Poonam Yadav¹, Hiteshi Tandon¹*, Babita Malik¹ and Tanmoy Chakraborty²

¹Department of Chemistry, Manipal University Jaipur, Jaipur, Rajasthan, India
²Department of Chemistry and Biochemistry, School of Basic Sciences and Research Sharda University, Greater Noida 201310, Uttar Pradesh, India

*Corresponding Author: Tanmoy Chakraborty, Department of Chemistry and Biochemistry, School of Basic Sciences and Research Sharda University, Greater Noida 201310, Uttar Pradesh, India.

Received: June 02, 2022; Published: June 22, 2022

Abstract

Nucleophilicity index (N) is a Conceptual Density Functional Theory-based reactivity descriptor which is used to define variety of physicochemical behaviours. Nucleophilicity index (N) is a measure of the electron donating power of an atom, molecule or ion and it is the inverse of electrophilicity index (ω) which is the electron attracting power of the species. In the present work we made an attempt to find out a correlation between Nucleophilicity index (N) and Hammett constant σ_p for 32CA reactions of a series of aromatic azides and alkynes, for this purpose we used a theoretical model to describe the Hammett substituent constants σ_p in terms of the nucleophilicity index (N). We have selected the B3LYP/6-31G(d) level of theory in most of the scales of the reactivity indices. We found a good linear correlation between them. The nucleophilic activation/deactivation is explained by theoretical scale of reactivity very nicely.

Keywords: Electrophilicity Index; Nucleophilicity Index; Hammett Constant

References

1. Huisgen R. “1,3-Dipolar Cycloaddition Chemistry”. Wiley: New York, USA, 1 (1984).
2. Ostrovskii VA., et al. “Tetrazoles”. Comprehensive Heterocyclic Chemistry (2008): 257-423.
3. Jewett John C and Carolyn R Bertozzi. "Cu-free click cycloaddition reactions in chemical biology”. Chemical Society Reviews4 (2010): 1272-1279.
4. Kolb Hartmuth C., et al. “Click chemistry: diverse chemical function from a few good reactions”. Angewandte Chemie International Edition11 (2001): 2004-2021.
5. Rostovtsev Vsevolod V., et al. "A stepwise huisgen cycloaddition process: copper (I)‐catalyzed regioselective “ligation” of azides and terminal alkynes”. Angewandte Chemie14 (2002): 2708-2711.
6. Domingo Luis R., et al. “A new model for C–C bond formation processes derived from the molecular electron density theory in the study of the mechanism of [3+2] cycloaddition reactions of carbenoid nitrile ylides with electron-deficient ethylenes”. Tetrahedron12 (2016): 1524-1532.
7. Domingo Luis R. "Molecular electron density theory: a modern view of reactivity in organic chemistry”. Molecules10 (2016): 1319.
8. Domingo Luis R and Saeed R Emamian. "Understanding the mechanisms of [3+ 2] cycloaddition reactions. The pseudoradical versus the zwitterionic mechanism”. Tetrahedron6 (2014): 1267-1273.
9. Siadati Seyyed A. "A theoretical study on stepwise-And concertedness of the mechanism of 1, 3-Dipolar cycloaddition reaction between tetra amino ethylene and trifluoro methyl azide”. Combinatorial Chemistry and High Throughput Screening2 (2016): 170-175.
10. Hammett Louis P. "Linear free energy relationships in rate and equilibrium phenomena”. Transactions of the Faraday Society34 (1938): 156-165.
11. Hansch Corwin., et al. “Comparative QSAR: toward a deeper understanding of chemicobiological interactions”. Chemical Reviews3 (1996): 1045-1076.
12. Domingo Luis R., et al. “Applications of the conceptual density functional theory indices to organic chemistry reactivity”. Molecules6 (2016): 748.
13. Hansch Corwin A Leo and R W Taft. "A survey of Hammett substituent constants and resonance and field parameters”. Chemical reviews2 (1991): 165-195.
14. Chattaraj Pratim K., et al. “Electrophilicity index”. Chemical reviews 106 (2006): 2065-2091.
15. Parr Robert G., et al. “Electrophilicity index”. Journal of the American Chemical Society9 (1999): 1922-1924.
16. Domingo Luis R., et al. “Electronic contributions to the σp parameter of the Hammett equation”. The Journal of Organic Chemistry15 (2003): 6060-6062.
17. Ben El Ayouchia Hicham., et al. "A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σp in [3+2] Cycloaddition Reactions of Aryl Azide/Alkyne Derivatives”. Molecules11 (2016): 1434.
18. Parr R G and W Yang. "Density-functional theory of atoms and molecules”. Oxford Univ. Press. ed: Oxford (1989).
19. Frisch MJ., et al. “Gaussian 09, Revision E.01”. Gaussian Inc.: Wallingford, CT, USA (2009).
20. Chattaraj P K and B Maiti. "Reactivity dynamics in atom− field interactions: a quantum fluid density functional study”. The Journal of Physical Chemistry A1 (2001): 169-183.
21. Mayr Herbert Bernhard Kempf and Armin R Ofial. "π-Nucleophilicity in carbon− carbon bond-forming reactions”. Accounts of Chemical Research1 (2003): 66-77.
22. Mayr Herbert., et al. "Reference scales for the characterization of cationic electrophiles and neutral nucleophiles”. Journal of the American Chemical Society39 (2001): 9500-9512.

Citation

Citation: Tanmoy Chakraborty., et al. “A New Approach to Find Out the Correlation Between Nucleophilicity Index (N) and Hammett Constant". Acta Scientific Pharmacology 3.7 (2022): 13-16.

Copyright

Copyright: © 2022 Hiteshi Tandon., et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.