Journal of Environmental Science International (한국환경과학회지)

The Korean Environmental Sciences Society (한국환경과학회)
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Dephosphorylation of an Organic Phosphinate by Nucleophile in Anionic and Cationic Micellar Solutions

음이온 및 양이온 미셀 용액에서 친핵체에 의한 유기 포스피네이트의 탈인산화반응

  • Published : 2006.05.01
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Abstract

In the aqueous solutions the dephosphorylations of isopropyl phenyl-4-nitrophenyl phosphinate(IPNPIN) mediated by hydroxide$(OH^{\theta})$ and o-iodosobenzoate$(IB^{\theta})$ ions ate relatively slow, because of hydrophobicity of the substrate, and however it appears that $OH^{\theta}$ is inherently better nucleophile than $IB^{\theta}$, which is more soft ion. On the other hand, in cetyltrimetyiammonium bromide(CTABr) solutions which contain cationic micelles, the dephosphorylations of IPNPIN mediated by $OH^{\theta}$ or $IB^{\theta}$ ate very accelerated to 120 or 100,000 times as compared with those in the aqueous solutions. The values of pseudo first order rate constants reach a maximum with increasing. Such rate maxima are typical of micellar catalysed bimolecular reactions and the rise in rate constant followed by a gradual decrese is characteristic of reactions of hydrophobic substrates. In the cationic micellar solutions of CTABr, $IB^{\theta}$ accelerates the reactions much more than that $OH^{\theta}$ does. The reason seems that $IB^{\theta}$ which is more hydrophobic and soft ion than $OH^{\theta}$ is more easily moved into the Stern layer of the CTABr micelles than $OH^{\theta}$. In the anionic micellar solutions of sodium dodecyl sulfate(SDS), the dephosrhorylations of IPNPIN ate slower than those in aqeous solutions. It means that $OH^{\theta}$ or $IB^{\theta}$ cannot easily move and approach to the Stern layer of the micelle in which almost all the hydrophobic substrate are located and which has a negative circumstance.

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References

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