N-allyl-4-methoxy-N-methylaniline | 150596-75-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: N-allyl-4-methoxy-N-methylaniline
• 英文别名: 4-methoxy-N-methyl-N-prop-2-enylaniline
• CAS: 150596-75-1
• 化学式: C₁₁H₁₅NO
• 分子量: 177.246
• InChiKey: PYOQLJOPPWUKFR-UHFFFAOYSA-N

物化性质

• 沸点：
  274.6±33.0 °C(Predicted)
• 密度：
  0.987±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-allyl-4-methoxy-N-methylaniline 在 iron(III) chloride hexahydrate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 14.5h， 生成 N-allyl-4-methoxy-N-methyl-2-(1-phenylvinyloxy)benzenamine
  参考文献：
  名称：

  铁 (III)-催化的 CH 官能化：N,N-二烷基苯胺的邻苯甲酰氧基化及其在 1,4-苯并恶氮中的应用

  摘要：

  介绍了通过邻位 N,N-二烷基苯胺的 C-H 官能化进行的 AC-O 键形成反应。铁催化的选择性邻苯甲酰氧基化遵循极性 Friedel-Crafts 机制，对苯胺的亲核性敏感。各种 N,N-二取代苯胺和 N-苯基杂环的苯甲酰氧基化是在极其温和的条件下进行的。此外，该方法已成功用于生成 1,4-苯并氧氮杂和 o-氨基苯酚。

  DOI：

  10.1002/ejoc.201402751
• 作为产物：
  描述：

  4-碘苯甲醚 在 lithium chloro-isopropyl-magnesium chloride 、 Li₂CoCl₄ 作用下， 以 四氢呋喃 为溶剂， 反应 32.25h， 生成 N-allyl-4-methoxy-N-methylaniline
  参考文献：
  名称：

  N-羟胺苯甲酸酯的钴催化新戊酸芳基和杂芳基锌的亲电胺化反应

  摘要：

  芳基-和三甲基乙酸盐heteroarylzinc可胺化以Ó在存在-benzoylhydroxylamines在25℃下2-4小时内2.5-5.0％氯化钴2 ⋅2的LiCl以提供相应的以良好的收率叔芳基化或heteroarylated胺。这种亲电胺化作用还提供了二芳基胺和芳基（杂芳基）胺的通道。使用该钴催化的胺化反应作为关键步骤，可以分六个步骤制备新的候选结核病药物（Q203），使总收率达到56％。

  DOI：

  10.1002/anie.201710931

文献信息

• Iron-Catalyzed Regioselective Direct Oxidative Aryl–Aryl Cross-Coupling
  作者：Malapaka Chandrasekharam、Barreddi Chiranjeevi、Kankatala S. V. Gupta、B. Sridhar

  DOI：10.1021/jo202152b

  日期：2011.12.16

  Regioselective iron-catalyzed cross-dehydrogenative coupling (CDC) of two aromatic compounds using tert-BuOOH as oxidant under mild conditions has been reported. The direct oxidative coupling reaction is selective toward creation of a carbon–carbon bond at the position ortho to the functional groups of the substrates, completely preventing the homocoupled products. The C–C bond-forming reaction makes

  据报道，在温和条件下，使用叔-BuOOH作为氧化剂的两种芳香族化合物的区域选择性铁催化的交叉脱氢偶联（CDC）。直接的氧化偶联反应对在基质功能基团邻位的碳-碳键产生选择性，从而完全阻止了均相偶联的产物。C–C键形成反应使该方法变得通用，从而导致功能化的2,2'-二取代联芳基。
• Copper‐Catalyzed 1,2‐Dicarbonylative Cyclization of Alkenes with Alkyl Bromides via Radical Cascade Process
  作者：Fengqian Zhao、Xing‐Wei Gu、Robert Franke、Xiao‐Feng Wu

  DOI：10.1002/anie.202214812

  日期：2022.12.5

  Here, we have described a new copper-catalyzed 1,2-dicarbonylative cyclization of 4-aryl-1-butenes with unactivated alkyl bromides. In this reaction, two carbonyl groups were introduced into the double bond by the insertion of two molecules of carbon monoxide, and four new C−C bonds could be constructed in one reaction. At the same time, the corresponding skeletons of α-tetralones as well as 2,3-d

