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Comparative computational studies for nucleophilic aromatic substitution of dinitro-substituted benzannulated heterocycles with 1H-1,2,3-triazole

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Abstract

The mechanistic pathways for nucleophilic aromatic substitution of the nitro groups of 5,7-dinitro-3H-quinazolin-4-one and 1,3-dinitro-10H-dibenzo[b,f][1,4]oxazepin-11-one with 1H-1,2,3-triazole have been studied in both gas and solvent phase employing DFT/B3LYP calculations using 6-31G(d,p) basis set. The energetic parameters, i.e., free energy profiles along the reaction route and H-bond energy, charge analysis, and structural parameters have supported mechanistic pathway involving one-step concerted mechanism via formation of transition state during the reaction course. Despite substantial steric hindrance at adjacent position to fusion point, the regioselective attack of 1H-1,2,3-triazole has been observed at peri-position of benzannulated heterocycles. This regioselectivity is credited to intramolecular hydrogen bond C–H···O = C which stabilizes peri-transition state formation rather than para-transition state. The hydrogen bond acceptor–donor interactions have been studied using AIM method. The DFT and AIM analysis-derived results are compared for different sized dinitro-substituted benzannulated heterocycles and these studies have confirmed the contribution of substantial steric hindrance at peri-position with increased size of heterocycle. As benzannulated heterocycles are quite significant from the perspective of medicinal and natural product chemistry, this work will fulfill the need to find an efficient synthetic method for benzannulated heterocycles.

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Funding

Funding is provided by Sri Guru Teg Bahadur Khalsa College, Sri Anandpur Sahib.

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Authors and Affiliations

  1. School of Basic and Applied Sciences, Maharaja Agrasen University, Baddi, India

    Amanjot & Raj Kumar

  2. Department of Physics, Panjab University, Chandigarh, India

    Amritpal Singh & Manish Dev Sharma

  3. Department of Chemistry, DAV College, Sector-10, Chandigarh, India

    Kulvinder Singh

  4. Department of Physics, Sri Guru Teg Bahadur Khalsa College, Sri Anandpur Sahib, Punjab, India

    Amrit Singh

  5. Department of Chemistry, Sri Guru Teg Bahadur Khalsa College, Sri Anandpur Sahib, Punjab, India

    Pratibha Sharma & Amandeep Saroa

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  1. Amanjot
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  2. Raj Kumar
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  3. Amritpal Singh
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  4. Kulvinder Singh
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  5. Manish Dev Sharma
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  6. Amrit Singh
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  7. Pratibha Sharma
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  8. Amandeep Saroa
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Contributions

Amanjot and Kulvinder Singh done the basic studies and helped with manuscript preparation, Amrit Singh and Pratibha Sharma performed computational evaluation of data and edited the manuscript, Amritpal Singh and Raj Kumar decided the problem for the present research work, Manish Dev Sharma provided the platform to perform Gaussian software calculations for the present work, and Amandeep Saroa performed computational evaluation of data and also wrote and edited the manuscript.

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Correspondence to Amandeep Saroa.

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Amanjot, Kumar, R., Singh, A. et al. Comparative computational studies for nucleophilic aromatic substitution of dinitro-substituted benzannulated heterocycles with 1H-1,2,3-triazole. Struct Chem 34, 505–517 (2023). https://doi.org/10.1007/s11224-022-01993-1

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