Novel base‐catalyzed acylation of benzenediols with vinyl acetate: a Hirshfeld surface study

Author:

Ali Imran1,Isaev Alexey Yu2,Chichigina Yana M2,Nakov Daniil D2,Shigabaeva Gulnara N2,Galunin Evgeny V2,Locatelli Marcello3,Almarhoon Zainab M4ORCID

Affiliation:

1. Department of Chemistry Jamia Millia Islamia (Central University) New Delhi India

2. Department of Organic and Ecological Chemistry Institute of Chemistry, University of Tyumen Tyumen Russian Federation

3. Department of Pharmacy Analytical and Bioanalytical Chemistry, University ‘G. d'Annunzio’ of Chieti‐Pescara Chieti Italy

4. Department of Chemistry, College of Science King Saud University Riyadh Saudi Arabia

Abstract

AbstractBACKGROUNDThe present work describes the facile, fast and economic base‐catalyzed acylation of benzenediols with vinyl acetate. The Hirshfeld surface analysis of benzene‐1,4‐diol O,O′‐diacetate is also described. NaOH, KOH and K2CO3 were the bases used for the catalysis of the acylation of benzene‐1,x‐diols (x = 2, 3, 4) with vinyl acetate to obtain the corresponding O,O′‐diacetyl derivatives.RESULTSThe yields were quite good, up to 99% under solvent‐free conditions. This method represents an alternative ‘green’ process for the preparation of O‐acetyl derivatives of hydroxyaryls. The benzene‐1,4‐diol O,O′‐diacetate crystal structure was obtained and described using Hirshfeld surface analysis. A noticeable contribution of the C⋯H contacts is shown (16.7%), despite the insignificant area of the Hirshfeld surface occupied by the carbon atoms (9.4%). By using two‐dimensional fingerprint plots, it was proved that C⋯H contacts were due to the presence of π‐stacking. The O⋯H contacts (41.4%) were the most numerous ones, relating mainly to typical hydrogen bonds (de + di ≈ 2.6 Å). The high saturation of the C⋯H and O⋯H contacts (enrichment ratios (E) = 1.30 and 1.36, respectively), despite their smaller contribution to the overall surface as compared to the H⋯H contacts (E = 0.84), is shown.CONCLUSIONThe novelty of this work is the development of a method based on an inexpensive, safe and easy‐to‐use catalyst (K2CO3). This method is fast with high yields. Besides, it may be used for acylation at an industrial scale. © 2024 Society of Chemical Industry (SCI).

Funder

King Saud University

Publisher

Wiley

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