6-dihydro-2H-pyran-2-yl) phosphonate derivatives were investigated. Aroyl phosphonates with electron-withdrawing groups generally resulted in better isolated chemical yields. A stoichiometric amount of AlCl3 rather than a catalytic amount was necessary to activate the cycloaddition reaction. The amount of AlCl3 catalyst and its effect on LUMO of ethyl ester benzoyl phosphonate were also investigated by performing density functional theory (DFT) (B97D/6-31+G(d, p)) computations in dichloromethane. An increased loading of AlCl3 induced a considerable decrease in the LUMO energy of ethyl ester of benzoyl phosphonate. The computed Gibbs free activation energy is 17.03 kcal/mol in DCM at 0°C using the same computational level.