• Bulletin of the Korean Chemical Society
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• 제19권7호
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1245-1250
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• 2003

Pseudo-first-order rate constants ($k_{obs}$) have been measured spectrophotometrically for the reactions of 4-nitrophenyl benzoate with a series of pyridines in $H_2O$ containing 20 mol % DMSO. The plots of kobs vs pyridine concentration are linear up to ca. 0.1 M pyridines, indicating that the effect of self-association of pyridines with their conjugate acids are insignificant in this concentration range. The Bronsted-type plot has been obtained to be linear with a ${\beta}_{nuc}$ value 1.11, suggesting that the pyridinolyses proceed through a rate-determining breakdown of the zwiterionic addition intermediate. The pyridines studied have shown higher reactivity than isobasic primary and secondary amines toward the substrate. 1-Benzoyl-4-dimethylaminopyridinium ion, a possible intermediate, has not been detected since the rate of its hydrolysis in the reaction condition is comparable with or even faster than its formation.

• 대한화학회지
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• 제19권3호
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• pp.156-162
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• 1975

메탄올 속에서 여러가지 치환기를 가진 아닐린과 염화메탄술포닐의 반응을 속도론적으로 연구한 결과 $S_N2 반응메카니즘으로 진행됨을 알았다. 아닐린의 치환기 효과는 Bronsted plot와 Hammett plot로 검토한 결과 직선관계를 얻었다. ${\beta}$값(${\beta}$=0.84)과 ${\rho}$값(${\rho}$=-2.46)으로 보아 전이상태에서 bond formation이 보다 진행된 상태임을 짐작 할수 있었다. 오르트 메틸아닐린의 반응속도는 아닐린의 오르토위치의 입체효과 때문에 아닐린의 메타, 파라치환체를 바탕으로 얻어진 Bronstedplot에서 벗어남을 보여주었다. 파라치환체에 있어서는 치환기의 electron donating ability가 증가함을 따라 ${\Delta}H^{\neq}$의 값은 감소하고 ${\Delta}S^{\neq}$의 값은 음의 값이 커지고 있음을 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제29권12호
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• pp.2509-2512
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• 2008

• Bulletin of the Korean Chemical Society
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• 제18권5호
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• pp.523-527
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• 1997

Apparent second-order rate constants (kapp) have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl benzoate (DNPB) with 6 secondary cyclic amines in H2O containing 20 mole% DMSO at 25.0±0.1 ℃. The Bronsted-type plot (log kapp vs. pKa) shows a break at pKa near 9.1, e.g. two straight lines with βapp values of 0.67 and 0.44 for the low basic (pKa < 9.1) and the highly basic (pKa > 9.1) amines, respectively. Using an estimated k2 value of 3×109 sec-1, all the other microconstants (k1, k-1 and K) involved in the present aminolysis have been calculated. The k value decreases with increasing the basicity of amines while k1 and K values increase with increasing the amine basicity, as expected. Good linear Bronsted-type plots have been obtained for these microconstants of the present aminolysis of DNPB. The magnitudes of the slope of the Bronsted-type plots, k1 and k-1 have been calculated to be 0.43 and - 0.24, respectively, indicating the k-1 step is about two folds less sensitive than the k1 step to the amine basicity. The K value has been calculated to be 0.66, which appears to be much smaller than the one for other aminolyses showing general base catalysis. The small K value has been attributed to the absence of general base catalysis in the present aminolysis of DNPB.

• Bulletin of the Korean Chemical Society
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• 제15권7호
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• pp.585-589
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• 1994

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of S-p-nitrophenyl thiobenzoate with various anionic nucleophiles including 6 ${\alpha}$-effect nucleophiles. A good Bronsted correlation has been observed for the reactions with 7 aryloxides. However, p-chlorothiophenoxide and hydroxide ions exhibit significantly positive and negative deviations, respectively, from the Bronsted plot. The deviations are attributed to the effect of polarizability and solvation rather than a change in the reaction mechanism. The ${\alpha}$-effect nuceophiles except highly basic ones demonstrate remarkably enhanced nucleophilicity. The effects of solvation and/or polarizability are proposed to be important for the cause of the ${\alpha}$-effect.

• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2455-2460
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• 2013

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the nucleophilic displacement reactions of 4-nitrophenyl X-substituted-cinnamates (4a-4e) and Y-substituted-phenyl cinnamates (5a-5e) with Z-substituted-phenoxide anions in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 4a-4e with 4-chlorophenoxide (4-$ClPhO^-$) consists of two intersecting straight lines, which might be taken as a change in the rate-determining step (RDS). However, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of substrates possessing an electron-withdrawing group in the cinnamoyl moiety through resonance interactions, since the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}X=0.89$ and r = 0.58. The Br${\o}$nsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.76$. The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4-$ClPhO^-$) is also linear with ${\beta}_{lg}=-0.72$. The Hammett plot correlated with ${\sigma}^-$ constants for the reactions of 5a-5d results in a much better linear correlation than that correlated with ${\sigma}^o$ constants, indicating that a partial negative charge develops on the O atom of the leaving aryloxide. Thus, the reactions have been concluded to proceed through a concerted mechanism.

• 대한화학회지
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• 제40권12호
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• pp.733-740
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• 1996

4'-[N-(9-Acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide(AMQD) 의 가수분해속도상수를 25.deg.C의 수용액속에서 자외선 분광법으로 측정하여 넓은 pH에서 잘 맞는 반응속도식을 구하였다. pH에 따르는 속도상수의 변화, Bronsted plot, 가수분해 생성물을 확인, 일반염기 및 치환기 효과 등으로부터 실험 사실에 잘 맞는 반응메카니즘을 제안하였다. 즉 pH 3.00 이하에서는 acridinyl기의 질소에 양성자가 첨가된 다음 quinonoid의 4'-위치에 물의 첨가가 일어나 가수분해가 진행되며, pH 3.00-9.00 사이에서는 물분자와 수산화 음이온의 첨가가 경쟁적으로 일어나 반응이 진행되었고, pH 9.00이상에서는 수산화 음이온의 농도에만 비례함을 알았다.

• 대한화학회지
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• 제23권1호
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• pp.37-41
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• 1979

Benzyl m-nitrobenzenesulfonate와 N,N-dimethylaniline類와의 反應速度를 아세톤 溶媒에서 電氣傳導度法으로 測定하였다. N,N-디메틸아닐린의 反應性에 關한 置換基效果와 直線 自由에너지 關係를 考察하였다. 反應速度常數 k는 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$였으며 置換基가 電子를 주는 能力이 클수록 反應은 빨랐다. Hammett 도시에서 置換基常數 ${\sigma}$와 ${\sigma}p$-MeO = -0.35의 새로운 값을 使用했을때 ${\rho}$ = -1.37의 좋은 直線이 얻어졌다. 本反應의 경우 r값은 브롬화벤질에 比해 큰 값을 가졌다. Bronsted 圖示에서 溶媒效果에 基因된 p-MeO基를 除外하고는 좋은 直線이 얻어졌으며 C${\cdot}{\cdot}{\cdot}$O 結合의 쪼개짐이 結合 形成보다 優先的인 $S_N2$ 轉移狀態를 갖는다고 推定된다.

• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1797-1802
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• 2007

The kinetics and mechanism of the nucleophilic substitution reactions of diphenyl phosphinic (1) and thiophosphinic (2) chlorides with substituted X-pyridines are investigated kinetically in acetonitrile at 35.0 and 55.0 oC, respectively. A concerted mechanism with backside nucleophilic attack is proposed for the pyridinolysis of 1, on the basis of the linear Bronsted plot with the βX value of 0.68. In the case of the pyridinolysis of 2, the Hammett and Bronsted plots are biphasic concave upwards with the break point at 3- phenyl pyridine. These results indicate a change in mechanism from a concerted SN2(P) process with direct backside nucleophilic attack for less basic nucleophiles (X = 3-CN-3-Ph) to a stepwise process with frontside attack for more basic nucleophiles (X = 4-MeO-3-Ph). Apparent secondary inverse kinetic isotope effects with deuterated pyridine (C5D5N), kH/kD < 1, are observed for the pyridinolysis of 1 and 2.