2-Methoxy-benzoesaeure-4-nitro-phenylester | 85966-06-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 缩酚酸和缩酚酸环醚类
• 英文名称: 2-Methoxy-benzoesaeure-4-nitro-phenylester
• 英文别名: 4-nitrophenyl 2-methoxybenzoate；(4-nitrophenyl) 2-methoxybenzoate
• CAS: 85966-06-9
• 化学式: C₁₄H₁₁NO₅
• 分子量: 273.245
• InChiKey: CPBMFVDCDPNIMB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  81.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  哌嗪 、 2-Methoxy-benzoesaeure-4-nitro-phenylester 以 乙腈 为溶剂， 生成 (2-甲氧基苯基)(哌嗪-1-基)甲酮
  参考文献：
  名称：

  Aminolysis of Y-Substituted-phenyl 2-Methoxybenzoates in Acetonitrile: Effect of the o-Methoxy Group on Reactivity and Reaction Mechanism

  摘要：

  Second-order rate constants (k(N)) were measured for aminolyses of Y-substituted-phenyl 2-methoxybenzoates 2a-i and 4-nitrophenyl X-substituted-benzoates 3a-j in MeCN at 25.0 degrees C. The Bronsted-type plot for the reactions of 2a-i with piperidine curves downward, indicating that a change in rate-determining step (RDS) occurs. The Hammett plot for the reactions of 3a-j with piperidine consists of two intersecting straight lines, which might be taken as evidence for a change in RDS. However, the nonlinear Hammett plot has been suggested not to be due to a change in RDS but rather to the stabilization of the ground state of substrates possessing an electron-donating group (EDG) (e.g., 3a-c) through a resonance interaction, since the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with rho = 0.54 and r = 1.54. The rho value found for the reactions of 3a-j in MeCN is much smaller than that reported previously for the corresponding reactions in H2O (i.e., rho = 0.75). It is proposed that the reactions of 3a-j in MeCN proceed through a forced concerted mechanism due to instability of T-+/- in the aprotic solvent, while the reactions of 2a-i proceed through a stepwise pathway with a stabilized T-+/- through an intramolecular H-bonding interaction.

  DOI：

  10.1021/jo201387h
• 作为产物：
  描述：

  对硝基苯酚 、 甲氧基苯甲酰氯 在 三乙胺 作用下， 以 乙醚 为溶剂， 生成 2-Methoxy-benzoesaeure-4-nitro-phenylester
  参考文献：
  名称：

  Aminolysis of Y-Substituted-phenyl 2-Methoxybenzoates in Acetonitrile: Effect of the o-Methoxy Group on Reactivity and Reaction Mechanism

  摘要：

  Second-order rate constants (k(N)) were measured for aminolyses of Y-substituted-phenyl 2-methoxybenzoates 2a-i and 4-nitrophenyl X-substituted-benzoates 3a-j in MeCN at 25.0 degrees C. The Bronsted-type plot for the reactions of 2a-i with piperidine curves downward, indicating that a change in rate-determining step (RDS) occurs. The Hammett plot for the reactions of 3a-j with piperidine consists of two intersecting straight lines, which might be taken as evidence for a change in RDS. However, the nonlinear Hammett plot has been suggested not to be due to a change in RDS but rather to the stabilization of the ground state of substrates possessing an electron-donating group (EDG) (e.g., 3a-c) through a resonance interaction, since the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with rho = 0.54 and r = 1.54. The rho value found for the reactions of 3a-j in MeCN is much smaller than that reported previously for the corresponding reactions in H2O (i.e., rho = 0.75). It is proposed that the reactions of 3a-j in MeCN proceed through a forced concerted mechanism due to instability of T-+/- in the aprotic solvent, while the reactions of 2a-i proceed through a stepwise pathway with a stabilized T-+/- through an intramolecular H-bonding interaction.

  DOI：

  10.1021/jo201387h

文献信息

• Aminolysis of Y-Substituted-phenyl 2-Methoxybenzoates in Acetonitrile: Effect of the <i>o</i>-Methoxy Group on Reactivity and Reaction Mechanism
  作者：Ik-Hwan Um、Ae Ri Bae

  DOI：10.1021/jo201387h

  日期：2011.9.16

  Second-order rate constants (k(N)) were measured for aminolyses of Y-substituted-phenyl 2-methoxybenzoates 2a-i and 4-nitrophenyl X-substituted-benzoates 3a-j in MeCN at 25.0 degrees C. The Bronsted-type plot for the reactions of 2a-i with piperidine curves downward, indicating that a change in rate-determining step (RDS) occurs. The Hammett plot for the reactions of 3a-j with piperidine consists of two intersecting straight lines, which might be taken as evidence for a change in RDS. However, the nonlinear Hammett plot has been suggested not to be due to a change in RDS but rather to the stabilization of the ground state of substrates possessing an electron-donating group (EDG) (e.g., 3a-c) through a resonance interaction, since the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with rho = 0.54 and r = 1.54. The rho value found for the reactions of 3a-j in MeCN is much smaller than that reported previously for the corresponding reactions in H2O (i.e., rho = 0.75). It is proposed that the reactions of 3a-j in MeCN proceed through a forced concerted mechanism due to instability of T-+/- in the aprotic solvent, while the reactions of 2a-i proceed through a stepwise pathway with a stabilized T-+/- through an intramolecular H-bonding interaction.