Dephosphorylation and aromatic nucleophilic substitution in nonionic micelles. The importance of substrate location

Abstract

Reactions of OH-and F-with p-nitrophenyl diphenyl phosphate (pNPDPP) are inhibited by very dilute dodecyl (10) and (23) polyoxyethylene glycol (C12E10and C12E23, respectively), but rate constants become independent of surfactant concentrations at concentrations above the critical micelle concentration. Low charge density anions, e.g., ClO4-, inhibit and low charge density cations, e.g., (n-C7H15)4N+, accelerate reactions, probably by controlling concentrations of nucleophiles in the palisade layer. Diphenyl phosphorofluoridate, generated by attack of F-, is not detected but is rapidly hydrolyzed to phenyl phosphorofluoridate or diphenyl phosphate ion with loss of phenol or F-. The products are different in DMSO containing modest amounts (<15 vol%) of water and no surfactant and are phenyl phosphorofluoridate and difluorophosphate ions generated by attack of F-on the initial phosphorofluoridate. These differences are consistent with the micellar palisade layer being water-rich. Although the nonionic surfactants do not intervene nucleophilically in reactions of pNPDPP, considerable amounts of ether are formed in the reaction of 2,4-dinitrochlorobenzene (DNCB), in C12E10and C12E23at high pH by attack of alkoxide ion with the relatively hydrophilic DNCB located close to the micellar surface. The differences in the chemistries of reactions of pNPDPP and DNCB appear to be associated largely with differences in locations of these substrates in the nonionic micelles.Key words: fluoridates, p-nitrophenyl diphenyl phosphate, 2,4-dinitrochlorobenzene, nonionic micelles, palisade layer.