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烯烃的氢甲酰化反应以及芳基卤化物与由1,6 -己二醇脱氢脱羰原位生成的合成气的还原羰基化反应。

Hydroformylation of olefins and reductive carbonylation of aryl halides with syngas formed ex situ from dehydrogenative decarbonylation of hexane-1,6-diol.

作者信息

Christensen Stig Holden, Olsen Esben P K, Rosenbaum Jascha, Madsen Robert

机构信息

Department of Chemistry, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark.

出版信息

Org Biomol Chem. 2015 Jan 21;13(3):938-45. doi: 10.1039/c4ob01958j.

DOI:10.1039/c4ob01958j
PMID:25410149
Abstract

A variety of primary alcohols have been investigated as convenient substrates for the ex situ delivery of carbon monoxide and molecular hydrogen in a two-chamber reactor. The gaseous mixture is liberated in one chamber by an iridium-catalysed dehydrogenative decarbonylation of the alcohol and then consumed in the other chamber in either a rhodium-catalysed hydroformylation of olefins or a palladium-catalysed reductive carbonylation of aryl halides. Hexane-1,6-diol was found to be the optimum alcohol for both reactions where moderate to excellent yields were obtained of the product aldehydes. A relatively low pressure of 1.5-2.4 bar was measured in the closed system during the two transformations.

摘要

已对多种伯醇进行了研究,它们是两室反应器中用于一氧化碳和分子氢异位输送的便利底物。在一个腔室中,醇通过铱催化的脱氢脱羰反应释放出气体混合物,然后在另一个腔室中,该气体混合物在烯烃的铑催化氢甲酰化反应或芳基卤化物的钯催化还原羰基化反应中被消耗。已发现己烷 - 1,6 - 二醇是这两种反应的最佳醇,产物醛的产率从中等到优异。在这两个转化过程中,封闭系统内测得的压力相对较低,为1.5 - 2.4巴。

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