4-Formyl-benzoic acid 4-nitro-phenyl ester | 131266-90-5

• 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: 4-Formyl-benzoic acid 4-nitro-phenyl ester
• 英文别名: Benzoic acid, 4-formyl-, 4-nitrophenyl ester；(4-nitrophenyl) 4-formylbenzoate
• CAS: 131266-90-5
• 化学式: C₁₄H₉NO₅
• 分子量: 271.229
• InChiKey: DRPWQWRXUPSARG-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：
  0.0
• 拓扑面积：
  89.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-Formyl-benzoic acid 4-nitro-phenyl ester 在 potassium permanganate 作用下， 以 吡啶 为溶剂， 以40 mg的产率得到Terephthalic acid mono-(4-nitro-phenyl) ester
  参考文献：
  名称：

  Acceleration of p-Nitrophenyl Ester Cleavage by Zn(II)-Organized Molecular Receptors

  摘要：

  Tris(2-aminoethyl)amine (TREN) has been functionalized by introducing phenolic residues in the tripodal ligand side arms. The resulting functionalized ligands 1-5 form stable complexes with Zn(II) ions at pH > 6-6.5. The conformation of the Zn(II) complexes is such to form an ill-defined cavity with the metal ion occupying its bottom and the aromatic residues defining its hydrophobic walls. In these Zn(II) complexes one of the phenolic hydroxyls is, depending on the structure of the ligand, up to 1.3 pK(a) units more acidic than that of phenol itself. This enhanced acidity is attributed to second sphere coordination to the metal center. The complexes, particularly 1 . Zn(II), behave as molecular receptors of p-nitrophenyl esters of carboxylic acids with binding constants greater than or equal to 300 M-1 for those substrates capable of coordination to the Zn(II) ion (p-nitrophenyl nicotinate, PNPN, p-nitrophenyl isonicotinate, PNPIN and p-nitrophenyl urocanoate, PNPU). At pH 8.3 they also accelerate the cleavage of these esters with rate accelerations with respect to the uncatalyzed: hydrolysis of up to 60 times, depending on the structure of the substrate. The kinetic analysis of the process shows that the rate effects are due to two independent mechanisms: a bimolecular process that does not comprise binding of the substrate and a pseudointramolecular process within the supramolecular complex made of ligand, metal ion, and substrate. In both cases the nucleophile is one of the phenolic hydroxyls of the functionalized side arms of the TREN-based complex which, in the first step, is acylated by the substrate and eventually slowly hydrolyzes turning over the catalyst. Determination of second-order rate constants shows that the nucleophilicity of the phenolic hydroxyls is higher than that of a substituted phenol of the same pK(a). Comparison of the metalloreceptor 1 . Zn(II) with cyclodextrins allowed one to highlight similarity and differences between the two receptors.

  DOI：

  10.1021/jo970783f
• 作为产物：
  描述：

  对醛基苯甲酸 在 氯化亚砜 、 三乙胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 5.0h， 生成 4-Formyl-benzoic acid 4-nitro-phenyl ester
  参考文献：
  名称：

  Acceleration of p-Nitrophenyl Ester Cleavage by Zn(II)-Organized Molecular Receptors

  摘要：

  Tris(2-aminoethyl)amine (TREN) has been functionalized by introducing phenolic residues in the tripodal ligand side arms. The resulting functionalized ligands 1-5 form stable complexes with Zn(II) ions at pH > 6-6.5. The conformation of the Zn(II) complexes is such to form an ill-defined cavity with the metal ion occupying its bottom and the aromatic residues defining its hydrophobic walls. In these Zn(II) complexes one of the phenolic hydroxyls is, depending on the structure of the ligand, up to 1.3 pK(a) units more acidic than that of phenol itself. This enhanced acidity is attributed to second sphere coordination to the metal center. The complexes, particularly 1 . Zn(II), behave as molecular receptors of p-nitrophenyl esters of carboxylic acids with binding constants greater than or equal to 300 M-1 for those substrates capable of coordination to the Zn(II) ion (p-nitrophenyl nicotinate, PNPN, p-nitrophenyl isonicotinate, PNPIN and p-nitrophenyl urocanoate, PNPU). At pH 8.3 they also accelerate the cleavage of these esters with rate accelerations with respect to the uncatalyzed: hydrolysis of up to 60 times, depending on the structure of the substrate. The kinetic analysis of the process shows that the rate effects are due to two independent mechanisms: a bimolecular process that does not comprise binding of the substrate and a pseudointramolecular process within the supramolecular complex made of ligand, metal ion, and substrate. In both cases the nucleophile is one of the phenolic hydroxyls of the functionalized side arms of the TREN-based complex which, in the first step, is acylated by the substrate and eventually slowly hydrolyzes turning over the catalyst. Determination of second-order rate constants shows that the nucleophilicity of the phenolic hydroxyls is higher than that of a substituted phenol of the same pK(a). Comparison of the metalloreceptor 1 . Zn(II) with cyclodextrins allowed one to highlight similarity and differences between the two receptors.

  DOI：

  10.1021/jo970783f

文献信息

• Pd-Catalyzed Decarbonylative Olefination of Aryl Esters: Towards a Waste-Free Heck Reaction
  作者：Lukas J. Gooßen、J. Paetzold

  DOI：10.1002/1521-3773(20020402)41:7<1237::aid-anie1237>3.0.co;2-f

  日期：2002.4.2
• Acceleration of <i>p</i>-Nitrophenyl Ester Cleavage by Zn(II)-Organized Molecular Receptors
  作者：Paolo Tecilla、Umberto Tonellato、Andrea Veronese、Fulvia Felluga、Paolo Scrimin

  DOI：10.1021/jo970783f

  日期：1997.10.1

  Tris(2-aminoethyl)amine (TREN) has been functionalized by introducing phenolic residues in the tripodal ligand side arms. The resulting functionalized ligands 1-5 form stable complexes with Zn(II) ions at pH > 6-6.5. The conformation of the Zn(II) complexes is such to form an ill-defined cavity with the metal ion occupying its bottom and the aromatic residues defining its hydrophobic walls. In these Zn(II) complexes one of the phenolic hydroxyls is, depending on the structure of the ligand, up to 1.3 pK(a) units more acidic than that of phenol itself. This enhanced acidity is attributed to second sphere coordination to the metal center. The complexes, particularly 1 . Zn(II), behave as molecular receptors of p-nitrophenyl esters of carboxylic acids with binding constants greater than or equal to 300 M-1 for those substrates capable of coordination to the Zn(II) ion (p-nitrophenyl nicotinate, PNPN, p-nitrophenyl isonicotinate, PNPIN and p-nitrophenyl urocanoate, PNPU). At pH 8.3 they also accelerate the cleavage of these esters with rate accelerations with respect to the uncatalyzed: hydrolysis of up to 60 times, depending on the structure of the substrate. The kinetic analysis of the process shows that the rate effects are due to two independent mechanisms: a bimolecular process that does not comprise binding of the substrate and a pseudointramolecular process within the supramolecular complex made of ligand, metal ion, and substrate. In both cases the nucleophile is one of the phenolic hydroxyls of the functionalized side arms of the TREN-based complex which, in the first step, is acylated by the substrate and eventually slowly hydrolyzes turning over the catalyst. Determination of second-order rate constants shows that the nucleophilicity of the phenolic hydroxyls is higher than that of a substituted phenol of the same pK(a). Comparison of the metalloreceptor 1 . Zn(II) with cyclodextrins allowed one to highlight similarity and differences between the two receptors.