2-((2-methyl-1H-indol-3-yl)methylene)malononitrile | 307338-60-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 2-((2-methyl-1H-indol-3-yl)methylene)malononitrile
• 英文别名: 2-[(2-methyl-1H-indol-3-yl)methylene]malononitrile；[(2-methyl-1H-indol-3-yl)methylene]malononitrile；2-[(2-methyl-1H-indol-3-yl)methylidene]propanedinitrile
• CAS: 307338-60-9
• 化学式: C₁₃H₉N₃
• 分子量: 207.235
• InChiKey: PVDNDPALUADGTO-UHFFFAOYSA-N

物化性质

• 沸点：
  433.3±40.0 °C(Predicted)
• 密度：
  1.277±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  63.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基吲哚 在 苯甲酰氯 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.75h， 生成 2-((2-methyl-1H-indol-3-yl)methylene)malononitrile
  参考文献：
  名称：

  通过亚胺盐与活性亚甲基试剂的原位缩合非常规立体选择性一锅合成Knoevenagel型吲哚

  摘要：

  描述了一种简单的一锅法，用于立体选择性合成Knoevenagel型吲哚。该方法基于在三乙胺存在下吲哚亚胺盐（已充分表征其中的四种）与无环对称和不对称活性亚甲基试剂的原位反应。总的来说，总产量是中等至良好。讨论了影响立体选择性的一些相关反应参数和空间效应。

  DOI：

  10.1016/j.tet.2013.10.086

文献信息

• Exploiting the Distal Reactivity of Indolyl Methylenemalononitriles: An Asymmetric Organocatalyzed [4+2] Cycloaddition with Enals Enables the Assembly of Elusive Dihydrocarbazoles
  作者：Gloria Rassu、Claudio Curti、Vincenzo Zambrano、Luigi Pinna、Nicoletta Brindani、Giorgio Pelosi、Franca Zanardi

  DOI：10.1002/chem.201602793

  日期：2016.8.26

  generation of indolyl ortho‐quinodimethanes from 2‐methylindole‐based methylenemalononitriles by amine‐mediated remote C(sp3)−H deprotonation was developed. These intermediates were efficiently trapped by diverse enals to provide a rapid entry to 2,9‐dihydro‐1H‐carbazole‐3‐carboxyaldehyde structures through a formal asymmetric [4+2] eliminative cycloaddition governed by a α,α‐diphenylprolinol trimethylsilyl

  通过胺介导的远程C（sp 3）-H去质子化作用，从2-甲基吲哚基的亚甲基丙二腈原位生成吲哚基邻喹啉甲烷的空前技术得到了发展。这些中间体被各种烯类有效地捕获，可以通过由α，α-二苯基脯氨醇三甲基甲硅烷基醚控制的形式不对称[4 + 2]消除环加成反应，快速进入2,9-二氢-1 H-咔唑-3-羧醛结构催化剂。
• Synthesis of Some Novel 3-Substituted Indole Derivatives Using Polyamine Functionalized Heterogeneous Catalyst
  作者：Rupali L. Magar、Prashant B. Thorat、Jagdish L. Waware、Rameshwar R. More、Usha A. Solanke、Bhagwan R. Patil、Rajendra P. Pawar

  DOI：10.1002/jhet.2265

  日期：2015.11

  have described the use of polyamine solid supported GN3 as catalyst in organic transformations using 1H‐indole‐3‐carbaldehyde. To the best of our knowledge, reports for the synthesis of chromen substituted at 3C position of indole are extremely rare in the literature. The polyamine functionalized immobilized silica (GN3) was found to be an excellent catalyst for synthesis of novel 2‐amino‐4‐(1H‐indol‐3‐yl)‐5‐oxo‐4

