Reactions of Elemental Phosphorus with Electrophiles in Super Basic Systems: XVII. Phosphorylation of Arylalkenes with Active Modifications of Elemental Phosphorus

Abstract

The example of the phosphorylation of styrene and 2-vinylnaphthalene with elemental phosphorus in the KOH3DMSO system at room or elevated temperature was used to show that the activated red phosphorus prepared from white phosphorus under ionizing radiation has a reactivity comparable with that of white phosphorus and significantly higher than that of ordinary technical red phosphorus.

Elemental Phosphorus and Electromagnetic Radiation

“…The essence of these reactions consists of the cleavage of the white‐phosphorus P–P bond in superbase media and their simultaneous capture with appropriate electrophiles to form phosphorus derivatives containing a C–P bond (Scheme ) 16e. It is important to point out that the reaction was also possible with two active varieties of red phosphorus (P n ), which were prepared by polymerization of white phosphorus (P 4 ) in the presence of carbon, graphite and organophosphorus molecules in benzene at room temperature under γ radiation ( 60 Co) and certain external treatment (X‐ray irradiation and mechanochemical treatment) 15c,16b,16c,16d. The two obtained new varieties of red phosphorus contain P–P, P–C and P–O–C bonds and more interestingly the presence of P–P–R defects, in which R is a graphite fragment or benzene, respectively, which were identified by IR and X‐ray electron spectroscopy.…”