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Development of new catalytic systems for efficient use of carbon monoxide

开发有效利用一氧化碳的新型催化系统

基本信息

批准号：
61430020
负责人：
SONODA Noboru
金额：
$ 19.2万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1986
资助国家：
日本
起止时间：
1986 至 1988
项目状态：
已结题

项目摘要

Development of efficient methods for the use of carbon monoxide is one of the most important subjects in the chemical industry. This project has been set up for this purpose focussing on the development of new catalytic system using elemental selenium rather than transition metals which have been frequently used for introduction of carbon monoxide into organic molecules. The results obtained in this project are summarized below.Selenium has been found to have an extremely high catalytic activity for carbonylation with carbon monoxide of a variety of organic molecules having protic hydrogen such as amines,alcohols,and thiols. Application of this reaction to diamines and aminoalcohols results in achievement of efficient methods for the syntheses of cyclic ureas and cyclic urethanes. A delailed study on the selenium catalyzed carbonylation of amines leading to urea derivatives has revealed that the reaction proceeds via carbamoselenoate and biscarbamoyl diselenide as the key intermediates. Such a high activity of selenium for the carbonylation may be based on the facile formation of carbonyl selenide (Se=C=O) from selenium and carbon monoxide, which reacts readily with nucleophiles in the reaction system. Several types of organoselenium compounds in which SeCO moiety is incorporated have been synthesized. Examination of synthetic utility of these compounds revealed that biscarbamoyl diselenides and Se-alkyl selenocarbonates can be used as carbamoylating and oxycarbonylating reagents, respectively. In addition to this selenium assisted carbonylation, a new method for homologation of esters and acetals by combined use of carbon monoxide, hydrosilanes and cobalt carbonyl has been developed, where carbon monoxide is incorporated as siloxymethyl group in the products.

开发一氧化碳的有效利用方法是化学工业中最重要的课题之一。该项目是为此目的而设立的，重点是开发使用元素硒而不是过渡金属的新催化系统，过渡金属经常用于将一氧化碳引入有机分子。本课题的研究结果如下：硒对胺、醇、硫醇等各种含质子氢的有机分子与一氧化碳的羰基化反应具有极高的催化活性。将该反应应用于二胺和氨基醇，可有效地合成环脲和环戊基脲。对硒催化的胺羰基化反应生成脲衍生物的研究表明，该反应通过氨基硒酸酯和双氨基甲酰基二硒醚作为关键中间体进行。硒对羰基化的这种高活性可以基于由硒和一氧化碳容易形成羰基硒化物（Se = C = O），其容易与反应体系中的亲核试剂反应。合成了几种含SeCO的有机硒化合物。这些化合物的合成效用的检查显示，双氨基甲酰基二硒醚和Se-烷基硒碳酸酯可分别用作氨基甲酰基化和氧羰基化试剂。除了这种硒辅助羰基化之外，还开发了一种通过组合使用一氧化碳、氢化硅烷和羰基钴对酯和缩醛进行同系化的新方法，其中一氧化碳作为叔丁基甲基并入产物中。