N,N-diethyl-2-(4-nitrophenyl)acetamide | 50507-86-3

• 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: N,N-diethyl-2-(4-nitrophenyl)acetamide
• CAS: 50507-86-3
• 化学式: C₁₂H₁₆N₂O₃
• 分子量: 236.271
• InChiKey: GDKVFFXDYCFHIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  66.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N-diethyl-2-(4-nitrophenyl)acetamide 在 sodium tetrahydroborate 、 10% palladium on activated charcoal 、 三氟化硼乙醚 、 氢气 、 三乙胺 、 barium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 生成 4β-(N-[4-[2-(diethylamino)ethyl]phenyl]amino)-4'-O-demethyl-4-desoxypodophyllotoxin
  参考文献：
  名称：

  Synthesis and biological evaluation of new 4β-anilino-4′-O-demethyl-4-desoxypodophyllotoxin derivatives as potential antitumor agents

  摘要：

  A series of new 4 beta-anilino-4'-O-demethyl-4-desoxypodophyllotoxin derivatives were prepared and evaluated for their cytotoxicities against four human cancer cell lines including KB, KB/VCR, A549 and 95D. Most compounds showed better growth-inhibition activities against tested cell lines than that of etoposide (VP-16). Preliminary structure-activity relationships (SARs) were concluded and it indicated that the side chains substituted at 4 beta position of podophyllotoxin significantly influenced the cytotoxic activity, especially for the drug resistance profile. In vivo studies of compound 26c on highly metastatic human lung cancer xenograft in nude mice showed that it can significantly inhibit tumor growth with administrating by oral route. (C) 2010 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2010.11.016
• 作为产物：
  描述：

  5-[(3-羧基-5-甲基-4-羰基-2,5-环己二烯-1-亚基)[4-(二乙胺基)苯基]甲基]-3-甲基水杨基<邻羟苄基>酸 在 水 作用下， 以 乙醚 为溶剂， 反应 3.5h， 生成 N,N-diethyl-2-(4-nitrophenyl)acetamide
  参考文献：
  名称：

  1-（芳基乙炔基）氮丙啶的合成

  摘要：

  DOI：

  10.1007/bf00475469

文献信息

• Ketene Reactions with Tertiary Amines
  作者：Annette D. Allen、John Andraos、Thomas T. Tidwell、Sinisa Vukovic

  DOI：10.1021/jo402438w

  日期：2014.1.17

  zwitterions, and these undergo amine catalyzed dealkylation forming N,N-disubstituted amides. Reactions of N-methyldialkylamines show a strong preference for methyl group loss by displacement, as predicted by computational studies. Loss of ethyl groups in reactions with triethylamine also occur by displacement, but preferential loss of isopropyl groups in the phenylketene reaction with diisopropylethylamine

  叔胺在乙腈中与芳基烯酮快速可逆地反应，形成可观察到的两性离子，并且这些胺经历胺催化的脱烷基化反应，形成N，N-二取代的酰胺。N-甲基二烷基胺的反应显示出对取代引起的甲基损失的强烈偏好，如计算研究所预测的那样。与三乙胺反应中乙基的损失也可通过置换而发生，但苯乙烯酮与二异丙基乙胺反应中异丙基的优先损失显然涉及消除。奎尼丁与芳基乙烯酮迅速形成长寿命的两性离子，为金鸡纳和相关生物碱在乙烯酮的立体选择性加成中提供了催化模型。
• Direct Amidation of Carboxylic Acids with Tertiary Amines: Amide Formation over Copper Catalysts through C-N Bond Cleavage
  作者：Biquan Xiong、Longzhi Zhu、Xiaofeng Feng、Jian Lei、Tieqiao Chen、Yongbo Zhou、Li-Biao Han、Chak-Tong Au、Shuang-Feng Yin

  DOI：10.1002/ejoc.201402332

  日期：2014.7

  A copper-catalyzed system for the amidation of carboxylic acids with tert-amines through C–N bond cleavage was developed. This protocol is practical and represents a simple way to produce functionalized amides from basic starting materials in moderate to good yields. A plausible mechanism is proposed for the reaction.

