Sustainable synthesis of heterocyclic fragrances via cycloaddition of 1,8-cineole and 1,4-cineole to aldehydes catalyzed by heteropoly acid

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL Applied Catalysis A: General Pub Date : 2025-01-25 DOI:10.1016/j.apcata.2025.120133

Núbia L. Lataliza-Carvalho , Izadora M. Costa , Kelly A. da Silva Rocha , Elena F. Kozhevnikova , Ivan V. Kozhevnikov , Elena V. Gusevskaya

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Abstract

1,8-cineole, also known as eucalyptol, is the main component of eucalyptus oils (75–90 %) and many other essential oils. The present work developed a novel synthesis of potentially valuable fragrant heterocyclic oxabicyclo[3.3.1]nonene compounds from bio-renewable 1,8-cineole and its structural isomer 1,4-cineole via their cycloaddition to aldehydes, such as benzaldehyde and trans-cinnamaldehyde, in the presence of silica-supported tungstophosphoric heteropoly acid H₃PW₁₂O₄₀ (HPW) or its acidic salt Cs_0.5H_0.5PW₁₂O₄₀ (CsPW) as solid acid catalysts. The reaction of 1,8-cineole with phenylacetaldehyde, in addition to the oxabicyclo[3.3.1]nonene, gave the Friedel-Crafts alkylation product with a fused tetracyclic structure. The same products were obtained starting from styrene oxide through a consecutive tandem process involving the acid-catalyzed isomerization of styrene oxide to phenylacetaldehyde followed by its cycloaddition to 1,8-cineole. The process can be performed in various green solvents under mild conditions without catalyst leaching, with the best yields obtained in dimethyl carbonate.

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杂多酸催化1,8-桉叶油脑和1,4-桉叶油脑与醛的环加成合成杂环香精

1,8-桉树脑，也被称为桉树醇，是桉树油（75-90 %）和许多其他精油的主要成分。本研究以生物可再生的1,8-桉树脑及其结构异构体1,4-桉树脑为原料，以硅负载的钨磷杂多酸H3PW12O40 （HPW）或其酸性盐Cs0.5H0.5PW12O40 （CsPW）为固体酸催化剂，通过与苯甲醛和反式肉桂醛等醛的环加成，合成了具有潜在应用价值的芳香杂环氧杂环[3.3.1]壬烯化合物。1,8-桉树脑与苯乙醛的反应，除了氧杂环[3.3.1]壬烯外，得到了具有融合四环结构的Friedel-Crafts烷基化产物。从氧化苯乙烯开始，通过酸催化氧化苯乙烯异构化成苯乙醛，然后环加成成1,8-桉树脑的连续串联工艺，得到了相同的产品。该工艺可在各种绿色溶剂中在温和条件下进行，无需催化剂浸出，以碳酸二甲酯收率最高。

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来源期刊

Applied Catalysis A: General 化学-环境科学

CiteScore

9.00

自引率

5.50%

发文量

415

审稿时长

24 days

期刊介绍： Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.

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