Tautomeric Equilibria of 3-Formylacetylacetone: Low-Temperature NMR Spectroscopy and ab Initio Calculations

被引：11

作者：

Janke, Eline M. Basilio ^{[2
]}

Schlund, Sebastian ^{[1
]}

Paasche, Alexander ^{[1
]}

Engels, Bernd ^{[1
]}

Dede, Ruediger ^{[4
]}

Hussain, Ibrar ^{[3
]}

Langer, Peter ^{[3
]}

Rettig, Michael ^{[4
]}

Weisz, Klaus ^{[4
]}

机构：

[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany

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

[3] Univ Rostock, Inst Chem, D-18059 Rostock, Germany

[4] Ernst Moritz Arndt Univ Greifswald, Inst Biochem, D-17489 Greifswald, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2009年 / 74卷 / 13期

关键词：

HYDROGEN-BOND GEOMETRIES; H-1-NMR SPECTROSCOPY; CHEMICAL-SHIFTS; PROTON-TRANSFER; BETA-DIKETONES; SOLVENT; DERIVATIVES; ENAMINES; URIDINE; COMPLEX;

D O I：

10.1021/jo9004475

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Keto-enol tautomerization of 3-formylacetylacetone has been studied by NMR spectroscopy, A initio, and DFT calculations in the gas phase and continuum solvation. By employing very low temperatures in a freonic solvent, tautomeric and conformational equilibria in the slow exchange regime were analyzed in detail. The P-tricarbonyl compound always adopts a structure with ail enolized keto group irrespective of all increasing dielectric constant of the solvent when lowering the temperature of the Freon mixture. This experimentally observed tautomeric distribution of 3-formylacetylacetone is correctly reproduced by continuum solvated DFT calculations.

引用

页码：4878 / 4881

页数：4

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