Glycine, N-[N-(4-methoxybenzoyl)glycyl]- | 57463-79-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Glycine, N-[N-(4-methoxybenzoyl)glycyl]-
• 英文别名: 2-[[2-[(4-methoxybenzoyl)amino]acetyl]amino]acetic acid
• CAS: 57463-79-3
• 化学式: C₁₂H₁₄N₂O₅
• mdl: MFCD00610542
• 分子量: 266.254
• InChiKey: HIWBDIBOVCRUPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  105
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  对甲氧基苯甲酰氯 在 三乙胺 作用下， 以 乙醚 、 水 、 二甲基亚砜 、 乙腈 为溶剂， 生成 Glycine, N-[N-(4-methoxybenzoyl)glycyl]-
  参考文献：
  名称：

  Kinetic Study on Nucleophilic Displacement Reactions of 2-Chloro-4-Nitrophenyl X-Substituted-Benzoates with Primary Amines: Reaction Mechanism and Origin of the α-Effect

  摘要：

  在 80 mol % $H_2O/20$ mol % DMSO 溶液中，于 $25.0^{\circ}C$.2-chloro-4-nitrophenyl benzoate (1d) 与一系列伯胺反应的 Br${emptyset}$nsted-type plot 曲线向下，这被认为是速率决定级（RDS）发生变化的阶梯机理的证据。1a-h 与肼和甘氨酰甘氨酸反应的 Hammett 图是非线性的，而 Yukawa-Tsuno 图则表现出很好的线性关系，$\{yrho}_X=1.22-1.35$ 和 ${\gamma}= 0.57-0.59$，这表明非线性哈米特图不是由于 RDS 的变化造成的，而是通过 EDG 与基质的 C=O 键之间的共振相互作用，使具有电子供体基团 (EDG) 的基质稳定下来造成的。随着取代基 X 从强 EDG 转变为强电子抽离基 (EWG)，肼表现出的 $\{alpha}$ 效应也随之增加。研究得出的结论是，通过相邻非键电子之间的电子斥力使肼失稳并不是取代基依赖性 ${\alpha}$ 效应的唯一原因，过渡态的稳定也是 ${\alpha}$ 效应的一个合理来源。

  DOI：

  10.5012/bkcs.2014.35.2.436

文献信息

• The α-Effect in Hydrazinolysis of 4-Chloro-2-Nitrophenyl X-Substituted-Benzoates: Effect of Substituent X on Reaction Mechanism and the α-Effect
  作者：Min-Young Kim、Tae-Eun Kim、Jieun Lee、Ik-Hwan Um

  DOI：10.5012/bkcs.2014.35.8.2271

  日期：2014.8.20

  Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reaction of 4-chloro-2-nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % $H_2O$/20 mol % DMSO at $25.0^\circ}C$. The Br$\o}$nsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with $\beta}_nuc}$ = 0.74 when hydrazine is excluded from the correlation. Such a linear Br$\o}$nsted-type plot is typical for reactions reported previously to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with $\rho}_X$ = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the $\alpha}$-effect). The $\alpha}$-effect increases as the substituent X in the benzoyl moiety becomes a stronger electron-withdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent $\alpha}$-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the $\alpha}$-effect observed in this study.

  二次速率常数（$k_N$）已通过分光光度法测定，用于4-氯-2-硝基苯基X取代苯甲酸酯（6a-6h）与一系列伯胺（包括80摩尔% $H_2O$/20摩尔% DMSO中的25.0°C下的联氨）的反应。当联氨被排除在相关性之外时，4-氯-2-硝基苯基苯甲酸酯（6d）反应的Br$\o}$nsted型图是线性的，$\beta}_nuc}$ = 0.74。这种线性Br$\o}$nsted型图是典型的反应，先前报道这些反应通过逐步机制进行，其中离去基团的排出发生在速率决定步骤（RDS）中。6a-6h与联氨和甘氨酰甘氨酸反应的Hammett图是非线性的。相比之下，Yukawa-Tsuno图显示出极佳的线性相关性，$\rho}_X$ = 1.29-1.45，r = 0.53-0.56，表明非线性Hammett图并非由于RDS的变化，而是由于具有供电子基团（EDG）的底物的共振稳定化所导致。联氨对6a-6h的反应性大约是同样碱性的甘氨酰甘氨酸的47-93倍（例如，$\alpha}$效应）。随着苯甲酰基中取代基X成为更强的吸电子基团（EWG），$\alpha}$效应增加，表明通过两个N原子上的非键电子对之间的排斥来破坏联氨的基态（GS）并不是唯一导致取代基依赖的$\alpha}$效应的原因。通过五元环过渡态（TS）的稳定化，这将增加反应中心的亲电性或离去基团的离核性，有助于在本研究中观察到的$\alpha}$效应。
• Effects of Amine Nature and Nonleaving Group Substituents on Rate and Mechanism in Aminolyses of 2,4-Dinitrophenyl X-Substituted Benzoates
  作者：Ik-Hwan Um、Kyung-Hee Kim、Hye-Ran Park、Mizue Fujio、Yuho Tsuno

