N-ethyl-N-(1-methoxyethyl)benzamide

• 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-ethyl-N-(1-methoxyethyl)benzamide
• 化学式: C₁₂H₁₇NO₂
• 分子量: 207.272
• InChiKey: JWHKSEATPXUMTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 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：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  苯甲酸 在 叠氮基三甲基硅烷 、 tetrabutylammonium tetrafluoroborate 、 N,N-二甲基甲酰胺 作用下， 以 乙腈 为溶剂， 反应 6.08h， 生成 N-ethyl-N-(1-methoxyethyl)benzamide
  参考文献：
  名称：

  三甲基甲硅烷基叠氮化物促进 N,N-二烷基酰胺的 Shono 氧化

  摘要：

  开发了通过 Shono 反应对N , N-二烷基酰胺进行烷氧基化的方法，该方法提供了一种简单有效的方法来获得 N-邻碳取代酰胺。TMSN 3在此转化中发挥着重要作用，并允许反应在温和条件下以广泛的底物范围进行。与经典方法相比，该反应在较低的电流下进行，并且产物产率高达 91%。基于控制实验提出了一种可能的机制。

  DOI：

  10.1055/a-2159-4847

文献信息

• Chemoselective Electrosynthesis Using Rapid Alternating Polarity
  作者：Yu Kawamata、Kyohei Hayashi、Ethan Carlson、Shobin Shaji、Dirk Waldmann、Bryan J. Simmons、Jacob T. Edwards、Christoph W. Zapf、Masato Saito、Phil S. Baran

  DOI：10.1021/jacs.1c06572

  日期：2021.10.13

  in the selective manipulation of functional groups (chemoselectivity) in organic synthesis have historically been overcome either by using reagents/catalysts that tunably interact with a substrate or through modification to shield undesired sites of reactivity (protecting groups). Although electrochemistry offers precise redox control to achieve unique chemoselectivity, this approach often becomes challenging

  有机合成中选择性操纵官能团（化学选择性）的挑战历来通过使用与底物可调节相互作用的试剂/催化剂或通过修饰以屏蔽不需要的反应位点（保护基团）来克服。尽管电化学提供了精确的氧化还原控制以实现独特的化学选择性，但在存在多种氧化还原活性功能的情况下，这种方法通常变得具有挑战性。从历史上看，电合成几乎完全使用直流电（DC）进行。相比之下，众所周知，应用交流电 (AC) 可以在分析规模上显着改变反应结果，但很少被战略性地用于复杂的制备有机合成。在这里，我们展示了如何使用方波来传递电流——快速交替极性（rAP）——能够控制羰基化合物化学选择性还原中的反应结果，这是最广泛使用的反应流形之一。观察到的反应性不能使用直流电解或化学试剂来重现。这种控制化学选择性的新方法所带来的合成价值在手性辅助去除等经典反应问题和PROTAC合成等前沿药物化学主题的背景下得到了生动的体现。
• Exploratory Synthetic Studies of the α-Methoxylation of Amides <i>via</i> Cuprous Ion-Promoted Decomposition of <i>o</i>-Diazobenzamides
  作者：Gyoonhee Han、Matthew G. LaPorte、Mathias C. McIntosh、Steven M. Weinreb、Masood Parvez

  DOI：10.1021/jo961529a

  日期：1996.1.1

  A convenient nonelectrochemical amide oxidation method has been developed. The process involves a cuprous ion-promoted decomposition of o-diazobenzamides like 4, generated in situ from the corresponding o-aminobenzamides, to give N-acyliminium ion intermediate 9 via a 1,5-H-atom transfer, followed by metal-catalyzed oxidation of the resulting alpha-amidyl radical. The transformation produces alpha-methoxybenzamides 15 in good yields. An attempt was made to apply this oxidation method to a total synthesis of the alkaloid (-)-anisomycin (16). Scalemic o-aminobenzamide pyrrolidine derivatives 18a/18b underwent oxidation to give a-methoxylated amide substrates 19a/ 19b, respectively, in good yields. However, alkylation of the N-acyliminium intermediate 20 with (p-methoxybenzyl)magnesium chloride gave the undesired anti-compounds 22a/22b as the major products. The amide oxidation exhibits good regioselectivity with many unsymmetrical 2-substituted piperidine and pyrrolidine systems. In general, it appears that the larger the C-2 substituent, the greater the methylene/methine H-atom abstraction ratio. A mechanistic rationale for this selectivity is suggested based upon amide rotamer populations. An extension of this methodology can be used to conduct two sequential amide oxidations using readily prepared 2-amino-6-nitrobenzamides such as 68 and 69.
• An experimentalist’s guide to electrosynthesis: the Shono oxidation
  作者：Paulino Alfonso-Súarez、Athanasios V. Kolliopoulos、Jamie P. Smith、Craig E. Banks、Alan M. Jones

  DOI：10.1016/j.tetlet.2015.10.090

  日期：2015.12

  Electrosynthesis is a powerful method to functionalise organic molecules without the need to use chemical reagents or protecting groups, yet it is not widely used in synthesis. In this study, we investigated the Shono oxidation of a tertiary amide (electrochemical functionalisation of a C-H bond adjacent to an amide nitrogen atom), demonstrating the value of performing cyclic voltammetry, varying voltage and charge per mole, selection of electrolyte and electrode material. We demystify the process to demonstrate a simple relationship between oxidation potential, and charge transfer required, which affords a high conversion to the desired alpha-methoxylated product using an undivided experimental cell. (C) 2015 Elsevier Ltd. All rights reserved.
• Trimethylsilyl Azide Promoted Shono Oxidation of N,N-Dialkyl Amides
  作者：Shengmei Guo、Hu Cai、Wenlin Luo、Ruixing Zhang、Qi Xu、Shengyu Zheng、Junpeng Yang、Meixia Liu

  DOI：10.1055/a-2159-4847

  日期：2023.12

  An alkoxylation of N,N-dialkyl amides by the Shono reaction has been developed that offers a simple and efficient way to access N-adjacent-carbon-substituted amides. TMSN3 plays an essential role in this transformation and permits the reaction to proceed with a broad substrate scope under mild conditions. This reaction proceeds at a lower current compared with the classical method and it affords the

  开发了通过 Shono 反应对N , N-二烷基酰胺进行烷氧基化的方法，该方法提供了一种简单有效的方法来获得 N-邻碳取代酰胺。TMSN 3在此转化中发挥着重要作用，并允许反应在温和条件下以广泛的底物范围进行。与经典方法相比，该反应在较低的电流下进行，并且产物产率高达 91%。基于控制实验提出了一种可能的机制。