New Synthetic Processes for the Utilization of Carbon Monoxide as Carbon Resource

利用一氧化碳作为碳资源的新合成工艺

基本信息

批准号：
12555253
负责人：
RYU Ilhyong
金额：
$ 8.32万
依托单位：
Osaka Prefecture University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

Carbon monoxide is a cheap and abundant feedstock and the development of new synthetic processes to synthesize basically important chemical products utilizing carbon monoxide is highly desirable. We focused on the new process to prepare carboxylic acid derivatives which does not require any transition metal catalysts. Using irradiation conditions, we found mat alkyl iodides react with carbon monoxide in the presence of amines to give good yields of amides. Similarly, in the presence of alcohols, esters were obtained in good yields. The role of photo-irradiation is the homolysis of carbon-iodine bond of alkyl iodide, and the resulting alkyl radical undergoes addition to carbon monoxide to form acyl radicals, which-then abstract iodine from alkyl iodide to form an acyl iodide, thus creating radical chain. We found that thermal initiation system, instead of irradiation, also led to the formation of amides and esters. Ionic quench of acyl iodides by aminolysts and alcoholysis are found to be crucial in. The basic principle was applied for the synthesis of heterocyclic rings having a carbonyl moiety in the ring. Such examples include synthesis of five to seven-membered ring lactones and precursors for nitrogen-heterocycles. New reaction processes incorporating two and three molecules of CO were also achieved with the aid of accelerating effect of palladium catalyst. In summary, through these achievements we developed new processes for the utilization of carbon monoxide in synthesis.

一氧化碳是一种廉价且丰富的原料，非常需要开发新的合成工艺来利用一氧化碳合成基本重要的化学产品。我们专注于不需要任何过渡金属催化剂的制备羧酸衍生物的新工艺。使用辐照条件，我们发现烷基碘化物在胺存在下与一氧化碳反应，产生良好的酰胺产率。类似地，在醇的存在下，以良好的产率获得酯。光照射的作用是烷基碘的碳-碘键均裂，生成的烷基自由基与一氧化碳加成形成酰基自由基，酰基自由基从烷基碘中夺取碘，形成酰基碘，从而产生自由基链。我们发现热引发系统而不是辐射也导致了酰胺和酯的形成。发现通过氨分解和醇解对酰基碘进行离子猝灭是至关重要的。基本原理被应用于环中具有羰基部分的杂环的合成。这些例子包括五至七元环内酯和氮杂环前体的合成。借助钯催化剂的加速作用，还实现了包含两分子和三分子CO的新反应过程。总之，通过这些成就，我们开发了在合成中利用一氧化碳的新工艺。