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首页> 外文期刊>Journal of the Korean Chemical Society >Chemical Reactions in Surfactant Solutions () : Micellar Rate Effect on Reactions of Hydroxide and o-Iodosobenzoate Ions with Organic Phosphinates
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Chemical Reactions in Surfactant Solutions () : Micellar Rate Effect on Reactions of Hydroxide and o-Iodosobenzoate Ions with Organic Phosphinates

机译：表面活性剂溶液中的化学反应（）：胶束速率对氢氧根和邻碘代苯甲酸酯离子与有机膦酸酯反应的影响

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摘要

Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by OH- or o-iodosobenzoate ion (IB-) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic OH-(or IB-) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> 10-3 M) of OH-(or IB-) in CTAX solutions are much larger amounts than those (6 ?? 10-6 M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of Cl- ion by OH-(or IB-) ion from the micelle, because of easier solvation Cl- ion by water molecules. The reactivity of IPNPIN with OH-(or IB-) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.
机译：在水溶液中，由OH-或邻碘代苯甲酸酯离子（IB-）介导的二苯基-或异丙基苯基-4-硝基苯基次膦酸酯（DPNPIN或IPNPIN）的去磷酸化相对较慢。但是，CTAX胶束溶液中的反应非常快，因为CTAX胶束可以将两种反应物容纳在它们的Stern层中，在其中它们可以轻松地反应，而亲水性OH-（或IB-）和疏水性次膦酸酯则不会在水中混合。即使CTAX溶液中的OH-（或IB-）浓度（> 10-3 M）远大于次膦酸酯的浓度（6 ?? 10-6 M），脱磷的速率常数在很大程度上受以下因素影响：离子浓度的变化，这意味着反应不会遵循拟一级动力学。与反应中CTAX的抗衡离子的作用相比，CTACl对DPNPIN（或IPNPIN）的去磷酸作用比CTABr更有效，因为OH-（或IB-）离子更容易将Cl-离子从胶束中排出，因为更容易被水分子溶剂化。 IPNPIN与OH-（或IB-）的反应性低于DPNPIN。原因似乎是IPNPIN的“大体积”异丙基会阻碍亲核试剂的攻击。通过捕获实验和测得的动力学同位素效应，IPNPIN与IB离子的反应机理被认为是“亲核的”而不是“一般的碱性”。

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