Selective synthesis and stabilization of peroxides via phosphine oxides?

New Journal of Chemistry Pub Date: 2019-10-22 DOI: 10.1039/C9NJ04858H

Abstract

Reaction of bis(dicyclohexylphosphino)ethane dioxide with hydrogen peroxide leads to an extended crystalline network based on the formation of hydrogen bonds with the P[double bond, length as m-dash]O groups of the diphosphine dioxide. The structural motif of the network is characterized by X-ray diffraction. A new selective synthesis for an industrially important MEKPO (methyl ethyl ketone peroxide) dimer is described. The dimer is created by reaction of dppe dioxide (bis(diphenylphosphino)ethane dioxide) with butanone and hydrogen peroxide. This peroxide is stabilized by forming strong hydrogen bonds to the phosphine oxide groups within an extended network, which has been characterized by single crystal X-ray diffraction. Reaction of acetylacetone with hydrogen peroxide, irrespective of the presence of phosphine oxide, leads to the stereoselective formation of two dioxolanes. Both cyclic peroxides have been obtained in crystalline forms suitable for single crystal X-ray diffractions.

Graphical abstract: Selective synthesis and stabilization of peroxides via phosphine oxides
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