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Investigation of condensation products of aldehydes with acetoacetic ester catalyzed by organic bases: absolute configuration determination by X-ray crystallography and tautomeric equilibria studies by NMR spectroscopy

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Abstract

Two condensation products of aldehydes with acetoacetic ester catalyzed by methylamine or piperidine, 3a and 3b, were unambiguously assigned by single-crystal X-ray diffraction. Their X-ray crystallographic observations in the solid state and the NMR analysis ever-reported in solution phase, which were complementary to each other, were compared for an in-depth study of reliable geometrical or conformational information of poly-substituted β-keto esters 3a–e, and good agreement is observed between them. Furthermore, keto–enol tautomeric equilibriums of β-keto esters 3a–e have also been investigated using NMR spectroscopy. The results indicated that β-keto esters 3a–e exist as a mixture of keto and enol isomers in chloroform solutions when giving sufficient time at room temperature. The equilibriums were on the side of the keto tautomer with the ratio [enol]/[keto] ranging from 0.11 to 0.66.

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Acknowledgments

The authors gratefully acknowledge the financial support from the Provincial Key Project of Natural Science Research for Colleges and Universities of Anhui Province (2014) and the Doctoral Fund of Anhui University of Science and Technology (11117).

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Authors and Affiliations

  1. School of Chemical Engineering, Anhui University of Science and Technology, No. 168, Shungeng Middle Road, Huainan, 232001, Anhui, People’s Republic of China

    Chao-yue Chen, Jin-song Hu, Kai-yun Xie, Hui Liu & Xiao-mei Zhang

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  1. Chao-yue Chen
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  2. Jin-song Hu
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  3. Kai-yun Xie
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Correspondence to Chao-yue Chen.

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Chen, Cy., Hu, Js., Xie, Ky. et al. Investigation of condensation products of aldehydes with acetoacetic ester catalyzed by organic bases: absolute configuration determination by X-ray crystallography and tautomeric equilibria studies by NMR spectroscopy. Res Chem Intermed 41, 5769–5780 (2015). https://doi.org/10.1007/s11164-014-1700-z

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