Carbobenzoxydiglycin | 141695-30-9

• 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: Carbobenzoxydiglycin
• 英文别名: 2-[[2-(Phenoxycarbonylamino)acetyl]amino]acetic acid
• CAS: 141695-30-9
• 化学式: C₁₁H₁₂N₂O₅
• mdl: MFCD12071096
• 分子量: 252.227
• InChiKey: CXXOBGPMWCOTQS-UHFFFAOYSA-N

物化性质

• 沸点：
  525.9±50.0 °C(Predicted)
• 密度：
  1.356±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.181
• 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：

  双甘肽 、 4-nitrophenyl phenyl carbonate 在 二甲基亚砜 作用下， 以 水 、 乙腈 为溶剂， 生成 Carbobenzoxydiglycin 、 4-硝基苯酚阴离子
  参考文献：
  名称：

  Aminolyses of 4-Nitrophenyl Phenyl Carbonate and Thionocarbonate:  Effect of Modification of Electrophilic Center from CO to CS on Reactivity and Mechanism

  摘要：

  [GRAPHICS]A kinetic study is reported for nucleophilic substitution reactions of 4-nitrophenyl phenyl carbonate (5) and 4-nitrophenyl phenyl thionocarbonate (6) with a series of primary amines. The thiono compound 6 is less reactive than its oxygen analogue 5 toward strongly basic amines but is more reactive toward weakly basic CF3CH2NH2. The Bronsted-type plots obtained from the aminolyses of 5 and 6 are curved downwardly. The reactions are proposed to proceed through a stepwise mechanism with a change in the RDS on the basis of the curved Bronsted-type plots. The microscopic rate constants (k(1) and k(2)/k(-1) ratio) associated with the current aminolyses are consistent with the proposed reaction mechanism. The replacement of the C=O bond in 5 by a polarizable C=S group results in a decrease in the k(1) value but an increase in the k(2)/k(-1) ratio. Besides, such a modification of the electrophilic center causes a decrease in pK(a)degrees, defined as the pK(a) at the curvature center of curved Bronsted-type plots, but does not alter the reaction mechanism. The larger k(2)/k(-1) ratio for the reactions of 6 compared to those of 5 is proposed to be responsible for the decreased pK(a)degrees value.

  DOI：

  10.1021/jo052417z

文献信息

• Aminolyses of 4-Nitrophenyl Phenyl Carbonate and Thionocarbonate:  Effect of Modification of Electrophilic Center from CO to CS on Reactivity and Mechanism
  作者：Ik-Hwan Um、Eun Young Kim、Hye-Ran Park、Sang-Eun Jeon

  DOI：10.1021/jo052417z

  日期：2006.3.1

  [GRAPHICS]A kinetic study is reported for nucleophilic substitution reactions of 4-nitrophenyl phenyl carbonate (5) and 4-nitrophenyl phenyl thionocarbonate (6) with a series of primary amines. The thiono compound 6 is less reactive than its oxygen analogue 5 toward strongly basic amines but is more reactive toward weakly basic CF3CH2NH2. The Bronsted-type plots obtained from the aminolyses of 5 and 6 are curved downwardly. The reactions are proposed to proceed through a stepwise mechanism with a change in the RDS on the basis of the curved Bronsted-type plots. The microscopic rate constants (k(1) and k(2)/k(-1) ratio) associated with the current aminolyses are consistent with the proposed reaction mechanism. The replacement of the C=O bond in 5 by a polarizable C=S group results in a decrease in the k(1) value but an increase in the k(2)/k(-1) ratio. Besides, such a modification of the electrophilic center causes a decrease in pK(a)degrees, defined as the pK(a) at the curvature center of curved Bronsted-type plots, but does not alter the reaction mechanism. The larger k(2)/k(-1) ratio for the reactions of 6 compared to those of 5 is proposed to be responsible for the decreased pK(a)degrees value.