  开发了一种铜催化系统，用于羧酸与叔胺通过 C-N 键裂解进行酰胺化。该协议是实用的，代表了一种从基本原料中以中等至良好的产率生产功能化酰胺的简单方法。提出了一个合理的反应机理。
• Palladium-Catalyzed Intermolecular α-Arylation of Zinc Amide Enolates under Mild Conditions
  作者：Takuo Hama、Darcy A. Culkin、John F. Hartwig

  DOI：10.1021/ja056076i

  日期：2006.4.1

  The intermolecular α-arylation and vinylation of amides by palladium-catalyzed coupling of aryl bromides and vinyl bromides with zinc enolates of amides is reported. Reactions of three different types of zinc enolates have been developed. The reactions of aryl halides occur in high yields with isolated Reformatsky reagents generated from α-bromo amides, with Reformatsky reagents generated in situ from

  报道了通过芳基溴化物和乙烯基溴化物与酰胺的烯醇锌的钯催化偶联，酰胺的分子间α-芳基化和乙烯基化。已经开发了三种不同类型的烯醇化锌的反应。芳基卤化物与由 α-溴酰胺产生的分离的 Reformatsky 试剂、由 α-溴酰胺原位产生的 Reformatsky 试剂以及通过用氯化锌淬灭酰胺的烯醇锂而产生的烯醇锌以高产率发生反应。这种使用锌烯醇化物代替碱金属烯醇化物极大地扩展了酰胺芳基化的范围。该反应在室温或 70 °C 下与含有氰基、硝基、酯、酮、氟、羟基或氨基官能团的溴芳烃以及溴吡啶发生反应。此外，该反应已开发与吗啉酰胺，其产物是酮和醛的前体。酰胺的烯醇锌的芳基化是用带有受阻五苯的催化剂进行的...
• Amination of phenylketenes. Substituent effect on amine-catalyzed tautomerization of amide enol
  作者：Md. Mizanur Rahman Badal、Min Zhang、Shinjiro Kobayashi、Masaaki Mishima

  DOI：10.1002/poc.3162

  日期：2013.12

  reaction of substituted phenylketenes with diethylamine in acetonitrile were suggested to be the amide enols rather than the zwitterions on the basis of the theoretical calculations. A single broad band at 1674 cm−1 observed for reaction with the primary amines was attributed to overlap of two bands of the intermediate (amide enol) and the final product (amide). The substituent effect for the second‐order

  根据理论计算，在取代的乙烯酮与二乙胺在乙腈中的反应中观察到的在1676–1680 cm -1处具有红外波段的瞬态中间体被认为是酰胺烯醇而不是两性离子。与伯胺反应观察到的在1674 cm -1的单个宽带归因于中间体（酰胺烯醇）和最终产物（酰胺）的两个谱带的重叠。由汤川-津野方程成功地分析了酰胺烯醇中间体的二乙胺-催化的互变异构化的二阶速率常数，得到酰胺的取代基的效果，给出0.63ρ值和- [R - 1.31值。的[R -苯酚的pK a的值大于1时，表明在过渡状态下酰胺烯醇的氧原子上形成的负电荷通过乙烯基显着离位到芳族π系统中。这[R -值被认为反映β-phenylenolate骨架的内在属性。ρ值非常小，归因于循环过渡结构，其中负电荷分散在六元环中。版权所有©2013 John Wiley＆Sons，Ltd.
• General Synthesis of Fully Substituted 4-Aminooxazoles from Amides and 1,4,2-Dioxazol-5-ones Based on Amide Activation and Umpolung Process
  作者：Yunxiang Weng、Lin Min、Lidong Shan、Hongchen Li、Xinyan Wang、Yuefei Hu

  DOI：10.1021/acs.joc.0c02015

  日期：2021.1.1

  A general and efficient synthesis of fully substituted 4-aminodixazoles was developed based on the strategies of amide activation and umpolung reaction. In this method, 1,4,2-dioxazol-5-ones were introduced as a rare type of umpolung reagent bearing a nucleophilic N-atom that could be used well together with the activating agent Tf2O. Because 1,4,2-dioxazol-5-ones played triple roles as an umpolung

  基于酰胺活化和化学反应的策略，开发了一种通用且有效的全取代4-氨基二唑合成方法。在这种方法中，引入了1,4,2-二恶唑-5-酮作为一种稀有类型的带有亲核性N原子的umpolung试剂，可以与活化剂Tf 2 O一起很好地使用。因为1,4,2 -dioxazol-5-ones作为一种物质，可作为基质保护剂，底物和弱碱，在极为方便的条件下顺利进行。