  在目前的工作中，我们已经描述了使用多胺固体负载的GN3作为催化剂使用1 H-吲哚-3-甲醛进行有机转化。据我们所知，在文献中极少见有吲哚的3C位取代的铬烯合成报告。发现多胺官能化的固定化二氧化硅（GN3）是合成新型2-氨基-4-（（1 H-吲哚-3-基）-5-氧代-4,5-二氢吡喃[3,2- c ]色烯-3-腈衍生物和Knoevenagel缩合。催化剂GN3能够为多种产品提供出色的产量。此外，该催化剂可重复使用并重复使用几次，而不会损失其催化活性。
• A Short, Novel, and Practical Synthesis of 3-Alkenylated Indoles
  作者：Mojgan Kargar、Rahim Hekmatshoar、Abdol Jalil Mostashari

  DOI：10.1080/00397911.2012.666817

  日期：2013.6.18

  Abstract Direct metal-free alkenylation of 2-methylindole via acid-mediated Michael addition–elimination reaction with ethoxymethylenemalononitrile or ethyl ethoxymethylenecyanoacetate affords 3-indolyl-2-cyanoacrylonitrile and ethyl 3-indolyl-2-cyanoacrylate. Behavior of 1H-indole is predictably different. GRAPHICAL ABSTRACT

  摘要 2-甲基吲哚通过酸介导的迈克尔加成消除反应与乙氧基亚甲基丙二腈或乙氧基亚甲基氰基乙酸乙酯直接无金属烯基化，得到3-吲哚基-2-氰基丙烯腈和3-吲哚基-2-氰基丙烯酸乙酯。1H-吲哚的行为可以预见是不同的。图形概要
• Unconventional Knoevenagel-type indoles: Synthesis and cell-based studies for the identification of pro-apoptotic agents
  作者：Andrea Spallarossa、Chiara Caneva、Matteo Caviglia、Silvana Alfei、Stefania Butini、Giuseppe Campiani、Sandra Gemma、Margherita Brindisi、Daniela M. Zisterer、Sandra A. Bright、Clive D. Williams、Emmanuele Crespan、Giovanni Maga、Giuseppina Sanna、Ilenia Delogu、Gabriella Collu、Roberta Loddo

  DOI：10.1016/j.ejmech.2015.08.009

  日期：2015.9

  A new series of indole-based analogues were recently identified as potential anticancer agents. The Knoevenagel-type indoles herein presented were prepared via a one-pot condensation of iminium salts with active methylene reagents and were isolated as single geometric isomers. Biological evaluation in different cell-based assays revealed an antiproliferative activity for some analogues already in the nanomolar range against leukaemia, breast. and renal cancer cell lines. To explain these effects, the most promising analogues of the series were engaged in further cell-based studies. Compounds 5e, I, p and 6a, b highlighted a pro-apoptotic potential being able to induce apoptosis in HL60, K562 and MCF-7 cell lines in a dose and time-dependent manner. The ability of these compounds to arrest cell cycle at the G2/M phase inspired the immunofluorescence studies which allowed us to identify tubulin as a potential target for compounds 5l and 6b. (C) 2015 Elsevier Masson SAS. All rights reserved.
• Unconventional stereoselective one-pot synthesis of Knoevenagel-type indoles via in situ condensation of iminium salts with active methylene reagents
  作者：Angelo Ranise、Francesco Lucchesini、Matteo Caviglia、Silvana Alfei、Andrea Spallarossa、Chiara Caneva

  DOI：10.1016/j.tet.2013.10.086

  日期：2013.12

  Knoevenagel-type indoles is described. The method is based on the in situ reaction of indole iminium salts (four of them are fully characterized) with acyclic symmetrical and unsymmetrical active methylene reagents in the presence of triethylamine. In general, the overall yields are moderate to good. Some of relevant reaction parameters and steric effects affecting stereoselectivity are discussed.

  描述了一种简单的一锅法，用于立体选择性合成Knoevenagel型吲哚。该方法基于在三乙胺存在下吲哚亚胺盐（已充分表征其中的四种）与无环对称和不对称活性亚甲基试剂的原位反应。总的来说，总产量是中等至良好。讨论了影响立体选择性的一些相关反应参数和空间效应。