2-(chloromethyl)-4,7-dimethoxy-1-methyl-1H-benzimidazole | 99922-29-9

• 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-(chloromethyl)-4,7-dimethoxy-1-methyl-1H-benzimidazole
• 英文别名: NoName_3872；2-(chloromethyl)-4,7-dimethoxy-1-methylbenzimidazole
• CAS: 99922-29-9
• 化学式: C₁₁H₁₃ClN₂O₂
• 分子量: 240.689
• InChiKey: YGJBMYVDJNDQFZ-UHFFFAOYSA-N

物化性质

• 沸点：
  406.4±35.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(chloromethyl)-4,7-dimethoxy-1-methyl-1H-benzimidazole 在 盐酸 、 氢溴酸 作用下， 反应 75.0h， 生成 1-methyl-2-(chloromethyl)-4,7-dimethoxybenzimidazole hydrochloride
  参考文献：
  名称：

  Studies of extended quinone methides. The hydrolysis mechanism of 1-methyl-2-(bromomethyl)-4,7-dihydroxybenzimidazole

  摘要：

  DOI：

  10.1021/jo00354a023
• 作为产物：
  描述：

  1-Methyl-2-(bromomethyl)-4,7-dimethoxybenzimidazole 在 buffer (pH 0 - 9) 、 potassium chloride 作用下， 以 水 、 二甲基亚砜 为溶剂， 生成 1-methyl-2-(hydroxymethyl)-4,7-dimethoxybenzimidazole 、 2-(chloromethyl)-4,7-dimethoxy-1-methyl-1H-benzimidazole
  参考文献：
  名称：

  Formation and fate of benzimidazole-based quinone methides. Influence of pH on quinone methide fate

  摘要：

  The influence of pH on quinone methide fate was assessed from a comparative hydrolytic study of benzimidazole hydroquinones and their O-methylated analogues. Elimination of a leaving group from the hydroquinones affords the carbocation or the quinone methide depending on the pH. The O-methylated analogues, on the other hand, can only afford the carbocation species. Evidence is presented herein that the quinone methide species is reversibly protonated to afford the carbocation species. The acid dissociation constant for this equilibrium is pK(a) 5.5. Above pH 5.5, the quinone methide species traps both nucleophiles and the proton. Below pH 5.5, the quinone methide species is protonated to afford the carbocation species, which exclusively traps nucleophiles. Therefore, the carbocation acid dissociation constant can be used to predict quinone methide fate as a function of pH.

  DOI：

  10.1021/jo00048a020

文献信息

• Visible-light unmasking of heterocyclic quinone methide radicals from alkoxyamines
  作者：Patrick Kielty、Pau Farràs、Patrick McArdle、Dennis A. Smith、Fawaz Aldabbagh

  DOI：10.1039/c9cc08261a

  日期：——

  In nature, the unmasking of heterocyclic quinones to form stabilized quinone methide radicals is achieved using reductases (bioreduction). Herein, an alternative controllable room-temperature, visible-light activated protocol using alkoxyamines and bis-alkoxyamines is provided. Selective synthetic modification of the bis-alkoxyamine, allowed chromophore deactivation to give one labile alkoxyamine moiety

  本质上，使用还原酶（生物还原）实现杂环醌的不掩蔽以形成稳定的醌甲基化物自由基。本文中，提供了使用烷氧基胺和双烷氧基胺的替代性可控的室温可见光活化方案。对双烷氧基胺的选择性合成修饰，使生色团失活，从而得到一个不稳定的烷氧基胺部分。
• Visible Light Activated Benzimidazolequinone Alkoxyamines of 1,1,3,3‐Tetramethylisoindolin‐2‐yloxyl (TMIO)
  作者：Patrick Kielty、Benjamin A. Chalmers、Pau Farràs、Dennis A. Smith、Fawaz Aldabbagh

  DOI：10.1002/ejoc.202101183

  日期：2021.12.28

  The first room-temperature dissociation of alkoxyamines of TMIO is rationalized by using kinetics experiments, UV-Vis spectra and DFT-derived parameters. The visible light activation provides a benign alternative to Nature's bioreductive activation for the generation of potentially chemotherapeutic quinone methides.

  通过使用动力学实验、UV-Vis 光谱和 DFT 衍生参数合理化了 TMIO 烷氧基胺的首次室温解离。可见光激活为自然的生物还原激活提供了一种良性的替代方案，可用于产生潜在的化学治疗性醌甲基化物。
• Ring-fused dimethoxybenzimidazole-benzimidazolequinone (DMBBQ): tunable halogenation and quinone formation using NaX/Oxone
  作者：Darren Conboy、Patrick Kielty、Joseph C. Bear、Jeremy K. Cockcroft、Pau Farràs、Patrick McArdle、Richard J. Singer、Dennis A. Smith、Fawaz Aldabbagh

  DOI：10.1039/d1ob00032b

  日期：——

  A new one-pot electrophilic chlorination and bromination with oxidative demethylation uses harmless and inexpensive sodium chloride and sodium bromide with Oxone to yield alicyclic ring-fused bis-benzimidazolequinones.

  一种新的一锅法亲电氯化和溴化方法，采用无害且廉价的氯化钠和溴化钠与氧化剂Oxone结合，可以生成螺环状双苯并咪唑醌化合物，并伴随着氧化去甲基化反应。
• Synthesis and cytotoxicity evaluation of some benzimidazole-4,7-diones as bioreductive anticancer agents
  作者：Armand Gellis、Hervé Kovacic、Narimène Boufatah、Patrice Vanelle

  DOI：10.1016/j.ejmech.2007.11.020

  日期：2008.9

  New benzimidazole-4,7-diones substituted at 2-position were synthesized via a microwave-assisted reaction using 2-chloromethyl-1,5,6-tri-methyl-1H-benzimidazole-4,7-dione 5b as a key intermediate compound. Their cytotoxicity has been evaluated on colon, breast and lung cancer cell lines. The dimer 17 was shown to possess excellent cytotoxicity comparable to that of mitomycin C. (C) 2008 Published by Elsevier Masson SAS.
• Studies of extended quinone methides. The hydrolysis mechanism of 1-methyl-2-(bromomethyl)-4,7-dihydroxybenzimidazole
  作者：Edward B. Skibo

  DOI：10.1021/jo00354a023

  日期：1986.2