3-(3',6'-Dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropanoic acid N-(p-methoxyphenyl)amide | 143859-68-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3-(3',6'-Dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropanoic acid N-(p-methoxyphenyl)amide
• 英文别名: N-(p-Methoxyphenyl)-3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionamide；3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionic acid amide p-anisidine；3-(2,4-dimethyl-3,6-dioxocyclohexa-1,4-dien-1-yl)-N-(4-methoxyphenyl)-3-methylbutanamide
• CAS: 143859-68-1
• 化学式: C₂₀H₂₃NO₄
• 分子量: 341.407
• InChiKey: VCTGZOWDDVFSGV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  72.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(3',6'-Dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropanoic acid N-(p-methoxyphenyl)amide 以 乙腈 为溶剂， 反应 24.0h， 以25%的产率得到4,4,2',4'-Tetramethyl-1-(p-methoxyphenyl)-1-azaspiro<4.1'>dec-4'-ene-2,3',6'-trione
  参考文献：
  名称：

  Facilitated intramolecular conjugate addition of N-(p-methoxyphenyl)-3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionamide. 1. Product characterization

  摘要：

  N-(p-Methoxyphenyl)-3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionamide (1), a pro-prodrug model, was chosen to study the reaction of quinone propionic amides in mildly acidic aqueous solution. The quinone propionic amide 1 equilibrates rapidly with its hydroxy dienone 6 and undergoes a much slower 1,4 conjugate addition to form its enol spirolactam 4. The enol spirolactam 4 then tautomerizes to give the keto spirolactam 5. Spectroscopic evidence suggests that the keto spirolactam 5 is present as a diastereomeric mixture, wherein the preferred diastereomer has the 2'-methyl and the lactam nitrogen anti to each other.

  DOI：

  10.1021/jo00049a018
• 作为产物：
  描述：

  甲氧苯胺 、 3-(2,4-二甲基-3,6-二氧代-1-环己-1,4-二烯基)-3-甲基丁酸 在 1-羟基苯并三唑 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以56%的产率得到3-(3',6'-Dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropanoic acid N-(p-methoxyphenyl)amide
  参考文献：
  名称：

  Facilitated intramolecular conjugate addition of N-(p-methoxyphenyl)-3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionamide. 1. Product characterization

  摘要：

  N-(p-Methoxyphenyl)-3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionamide (1), a pro-prodrug model, was chosen to study the reaction of quinone propionic amides in mildly acidic aqueous solution. The quinone propionic amide 1 equilibrates rapidly with its hydroxy dienone 6 and undergoes a much slower 1,4 conjugate addition to form its enol spirolactam 4. The enol spirolactam 4 then tautomerizes to give the keto spirolactam 5. Spectroscopic evidence suggests that the keto spirolactam 5 is present as a diastereomeric mixture, wherein the preferred diastereomer has the 2'-methyl and the lactam nitrogen anti to each other.

  DOI：

  10.1021/jo00049a018

文献信息

• Facilitated Intramolecular Conjugate Addition of Amides of 3-(3‘,6‘-Dioxo-2‘,4‘-dimethyl-1‘,4‘-cyclohexadienyl)-3,3-dimethylpropionic Acid. 2. Kinetics of Degradation
  作者：Michalis G. Nicolaou、Janet L. Wolfe、Richard L. Schowen、Ronald T. Borchardt

  DOI：10.1021/jo961069l

  日期：1996.1.1

  the intramolecular 1,2- or 1,4- conjugate addition of the amide nitrogen to the quinone ring. This conjugate addition was found to be specific base-catalyzed and independent of the para substituent on the aromatic ring of the amine. The predominant route of degradation yielded a five-membered ring spirolactam. By altering the nature of the amine component of the amide, these degradation reactions were

  3-（3'，6'-dioxo-2'，4'-二甲基-1'，4'-环己二烯基）-3,3-二甲基丙酸（Qa）[Qop（aj）]的酰胺的化学稳定性研究为了确定该氧化还原敏感系统作为有机合成中潜在的前药促发基团或氧化还原敏感保护基的实用性，进行了研究。这项研究表明，苯胺衍生物[Qop（ad）]的醌丙酰胺在中等酸性条件下（pH 4.5-6.0）经历了快速降解，从而产生了分子内1,2-或1,4-共轭物添加的降解产物。酰胺氮连接至醌环。发现该共轭加成是特定的碱催化的并且独立于胺的芳环上的对取代基。降解的主要途径产生了五元环螺内酰胺。通过改变酰胺的​​胺成分的性质，防止了这些降解反应。发现Qa的酰胺比苯胺型[Qop（ej）]的酰胺更稳定，因此被提议作为该潜在的对氧化还原敏感的前药系统和对胺和醇的氧化还原敏感保护基的更合适的候选物。在有机合成中。
• Development of a Novel Redox-Sensitive Protecting Group for Amines Which Utilizes a Facilitated Lactonization Reaction
  作者：Binghe Wang、Siming Liu、Ronald T. Borchardt

  DOI：10.1021/jo00108a013

  日期：1995.2

  Selective protection and deprotection of functional groups are essential components of modern organic and peptide synthesis. To cope with the demand for the synthesis of organic molecules and peptides with increasing complexity, there has been a need to develop novel protecting groups which are readily cleavable under fundamentally different conditions to ensure selective modifications of specified functional groups. This report is focused on the development of a redox-sensitive amine protecting group using a substituted quinone propionic acid (1a). The key feature of this protecting group is that upon reduction of the quinone 1 to the hydroquinone 2, it undergoes a spontaneous lactonization to release the functional group attached to the carboxyl group (HXR). High yields were achieved for both the protection and deprotection reactions, and the reduction conditions required for the deprotection are very mild (Na2S2O4 or electrochemically) and thus very compatible with most functional groups encountered in organic molecules and peptides.
• Facilitated intramolecular conjugate addition of N-(p-methoxyphenyl)-3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionamide. 1. Product characterization
  作者：Janet L. Wolfe、David Vander Velde、Ronald T. Borchardt

  DOI：10.1021/jo00049a018

  日期：1992.11

  N-(p-Methoxyphenyl)-3-(3',6'-dioxo-2',4'-dimethylcyclohexa-1',4'-dienyl)-3,3-dimethylpropionamide (1), a pro-prodrug model, was chosen to study the reaction of quinone propionic amides in mildly acidic aqueous solution. The quinone propionic amide 1 equilibrates rapidly with its hydroxy dienone 6 and undergoes a much slower 1,4 conjugate addition to form its enol spirolactam 4. The enol spirolactam 4 then tautomerizes to give the keto spirolactam 5. Spectroscopic evidence suggests that the keto spirolactam 5 is present as a diastereomeric mixture, wherein the preferred diastereomer has the 2'-methyl and the lactam nitrogen anti to each other.