  在这里，我们描述了一种新的铜催化的 4-芳基-1-丁烯与未活化的烷基溴的 1,2-二羰基环化反应。在该反应中，通过插入两分子一氧化碳将两个羰基引入双键，一次反应可构建四个新的CC键。同时顺利得到相应的α-四氢萘酮和2,3-二氢喹啉-4-酮骨架，通过后续衍生化也可以转化为三个连续的环状结构。
• A highly efficient method to access unprotected C-3 bifunctional quaternary 3-allyl-3-(amino)oxindoles
  作者：Xunbo Lu、Guoling Huang、Fangpeng Liang、Siyu Sun、Yalin Chen、Zi Liang

  DOI：10.1039/d3ob00478c

  日期：——

  possess 3-allyl and 3-amino simultaneously, was first achieved by employing an intermolecular [2,3]-sigmatropic rearrangement reaction between diazooxindoles and tertiary allylic amines. Utilizing readily available allylamines as the nitrogen and allyl source concurrently, a wide range of bio-active 3-allyl-3-(amino)oxindoles were obtained in excellent yields under very mild reaction conditions; meanwhile

  一种高效的 Rh( II ) 催化非自由基方案获得不含 NH 的 C-3 双功能羟吲哚，其同时具有 3-烯丙基和 3-氨基，首先通过采用分子间 [2,3]-σ 重排反应实现在二氮杂吲哚和烯丙基叔胺之间。同时利用现成的烯丙胺作为氮源和烯丙基源，在非常温和的反应条件下以优异的收率获得了多种具有生物活性的 3-allyl-3-(氨基)oxindoles；同时，TON 可高达 90 000。我们的研究通过研究铵盐叶立德与重氮酰胺的分子间重排填补了文献中的一个空白，这些重氮酰胺的研究相对较少。
• Lewis acid-promoted 3-aza-Cope rearrangement of N-alkyl-N-allylanilines
  作者：Lars G. Beholz、John R. Stille

  DOI：10.1021/jo00071a018

  日期：1993.9

  The 3-aza-Cope rearrangement of N-alkyl-N-allylaniline substrates, which required 250-degrees-C to proceed thermally, was promoted by Lewis acid reagents at 111-140-degrees-C. Systematic studies of this reaction were performed to examine a number of reaction variables such as concentration, the stoichiometry of the Lewis acid with the substrate, the optimum temperature for rearrangement, and the type of Lewis acid reagent. Of the many Lewis acids investigated, ZnCl2 (140-degrees-C) and Et2O.BF3 (111-degrees-C) were the most generally successful reagents for promoting the aromatic 3-aza-Cope rearrangement. With respect to substrate variation, the presence of a methoxy substituent para to the N-allyl group slowed the reaction slightly, while a meta substituent accelerated the rate of [3,3] rearrangement and produced moderate site selectivity on the aromatic ring. Lewis acid-promoted rearrangement of an unsymmetrically substituted allyl moiety resulted in [3,3] sigmatropic rearrangement to give the 1-hexen-3-yl substituent on the aromatic ring. Overall, both ZnCl2 and Et2O.BF3 were shown to efficiently accelerate the regiospecific 3-aza-Cope rearrangement of N-alkyl-N-allylanilines for the purpose of forming a carbon-carbon bond between a secondary alkyl substituent and an aromatic ring.
• Lewis acid-catalyzed reactions of N-allylanilines with diazo compounds involving aza-Claisen rearrangement
  作者：Alexander G. Badamshin、Leonid V. Spirikhin、Rinat F. Salikov、Vladimir A. Dokichev、Yury V. Tomilov

  DOI：10.1016/j.mencom.2015.11.013

  日期：2015.11

  N-Allyl-N-methylanilines react with methyl diazoacetate or diazoacetone in the presence of Y, Sc or Sm triflates to give the corresponding methyl N-(2-allylaryl)-N-methylglycinates or 2-allyl-N-methyl-N-(2-oxopropyl)aniline. The formation of these compounds involves the aza-Claisen rearrangement.