hazardous and corrosive PCl3, are the fundamental reactive starting materials used in organophosphorus chemistry. Here, a KBr-mediated synthesis of DAPIs involving P4, alcohols and water is presented. With the use of silica gel as the catalyst, oxone as the safe oxidant, industrially important (EtO)2P(O)H, (i-PrO)2P(O)H and (MeO)2P(O)H are prepared in 70–90% yields. Furthermore, rare metal extractant bis(2-ethylhexyl)