Photodimerizations of hydroxy- and benzoylated 4-azachalcones and quantum chemical investigation of the reactions
Küçük Resim Yok
Tarih
2010
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
Photodimerization reactions of compounds 4-6 gave four new cyclobutane-containing compounds (7-9) with full control over the stereochemistry at the four stereogenic centers. These new cyclobutane- containing compounds had ?-truxinic (7a), ?-truxinic (7b and 9), and ?-truxillic (8) structures. However, o-, m-, and p-hydroxy 4-azachalcones (1-3) did not give photochemical cyclization products under any conditions (in solvent or in their solid or molten states). Experimental data suggested the possibility of frontier orbital control over stereochemical behavior, so some theoretical calculations were performed. Full geometrical optimization of compounds 1-9 was performed via DFT B3LYP/6-31+G**, and their electronic structures were also investigated. The geometries of the singlet and triplet states were initially optimized by density functional theory (DFT) and the configuration interaction singles (CIS) B3LYP/3-21 +G**level. An additional calculation was performed for the triplet state using the ground-state geometry. The possible photochemical dimerization products of compounds 7-9 (a-g) and the intrinsic reaction coordinates (IRCs) of the reactions of compounds 4-6 were calculated theoretically by the DFT/3-21+G**method. The configurations (reactant, transition state, product, and reaction pathway) corresponding to the stationary points (minima or saddle points) were determined. The intrinsic reaction coordinates were followed to verify the energy profiles that connect each TS to the appropriate local minimum. The dimeric products expected from the calculations coincided with the dimers produced experimentally. © Springer-Verlag 2010.
Açıklama
Anahtar Kelimeler
Azachalcones, IRC, Photodimerization reactions, Theoretical calculations, 2 hydroxy 4 azachalcone, 3 hydroxy 4 azachalcone, 4 hydroxy 4 azachalcone, beta truxinic, chalcone derivative, epsilon truxinic, gamma truxinic, unclassified drug, article, chemical reaction, controlled study, cyclization, density functional theory, dimerization, geometry, phase transition, photochemistry, photodimerization, priority journal, quantum chemistry, stereochemistry, theoretical model, Benzene, Chalcone, Dimerization, Electrons, Hydroxylation, Light, Models, Chemical, Models, Molecular, Quantum Theory, Thermodynamics, Azachalcones, IRC, Photodimerization reactions, Theoretical calculations, 2 hydroxy 4 azachalcone, 3 hydroxy 4 azachalcone, 4 hydroxy 4 azachalcone, beta truxinic, chalcone derivative, epsilon truxinic, gamma truxinic, unclassified drug, article, chemical reaction, controlled study, cyclization, density functional theory, dimerization, geometry, phase transition, photochemistry, photodimerization, priority journal, quantum chemistry, stereochemistry, theoretical model, Benzene, Chalcone, Dimerization, Electrons, Hydroxylation, Light, Models, Chemical, Models, Molecular, Quantum Theory, Thermodynamics
Kaynak
Journal of Molecular Modeling
WoS Q Değeri
Q1
Scopus Q Değeri
Q3
Cilt
16
Sayı
8