3-hydroxy-2-methylene-3-(2-nitrophenyl) propionamide

• 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: 3-hydroxy-2-methylene-3-(2-nitrophenyl) propionamide
• 英文别名: 3-hydroxy-2-methylene-3-(2-nitrophenyl)propionamide；2-[hydroxy(2-nitrophenyl)methyl]acrylamide；2-[Hydroxy-(2-nitrophenyl)methyl]prop-2-enamide
• 化学式: C₁₀H₁₀N₂O₄
• 分子量: 222.2
• InChiKey: VUAOTHSDAVZFIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  109
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  丙烯酰胺 、 邻硝基苯甲醛 在 1,3,5-三氮杂-7-磷杂金刚烷 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以82%的产率得到3-hydroxy-2-methylene-3-(2-nitrophenyl) propionamide
  参考文献：
  名称：

  1,3,5-Triaza-7-phosphaadamantane（PTA）：一种实用，多功能的亲核膦膦有机催化剂。

  摘要：

  在本文中，据报道，空气稳定且容易获得的1,3,5-triaza-7-phosphaadmantane（PTA）是一种实用且用途广泛的亲核膦有机催化剂。在15–30 mol％的PTA的介导下，各种亲电试剂（如醛和亚胺）容易与各种活化的烯烃发生Morita-Baylis-Hillman反应，从而以高收率得到相应的加合物。在4-取代的2,3-丁二烯酸酯与N-甲苯胺的膦催化的[3 + 2]环加成反应中，PTA也被证明是与三丁基膦类似的催化剂（PBu 3）。通过与其他结构相似的N，P催化剂的系统比较，得出的结论是PTA在上述亲核催化中的优越性归因于其与三烷基膦可比的亲核性。还讨论了使用PTA替代对空气敏感的三烷基膦的替代催化剂的可行性。

  DOI：

  10.1002/adsc.200700071

文献信息

• IMPROVED PROCEDURES FOR THE BAYLIS-HILLMAN REACTION
  作者：San-Hu Zhao、Hong-Yan Bie、Zhao-Bin Chen

  DOI：10.1080/00304940509354952

  日期：2005.6

  synthesis.' Although numerous catalytic systems, such as tertiary amines? phosphines,3 TiCl, and others? have been used as catalysts to mediate this reaction, 1,4diazabicyclo[2.2.2]octane (DABCO), first introduced by Baylis and Hillman: is arguably still the most widely used one. Hexamethylenetetramine (HMTA), a very inexpensive hindered tertiary amine, is a nucleophilic base. It can effectively attack the

  Baylis-Hillman 反应是有机合成中原子经济且极其有用的 CC 键形成反应。尽管有许多催化系统，例如叔胺？膦、3 TiCl 等？已被用作介导该反应的催化剂，1,4-二氮杂双环 [2.2.2] 辛烷 (DABCO)，由 Baylis 和 Hillman 首次引入：可以说仍然是最广泛使用的一种。六亚甲基四胺 (HMTA) 是一种非常便宜的受阻叔胺，是一种亲核碱。它可以有效地攻击活性烯烃的末端碳，因此应该是 Baylis-Hillman 反应的有用催化剂。尽管如此，Tang 等人。最近描述了一项实验，使用 HMTA（乌洛托品）作为促进剂，以二恶烷-水（1:1）为溶剂，制备 3 小时，收率良好（87%）；该催化剂的范围和通用性没有针对各种醛类和活性烯烃进行测试。本论文描述了由六亚甲基四胺 (HMTA) 和离子液体（方案 I）催化的 Baylis-Hillman 反应的研究。
• N‐Methylpiperidine—A Useful Base Catalyst in the Morita–Baylis–Hillman Reaction
  作者：San‐Hu Zhao、Zhao‐Bin Chen

  DOI：10.1080/00397910500278776

  日期：2005.12

  N-methylpiperidine, a commercially available mild base, has effectively been utilized as a catalyst in the Morita-Baylis-Hillman reaction. Moderate to excellent yields (34-95%) and significant rate enhancement have been observed.
• The N,N,N′,N′–Tetramethylethylenediamine Mediated Baylis‐Hillman Reaction
  作者：Sanhu Zhao、Zhaobin Chen

  DOI：10.1081/scc-200046521

  日期：2005.1.1

  The Baylis-Hillman reaction of aromatic aldehydes with various activated alkenes catalyzed by N,N,N',N'-Tetramethylethylenediamine (TMEDA) in aqueous medium were reported. The efficiency of this catalyst was examined in comparison with DABCO. It was demonstrated that this amine is not only a very efficient catalyst for the Baylis-Hillman reaction, it also outperforms the most widely used catalyst DABCO.
• Acrylamide in the Baylis−Hillman Reaction:  Expanded Reaction Scope and the Unexpected Superiority of DABCO over More Basic Tertiary Amine Catalysts
  作者：Cornelia Faltin、Eimear M. Fleming、Stephen J. Connon

  DOI：10.1021/jo0490907

  日期：2004.9.1

  DMAP, DBU, and quinuclidine efficiently promote novel hydroalkoxylation reactions of acrylamide in primary alcohol solvents. DABCO is a comparatively poor hydroalkoxylation promoter and can effect clean, selective Baylis-Hillman reactions between acrylamide and aldehydes in alcoholic/aqueous media in which more basic nucleophilic catalysts promote hydroalkoxylation preferentially. Optimization of the reaction conditions has allowed acrylamide to be reacted with a range of aromatic aldehydes in moderate to excellent yields, including the first examples involving deactivated, electron-rich substrates such as p-tolualdehyde and o-anisaldehyde.
• Successful Baylis−Hillman Reaction of Acrylamide with Aromatic Aldehydes
  作者：Chengzhi Yu、Longqin Hu

  DOI：10.1021/jo016004j

  日期：2002.1.1

  Acrylamide and aromatic aldehydes were found to undergo the Baylis-Hillman reaction at ambient temperature in an aqueous medium in the presence of a stoichiometric amount of base catalyst, DABCO, to give the corresponding 3-hydroxy-2-methylenepropionamides in 61-99% yield. A faster competing, but reverible, non-Baylis-Hillman reaction was initially observed under the conditions to form N-acylhemiaminals, which later disappeared, as the desired Baylis-Hillman adduct was formed as the major product over an extended period of time (12-48 h). This represents the first demonstration of the Baylis-Hillman reaction of aldehydes with acrylamides, which were thought to be inert under atmospheric pressure and at ambient temperature.