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Development of New Processes for the Carbon Monoxide in Chemical Industries

化学工业一氧化碳新工艺的开发

基本信息

批准号：
03555183
负责人：
SONODA Noboru
金额：
$ 9.15万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

The aim of this project was to develop new carbonylation processes by the use of carbon monoxide as a carbonylation reagent. The research interest was focused on the processes promoted by typical elements, especially heavy heteroatom compounds, rather than transition metals which play important roles as catalysts in a number of useful carbonylation reactions not only in synthetic chemistry but also in chemical industries This project comprised three major themes mentioned below and brought several important results which will open up new fields of carbonylation reactions with carbon monoxide. 1. The first theme "Carbonylation by Selenium" led to a development of a new selenocarboxylation reaction at the alpha-carbon of carbonyl compounds, such as ketones, aldehydes, and amides. This reaction proceeds under atmospheric pressure of carbon monoxide at room temperature or below to give Se-alkyl selenocarboxylates after trapping of lithium selenocarboxylates, which are formed in situ via introduction of a SeCO unit at an alpha-carbon of carbonyl compounds, with alkyl halides. 2. The "Concomitant Introduction of Carbon Monoxide and Heteroatom Moieties" into alkynes was achieves by the use of a palladium catalyst, where phenylseleno and phenylselenocarbonyl groups are introduced regioselectively at the carbons of carbon-carbon triple bonds to give Se-phenyl acrylates in good yields. A convenient method for the selective reduction of phenylselenocarbonyl group to formyl group was also established, and so the combination of these two reactions led to the achievement of selenoformylation reaction. 3. Very efficient "Radical Carbonylation" reactions of organo halides with carbon monoxide were achieved also by the use of stannanes or silanes in the presence of AIBN as a radical initiator. This reaction is very unique nad will be a useful method for the carbonylation of alkyl halides to give aldehydes and ketones.

该项目的目的是通过使用一氧化碳作为羰化试剂来开发新的羰化工艺。人们的研究兴趣集中在典型元素，特别是重杂原子化合物促进的过程，而不是在合成化学和化学工业中起重要作用的过渡金属的催化作用。本项目包括以下三个主要主题，并取得了几项重要成果，将开辟一氧化碳羰化反应的新领域。1.第一个主题“硒的羧化”导致了酮、醛和酰胺等酮类化合物的α-碳上的新的硒羧化反应的发展。在常温或更低的常压下，该反应在一氧化碳的压力下进行，在硒羧酸锂与烷基卤化物的α-碳处引入SECO单元而形成的硒-烷基硒羧酸盐被捕获后生成硒-烷基硒羧酸盐。2.在钯催化剂的作用下，实现了“一氧化碳和杂原子基团的相伴引入”，在碳-碳三键的碳原子上区域选择性地引入了苯基亚硒基和苯基亚硒酰基，从而以较高的产率合成了丙烯酸硒-苯基酯。此外，还建立了一种简便的将苯基硒甲酰基选择性还原为甲酰基的方法，从而使这两个反应相结合，实现了硒甲酰化反应。3.在AIBN存在下，以锡烷或硅烷为引发剂，有机卤化物与一氧化碳的“自由基羰化”反应也得到了非常有效的实现。该反应是一种非常独特的反应，对于烷基卤代化合物的羰基化生成醛和酮将是一种有用的方法。