H2O2 is a widely used, cheap, and environmentally friendly oxidant. As an explosive it is handled in aqueous solutions, which ensues biphasic systems in most applications. H2O2 adducts of triarylphosphine oxides (R3PO●H2O2)2 (Hilliard adducts) and the di(hydroperoxy)alkane adducts R3PO●(HOO)2CR2 (Ahn adducts) represent new groups of safe, stable, and solid oxidizers (R = aryl, alkyl). They display consistent composition and structure, and they are highly soluble in all common organic solvents. Therefore, no biphasic reaction systems are needed. The key structural components, a chair-type configuration of the core of R3PO●(H2O2)2●OPR3, and a twist boat in R3PO●(HOO)2CR2, were determined by single crystal X-ray diffraction. The association via hydrogen bonding was studied in solution with 31P DOSY and 17O NMR. The controlled decomposition of Hilliard and Ahn adducts was monitored at elevated temperatures in different solvents and the stepwise release of oxygen led to isolable adducts of the type (R3PO)2●H2O2 and R3PO●(HOO)(HO)CR2. Interestingly, an extended hydrogen-bonded network structure, [Cy2P(O)CH2CH2Cy2PO●H2O2]n could be identified and characterized by X-ray diffraction. Furthermore, a new selective synthesis for the industrially important MEKPO (methyl ethyl ketone peroxide) dimer and its stabilization by hydrogen-bonding to dppe dioxide was discovered. The structure of this dimer, [(CH2Ph2PO)2●(HOOCMeEtO)2]n, and its characterization and favorable safety profile, will be discussed in this presentation.

Synthesis and stabilization of peroxides as phosphine oxide adducts

Macromolecular Chemistry: The Second Century

[Author Benefits](https://scimeetings.acs.org/?utm_source=pubs_content_marketing&utm_medium=website&utm_campaign=0320_MCF_NPI_Launch_Spring_Homepage&ref=pubs_content_marketing)

[How to use SciMeetings](https://storage.googleapis.com/dl.morressier.com/acs/SciMeetings-ACSSpring2020-HowToGuide_M3020-Final.pdf)

[Frequently Asked Questions](https://storage.googleapis.com/dl.morressier.com/acs/SciMtng_ACSNMSp2020_FAQ_M3120_Final.pdf)

ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.