• Bulletin of the Korean Chemical Society
• /
• 제18권4호
• /
• pp.395-401
• /
• 1997

The substituent effects in the gas-phase rearrangement of carbenes to ketenes involved in the Wolff reaction have been investigated theoretically using the AM1 method. In the initial state, carbene, there is a relatively strong vicinal n-σ* interaction between the lone pair (n) and carbonyl group (σ*). In the bridged transition state (TS), electronic charge is transferred from the migrating ring (Z-ring) toward the nonmigrating ring (Y-ring). The carbenes are stabilized by an electron donor Y (δσY < 0) whereas the TS is stabilized by an electron acceptor Y (δσY > 0). Multiple regression analysis of log (kYZ/kHH)(=-δΔG≠/2.3RT) leads to a relatively large negative cross-interaction constant, ρYZ=-0.53, log (kYZ/kHH)=2.96 σY--1.40 σZ-0.53 σY-σZ reflecting an extensive structural change in the transition state due to the stabilization of the initial state by the vicinal n-σ* overlap. When the solvent (water) effects are accounted for by the SM2.1 model of the Cramer and Truhlar method, the magnitude of all the selectivity parameters, ρY-, ρZ and ρYZ (=-0.66) are increased.

• Bulletin of the Korean Chemical Society
• /
• 제24권7호
• /
• pp.931-936
• /
• 2003

By the use of multi-loop thermodynamic boxes developed here by us, we show that models of enzyme catalysis (e.g., split-site model) developed in an attempt to emphasize the importance of the reactant-state destabilization and, thus, demonstrate misleading nature of the fundamentalist position which defines Pauling's transition-state stabilization as the entire and sole source of enzyme catalytic power, should be reduced to the fundamentalist formulation which completely neglects dynamical aspects of mechanism between the reactant and the transition states and dwells only on events restricted to the reactant and transition states alone, because the splitsite (and other canonical) formulations as well as fundamentalist formulations are based, in common, on equilibrium assumptions stipulated by the thermodynamic box logics. We propose to define the equilibrium assumptions as the requisite and sufficient conditions for the fundamentalist position to enjoy its primacy as central dogma, but not as sufficient conditions for its validity, because it is subjected to contradictions presented by existing data.

• Bulletin of the Korean Chemical Society
• /
• 제6권6호
• /
• pp.362-366
• /
• 1985

The hydrogen atom transfer reaction between substituted methane, $CH_3X,$ and its radical, $CH_2X(X=H,F,CH_3,CN,OH\;and\;NH_2$ was studied by MINDO/3 method. The transition state(TS) structure and energy barriers were determined and variation of the transition state and of the reactivity due to the change of X were analyzed based on the potential energy surface characteristics. It was found that the greater the radical stabilization energy. the looser the TS becomes; the TS occurs at about 15% stretch of the C-H bond, which becomes longer as the radical stabilization energy of $CH_2X$ increasers. The intrinsic barrier, ${\Delta}E*_{x.x},$ of the reaction with X was found to increase in the order $H The degree of bond stretch of the C-H bond stretch of the C-H bond at the TS also had the same order indicating that the homolytic bond cleavage of the C-H bond is rate-determining. Orbital interactions at the TS between LUMO of the fragment $C{\ldots}H{\ldots}C$ and the symmetry adapted pair of nonbonding, $n{\pm}(=n_1{\pm}n_2),$ or pi orbitals of the two X atoms were shown to be the dominant contribution in determining tightness or looseness of the TS. The Marcus equation was shown to apply to the MINDO/3 barriers and energy changes of the reaction.

• 대한화학회지
• /
• 제22권3호
• /
• pp.111-116
• /
• 1978

메탄올-물, 에탄올-물, 아세톤-물 및 아세토니트릴-물의 二成分 混合溶媒에서 鹽化페닐메탄술포닐의 加溶媒分解反應을 速度論的으로硏究하였다. 反應速度는 反陽性子溶媒에서 보다 陽性子溶媒에서 더 빨랐으며, 이온化能力에 對한 反應速度의 感度 즉 Winstein 圖示의 m와 轉移狀態의 溶媒和數는 陽性子溶媒에서 훨씬 작았다. 이것은 陽性子溶媒의 水素結合溶媒和에 依한 初期狀態의 安定化로서 생각할 수 있다. 反應은 모든 溶媒系에 있어서 轉移狀態의 結合形成이 結合破壤을 앞지르는$S_N2$ 메카니즘으로 일어난다 할 수 있다.

