Density functional theory rationalization of the substituent effects in trifluoromethyl-pyridinol derivatives

被引：17

作者：

Fallas, Jorge A. ^{[2
]}

Gonzalez, Leticia ^{[1
]}

Corral, Ines ^{[1
]}

机构：

[1] Univ Jena, Inst Phys Chem, D-07743 Jena, Germany

[2] Free Univ Berlin, Inst Chem & Biochem, D-14195 Berlin, Germany

来源：

TETRAHEDRON | 2009年 / 65卷 / 01期

关键词：

Trifluoromethyl-pyridinol derivatives; Density functional theory calculations; Proton affinities; Gas phase basicities; Intramolecular hydrogen bonds; ANTI-HYDROGEN BOND; VIBRATIONAL ANALYSIS; HARTREE-FOCK; ASSIGNMENT; COMPLEXES; MOLECULES; MECHANISM;

D O I：

10.1016/j.tet.2008.10.065

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The influence of alpha-substitution in the structure, bonding and thermochemical properties of trifluoromethyl-pyridinol derivatives and their protonated counterparts has been studied by means of density functional theory. The geometries of the neutral and protonated species were optimized at the B3-LYP/6-311G(d,p) level of theory. Final energies were obtained through single point B3-LYP/6-311+G(3df,2p) calculations. The relative orientation of the different substituents within the heterocycle ring favours the formation of unexpected intramolecular hydrogen bonds (IHB), which have been characterized by means of the Atoms in Molecules theory of Bader. Although weak, these IHB are of great importance for understanding the gas phase structure and the thermodynamical properties of these compounds. Surprisingly, most of the substituted investigated pyridinols present proton affinities below or close to that calculated for the unsubstituted pyridine molecule. Only pyridinols bearing strong sigma or pi donor activating groups show proton affinities greater than that of pyridine. (C) 2008 Elsevier Ltd. All rights reserved.

引用

页码：232 / 239

页数：8

共 39 条

[1] SSR182289A, a selective and potent orally active thrombin inhibitor [J].

Altenburger, JM ;

Lassalle, GY ;

Matrougui, M ;

Galtier, D ;

Jetha, JC ;

Bocskei, Z ;

Berry, CN ;

Lunven, C ;

Lorrain, J ;

Herault, JP ;

Schaeffer, P ;

O'Connor, SE ;

Herbert, JM .

BIOORGANIC & MEDICINAL CHEMISTRY, 2004, 12 (07) :1713-1730

[2] Anticancer activities of some newly synthesized pyridine, pyrane, and pyrimidine derivatives [J].

Amr, Abdel-Galil E. ;

Mohamed, Ashraf M. ;

Mohamed, Salwa F. ;

Abdel-Hafez, Nagla A. ;

Hammam, Abu El-Fotooh G. .

BIOORGANIC & MEDICINAL CHEMISTRY, 2006, 14 (16) :5481-5488

[3]

[Anonymous], 2017, J MOL STRUCT, DOI DOI 10.1016/J.MOLSTRUC.2017.03.014

[4] ATOMS IN MOLECULES [J].

BADER, RFW .

ACCOUNTS OF CHEMICAL RESEARCH, 1985, 18 (01) :9-15

[5] Synthesis of novel pyrido[3′,2′:4,5]thieno[3,2-d]pyrimidines, pyrido [3′′,2′′:4′,5′]thieno[3′,2′:4,5]pyrimido[1,6-a]benzimidazoles and related fused systems [J].

Bakhite, EA ;

Al-Sehemi, AG ;

Yamada, Y .

JOURNAL OF HETEROCYCLIC CHEMISTRY, 2005, 42 (06) :1069-1077

[6] DFT calculation of NMR JFF spin-spin coupling constants in fluorinated pyridines [J].

Barone, V ;

Peralta, JE ;

Contreras, RH ;

Snyder, JP .

JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (23) :5607-5612

[7] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[8]

BIEGLERKONIG F, 2000, AIM2000 VERSION 1 0

[9] Cyclopropanation of styrene with diazoacetates catalyzed by copper and rhodium complexes of new chiral 2,2':6',2"-terpyridines derived from natural occurring compounds [J].

Chelucci, G ;

Saba, A ;

Soccolini, F ;

Vignola, D .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2002, 178 (1-2) :27-33

[10]

Cottet F, 2002, EUR J ORG CHEM, V2002, P327

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