4-oxo-3-[phenyl(tributylphosphaniumyl)methyl]pent-2-en-2-olate | 409095-68-7

• 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: 4-oxo-3-[phenyl(tributylphosphaniumyl)methyl]pent-2-en-2-olate
• CAS: 409095-68-7
• 化学式: C₂₄H₃₉O₂P
• 分子量: 390.546
• InChiKey: BUUBTKOAIYRCDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  27
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  环己基异氰酸酯 、 4-oxo-3-[phenyl(tributylphosphaniumyl)methyl]pent-2-en-2-olate 生成 (Z)-1-[acetyl(cyclohexyl)amino]-3-oxo-2-[phenyl(tributylphosphaniumyl)methyl]but-1-en-1-olate
  参考文献：
  名称：

  Bu n 3 P和PhCH=C[C(:O)Me] 2 异氰酸酯与P-两性离子反应中乙酰基的C→N迁移

  摘要：

  DOI：

  10.1080/10426500213288
• 作为产物：
  描述：

  三丁基膦 、 3-亚苄基-2,4-戊二酮 以 二氯甲烷 为溶剂， 以67%的产率得到4-oxo-3-[phenyl(tributylphosphaniumyl)methyl]pent-2-en-2-olate
  参考文献：
  名称：

  摘要：

  Reactions between isocyanates and carbanions with an acetyl group at the carbanion center occur via rearrangement of the intermediate N-anions into isomeric C-anions by C -->N-migration of the MeC(O) group. The acetyl group undergoes migration easier than the ethoxycarbonyl group. The P-zwitterionic rearrangement products were subjected to X-ray diffraction analysis.

  DOI：

  10.1023/a:1013158208411

文献信息

• C→N migration of methoxycarbonyl and acetyl groups in reactions of functionally substituted carbanions with aryl isocyanates. Kinetics and mechanism of the reactions
  作者：V. I. Galkin、Yu. V. Bakhtiyarova、D. B. Mal’tsev、I. V. Galkina、Yu. G. Gololobov、O. A. Linchenko

  DOI：10.1007/s11172-006-0346-4

  日期：2006.5

  The kinetics and mechanism of C→N migrations of methoxycarbonyl and acetyl groups in the reactions of the sodium derivative of methyl (2-cyano-2-phenyl)acetate and 1,1-diacetyl-2-phenyl-2-tributylphosphonioethanide with aryl isocyanates were studied by spectrophotometry. The reactions afford a prereaction complex via a concerted mechanism, according to which the nucleophilic attack of the carbanionic

  (2-氰基-2-苯基)乙酸甲酯钠衍生物和1,1-二乙酰-2-苯基-2-三丁基膦酰乙烷与异氰酸芳基酯反应中甲氧基羰基和乙酰基的C→N迁移动力学和机理用分光光度法研究。该反应通过协同机制提供预反应复合物，根据该机制，碳离子中心对异氰酸酯基团的碳原子进行亲核攻击，随后氮原子对羰基碳原子进行亲核攻击，导致 CC 键断裂, 几乎同时发生在同一过渡态的框架内。
• ——
  作者：Yu. G. Gololobov、M. A. Galkina、O. V. Dovgan'、I. Yu. Krasnova、P. V. Petrovskii、R. Schmutzler、A. Karasar、M. Freitag、P. G. Jones

  DOI：10.1023/a:1013158208411

  日期：——

  Reactions between isocyanates and carbanions with an acetyl group at the carbanion center occur via rearrangement of the intermediate N-anions into isomeric C-anions by C -->N-migration of the MeC(O) group. The acetyl group undergoes migration easier than the ethoxycarbonyl group. The P-zwitterionic rearrangement products were subjected to X-ray diffraction analysis.
• C→N Migration of the Acetyl Group in the Reactions of Isocyanates with the P-Zwitterion from Bu n 3 P and PhCH=C[C(:O)Me] 2
  作者：Yuri G. Gololobov、Olga V. Dovgan、Irina Yu. Krasnova、Reinhard Schmutzler、Peter G. Jones、Atilla Karaçar、Matthias Freytag

  DOI：10.1080/10426500213288

  日期：2002.8