• Bulletin of the Korean Chemical Society
• /
• 제34권10호
• /
• pp.2877-2882
• /
• 2013

Second-order rate constants ($k_{Ox^-}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl X-substituted-cinnamates (7a-7e) and Y-substituted-phenyl cinnamates (8a-8e) with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 7a-7e consists of two intersecting straight lines while the Yukawa-Tsuno plot exhibits an excellent linearity with ${\rho}_X$=0.85 and r=0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step but is caused by resonance stabilization of the ground state (GS) of the substrate possessing an electron-donating group (EDG). The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (8a-8e) is linear with ${\beta}_{lg}$ = -0.64, which is typical of reactions reported previously to proceed through a concerted mechanism. The ${\alpha}$-nucleophile ($Ox^-$) is more reactive than the reference normal-nucleophile ($4-ClPhO^-$). The magnitude of the ${\alpha}$-effect (i.e., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent X in the nonleaving group but increases linearly as the substituent Y in the leaving group becomes a weaker electron-withdrawing group (EWG). It has been concluded that the difference in solvation energy between $Ox^-$ and $4-ClPhO^-$ (i.e., GS effect) is not solely responsible for the ${\alpha}$-effect but stabilization of transition state (TS) through a cyclic TS structure contributes also to the Y-dependent ${\alpha}$-effect trend (i.e., TS effect).

• Bulletin of the Korean Chemical Society
• /
• 제17권3호
• /
• pp.254-257
• /
• 1996

Nucleophilic substitution reactions of 1- and 2-naphthylethyl arenesulfonates, 2 and 3, with anilines and benzylamines in methanol at 65.0 ℃ are investigated. The rates are slower than those for the corresponding derivatives of 2-phenylethyl arenesulfonates, 1, which can be attributed to a greater degree of positive charge stabilization at Cα in the transition state (TS) by a greater electron supply from a phenyl ring compared to a naphthyl ring. The mechanism for the two naphthylethyl systems are similar to that for the 2-phenylethyl derivatives, except that the transition state is formed at somewhat an earlier position along the reaction coordinate. The secondary kinetic isotope effects involving deuterated nucleophilies indicate that naphthylethyl series are sterically more crowded in the TS than 2-phenylethyl system. The data in this work can not elucidate the possible participation of the aryl-assisted pathway in the reaction.

• Bulletin of the Korean Chemical Society
• /
• 제34권1호
• /
• pp.49-53
• /
• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

• Bulletin of the Korean Chemical Society
• /
• 제16권7호
• /
• pp.574-577
• /
• 1995

Solvatochromic effect and hydrogen bonding interaction of NPNOH, NPNO- and NPNOR were investigated. Electronic transition energies of the dyes were plotted against empirical solvent polarity parameters, Taft's π* and Reichardt's ET(30). Good correlations were observed when the excitation energies were plotted against the energy calculated by multiple linear regression method which was developed by Taft. There is an intrinsic difference between betaine for ET(30) polarity scale and the azoderivative, which is derived from the specific hydrogen bond incurred with probe molecules and solvents. The hydrogen bonding plays a very important role for stabilization of an excited state molecule by solvents especially when a solute possesses a negative charge as with NPNO-.

• Bulletin of the Korean Chemical Society
• /
• 제10권2호
• /
• pp.151-154
• /
• 1989

4-Methoxy-4-methylcyclohexa-2,5-dienone 1 in aqueous sulfuric acid underwent the normal dienone-phenol rearrangement with methyl group migration. The fact that methyl is migrating group and methoxy is remaining group can be rationalized by the stabilization of positive charge at C-4 during the transition state. Methoxy methyl dienone 1 $((H_0)_{1/2} = - 4.6)$ is less basic than 4,4-dimethylcyclohexa-2,5-dienone whose half protonation acidity is reported as - 3.15 or - 3.66. This basicity difference comes from the unstabilization of the protonated methoxy methyl dienone 1 due to the electron withdrawing inductive effect of a methoxy group.

• Journal of Life Science
• /
• 제9권2호
• /
• pp.44-48
• /
• 1999

The ionization of tyrosine residue is known to be involved in the stabilization of transition-state in catalysis of astacin based upon the astacin-transition state analog structure. Two tyrosine residues, Tyr-216 and Tyr-219, are conserved in all MMPs related with astacin family, We replaced Tyr-216 and Tyr-219 into phenylalanine, respectively and the zinc binding properties, kinetic parameters, and pH dependence of each mutant are determined in order to examine the role of tyrosine residue in matrilysin catalysis. Both mutants contain two zinc atoms per mol of enzyme, indicating that either tyrosime does not affect the zinc binding property of the enzyme. Y216F and Y219F mutants are highly active and the kcat/Km values are only decreased 1.1-1.5-fold compared to the wild-type enzyme. The decrease in the activity of the mutants is essentially due to the increase in Km value. The pH dependencies of the kcat/Km values for both mutants are similar to the corresponding dependencies obtained with the wild type enzyme. The pKa values at the alkaline side of both mutants are not changed. These kinetic and pH dependence results indicate that the ionization of active site tyrosine residue of matrilysin is not reflected in the kinetics of peptide hydrolysin as catalyzed by astacin.