5-Cyclopropylmethyl-1,5-dimethyl-3,4-diphenyl-1,5-dihydro-pyrrol-2-one | 143841-10-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 5-Cyclopropylmethyl-1,5-dimethyl-3,4-diphenyl-1,5-dihydro-pyrrol-2-one
• 英文别名: 5-(cyclopropylmethyl)-1,5-dimethyl-3,4-diphenylpyrrol-2-one
• CAS: 143841-10-5
• 化学式: C₂₂H₂₃NO
• 分子量: 317.431
• InChiKey: VHFDIAYOIMLRCD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 生成 5-Cyclopropylmethyl-1,5-dimethyl-3,4-diphenyl-1,5-dihydro-pyrrol-2-one 、 3-Cyclopropylmethyl-1,5-dimethyl-3,4-diphenyl-1,3-dihydro-pyrrol-2-one
  参考文献：
  名称：

  Reaction of aminocarbene complexes of chromium with alkynes. 1. Formation and rearrangement of ketene and nitrogen ylide complexes

  摘要：

  The title reactions of chromium-containing carbene complexes (CO)5Cr=C(R1)N(R2R3) (R1 = H, Me, Ph; R2 = Me; R3 = Me, C3H5, CH2C3H5; R2R3 = (CH2)5) 8 and (CO)5Cr=C[(CH2)3C=CPh]N(R1R2) (R1 = R2 = Me; R1R2 = (CH2)5; R1R2 = (CH2)4) 9, bearing alkyl groups of low migratory aptitude on nitrogen, have been examined. In contrast to complexes in which nitrogen bears either an alkyl and an allyl or a benzyl group or is part of a strained cycle, which give heterocycles upon alkyne/CO insertions followed by nitrogen-to-carbon migrations (e.g., 1 --> 7), complexes 8 and 9 lead to stable nitrogen ylides, which could be fully characterized by X-ray crystallography in the case of 8a and 9a. Moreover, in the case of complexes of the general structure 9, ketene precursors of the ylides could either be detected (R1 = Me; R2 = CH2Ph) or isolated and characterized (R2R3 = (CH2)5). The new ylide complexes undergo, upon moderate heating, Stevens-type rearrangements to the expected heterocyclic compounds as a result of nitrogen-to-carbon migrations of various alkyl groups, and upon treatment with dimethyldioxirane, they undergo oxidation to lactone complexes.

  DOI：

  10.1021/ja00047a018

文献信息

• Reaction of aminocarbene complexes of chromium with alkynes 9.
  作者：Henri Rudler、Andrée Parlier、Michèle Rudler、Jacqueline Vaissermann

  DOI：10.1016/s0022-328x(98)00672-x

  日期：1998.9

  to give pyrrolinones as the result of the insertions of the alkyne, of CO and the migration of an alkyl group from nitrogen to a carbon atom in α or γ with respect to the nitrogen atom. The mechanism of this new reaction has been thoroughly investigated: a nitrogen ylid originating from the interaction of the nitrogen atom of the starting aminocarbene complex with the central carbon of the ketene formed

  铬的络合物Aminocarbene具有通式结构（CO）5 CrC（R）NR 1 - [R 2与二苯基乙炔反应，得到pyrrolinones作为炔的插入，CO和一个烷基的选自氮到迁移的结果在碳原子α或γ相对于氮原子上。已对该新反应的机理进行了深入研究：源自起始氨基卡宾配合物的氮原子与炔烃和CO插入氨基卡宾配合物形成的乙烯酮中心碳相互作用的氮基是这些反应中的关键中间体。这种ylid配合物，其结构可以确定为25，导致在热解时观察到的吡咯烷酮。基于环丙基羰基取代的氨基卡宾配合物45a，b的反应，已经放弃了涉及自由基的机理：如吡咯烷酮46b的X射线结构所示，在其迁移时未观察到环丙基羰基的重排。还消除了涉及离子对或金属参与的机理。为此，已经建立了两个配合物51和52的X射线结构，其中金属不与迁移基团的苯环键合。最后，在氢中，从氮到五元杂环碳的烷基一致的（1,5）σ迁移。25个观察结果最佳。金属的作用