Effects of nonionic micelles on dephosphorylation and aromatic nucleophilic substitution.

Terminal hydroxyl groups of micellized dodecyl (10) and (23) polyoxyethylene glycol (C12E10 and C12E23, respectively) are deprotonated by OH-, and the alkoxide ions react with 2,4-dinitrochlorobenzene (DNCB) giving ethers, but do not react with p-nitrophenyl dimethyl and diethyl phosphate (pNPDMP and pNPDEP, respectively), which react wholly with OH-. These substrates have similar hydrophobicities and should locate similarly in the micellar interfacial regions. These differences in reactivities are due to differences in relative nucleophilicities of OH- and alkoxide ions in aromatic nucleophilic substitution and dephosphorylation in micelles.

Oxidation of thioanisole by peroxomolybdate in assemblies of cetylpyridinium chloride and methyltri-n-octylammonium chloride.

Methyltri-n-octylammonium chloride (Aliquat 336) is sparingly soluble in water but is readily soluble with a 2-fold excess of micellized cetylpyridinium chloride (CPyCl), and the mixtures show breaks in plots of surface tension or electrolytic conductance against concentration indicative of a critical micelle concentration slightly lower than that of CPyCl. Micellization markedly increases 35Cl and 14N NMR line widths of CPyCl, but addition of NaCl reduces the 35Cl line width and addition of Aliquat increases it. Mixing Aliquat and CPyCl has little effect on their 14N line widths.