• Bulletin of the Korean Chemical Society
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• v.19 no.9
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• pp.968-973
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• 1998

Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

• Journal of the Korean Chemical Society
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• v.38 no.10
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• pp.753-762
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• 1994

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 ($6{\times}10^{-6}$ 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.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.123-131
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• 2002

Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2000.11a
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• pp.232-236
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• 2000

Multi-regression statistical analyses were applied for the water quality data of shallow alluvial ground water (n = 47) collected from the Youngdeok area, in order to quantitatively generalize the natural (non-anthropogenic) causes of regional water quality variation. Seven samples having the high contamination index ( $C_{a}$ > 3) reflect the striong effects by anthropogenic activity. Most of the alluvial groundwaters have acquired their quality primarily due to the dissolution of carbonate minerals. The results of multi-regression analysis show that chlorine is mainly derived from seawater effect. Sulfur isotopic compositions of dissolved sulfur and the S $O_4$/Cl ratio also enable us to discriminate the samples (n = 18) which are affected by atmospheric input of marine aerosol (sea-spray) and also by mixing between freshwater and seawater. Hydrogen and oxygen isotope data of the samples collected lie close to the local meteoric water line obtained from nearby Pohang city but has lower slope (5.45) on the $\delta$D-$^{18}$ O plot, indicating that alluvial groundwater was recharged from infiltrated meteoric water which has undergone some degree of kinetic evaporation. The estimated initial isotopic composition of the recharged water ($\delta$D = -74.8$^{0}$ /$_{00}$, $\delta$$^{18}$ O = -10.8$^{[-1000]}$ /$_{[-1000]}$ ) suggests that the alluvial ground water recharge largely occurs during summer storm events.s.s.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.790-794
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• 2008

Nucleophilic addition reaction of benzenethiols (PhSH) to 1-(2-nitrovinyl) benzenes ($\beta$ NS) in the presence of triethylamine (TEA) has been studied in acetonitrile at 25 ${^{\circ}C}$. The rate is first order with respect to [PhSH], [TEA] and [$\beta$ NS]. The reaction is found to proceed with the formation of ion-pair between benzenethiol and TEA. A suitable mechanism with the formation of an adduct between ion-pair and substrate in a slow step followed by its rearrangement to 1,2-addition product in a fast step has been proposed and corresponding rate law derived. From the rate law, the rate constants for the interaction between ion-pair and $\beta$NS have been evaluated. Interestingly, in both para-substituted substrates and benzenethiols the rate increases with the electron-withdrawing power of the substituents. The positive sign of $\rho_x$ in benzenethiols has been explained. The magnitude of cross-interaction constant, $\rho_{xy}$ is small (0.08). The magnitude of the Hammett $\rho_x$ values is higher than that of the Bronsted, $\beta_x$ values for benzenethiols. The kinetic isotope effect, $k_H/k_D$, is found to be greater than unity. A suitable transition state with simultaneous formation of $C_\beta$ -H and $B_\alpha$ -S bonds involving the ion-pair and $\beta$NS in a single concerted step has been proposed to account for these observations.

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1293-1302
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• 2003

Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

• Journal of Environmental Science International
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• v.2 no.1
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• pp.43-49
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• 1993

Concentrations of sulfate and 6-values of sulfate, $({\delta}^{34}SO_4_){pw}$, dissolved In pore waters were measured from the sediment cores of the two different marine environments : deep northeast Pacific (57-1) and coastal Kyunggi Bay of Yellow Sea (57-2) . Sulfate concentration in pore waters decreases with depth at both cores, reflecting sulfate reduction in the sediment columns. However, much higher gradient of pore water sulfate at 57-2 than 57-1 indicates more rapid sulfate reduction at 57-2, because of high sedimentation rate at the coastal area compared to the deep-sea. The measured 6-values, $({\delta}^{34}SO_4_){pw}$, follow extremely well the predicted trend of the Rayleigh fractionation equation. The range of 26.756 to 61.35% at the coastal core 57-2 is not so great as that of 32.4$\textperthousand$ to 97.8$\textperthousand$ at the deep-sea core 57-1. Despite greater graclient of pore water sulfate at 57-2, the 6-values become lower than those of the deep- sea core 57-1. This inverse relation between the 6-values and the gradients of pore water sulfate could be explained by the combination of the two subsequent factors : the kinetic effect by which the residual pore water sulfate becomes progressively enriched with respect to the heavy isotope of $^{34}S$ as sulfate reduction proceeds, and the intrinsic formulation effect of the Rayleigh fractionation equation in which the greater becomes the fractionation factor, the more diminished values of $({\delta}^{34}SO_4_){pw}$ are predicted.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.97-105
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• 1989

