研磨环境对铜催化机械化学合成甲苯磺酰胺的影响

Kathleen Floyd, Lori Gonnet, Tomislav Friščić and James Batteas
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引用次数: 0

摘要

我们系统地研究了大气中的氧气和研磨组件(即研磨罐和球材料)的选择对一个典型的药物机械化学反应的作用:铜催化的异氰酸酯和磺酰胺偶联生成磺酰脲类甲苯磺丁酰胺。我们利用内部开发的设备在可控大气研磨条件下工作,发现该反应实际上是由 Cu(II)物种催化的,传统使用的 CuCl 充当前催化剂,在研磨过程中通过有氧氧化被激活。令人意想不到的是,研磨罐材料的选择对耦合产生了深远的影响,铝罐有效地 "关闭 "了反应性,这很可能是通过阻止 CuCl 氧化实现的。因此,与直接机械催化(用于描述由研磨罐或研磨球材料促进的反应)相反,这一观察结果揭示了直接机械抑制的可能性,即研磨罐对机械化学反应的抑制。这些结果突显了对研磨组件和气氛进行系统研究对于理解和控制有机机械化学转化的重要性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

The role of the milling environment on the copper-catalysed mechanochemical synthesis of tolbutamide†

The role of the milling environment on the copper-catalysed mechanochemical synthesis of tolbutamide†

We provide a systematic investigation of the role of atmospheric oxygen and choice of milling assembly (i.e., the milling jar and ball materials) on a prototypical medicinal mechanochemistry reaction: the copper-catalysed coupling of isocyanate and sulfonamide to form the sulfonylurea tolbutamide. Using in-house developed equipment for work under controlled-atmosphere milling conditions, we reveal that the reaction is in fact catalysed by Cu(II) species, with the conventionally used CuCl acting as a pre-catalyst, which becomes activated via aerobic oxidation during milling. Unexpectedly, the choice of milling jar material was found to have a profound effect on the coupling, with aluminium jars effectively “shutting down” reactivity, most likely by preventing CuCl oxidation. Hence, opposite to direct mechanocatalysis, a term used to describe reactions promoted by the milling jar or ball material, this observation reveals the possibility of direct mechanoinhibition – i.e., the inhibition of a mechanochemical reaction by the jar. These results highlight the importance of systematic investigations of both the milling assembly, as well as atmosphere, in understanding and controlling organic mechanochemical transformations.

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