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1,3-Dioxolane compounds (DOXs) as biobased reaction media
Green Chemistry ( IF 9.3 ) Pub Date : 2023-03-02 , DOI: 10.1039/d3gc00227f Massimo Melchiorre 1, 2 , Peter H. M. Budzelaar 1 , Maria E. Cucciolito 1, 3 , Roberto Esposito 1, 3 , Emanuela Santagata 1 , Francesco Ruffo 1, 3
Green Chemistry ( IF 9.3 ) Pub Date : 2023-03-02 , DOI: 10.1039/d3gc00227f Massimo Melchiorre 1, 2 , Peter H. M. Budzelaar 1 , Maria E. Cucciolito 1, 3 , Roberto Esposito 1, 3 , Emanuela Santagata 1 , Francesco Ruffo 1, 3
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Solvents constitute around 80% of the total volume of chemicals used in fine-chemical processes and contribute significantly to their environmental impact and hazard profile. Thus, there is a strong driving force towards the replacement of traditional fossil-based solvents by alternatives that are more benign in terms of their origin, availability, convenience of synthesis, handling, biodegradability and environmental impact. In the class of polar aprotic solvents, the most successful “green” replacement is γ-valerolactone (GVL). Here, we propose the use of a structurally related compound, 5-methyl-1,3-dioxolane-4-one (LA-H,H), as a reaction medium. It is easily prepared from lactic acid and formaldehyde and satisfies the criteria for a green solvent. It is stable under neutral or basic conditions. Despite the presence of a ketal functionality, it even survives mildly acidic conditions. Evaluation of the Kamlet–Taft and Hansen solvent parameters shows that indeed LA-H,H and GVL are closely similar, suggesting that LA-H,H is an effective new green entry in the class of polar aprotic solvents. We have tested its performance in Pd-catalyzed Heck arylation of methyl acrylate and in the Menschutkin reaction of N-methylimidazole with 1-iodobutane. LA-H,H is also the parent of a whole family of potential solvents easily prepared from two green precursors: α-hydroxy carboxylic acids (lactic, mandelic, and α-hydroxyisobutyric acids) and aldehydes/ketones (formaldehyde, acetaldehyde, and acetone); five such variations were briefly examined. Interestingly, LA-H,H has the unusual property of forming a three-phase system when combined with water and hexane, which may allow technological variations that are not possible with the more normal one- and two-phase systems. As a curiosity, a rare four-phase system is achievable combining LA-H,H with octane, water and perfluorodecaline.
中文翻译：
1,3-二氧戊环化合物 (DOX) 作为生物基反应介质
溶剂占精细化工过程中使用的化学品总量的 80% 左右，对环境影响和危害影响很大。因此，存在用在来源、可用性、合成便利性、处理、生物降解性和环境影响方面更良性的替代品替代传统化石基溶剂的强大驱动力。在极性非质子溶剂类别中，最成功的“绿色”替代品是 γ-戊内酯 (GVL)。在这里，我们建议使用结构相关的化合物 5-methyl-1,3-dioxolane-4-one (LA-H,H) 作为反应介质。它很容易由乳酸和甲醛制备，满足绿色溶剂的标准。在中性或碱性条件下稳定。尽管存在缩酮功能，它甚至可以在弱酸性条件下存活。Kamlet-Taft 和 Hansen 溶剂参数的评估表明 LA-H,H 和 GVL 确实非常相似，这表明 LA-H,H 是极性非质子溶剂类别中的一种有效的新型绿色化合物。我们已经测试了它在 Pd 催化的丙烯酸甲酯 Heck 芳基化和 Menschutkin 反应中的性能N-甲基咪唑与1-碘丁烷。LA-H,H 也是一整套潜在溶剂的母体，可轻松由两种绿色前体制备：α-羟基羧酸（乳酸、扁桃酸和 α-羟基异丁酸）和醛/酮（甲醛、乙醛和丙酮） ); 简要审查了五个此类变体。有趣的是，LA-H,H 具有在与水和己烷结合时形成三相系统的不寻常特性，这可能允许更正常的单相和两相系统无法实现的技术变化。令人好奇的是，将 LA-H,H 与辛烷、水和全氟萘烷结合，可以实现一种罕见的四相系统。
更新日期：2023-03-02
中文翻译：
1,3-二氧戊环化合物 (DOX) 作为生物基反应介质
溶剂占精细化工过程中使用的化学品总量的 80% 左右，对环境影响和危害影响很大。因此，存在用在来源、可用性、合成便利性、处理、生物降解性和环境影响方面更良性的替代品替代传统化石基溶剂的强大驱动力。在极性非质子溶剂类别中，最成功的“绿色”替代品是 γ-戊内酯 (GVL)。在这里，我们建议使用结构相关的化合物 5-methyl-1,3-dioxolane-4-one (LA-H,H) 作为反应介质。它很容易由乳酸和甲醛制备，满足绿色溶剂的标准。在中性或碱性条件下稳定。尽管存在缩酮功能，它甚至可以在弱酸性条件下存活。Kamlet-Taft 和 Hansen 溶剂参数的评估表明 LA-H,H 和 GVL 确实非常相似，这表明 LA-H,H 是极性非质子溶剂类别中的一种有效的新型绿色化合物。我们已经测试了它在 Pd 催化的丙烯酸甲酯 Heck 芳基化和 Menschutkin 反应中的性能N-甲基咪唑与1-碘丁烷。LA-H,H 也是一整套潜在溶剂的母体，可轻松由两种绿色前体制备：α-羟基羧酸（乳酸、扁桃酸和 α-羟基异丁酸）和醛/酮（甲醛、乙醛和丙酮） ); 简要审查了五个此类变体。有趣的是，LA-H,H 具有在与水和己烷结合时形成三相系统的不寻常特性，这可能允许更正常的单相和两相系统无法实现的技术变化。令人好奇的是，将 LA-H,H 与辛烷、水和全氟萘烷结合，可以实现一种罕见的四相系统。
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