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Hansch’s analysis application to chalcone synthesis by Claisen–Schmidt reaction based in DFT methodology

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Abstract

Chalcones are bioactive compounds obtained from either natural sources or synthetic procedures and widely used due to their several biological properties. The most common experimental methodology in obtaining these compounds is Claisen–Schmidt reaction, which is a particular type of aldolic condensation. In this work, we have synthesized 23 chalcones and by density functional theory (DFT) calculation, we have studied the difference in reactivity of the several benzaldehydes and their effects on the yield of this reaction. From molecular orbital descriptors were obtained two quantitative structure–reactivity relationship (QSRR) models based on Hansch’s analysis. The results of this study showed that, for the most benzaldehydes (15 of 23 compounds), their reactivity was correlated with LUMO energy and global Electrophilicity Index (ω) values, which are determined in the first step of Claisen–Schmidt condensation mechanism (nucleophilic addition). Likewise, for the smallest group of benzaldehydes, their reactivity was related to their HOMO and ΔL − H (LUMO − HOMO) energies, which were determined in the second step of the mechanism (trans-elimination). This is the first report of a QSRR model analyzing the yield of chalcone synthesis based on DFT methodology.

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Acknowledgements

The authors thank the Dirección de Investigación y Postgrado (DGIP) of Universidad Técnica Federico Santa María; scientific initiation project 2015 (PIIC-MM), CONICYT Programa Formación de Capital Humano Avanzado 21130456; Proyecto VRIEA-PUCV “37.0/2017” and Dr. Guillermo Díaz Felming of Laboratorio de Espectroscopia Atómica y Molecular of Universidad de Playa Ancha.

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Authors and Affiliations

  1. Instituto de Química, Facultad de Ciencias, Pontificia Universidad Católica de Valparaíso, Av. Universidad 330, Valparaíso, Chile

    Marco Mellado

  2. Departamento de Química, Universidad Técnico Federico Santa María, Av. España 1680, Valparaíso, Chile

    Marco Mellado

  3. Departamento de Química, Facultad de Ciencias Naturales y Exactas, Universidad de Playa Ancha, Avda. Leopoldo Carvallo 270, Valparaíso, Chile

    Alejandro Madrid

  4. Colegio Nueva Era Siglo XXI, Av. Cardenal Samoré 1850, Valparaíso, Chile

    Úrsula Martínez

  5. Instituto de Química y Bioquímica, Facultad de Ciencias, Universidad de Valparaíso, Av. Gran Bretaña 1111, Playa Ancha, Casilla 5030, Valparaíso, Chile

    Jaime Mella

  6. Departamento de Química Orgánica, Pontificia Universidad Católica de Chile, Avda. Vicuña Mackenna 4860, Macul, Santiago, Chile

    Cristian O. Salas

  7. Facultad de Farmacia, Universidad de Valparaíso, Av. Gran Bretaña 1093, Valparaíso, Chile

    Mauricio Cuellar

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  1. Marco Mellado
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  2. Alejandro Madrid
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  3. Úrsula Martínez
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Correspondence to Marco Mellado.

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Mellado, M., Madrid, A., Martínez, Ú. et al. Hansch’s analysis application to chalcone synthesis by Claisen–Schmidt reaction based in DFT methodology. Chem. Pap. 72, 703–709 (2018). https://doi.org/10.1007/s11696-017-0316-3

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  • DOI: https://doi.org/10.1007/s11696-017-0316-3

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