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RESEARCH PRODUCT

Substituent and temperature controlled tautomerism: Multinuclear magnetic resonance, X-ray, and theoretical studies on 2-phenacylquinolines

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Proton-transfer equilibria in chloroform solution of twelve 2-phenacylquinolines were studied by 1H, 13C and 15N NMR spectroscopies. The (Z)-enaminone form stabilized by an intramolecular hydrogen bond was found to prevail in all cases. Electron-donating substituents in the phenacyl part of the molecule lead to an increase of the ketimine form (to 33% for p-NMe2). Variable temperature 1H NMR measurements show that higher temperatures have the same effect. The negative logarithm values of the equilibrium constant, pKT, were found to be linearly dependent on Hammett σ substituent constants. The pKTvs. temperature correlation also has a linear character. In general, strong electron-withdrawing substituents cause transformation of the ketimine to the enaminone form to become more exothermic but values of the heat of reaction for 2-phenacylquinolines studied are not linearly dependent on σ. X-Ray data show that the strength of the internal hydrogen bond in the enaminone form increases for strong electron-withdrawing substituents. Rough estimation shows this bond to be stronger in chloroform solution than in the crystalline state. π-Electron delocalization in the six-membered quasi-ring involving the H⋯O bond is very strong. This effect is responsible for the predominance of the tautomeric enaminone form in 2-phenacylquinolines. On the other hand, semiempirical AM1 and PM3 calculations show that in the gas phase the ketimine tautomer is energetically favored in most cases.