This study deals with micellar effects on hydrolyses of p-nitrophenyl carboxylic esters(p-NPCE) mediated by 2-alkylbenzimidazole(R-BI) and sodium 2-alkylbenzimidazole-5-sulfonate(R-BISO$_3$Na) in aqueous and CTABr solutions. The reactions mediated by R-BI and R-BISO$_3$Na in micellar solutions are obviously slower than those by benzimidazole(BI) and sodium benzimidazole-5-sulfonate(BISO$_3$Na) respectively, and the reaction rates were decreased with increase of lengths of alkyl groups. This prestents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups for R-BI and R-BISO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(${\Delta}H^{\neq},\;{\Delta}G^{\neq}\;and\;{\Delta}S^{\neq}$) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole(BI) moiety of R-BISO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) which form a micelle of themselves increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr. We measured the isotope effects to elucidate the mechanism of hydrolyses of p-nitrophenyl carboxylic esters, and the relative first order rate constant($k'_{H_2O}/k'_{D_2O}$) are on range of 2.5∼3.2. This range is too high to conclude that the hydrolyses of p-NPA mediated by various R-BISO$_3$Na proceed by nucleophilic mechanism. In other words, the reactions are assumed to proceed in part by general basic one, as compared with the reaction catalyzed by imidazole(IM) in aqueous solution.

• Journal of the Korean Chemical Society
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• v.29 no.4
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• pp.426-436
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• 1985

Preparative and kinetic photochemical reactions of several benzanilides were studied. Several substituted benzanilides were synthesized by acylation of substituted anilines with substituted benzoyl chlorides. While benzanilide gave a photo-Fries type reaction product, 2-chlorobenzaniline, 2-bromobenzanilide, and 2-methoxybenzanilide gave a photocyclization reaction product, phenanthridone. Since 8-chlorophenanthridone was obtained from 2,2'-dichlorobenzanilide, the carbonyl phenyl is the excited site. Quantum yield of photocyclization of 2-chlorobenzanilide, 2'-chlorobenzanilide, and 2-methoxybenzanilide were obtained. 2-Chlorobenzanilide was photocyclized effectively and 2'-chlorobenzanilide ineffectively. Since the oxygen present in the reaction medium retarded the photocyclization reaction of 2-chlorobenzanilide, the triplet state of 2-chlorobenzanilide is involved. The mechanism of the photocyclization of 2-chlorobenzanilide is suggested: $\pi-complex$ between carbonyl phenyl and N-phenyl was formed from the triplet state of 2-chlorobenzanilide; neighbour phenyl (N-phenyl) assists for leaving of chlorine from carbonyl phenyl to make an intermediate, cyclized conjugated radical, because electron donating group on the N-phenyl ring accelerated the reaction; hydrogen detachment from the intermediate is obviously not a rate determined step because there was no isotope effect on the rate of photocyclization. The photocyclization reaction rate of 2-methoxybenzanilide was faster in the presence of oxygen than in the absence of oxygen. Thus, the singlet excited state of 2-methoxybenzanilide is involved in the reaction. Probably, the intermediate, methoxyhydro-phenanthridone is oxidized by oxygen in the medium to give phenanthridone.

• Journal of the Korean Chemical Society
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• v.59 no.5
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• pp.373-378
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• 2015

The solvolysis rate constants of di-n-butyl phosphorochloridate ((CH₃CH₂CH₂CH₂O)₂POCI, 1) in 28 different solvents are well correlated with the extended Grunwald-Winstein equation, using the N_T solvent nucleophilicity scale and Y_Cl solvent ionizing scale, with the sensitivities values of 1.40 and 0.42 for l and m, respectively. These l and m values can be considered to support an S_N2 reaction pathway. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH^≠ (8.0 to 15.9 kcal·mol⁻¹ ) values and large negative ΔS^≠ (−25.8 to −53.1 cal·mol⁻¹ ·K⁻¹ ) values, the Kivinen’s n values (0.9~1.7), and the solvent kinetic isotope effect (1.62).