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Access to Cyclopropanol via Supply-Centered Synthesis
Organic Process Research & Development ( IF 3.1 ) Pub Date : 2024-01-09 , DOI: 10.1021/acs.oprd.3c00399
David R. Snead 1 , Yang Wang 2 , Shuqiang Liu 2 , Liujun Lin 2
Affiliation  

Access to cyclopropanol is improved by developing a route from highly available cyclopropyl methyl ketone. The Baeyer–Villiger oxidation inserts oxygen between the cyclopropyl and ketone functionalities, and the alcohol is subsequently unmasked by cleaving the ester with an amine. Optimization resulted in high yield (>90% for each step), isolation of volatile and water-soluble cyclopropanol, selection of a peroxide with improved safety profile (urea hydrogen peroxide, UHP), and implementation of continuous flow to handle an exotherm. The urea present in the peroxide unexpectedly enhanced conversion of the ketone to the ester, and the addition of a rheology modifier to a 20 wt % suspension of UHP in DCM facilitated continuous delivery of an otherwise difficult-to-pump slurry.

中文翻译:


通过以供应为中心的合成获得环丙醇



通过开发高可用性环丙基甲基酮的路线,改善了环丙醇的获取。拜尔-维利格氧化在环丙基和酮官能团之间插入氧,随后通过用胺裂解酯来暴露醇。优化实现了高产率(每个步骤 >90%)、挥发性和水溶性环丙醇的分离、选择具有改进安全性的过氧化物(过氧化氢尿素、UHP)以及实施连续流来处理放热。过氧化物中存在的脲出乎意料地增强了酮向酯的转化,并且向UHP在DCM中的20重量%悬浮液中添加流变改性剂促进了难以泵送的浆料的连续输送。
更新日期:2024-01-09
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