1-[(2-chloro)benzene]-3-[(2-carboxymethyl)benzene]triazene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-[(2-chloro)benzene]-3-[(2-carboxymethyl)benzene]triazene
• 英文别名: Methyl 2-[2-(2-chlorophenyl)iminohydrazinyl]benzoate
• 化学式: C₁₄H₁₂ClN₃O₂
• 分子量: 289.721
• InChiKey: OZVOTGAYPWSKEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  63
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-[(2-chloro)benzene]-3-[(2-carboxymethyl)benzene]triazene 在 disodium hydrogenphosphate 、 potassium dihydrogenphosphate 、 水 作用下， 以 甲醇 为溶剂， 生成 3-(2-chlorophenyl)benzo-1,2,3-triazin-4(3H)-one
  参考文献：
  名称：

  Steric Effects in the Base-Catalyzed Cyclization of 1-[2-(Methoxycarbonyl)phenyl]-3-(2-substituted Phenyl)triazenes

  摘要：

  合成了11种模型1-[2-(甲氧羰基)苯基]-3-(2-取代苯基)三氮唑，并在不同pH值的水甲醇缓冲溶液中研究了它们的环化动力学。3(2-取代苯基)苯并[d][1,2,3]三氮唑-4(3H)-酮被确定为环化产物。log k_obs与pH的图像呈线性关系，斜率为1。研究取代基在ortho位置的立体和电子效应表明，与N(3)氮键合的环上的取代基仅通过其立体效应影响环化速率，而其电子效应在统计学上是不显著的。这个事实可以用环从模型底物的剩余共轭碱基阴离子所在的平面倾斜来解释。假定和确认的涉及特定碱催化的B_Ac2机理从去质子化三氮唑开始，形成四面体中间体，最终消除甲醇酸根离子。其他机理，如通过酮中间体的消除-加成机理或涉及一般碱催化的机理，则不太可能。

  DOI：

  10.1135/cccc19982075
• 作为产物：
  描述：

  邻氯苯胺 、 邻氨基苯甲酸甲酯 在 盐酸 、 sodium nitrite 、 sodium acetate 作用下， 以 水 为溶剂， 反应 3.5h， 生成 1-[(2-chloro)benzene]-3-[(2-carboxymethyl)benzene]triazene
  参考文献：
  名称：

  镍，1,2,3-苯并三嗪-4（3H）-酮与苯并zy的脱氮环化反应用于构建菲啶酮骨架

  摘要：

  Ni（0）/ dppm催化的具有芳烃的1,2,3-苯并三嗪-4-（3 H）-酮的脱氮环化反应成功地合成了菲啶酮类化合物。制备了各种菲啶酮，收率良好至优异。基于此方法，合成了天然产物N-甲基crinasidine。

  DOI：

  10.1002/adsc.201701143

文献信息

• Steric Effects in the Base-Catalyzed Cyclization of 1-[2-(Methoxycarbonyl)phenyl]-3-(2-substituted Phenyl)triazenes
  作者：Miroslav Ludwig、Ingrid Bauerová

  DOI：10.1135/cccc19982075

  日期：——

  Eleven model 1-[2-(methoxycarbonyl)phenyl]-3-(2-substituted phenyl)triazenes were synthesized and their cyclization kinetics examined in aqueous-methanolic buffer solutions (51 wt.% methanol) at various pH values. 3(2-Substituted phenyl)benzo[d][1,2,3]triazin-4(3H)-ones were identified as the cyclization products. The log k_obs vs pH plot was linear with a slope of unity. Investigation of the steric and electronic effects of substituents in the ortho position revealed that substituents at the ring which is bonded to the N(3) nitrogen affect the cyclization rate through their steric effect only, while their electronic effects are statistically insignificant. This fact was explained in terms of the ring being tilted from the plane in which the remaining part of the conjugate base anion of the model substrate lies. The assumed and confirmed B_Ac2 mechanism involving specific base catalysis begins by deprotonation of the triazene giving rise to the conjugate base, continues with formation of a tetrahedral intermediate, and ends with elimination of the methanolate ion. Other mechanisms, such as the elimination-addition mechanism via a ketene intermediate or the mechanism involving general base catalysis, are unlikely.

  合成了11种模型1-[2-(甲氧羰基)苯基]-3-(2-取代苯基)三氮唑，并在不同pH值的水甲醇缓冲溶液中研究了它们的环化动力学。3(2-取代苯基)苯并[d][1,2,3]三氮唑-4(3H)-酮被确定为环化产物。log k_obs与pH的图像呈线性关系，斜率为1。研究取代基在ortho位置的立体和电子效应表明，与N(3)氮键合的环上的取代基仅通过其立体效应影响环化速率，而其电子效应在统计学上是不显著的。这个事实可以用环从模型底物的剩余共轭碱基阴离子所在的平面倾斜来解释。假定和确认的涉及特定碱催化的B_Ac2机理从去质子化三氮唑开始，形成四面体中间体，最终消除甲醇酸根离子。其他机理，如通过酮中间体的消除-加成机理或涉及一般碱催化的机理，则不太可能。
• Grammaticakis, Bulletin de la Societe Chimique de France, 1957, p. 129,130
  作者：Grammaticakis

  DOI：——

  日期：——
• Nickel-Catalyzed Denitrogenative Annulation of 1,2,3-Benzotriazin-4-(3<i>H</i> )-ones with Benzynes for Construction of Phenanthridinone Scaffolds
  作者：Vijaykumar H. Thorat、Nitinkumar Satyadev Upadhyay、Masahiro Murakami、Chien-Hong Cheng

  DOI：10.1002/adsc.201701143

  日期：2018.1.17

  The synthesis of phenanthridinones via denitrogenative annulation of 1,2,3‐benzotriazin‐4‐(3H)‐ones with arynes catalysed by Ni(0)/dppm was successfully developed. A variety of phenanthridinones were prepared in good to excellent yields. Based on this method, nature product, N‐methylcrinasidine, was synthesized.

  Ni（0）/ dppm催化的具有芳烃的1,2,3-苯并三嗪-4-（3 H）-酮的脱氮环化反应成功地合成了菲啶酮类化合物。制备了各种菲啶酮，收率良好至优异。基于此方法，合成了天然产物N-甲基crinasidine。
• Design, synthesis, characterization and electrocatalytic behaviour of a dinuclear palladium(I) complex supported by 1-[(2-chloro)benzene]-3-[(2-carboxmethyl)benzene]triazenide ions
  作者：Jun-Zheng Zhan、Zhen-Lang Xie、Qi-Hao Liu、Shu-Zhong Zhan

  DOI：10.1016/j.poly.2019.01.063

  日期：2019.5

  In the presence of HCl, the reaction of 2-chloroaniline, methyl anthranilate and sodium nitrite formed 1-[(2-chloro)benzene]-3-[(2-carboxymethyl)benzene]triazene (HL). In the presence of triethylamine (Et3N), the reaction of HL and [Pd(CH3CN)(2)]Cl-2 gave a new dinuclear triazenido complex, [Pd-2(1)(L)(2)] with metal-metal bond, which has been characterized by physico-chemical and spectroscopic methods. The irradiation by a 100-W high-pressure mercury lamp led to a cleavage of the Pd-Pd bond in [Pd-2(1)(L)(2)]. Electrochemical studies showed that [Pd-2(1)(L)(2)] can electro-catalyze hydrogen evolution both from acetic acid and water. Spectroscopic investigations indicated that the introduction of palladium ion leads the strength of photoluminescence of HL to a significant decrease. (C) 2019 Elsevier Ltd. All rights reserved.