• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.483-488
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• 2014

The nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $35.0^{\circ}C$. The Hammett and Bronsted plots with X in the nucleophiles for both substrates exhibit biphasic concave upwards with a break region between X = 3-Me and H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are negative with 8 while positive with 10 despite the same free energy correlations with X for both substrates. A stepwise mechanism with a rate-limiting bond formation is proposed with 8, whereas a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed with 10 based on the sign of ${\rho}_{XY}$, negative and positive with 8 and 10, respectively. A frontside nucleophilic attack is proposed with strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values while a backside attack is proposed with weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$ for both substrates.

• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3587-3591
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• 2011

The reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-benzylamines are kinetically investigated in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}x$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots are biphasic concave downwards for substituent X variations in the nucleophiles with a break point at X = H. The signs of the cross-interaction constants (${\rho}xz$) are positive for both the strongly and weakly basic nucleophiles. Considerably great magnitude of ${\rho}xz$ (= 6.56) value is observed with the weakly basic nucleophiles, while ${\rho}xz$ = 0.91 with the strongly basic nucleophiles. Proposed reaction mechanism is a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving a backside nucleophilic attack with the strongly basic nucleophiles and a frontside attack with the weakly basic nucleophiles. The kinetic results are compared with those of the benzylaminolysis of O,O-diphenyl Z-S-aryl phosphorothioates.

• Bulletin of the Korean Chemical Society
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• 제21권9호
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• pp.891-895
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• 2000

Transmission of substituent effects through 5-membered heteroaromaticrings isinvestigated theoretically at the RHF/6-31+G* and B3LYP/6-31+G* levelsusing the deprotonation equilibria of phenol analogues with heteroatoms Y = NH, O, PHand S. The incr ease in the resonance delocalization of the $\pilone-pair$ on the phe-nolic oxygen atom, $n\pi(O)$, accompanied with the deprotonation depends on the heteroatom Y,in the order NH < O < PH < S. This represents the $\pielectron$ accepting ability, or conversely reverse order of the $\pielectron$ donating ability of the $\pilone-pair$ on Y, $n\pi(Y).$ The transmission efficiency of substituenteffects is, however,in the reverse order NH > O > S, which represents the order of delocalizability of $n\pi(Y).$ A better correlation is obtained with ${\sigma}p$ - than with ${\sigma}p$ for the Hammett type plots with the positive slope, $\rho-$ > 0, of the magnitude in the same order as that for the delocalizability of $n\pi(Y).$ Thedeprotonation energy, ΔG = [G(PA) + G(H+)] -G(P), decreases with the increasein the extence delocalization in the order NH > O > PH > S.

• Bulletin of the Korean Chemical Society
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• 제20권10호
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• pp.1177-1180
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• 1999

The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

• Bulletin of the Korean Chemical Society
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• 제21권12호
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• pp.1202-1206
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• 2000

Transmission of substituent effects through 5-membered heteroaromatic rings is investigated theoretically at the RHF/6-31+G and B3LYP/6-31+G levels using the equilibria for the $OH^- addition to five-membered heteroaromatic aldehydes (5MHA). The transmission efficiency (S) in 5MHA(A) increases in the order NH>O>S>PH but the order exactly reverses in 5MHA($T^-$). This is originated by the delocalizability of the ${\pi}$ lonepair on Y, $$n_\pi$(Y)$. A better correlation is obtained with ${\sigma}_p^-$ in the Hammett plots with positive slope, $p_z$ > 0, indicating that the substituent (Z) effects are not transmitted by a direct conjugation. The magnitude of $p_z$ for Y=NH is the largest among the heteroaromatic systems, which is consistent with the largest transmission efficiency change $({\Delta}S)$. The equilibria for the addition processes are favorable in the gas phase $({\Delta}G^o<0)$, which reverses to unfavorable in aqueous solution $({\Delta}G^o>0)$ due to the relatively large salvation energy of $OH^-$ in the initial state in aqueous solution. The orders of ${\Delta}G^o$ and $p_z$ in the gas phase are almost maintained in solution.

• Bulletin of the Korean Chemical Society
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• 제19권3호
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• pp.349-353
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• 1998

Solvolysis rates of substituted 2-aryl-1,1-dimethylethyl bromides (1) were determined in a variety of solvents such as aqueous mixtures of ethanol, acetone, 2,2,2-trifluoroethanol, and also mixtures of ethanol and TFE at 25 ℃, 35 ℃, and 45 ℃. The solvent effects were analyzed in terms of Winstein-Grunwald equation. The solvent effects of 1-4-MeO failed to give a single linear correlation against either Y or YCl (YBr), but exhibited a wide split pattern which could not be related to the solvent nucleophilicity. On the other hand 1-4-CH3 and 1-H gave a fairly good linearity. In the case of 1-4-MeO, a fairly good linearity was observed against YΔ defined from the solvolysis of 4-methoxyneophyl tosylate. It is assumed that resonance interaction between reaction site and aryl-π-system operates to give charge delocalization regardless of the different solvolysis mechanisms. The Hammett-Brown treatment of the solvolytic rate constant of compounds 1 was obtained non-linear two separated lines of - 1.06 to - 1.46, suggesting of mechanistic changeover from kc-ks to kΔ on going from electron-withdrawing to electron-donating substituents as a basis of 4-CH3 group.

