N-[(4-chlorophenyl)carbonyl]glycylglycine

• 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: N-[(4-chlorophenyl)carbonyl]glycylglycine
• 英文别名: 2-[[2-[(4-chlorobenzoyl)amino]acetyl]amino]acetic acid
• 化学式: C₁₁H₁₁ClN₂O₄
• mdl: MFCD00761587
• 分子量: 270.672
• InChiKey: UETHUJKPEUVLPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.181
• 拓扑面积：
  95.5
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  双甘肽 、 4-nitrophenyl 4-chlorobenzoate 以 水 、 二甲基亚砜 为溶剂， 生成 对硝基苯酚 、 N-[(4-chlorophenyl)carbonyl]glycylglycine
  参考文献：
  名称：

  An unusual ground-state stabilization effect and origins of the alpha-effect in aminolyses of Y-substituted phenyl X-substituted benzoates

  摘要：

  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.

  DOI：

  10.1139/cjc-76-6-729

文献信息

• 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
• 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.