  DOI：10.1021/jo049694a

  日期：2004.5.1

  rate-determining step as the basicity of amines increases. The corresponding Brønsted-type plot for the reactions with secondary amines is also biphasic with β1 = 0.34, β2 = 0.74, and pKa° = 9.1, indicating that the effect of amine nature on the reaction mechanism and pKa° is insignificant. However, primary amines have been found to be less reactive than isobasic secondary amines. The microscopic rate constants

  在25.0±0.1°C的条件下，在80 mol％H 2 O / 20 mol％DMSO中，测量了2,4-二硝基苯基X-取代的苯甲酸酯（1a - f）与一系列伯胺的反应的二级速率常数。。用于反应中的布朗斯台德型情节1D与伯胺是双相与斜率β 1在高p值= 0.36 ķ一个区域和β 2 = 0.78在低p- ķ一个区域，并在P中的曲率中心ķ一个°＝ 9.2，表明反应通过加成中间体进行，随着胺的碱度增加，速率确定步骤改变。用于与仲胺的反应中相应的布朗斯台德型情节也双相与β 1 = 0.34，β 2 = 0.74，且p ķ一个°= 9.1，表明胺性质的反应机理和对效果ķ一个°是微不足道的。然而，已发现伯胺比等压仲胺的反应性低。与氨解有关的微观速率常数表明，k 1越小与伯胺的反应是其较低反应性的完全原因。对于1a - f与伯胺和仲胺的反应，非离去基团中的供电子取代基相对于Hammett图具有负偏差，而
• Kinetics and mechanisms of the aminolysis of N-hydroxysuccinimide esters in aqueous buffers
  作者：Gary W. Cline、Samir B. Hanna

  DOI：10.1021/jo00250a031

  日期：1988.7
• An unusual ground-state stabilization effect and origins of the alpha-effect in aminolyses of Y-substituted phenyl X-substituted benzoates
  作者：Ik-Hwan Um、Eun-Kyung Chung、So-Mi Lee

  DOI：10.1139/cjc-76-6-729

  日期：——

  Second-order rate constants have been measured spectrophotometrically for the reactions of X-C6H4CO2C6H4-Y with a series of primary amines in H2O containing 20 mol% DMSO at 25.0 +/- 0.1 degrees C. The reactivity increases as the substituent (X and Y) becomes a stronger electron-withdrawing group. The sigma(+) constants give better Hammett correlation than sigma constants for the reactions of 4-nitrophenyl X-substituted benzoates with glycylglycine (glygly) and hydrazine (NH2NH3, indicating that the ground-state stabilization effect is unusually significant on the reaction rates. The reactions of X-C6H4CO2C6H4-Y with glygly and NH2NH2 appear to proceed through the same mechanism, but the degree of leaving-group departure and the negative charge developed in the acyl moiety at the rate-determining TS is considered to be more significant for the glygly system than the NH2NH2 system based on beta(1g) and rho(x) values. The magnitude of the alpha-effect is observed to be not always dependent on the beta(nuc) value but dependent on the electronic nature of the substituent X and Y, i.e., an electron-donating substituent increases the alpha-effect, while an electron-withdrawing one decreases the alpha-effect. The present study has led to the conclusion that the ground-state effect is important for the reaction rates but it is not solely responsible for the alpha-effect, and the intramolecular H-bonding interactions (4) are proposed for the cause of the increasing or decreasing a-effect trends observed in the present system.
• Kinetic Study on Nucleophilic Displacement Reactions of 2-Chloro-4-Nitrophenyl X-Substituted-Benzoates with Primary Amines: Reaction Mechanism and Origin of the α-Effect
  作者：Tae-Il Um、Min-Young Kim、Tae-Eun Kim、Ik-Hwan Um

  DOI：10.5012/bkcs.2014.35.2.436

  日期：2014.2.20

  8.31 13.96 hydrazine 8.20 6627 glycine ethyl ester 7.68 7.068 1,2-diaminopropane-H + 7.13 4.459 trifluoroethylamine 5.68 0.124 Figure 1. Bronsted-type plot for the reactions of 2-chloro-4-nitro-phenyl benzoate ( 1d ) with primary amines in 80 mol % of H 2 O/20mol % DMSO at 25.0 ± 0.1 o C. The identity of points is given inTable 1, and hydrazine is excluded in the correlation. Table 2. Summary of Second-Order

  在 80 mol % $H_2O/20$ mol % DMSO 溶液中，于 $25.0^\circ}C$.2-chloro-4-nitrophenyl benzoate (1d) 与一系列伯胺反应的 Br$emptyset}$nsted-type plot 曲线向下，这被认为是速率决定级（RDS）发生变化的阶梯机理的证据。1a-h 与肼和甘氨酰甘氨酸反应的 Hammett 图是非线性的，而 Yukawa-Tsuno 图则表现出很好的线性关系，$\yrho}_X=1.22-1.35$ 和 $\gamma}= 0.57-0.59$，这表明非线性哈米特图不是由于 RDS 的变化造成的，而是通过 EDG 与基质的 C=O 键之间的共振相互作用，使具有电子供体基团 (EDG) 的基质稳定下来造成的。随着取代基 X 从强 EDG 转变为强电子抽离基 (EWG)，肼表现出的 $\alpha}$ 效应也随之增加。研究得出的结论是，通过相邻非键电子之间的电子斥力使肼失稳并不是取代基依赖性 $\alpha}$ 效应的唯一原因，过渡态的稳定也是 $\alpha}$ 效应的一个合理来源。