• Bulletin of the Korean Chemical Society
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• 제8권3호
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• pp.168-170
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• 1987

The reaction between 1-benzyl-3-carbamoyl-1,4-dihydropyridine (BNAH) 1 and various 1-arylpyridinium salts 2, and the reaction between 1-(4-methylphenyl)-1,4-dihydropyridine 4b and 1-aryl-3-carbamoylpyridinium (1-arylnicotinamide) salts 5 were carried out. The extents of reaction in equilibrium were estimated by nmr integration data. The equilibrium constants for the reactions, K, and the standard Gibbs free energy changes for the reduction of the pyridinium salts to the corresponding 1,4-dihydropyridines ${\Delta}G^{\circ}'$ were evaluated. The Hammett plot of log K for the reaction between 1 and 2, and ${\Delta}G^{\circ}'$ against ${\sigma}_p$ of the substituents in 1-aryl moiety shows linear correlation with the reaction constant ${\rho}$ of 9.4 (for log K vs ${\sigma}_p$) and -54.5 KJ/mole (for ${\Delta}G^{\circ}'$ vs ${\sigma}_p$). It was found that 1-aryl-1,4-dihydropyridines have much higher reducing power than the corresponding 1-aryl-1,4-dihydronicotinamides, and the power is affected greatly by the electron-withdrawing ability of the substituents in aryl group. The reactions were utilized for preparation of 1,4-dihydropyridines bearing highly electron-withdrawing groups such as 4-nitrophenyl and 2,4-dinitrophenyl, which could not be obtained by conventional dithionite reduction of the corresponding pyridinium salts due to the base-labile nature of the salts.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1153-1157
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• 2011

A kinetic study is reported for aminolysis of S-4-nitrophenyl X-substituted thiobenzoates 3a-g in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Thiol esters 3a-g are 7.8-47.6 fold more reactive than the corresponding oxygen esters (i.e., 4-nitrophenyl X-substituted benzoates 1a-g). Such reactivity order appears to be in accordance with the expectation that 4-nitrothiophenoxide in 3a-g is a better nucleofuge than 4-nitrophenoxide in 1a-g since the former is 2.64 pKa units less basic than the latter. Hammett plot for the reactions of 3a-g exhibit poor correlation coefficients ($R^2$ = 0.977-0.986) with negative deviation by substrates possessing an electrondonating group (EDG), while the Yukawa-Tsuno plots result in excellent linear correlation ($R^2$ = 0.995-0.997) with ${\rho}$ = 0.93-1.23 and r = 0.57-0.67, indicating that the negative deviation shown by substrates possessing an EDG is caused by ground-state stabilization through resonance interactions but not due to a change in ratedetermining step upon changing the nonleaving-group substituent X. The ${\rho}$ value increases as the incoming amine becomes more basic and more reactive, indicating that the RSP is not operative in the current reactions.

• Bulletin of the Korean Chemical Society
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• 제30권10호
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• pp.2403-2407
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• 2009

Second-order rate constants have been measured for two series of nucleophilic displacement reactions, i.e., reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides and those of Y-substituted phenyl benzoates (1a-h) with 4-chlorophenoxide (4-ClPhO–) in 80 mol% $H_2O$/20 mol% DMSO at 25.0 ${\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot for reactions of 4-nitrophenyl benzoate with Z-substituted phenoxides exhibits an excellent linear correlation with ${\beta}_{nuc}$ = 0.72. Reactions of 1a-h with 4-chlorophenoxide result in also a linear Br$\phi$nsted-type plot with ${\beta}_{lg}$ = –0.62, a typical ${\beta}_{lg}$ value for a concerted mechanism. The Hammett plots correlated with ${\sigma}^o\;and\;{\sigma}^-$ constants show many scattered points for reactions of 1a-h with 4-chlorophenoxide. In contrast, the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with $\rho_Y$ = 2.26 and r = 0.53, indicating that expulsion of the leaving group occurs at the rate-determining step (RDS) either in a concerted mechanism or in a stepwise pathway. However, a stepwise mechanism with leaving group departure being the RDS is excluded since the leaving Y-substituted phenoxide is less basic and a better nucleofuge than the incoming 4-ClPh$O^-$. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which bond formation between the nucleophile and electrophilic center is more advanced than expulsion of the leaving group in the transition state on the basis of the magnitude of ${\beta}_{nuc}\;and\;{\beta}_{lg}$ values.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3253-3257
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• 2012

Second-order rate constants for the reactions of phenyl Y-substituted-phenyl carbonates 5a-g with Z-substituted-phenoxides ($k_{Z-PhO^-}$) have been measured spectrophotometrically in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. 4-Nitrophenyl phenyl carbonate (5e) is up to 235 times more reactive than 4-nitrophenyl benzoate (4e). The Br$\o$nsted-type plot for the reactions of 5e with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.54$, which is typical for reactions reported previously to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for the reactions of 5a-f with 4-chlorophenoxide exhibit highly scattered points. In contrast, the Yukawa-Tsuno plot results in an excellent linear correlation with ${\rho}_Y=1.51$ and r = 0.52, indicating that the leaving-group departure occurs at the rate-determining step (RDS). A stepwise mechanism, in which leaving-group departure occurs at RDS, has been excluded since the incoming 4-$ClPhO^-$ is more basic and a poorer nucleofuge than the leaving Y-substituted-phenoxides. Thus, the reaction has been concluded to proceed through a concerted mechanism. Our study has shown that the modification of the nonleaving group from benzoyl to phenyloxycarbonyl causes a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as an increase in the reactivity.