N-Methyl-3-(2-vinylphenyl)propionamide | 163810-50-2

• 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-Methyl-3-(2-vinylphenyl)propionamide
• 英文别名: 3-(2-ethenylphenyl)-N-methylpropanamide
• CAS: 163810-50-2
• 化学式: C₁₂H₁₅NO
• 分子量: 189.257
• InChiKey: WMJYWCLXTMKXJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-Methyl-3-(2-vinylphenyl)propionamide 在 sodium periodate 作用下， 以 甲醇 、 水 、 苯 为溶剂， 反应 15.0h， 生成 N-ethanesulfinylacetyl-N-methyl-3-(2-vinylphenyl)propionamide
  参考文献：
  名称：

  通过亚氨基亚砜的Pummerer环化-去质子化-环加成级联反应合成取代的2-吡啶酮。

  摘要：

  由δ-戊内酰胺分两步通过与乙基亚磺酰基乙酰氯一起加热然后高碘酸钠氧化来制备1-乙亚磺酰基乙酰基哌啶-2-酮。将亚氨基亚砜缓慢添加到甲苯，乙酸酐（10当量）和对甲苯磺酸（1摩尔％）的回流混合物中导致形成异丁香酮偶极，该偶极偶极子以高收率进行了双分子捕集。环加合物的立体化学归属是根据X射线晶体学确定的，这是相对于偶极的内环加成的结果。环加成的区域化学与HOMO-偶极子控制过程一致。制备了几种含有链烯基的相关亚氨基亚砜，并使其经受了Pummerer反应条件。由环化-去质子化序列形成的所得介电偶极子经过整个悬垂烯烃进行偶极环加成，从而以高收率提供分子内环加合物。在痕量对甲苯磺酸的存在下将这些环加合物暴露于乙酸酐会导致开环，从而产生5-乙酰氧基取代的2-吡啶酮。酰胺氮上的孤对电子有助于打开氧桥以产生瞬态N-酰基亚胺离子，随后失去质子。在某些情况下，带有氧桥的酰胺电子对从反平面排列部分扭曲，并且发生竞

  DOI：

  10.1021/jo982315r
• 作为产物：
  描述：

  三丁基乙烯基锡 、 3-(2-bromophenyl)-N-methylpropanamide 在 四(三苯基膦)钯 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以90%的产率得到N-Methyl-3-(2-vinylphenyl)propionamide
  参考文献：
  名称：

  An Approach to Lysergic Acid Utilizing an Intramolecular Isomuenchnone Cycloaddition Pathway

  摘要：

  A series of alkenyl- and alkynyl-substituted diazo imides were prepared to demonstrate that the intramolecular cycloaddition across a transient isomunchnone dipole was a viable approach to the quinoline ring system (rings C and D) of the ergot alkaloids. The diazo imides were synthesized by N-malonylacylation of the appropriate amide followed by exposure to standard diazo transfer conditions. The carbenoid intermediate derived by treatment of the diazo imide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Exposure of the olefinic cycloadduct to boron trifluoride etherate resulted in exclusive carbon-oxygen bond cleavage producing a transient N-acyliminium ion which undergoes rapid proton loss to afford an enamide derivative. In contrast, exposure of the acetylenic cycloadduct to boron trifluoride etherate resulted in exclusive carbon-nitrogen bond cleavage. The resulting oxonium ion underwent reduction with triethylsilane, producing a dihydrofuran derivative. In the absence of a reducing agent, the alkyne cycloadduct underwent a retro Diels-Alder reaction to give a substituted furan derivative in high yield. The Rh(II) acetate catalyzed reaction of the appropriate diazo imide precursor to lysergic acid resulted in a mixture of the desired dipolar cycloadduct as well as a C-H insertion product. Switching to rhodium(II) perfluorobutyrate as the catalyst significantly enhanced the cycloadditon pathway. The inability to carry out a double-bond isomerization thwarted our efforts to synthesize lysergic acid.

  DOI：

  10.1021/jo00114a017

文献信息

• Synthesis of Substituted 2-Pyridones via the Pummerer Cyclization−Deprotonation−Cycloaddition Cascade of Imidosulfoxides
  作者：Albert Padwa、Todd M. Heidelbaugh、Jeffrey T. Kuethe

  DOI：10.1021/jo982315r

  日期：1999.3.1

  p-toluenesulfonic acid results in ring opening to give 5-acetoxy-substituted 2-pyridones. The lone pair of electrons on the amide nitrogen assists in opening the oxy bridge to generate a transient N-acyliminium ion, which subsequently loses a proton. In certain cases, the amide electron pair with the oxy bridge is partially twisted from an antiperiplanar arrangement and a competive ring cleavage also occurs to

  由δ-戊内酰胺分两步通过与乙基亚磺酰基乙酰氯一起加热然后高碘酸钠氧化来制备1-乙亚磺酰基乙酰基哌啶-2-酮。将亚氨基亚砜缓慢添加到甲苯，乙酸酐（10当量）和对甲苯磺酸（1摩尔％）的回流混合物中导致形成异丁香酮偶极，该偶极偶极子以高收率进行了双分子捕集。环加合物的立体化学归属是根据X射线晶体学确定的，这是相对于偶极的内环加成的结果。环加成的区域化学与HOMO-偶极子控制过程一致。制备了几种含有链烯基的相关亚氨基亚砜，并使其经受了Pummerer反应条件。由环化-去质子化序列形成的所得介电偶极子经过整个悬垂烯烃进行偶极环加成，从而以高收率提供分子内环加合物。在痕量对甲苯磺酸的存在下将这些环加合物暴露于乙酸酐会导致开环，从而产生5-乙酰氧基取代的2-吡啶酮。酰胺氮上的孤对电子有助于打开氧桥以产生瞬态N-酰基亚胺离子，随后失去质子。在某些情况下，带有氧桥的酰胺电子对从反平面排列部分扭曲，并且发生竞
• An Approach to Lysergic Acid Utilizing an Intramolecular Isomuenchnone Cycloaddition Pathway
  作者：Joseph P. Marino、Martin H. Osterhout、Albert Padwa

  DOI：10.1021/jo00114a017

  日期：1995.5

  A series of alkenyl- and alkynyl-substituted diazo imides were prepared to demonstrate that the intramolecular cycloaddition across a transient isomunchnone dipole was a viable approach to the quinoline ring system (rings C and D) of the ergot alkaloids. The diazo imides were synthesized by N-malonylacylation of the appropriate amide followed by exposure to standard diazo transfer conditions. The carbenoid intermediate derived by treatment of the diazo imide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Exposure of the olefinic cycloadduct to boron trifluoride etherate resulted in exclusive carbon-oxygen bond cleavage producing a transient N-acyliminium ion which undergoes rapid proton loss to afford an enamide derivative. In contrast, exposure of the acetylenic cycloadduct to boron trifluoride etherate resulted in exclusive carbon-nitrogen bond cleavage. The resulting oxonium ion underwent reduction with triethylsilane, producing a dihydrofuran derivative. In the absence of a reducing agent, the alkyne cycloadduct underwent a retro Diels-Alder reaction to give a substituted furan derivative in high yield. The Rh(II) acetate catalyzed reaction of the appropriate diazo imide precursor to lysergic acid resulted in a mixture of the desired dipolar cycloadduct as well as a C-H insertion product. Switching to rhodium(II) perfluorobutyrate as the catalyst significantly enhanced the cycloadditon pathway. The inability to carry out a double-bond isomerization thwarted our efforts to synthesize lysergic acid.