Synthesis of (3,6-dihydro-2H-pyran-2-yl)phosphonate derivatives and investigation of catalyst effect on frontier molecular orbitals using DFT method
[ X ]
Tarih
2016
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Taylor & Francis Ltd
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
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 17.03kcal/mol in DCM at 0 degrees C using the same computational level.
Açıklama
Anahtar Kelimeler
Aroyl phosphonate, cycloaddition reaction, 2, 3-dimethyl 1, 3-butadiene, B97D, frontier molecular orbital
Kaynak
Phosphorus Sulfur and Silicon and The Related Elements
WoS Q Değeri
Q4
Scopus Q Değeri
Q3
Cilt
191
Sayı
9
