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Updated: Feb 23, 2026
Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Di(hydroperoxy)alkane Adducts of Phosphine Oxides: Safe, Solid, Stoichiometric, and Soluble Oxidizing Agents
Shin Hye Ahn1, Nattamai Bhuvanesh1, Janet Blümel1
1Department of Chemistry, Texas A&M University, College Station, TX, 77842-3012, USA.
Abstract:
The di(hydroperoxy)alkane adducts of phosphine oxides 1-9, Ph3 PO⋅(HOO)2 CMe2 , Cy3 PO⋅(HOO)2 CMe2 , Ph3 PO⋅ (HOO)2 CMeEt, Cy3 PO⋅(HOO)2 CMeEt, Cy3 PO⋅(HOO)2 CEt2 , Cy3 PO⋅ (HOO)2 C(CH2 )5 , Cy3 PO⋅(HOO)2 CMePh, (Ph2 P(O)CH2 CH2 P(O)Ph2 )⋅ ((HOO)2 CEt2 )2 , and Ph2 P(O)CH2 P(O)Ph2 ⋅(HOO)2 CMe2 , respectively, are synthesized and fully characterized by 1 H, 13 C, and 31 P NMR, and IR spectroscopies. Single crystal X-ray structures are reported for 3-9. Different one-pot synthetic pathways, starting from R3 P, R3 PO, R3 PO⋅H2 O, and R3 PO⋅H2 O2 are explored and discussed and a mechanism for the formation of the di(hydroperoxy)alkane adducts of phosphine oxides is suggested. The longevity of the adducts is tested by monitoring the oxidation of Ph3 P with quantitative NMR. The solubilities of the adducts in organic solvents are presented, and their applicability as stoichiometric oxidizing agents for the selective oxidation of sulfides to sulfoxides is reported.
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