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

IF 2.8 4区生物学 Q3 BIOTECHNOLOGY & APPLIED MICROBIOLOGY

Journal of chemical technology and biotechnology Pub Date : 2024-07-10 DOI:10.1002/jctb.7709

Imran Ali, Alexey Yu Isaev, Yana M Chichigina, Daniil D Nakov, Gulnara N Shigabaeva, Evgeny V Galunin, Marcello Locatelli, Zainab M Almarhoon

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引用次数: 0

Abstract

BACKGROUND

The 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.

RESULTS

The 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 (d_e + d_i ≈ 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.

CONCLUSION

The 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).

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苯二酚与乙酸乙烯酯的新型碱催化酰化反应：Hirshfeld 表面研究

背景本研究描述了苯二酚与乙酸乙烯酯进行简便、快速和经济的碱催化酰化反应。同时还介绍了苯-1,4-二醇 O,O′-二乙酸酯的 Hirshfeld 表面分析。NaOH、KOH 和 K2CO3 被用于催化苯-1,x-二醇（x = 2、3、4）与乙酸乙烯酯的酰化反应，以获得相应的 O,O′-二乙酰基衍生物。该方法是制备羟基芳基 O-乙酰基衍生物的另一种 "绿色 "工艺。利用 Hirshfeld 表面分析法获得并描述了苯-1,4-二醇 O,O′-二乙酸酯晶体结构。尽管碳原子在 Hirshfeld 表面所占的面积很小（9.4%），但 C⋯H 接触的贡献却很明显（16.7%）。通过使用二维指纹图，证明了 C⋯H 接触是由于 π 堆积的存在。O⋯H 接触（41.4%）最多，主要与典型的氢键（de + di ≈ 2.6 Å）有关。C⋯H 和 O⋯H 触点的饱和度很高（富集比 (E) 分别为 1.30 和 1.36），尽管与 H⋯H 触点 (E = 0.84) 相比，它们对整个表面的贡献较小。该方法速度快、产率高。此外，它还可用于工业规模的酰化反应。© 2024 化学工业学会（SCI）。

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来源期刊

Journal of chemical technology and biotechnology 工程技术-工程：化工

CiteScore

7.00

自引率

5.90%

发文量

268

审稿时长

1.7 months

期刊介绍： Journal of Chemical Technology and Biotechnology(JCTB) is an international, inter-disciplinary peer-reviewed journal concerned with the application of scientific discoveries and advancements in chemical and biological technology that aim towards economically and environmentally sustainable industrial processes.