2,4,6-trinitrophenyl benzoate | 58156-44-8

• 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: 2,4,6-trinitrophenyl benzoate
• 英文别名: picryl benzoate；(2,4,6-trinitrophenyl) benzoate
• CAS: 58156-44-8
• 化学式: C₁₃H₇N₃O₈
• 分子量: 333.214
• InChiKey: CMODIHOUXMFEQD-UHFFFAOYSA-N

物化性质

• 熔点：
  128-129 °C(Solv: chloroform (67-66-3); methanol (67-56-1))
• 沸点：
  575.1±50.0 °C(Predicted)
• 密度：
  1.599±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  164
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,4,6-trinitrophenyl benzoate 在 盐酸 、 tin 、 tin(ll) chloride 作用下， 生成 2-phenyl-benzoxazole-5,7-diyldiamine
  参考文献：
  名称：

  Kym, Chemische Berichte, 1899, vol. 32, p. 1428

  摘要：

  DOI：
• 作为产物：
  描述：

  苦味酸 、 苯甲酰氯 以 氯仿 为溶剂， 反应 3.0h， 以75%的产率得到2,4,6-trinitrophenyl benzoate
  参考文献：
  名称：

  DFT calculations of 2,4,6-trinitrophenylbenzoate derivatives: Structure, ground state properties and spectral properties

  摘要：

  2,4,6-Trinitrophenylbenzoate derivatives 3(a-g) were synthesised and their optimum molecular geometries, ground state properties, IR, UV and NMR spectra were calculated using the B3LYP method with 6-31G** Pople basis set. The predicted geometry showed that the aryl-oxygen bond is stronger than acyl-oxygen bond. Bond lengths are affected by the presence of electron donating or electron withdrawing groups in benzoyl moiety. The orientation of the two aryl rings with respect to each other is neither in the same plane nor perpendicular. Hammett plot showed good linearity between substituent constant and the HOMO as well as LUMO energies. Mulliken and NBO charges indicate that the carbonyl carbon (C7) is more positively charged than the ipso carbon (C10), while the inspection of the coefficient on the carbonyl carbon and the ipso carbon atom for LUMO showed that its value is greater for C10 compared to C7. The correlation between the experimental and the theoretical results indicates that density functional theory B3LYP method is able to provide satisfactory results for predicting IR., UV and NMR properties. Crown Copyright (C). 2011 Published by Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2011.09.024

文献信息

• Reactivity of α-Amino Acids in the Reaction with Esters in Aqueous–1,4-Dioxane Media
  作者：L. B. Kochetova、T. P. Kustova、L. V. Kuritsyn

  DOI：10.1134/s1070363218010127

  日期：2018.1

  The kinetics of the reaction of a series of α-amino acids with 4-nitrophenyl acetate, 4-nitrophenyl benzoate, and 2,4,6-trinitrophenyl benzoate in aqueous 1,4-dioxane medium has been studied. Kinetics of the reactions involving 4-nitrophenyl acetate and 2,4,6-trinitrophenyl benzoate has complied with the Brønsted dependence and revealed linear correlation between rate constant logarithm and the energy

  研究了一系列α-氨基酸与4-硝基苯基乙酸酯，4-硝基苯基苯甲酸酯和2,4,6-三硝基苯基苯甲酸酯在1,4-二恶烷水溶液中的反应动力学。涉及乙酸4-硝基苯酯和2,4,6-三硝基苯甲酸苯酯的反应动力学符合布朗斯台德依赖性，并揭示了速率常数对数与α-氨基酸阴离子前沿轨道的能量差之间的线性关系。
• Anilinolysis of Picryl Benzoate Derivatives in Methanol: Reactivity, Regioselectivity, Kinetics, and Mechanism
  作者：Mahmoud F. Ibrahim、Mohamed A. El-Atawy、Samir K. El-Sadany、Ezzat A. Hamed

  DOI：10.1002/kin.20779

  日期：2013.9

  The reaction of picryl benzoate derivatives 1a–g with aniline in methanol proceeds through COO and ArO bond cleavage pathways. Furthermore, the reactivity of these esters toward anilinolysis is correlated to the energy gap between highest occupied molecular orbital aniline and lowest unoccupied molecular orbital of each ester. The regioselectivity of acyloxygen versus aryloxygen cleavage is also

  甲醇中苯甲酸吡啶酯衍生物1a–g与苯胺在甲醇中的反应通过COO和ArO键的裂解途径进行。此外，这些酯对苯胺分解的反应性与每个酯的最高占据分子轨道苯胺和最低未占据分子轨道之间的能隙相关。还讨论了酰基氧对芳基氧裂解的区域选择性。整体速率常数ķ TOT分成ķ CO  Ô（酰基-氧裂解速率常数）和ķ氩 Ò（芳基氧裂解速率常数）。该CO 通过逐步机制O键裂解的进步，其中所述四面体中间体的形成是限速步骤。上述Ar  O键裂解继续通过A S Ñ其中所述离去基团从所述迈森海梅复杂离开其在速率决定步骤形成后迅速发生的Ar机制。
• Reactivity of Tyrosyl–Proline toward Benzoylation in Aqueous 1,4-Dioxane
  作者：T. P. Kustova、I. I. Lokteva、L. B. Kochetova、D. S. Khachatryan

  DOI：10.1134/s1070428020060111

  日期：2020.6

  The kinetics of the reaction of L-tyrosyl-L-proline (Tyr-Pro) with di- and trinitrophenyl benzoates in aqueous 1,4-dioxane (40 wt % of water) were studied in the temperature range 298-313 K. The reaction rate constant k(298) was found to vary in the range from 0.035 to 0.564 L.mol(-1).s(-1), and the activation barrier changed from 39 to 51 kJ/mol. The neutral and anionic forms of the dipeptide were simulated by the DFT/B3LYP/cc-pVTZ method. Natural bond orbital analysis of the electron density distribution in these forms showed that the preferred nucleophilic center in the dipeptide molecule is the nitrogen atom of the primary amino group rather than the oxygen atom of the phenolic hydroxy group.
• Belousova; Simanenko; Savelova, Russian Journal of Organic Chemistry, 2000, vol. 36, # 11, p. 1656 - 1664
  作者：Belousova、Simanenko、Savelova、Suprun

  DOI：——

  日期：——
• Effect of pH on the reactivity of dipeptides and α-amino acids in the N-acylation
  作者：L. V. Kuritsyn、N. V. Kalinina、L. B. Kochetova

  DOI：10.1134/s1070363212110126

  日期：2012.11

  The reaction kinetics of Gly, L-alpha-Ala, Gly-Gly, L-alpha-Ala-L-alpha-Ala and beta-Ala-beta-Ala with picryl benzoate in water (40 wt %)-2-propanol was investigated. At pH = 4-8 the rate constants of N-acylation of the anionic form of dipeptides are less than those of the corresponding amino acid anions, in agreement with their basicity, whereas the relative effective rate constants of reactions depend on pH: in acidic, neutral and slightly alkaline media the k (ef) values are higher for the dipeptides, and in a strongly alkaline medium, for the amino acids. These differences are due to the changes in the concentrations of reactive forms of amino acids and dipeptides in the system at varying the medium pH.