2-(2-aminophenyl)-1-methyl-1H-benzimidazole-4-carboxylic acid | 560086-22-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 英文名称: 2-(2-aminophenyl)-1-methyl-1H-benzimidazole-4-carboxylic acid
• 英文别名: 1H-Benzimidazole-4-carboxylic acid, 2-(2-aminophenyl)-1-methyl-；2-(2-aminophenyl)-1-methylbenzimidazole-4-carboxylic acid
• CAS: 560086-22-8
• 化学式: C₁₅H₁₃N₃O₂
• 分子量: 267.287
• InChiKey: VUWSBNTVIVITPN-UHFFFAOYSA-N

物化性质

• 熔点：
  214.0-215.0 °C(Solv: ethanol (64-17-5))
• 沸点：
  561.5±56.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  81.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(2-aminophenyl)-1-methyl-1H-benzimidazole-4-carboxylic acid 在 N-甲基吗啉 、 (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate 作用下， 以 二氯甲烷 为溶剂， 反应 144.0h， 以46%的产率得到33,34-Dimethyl-8,16,24,32,33,34-hexazaheptacyclo[28.2.1.114,17.02,7.010,15.018,23.026,31]tetratriaconta-1(32),2,4,6,10(15),11,13,16,18,20,22,26(31),27,29-tetradecaene-9,25-dione
  参考文献：
  名称：

  Ruffling-Induced Chirality:  Synthesis, Metalation, and Optical Resolution of Highly Nonplanar, Cyclic, Benzimidazole-Based Ligands

  摘要：

  Expedient five-step syntheses of a cyclic bis(benzimidazole)-based amide 5 and two sterically more hindered analogues 23-24 have been developed. These amides are chiral due to the inherent ruffling of the macrocyclic plane. Racemization of the optical antipodes of these compounds has been studied using dynamic chiral stationary phase HIPLC. These studies reveal that, while the parent amide 5 racemizes rapidly, for the sterically more hindered amides 23-24, the rate of racemization is significantly reduced. Bis(benzimidazole)-based amides 5 and 23-24 form stable Ni(II) complexes 25-27, respectively. Like their parent ligands, complexes 25-27 are chiral due to their highly ruffled geometry. Studies of these complexes by chiral stationary phase HPLC reveal that metalation leads to a much lower rate of racemization. Incorporation of a strap can slow racemization even further. A series of strapped cyclic amides 54-57, along with their corresponding dinners 58-61, have been prepared. The rate of racernization for amides 54-57 is strongly dependent on the length of the strap. X-ray single-crystal structure analysis of the Ni(II) complex of strapped amide 54 reveals that the bis(benzimidazole) core retains its highly ruffled shape, with the two phenyl rings of the macrocycle located anti to the strap. Chiral separation of strapped ligands 54-57 and their corresponding Ni(II) complexes is shown to be facile by chiral stationary phase HPLC.

  DOI：

  10.1021/ja030196d
• 作为产物：
  描述：

  邻硝基苯甲酸 在 palladium on activated charcoal sodium hydroxide 、 草酰氯 、 氢气 、 sodium hydride 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 68.42h， 生成 2-(2-aminophenyl)-1-methyl-1H-benzimidazole-4-carboxylic acid
  参考文献：
  名称：

  Ruffling-Induced Chirality:  Synthesis, Metalation, and Optical Resolution of Highly Nonplanar, Cyclic, Benzimidazole-Based Ligands

