1,4,8,11-tetraazabicyclo[9.3.3]heptadecane-5,7-dione | 245414-31-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane-5,7-dione
• 英文别名: 1,4,8,11-Tetrazabicyclo[9.3.3]heptadecane-5,7-dione
• CAS: 245414-31-7
• 化学式: C₁₃H₂₄N₄O₂
• 分子量: 268.359
• InChiKey: LCJREJSSHQEMSL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  64.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(acetylacetonate)nickel(II) 、 1,4,8,11-tetraazabicyclo[9.3.3]heptadecane-5,7-dione 以 乙腈 为溶剂， 以21%的产率得到
  参考文献：
  名称：

  A new structurally constrained dioxocyclam ligand: synthesis, characterization and molecular structure comparison of its nickel(II) complex with the nickel(II) complex of dioxocyclam

  摘要：

  The structurally constrained dioxocyclam ligand, 1,4,8,11-tetraazabicyclo[9.3.3]heptadecacane-5,7-dione, H(2)dc3, was prepared by refluxing 1,3-propanediol di-p-tosylate with dioxocyclam. The corresponding Ni(II) complex, Ni(dc3), has been prepared and structurally characterized by X-ray crystallography. In addition, the structure of the dioxocyclam complex of Ni(II), Ni(dc), has been determined for comparison with Ni(dc3). In both cases, the Ni(II) sits in a square planar array of four nitrogens. However, the constraint imposed by the additional trimethylene strap in Ni(dc3) causes the Ni(II) to be farther out of the plane of the four nitrogens (0.089(1) Angstrom) than in Ni(dc) (0.039(1) Angstrom), resulting in a lower than expected ligand field strength for Ni(dc3). The arrangement of the three carbon straps and their potential to interact with the metal center are also discussed. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00184-x

文献信息

• Chemistry of Constrained Dioxocyclam Ligands with Co(III):  Unusual Examples of C−H and C−N Bond Cleavage
  作者：Chuanjiang Hu、Robert M. Chin、Thoi D. Nguyen、Khoi T. Nguyen、Paul S. Wagenknecht、Lawrence C. Nathan

  DOI：10.1021/ic0302027

  日期：2003.11.1

  ionic character in the cobalt-carbon bond. However, we were unable to cleave this bond in the presence of strong acid. In the absence of base, the reaction of Co(acac)(3) with H(2)dc3 resulted in C-N cleavage of the ligand and the formation of a complex of dioxocyclam, Co(dc)(acac), 2. This complex has subsequently been prepared in high yield by the reaction of Co(acac)(3) with dioxocyclam. An X-ray crystallographic

  H（2）dc3和Co（acac）（3）之间的反应已在存在和不存在碱的条件下进行了研究。在存在碱的情况下，大概是通过杂化CH键活化作用形成的，带有分子内Co-C键的复合物Co（dc3-C-（8））（H（2）O）1。X射线晶体学研究表明存在Co-C键，并表明二氮杂环辛烷（daco）亚基相对于金属采用了椅形结构。钴碳键在大环中诱导应变，如键角明显偏离四面体所示。结合到钴上的碳原子的（13）C NMR共振（-10.5 ppm）表明钴-碳键具有明显的离子特征。但是，在强酸存在下我们无法裂解该键。在没有基地的情况下，Co（acac）（3）与H（2）dc3的反应导致CN裂解配体，并形成二氧环素Co（dc）（acac），2的配合物。 Co（acac）（3）与二氧杂环丁烷的反应产生收率。X射线晶体学研究表明，二氧杂环丁烷采用迄今未报道的顺式构型，并沿垂直于Co-acac平面的N-Co-N轴折叠。