Direct Synthesis of Dialkylphosphites from White Phosphorus

Abstract

Abstract Dialkyl phosphites (DAPIs), traditionally prepared from hazardous and corrosive PCl 3 , are the fundamental reactive starting materials used in organophosphorus chemistry. Here, a KBr‐mediated synthesis of DAPIs involving P 4 , alcohols and water is presented. With the use of silica gel as the catalyst, oxone as the safe oxidant, industrially important (EtO) 2 P(O)H, (i‐PrO) 2 P(O)H and (MeO) 2 P(O)H are prepared in 70–90% yields. Furthermore, rare metal extractant bis(2‐ethylhexyl) phosphate (D2EHPA) is obtained in 73% yield. The reaction is characterized by a complete conversion of white phosphorus. Moreover, this method can be easily adapted to large‐scale preparation. magnified image