The synthesis of new phenylhydroxyiodonium phosphates from (diacetoxyiodo) benzene and dialkyl phosphates, and their use in the phosphorylation of ketones was investigated. Reaction of diphenyl phosphate, (PhO)2P(O)OH, with (diacetoxyiodo) benzene, PhI(OAc)2, in the presence of water gave [hydroxy((bis(phenyl)phosphoryl)oxy)iodo] benzene, (PhI(OH)OPO(OPh)2, HPIB) as a white solid in excellent yield. Similarly prepared are PhI(OH)OPO(OCH3)2, PhI(OH)OPO (OCH2CH3)2, PhI(OH)OPO(OCH2CH2Cl)2, PhI(OH)OPO(OCH2CCl3)2, and PhI(OH)OPO(OCH2CF3)2 from the corresponding monobasic acid phosphates (RO)2P(O)OH (R= CH3, CH3CH2, CH2ClCH2, CCl3CH2, and CF3CH2) in 77-93 % yield.
These ketones (acetophenone, 4-methoxyacetophenone, p-nitroacetophenone, acetone, and pinacolone) were directly phosphorylated at the carbon with the iodine (III) reagent, HPIB, or its alkyl derivatives to give the corresponding phosphoryloxy derivatives in 41-89 % yield.