Nanocomposites of red phosphorus as novel phosphorylating reagents

Elemental phosphorus in strongly basic media as phosphorylating reagent: a dawn of halogen-free ‘green’ organophosphorus chemistry

“…The conversions of the red phosphorus nanocomposite and α-methylstyrene are almost 100 and 17%, respectively (Scheme 8). 20 Under analogous conditions, common red phosphorus reacts with the same olefin less efficiently though more selectively to P give tertiary phosphine oxide in 15% yield (the conversions of P n and the olefin are 82 and 18%, respectively). 20…”

“…According to electron microscopy, the nanocomposites contain nanoparticles mainly of 30-50 nm. 20 In the presence of strong bases, these nanocomposites are more active in phosphorylation of arylethenes than red phosphorus. For instance, the reaction with α-methylstyrene proceeds (120°C, 3 h) in a KOH/DMSO system to produce secondary and tertiary phosphine oxides and potassium phosphinate in 95% total yield.…”

“…The presence of carbon and hydrogen in the composites indicates to the chemical insertion of benzene molecules or their fractions into the polymeric structure of phosphorus probably by the termination of chains with organic radicals or radical cations produced by benzene under the action of γ-radiation. 20 Oxygen is involved in the composites owing to the oxidation of the most chemically reactive sites (defects) and represented as functional groups with phosphorus-oxygen bonds. According to electron microscopy, the nanocomposites contain nanoparticles mainly of 30-50 nm.…”

“…19 (b) Phosphorylation in the nanocomposites of red phosphorus/KOH/DMSO system Recently, it has been shown that elemental phosphorus nanocomposites have enhanced reactivity as compared with common red phosphorus. 20 The nanocomposites of red phosphorus with carbon, graphite or organophosphorus inclusions have been obtained by radiation-induced ( 60 Co γ-radiation) polymerization of white phosphorus in benzene at ambient temperature (Scheme 7). 20 These nanocomposites consist of mainly phosphorus (> 80%) and minor inclusions: carbon (~8-10%), hydrogen (< 1%) and oxygen (about 10%).…”

“…20 The nanocomposites of red phosphorus with carbon, graphite or organophosphorus inclusions have been obtained by radiation-induced ( 60 Co γ-radiation) polymerization of white phosphorus in benzene at ambient temperature (Scheme 7). 20 These nanocomposites consist of mainly phosphorus (> 80%) and minor inclusions: carbon (~8-10%), hydrogen (< 1%) and oxygen (about 10%). The presence of carbon and hydrogen in the composites indicates to the chemical insertion of benzene molecules or their fractions into the polymeric structure of phosphorus probably by the termination of chains with organic radicals or radical cations produced by benzene under the action of γ-radiation.…”