• Journal of the Korean Chemical Society
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• v.42 no.4
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• pp.383-390
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• 1998

The interaction of phenoxide anion with several cationic surfactant micelles (DTAB, TTAB, CTAB, CDEAB, and CTAC) was studied by UV/Vis spectrophotometric method. The solubilization constants of phenoxide anion into the cationic micellar phase and the critical micelle concentration of these surfactants in the presence of the phenoxide anion could be determined from the absorbance changes. The measured solubilization constants were changed according to the following order: $K_s(CTAC)>K_s(CDEAB)>K_s(CTAB)>K_s(TTAB)>K_s(DTAB).$ Effects of salts(NaCl and NaBr) and n-alcohols(butanol, pentanol, and hexanol) on the solubilization of phenoxide anion by the TTAB system have been also measured and analyzed. There was a great decrease of solubilization constant and CMC with these additives. The standard Gibbs free energy, enthalpy, and entropy changes for the solubilization of phenoxide anion by the TTAB system were calculated from the temperature dependence of $K_s$ values.

• Journal of the Korean Chemical Society
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• v.44 no.3
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• pp.177-183
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• 2000

The interaction of phenoxide anion with .the mixed micelles of CTAB(Cetyl-trimethylammonium bromide) and TTAB(Tetradecyltrimethylammonium bromide) was studied by UV/Vis spectrophotometric method. The solubilization constants($K_s$) of phenoxide anion into the mixed micellar phase and the critical micellar concentrations(CMC) of those mixed surfactant systems have been measured and analyzed with the change of overall mole fraction of CTAB($\alpha_{CTAB}$) The effects of additives(n-pentanol and NaBr) on the solubilization of phenoxide anion by those mixed surfactant systems have been also measured. There was a great decrease on the values of solubilization constant and CMC with these additives. For the thermodynamic study, the dependence of $K_s$ values on temperature has been measured and various thermodynamic parameters(${\Delta}G^0_s$, ${\Delta}H^0_s$ and ${\Delta}S^0_s$) have been also calculated. The results show that all the values of ${\Delta}G^0_s$ and ${\Delta}H^0_s$ are negative within the measured temperature region but the values of ${\Delta}S^0_s$ are positive.

• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.33-34
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• 2006

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.182-188
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• 1991

The reactions of aniline with benzyl and phenacyl compounds are studied by the AM1 method. Two types of modeling were adopted: Cation-neutral, in which a proton is attached to the leaving group F and anion-neutral model, in which aniline was replaced by phenoxide with Cl as the leaving group. The cation-neutral model represented the reactvery well, reproducing the various solution-phase experimental results. In the benzyl system, the ${\pi}$-electrons of the two rings (X-ring in the nucleophile and Y-ring in the substrate) interact conjugatively in the transition state (TS) resulting in a bond contraction of the $C_{\alpha}-C_{Y1}$ bond (benzylic effect), whereas in the phenacyl system the ${\pi}$ electrons of the X-ring delocalizes more efficiently into the carbonyl group than into the Y-ring (resonance shunt effect) with a bond contraction of the $C_{\alpha}-C_{\beta}$ bond. The bond contraction in the benzylic effect was substantially greater than that in the resonance shunt effect. The TS was rather loose for benzyl while it was tighter for phenacyl system. Various bond length changes with substituents in the TS were, however, found to be irregular.