  摘要：

  Expedient five-step syntheses of a cyclic bis(benzimidazole)-based amide 5 and two sterically more hindered analogues 23-24 have been developed. These amides are chiral due to the inherent ruffling of the macrocyclic plane. Racemization of the optical antipodes of these compounds has been studied using dynamic chiral stationary phase HIPLC. These studies reveal that, while the parent amide 5 racemizes rapidly, for the sterically more hindered amides 23-24, the rate of racemization is significantly reduced. Bis(benzimidazole)-based amides 5 and 23-24 form stable Ni(II) complexes 25-27, respectively. Like their parent ligands, complexes 25-27 are chiral due to their highly ruffled geometry. Studies of these complexes by chiral stationary phase HPLC reveal that metalation leads to a much lower rate of racemization. Incorporation of a strap can slow racemization even further. A series of strapped cyclic amides 54-57, along with their corresponding dinners 58-61, have been prepared. The rate of racernization for amides 54-57 is strongly dependent on the length of the strap. X-ray single-crystal structure analysis of the Ni(II) complex of strapped amide 54 reveals that the bis(benzimidazole) core retains its highly ruffled shape, with the two phenyl rings of the macrocycle located anti to the strap. Chiral separation of strapped ligands 54-57 and their corresponding Ni(II) complexes is shown to be facile by chiral stationary phase HPLC.

  DOI：

  10.1021/ja030196d

文献信息

• [EN] STRAPPED AND MODIFIED BIS (BENZIMIDAZOLE) DIAMIDES FOR ASYMMETRIC CATALYSTS AND OTHER APPLICATIONS<br/>[FR] BIS(BENZIMIDAZOLE)DIAMIDES PONTES ET MODIFIES POUR CATALYSEURS ASYMETRIQUES ET AUTRES APPLICATIONS
  申请人：UNIV OHIO STATE RES FOUND

  公开号：WO2003057667A2

  公开（公告）日：2003-07-17

  New compounds that are similar in function to tetrapyrrole ligands are provided. The basic framework consists of three classes of homochiral cyclic bis(benzimidazole) ligands: (1) bis(benzamidazoles) having Schiff base linkages; (2) bis(benzimidazoles) with diamime linkages; and (3) bis(benzimidazoles) with diamide linkages. Complexes of these ligands are also provided. The bis(benzimidazole) ligands further comprise a strap that lessens or precludes racemization of ligands or their complexes. These homochiral ligands are useful as catalysts for many types of reactions, including asymmetric epoxidation, epoxide ring opening. Diels-Alder, hereto Diels-Alder, asymmetric oxidation of benzylic hydrocarbons, oxidation of sulfides, hydroxylation, aziridination, cyclopropanation, kinetic resolution of allenes and other cumulenes, and the addition of HCN to imines. Also provided are polymer supports comprising the homochiral bis(benzimidazole) ligands and complexes.
• Ruffling-Induced Chirality:  Synthesis, Metalation, and Optical Resolution of Highly Nonplanar, Cyclic, Benzimidazole-Based Ligands
  作者：Tomasz Fekner、Judith Gallucci、Michael K. Chan

  DOI：10.1021/ja030196d

  日期：2004.1.1

  Expedient five-step syntheses of a cyclic bis(benzimidazole)-based amide 5 and two sterically more hindered analogues 23-24 have been developed. These amides are chiral due to the inherent ruffling of the macrocyclic plane. Racemization of the optical antipodes of these compounds has been studied using dynamic chiral stationary phase HIPLC. These studies reveal that, while the parent amide 5 racemizes rapidly, for the sterically more hindered amides 23-24, the rate of racemization is significantly reduced. Bis(benzimidazole)-based amides 5 and 23-24 form stable Ni(II) complexes 25-27, respectively. Like their parent ligands, complexes 25-27 are chiral due to their highly ruffled geometry. Studies of these complexes by chiral stationary phase HPLC reveal that metalation leads to a much lower rate of racemization. Incorporation of a strap can slow racemization even further. A series of strapped cyclic amides 54-57, along with their corresponding dinners 58-61, have been prepared. The rate of racernization for amides 54-57 is strongly dependent on the length of the strap. X-ray single-crystal structure analysis of the Ni(II) complex of strapped amide 54 reveals that the bis(benzimidazole) core retains its highly ruffled shape, with the two phenyl rings of the macrocycle located anti to the strap. Chiral separation of strapped ligands 54-57 and their corresponding Ni(II) complexes is shown to be facile by chiral stationary phase HPLC.