Phase Transfer Catalyst Assisted Carbonylation of Benzyl Halides to Phenylacetic Acid by Ironpentacarbonyl and its Triphenylphosphine Derivatives

相轉移觸媒影響下五羰鐵及其三苯膦衍生物催化鹵化甲苯為苯甲酸之碳醯化反應

劉陵崗(Ling-Kang Liu) ； 林月華(Yueh-Hwa Lin) ； 歐超班(Chau-Ban Ou)

《中央研究院化學研究所集刊》 33期 (1986/03) Pp. 41-45

https://doi.org/10.6522/BICAS.1986.33.6

摘要

五羰鐵在醛、酮、羧酸衍生物之有機合成上是非常有效的碳醯化試劑，本研究中在二相系加入硫酸氫四丁銨以提供相轉移過程，使得五羰鐵對鹵甲苯之碳醯化反應為觸媒反應。自碘甲苯和溴甲苯生成苯甲酸之產率相差不遠，但自氯甲苯生成苯甲酸則產率低很多。在硫酸氫四丁銨之溶解限度內增加其濃度可以增加自溴甲苯生成苯甲酸之產率，但在二相系中加入三苯磷則減低其產率。在五羰鐵上取代三苯磷或1,2-雙（二苯磷基）乙烷也降低其產率。

並列摘要

Being an effective carbonylating reagent for the organic synthesis of aldehyde, ketone, carboxylic acid derivatives, etc., ironpentacarbonyl has been studied for its carbonylation of benzyl halides in a two-phase system where tetra-butylammonium hydrogen sulfate contributes a phase transfer process, allowing a catalytic carbonylation. The yields of phenylacetic acid from benzyl iodide and from benzyI bromide have been found to be similar while that from benzyl chloride is much less. Increasing the concentration of tetrabutylammonium hydrogen sulfate within its solubility would increase the yield of phenylacetic acid from benzyl bromide, but adding triphenylphosphine to the two-phase system would decrease the yield. Substituting the carbonyl ligands in ironpentacarbonyl by triphenylphosphine or 1,2-bis(diphenylphosphino)ethane decreases the yield as well.