2,6,10-tris(tosylamino)-12c-methyl-4,8,12-trioxatricornan | 136016-27-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2,6,10-tris(tosylamino)-12c-methyl-4,8,12-trioxatricornan
• CAS: 136016-27-8
• 化学式: C₄₁H₃₃N₃O₉S₃
• 分子量: 807.926
• InChiKey: ABKCAZNPMDZMRK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.69
• 重原子数：
  56.0
• 可旋转键数：
  9.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  166.2
• 氢给体数：
  3.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  N-(2-溴乙基)邻苯二甲酰亚胺 、 2,6,10-tris(tosylamino)-12c-methyl-4,8,12-trioxatricornan 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 2,6,10-tris-12c-methyl-4,8,12-trioxatricornan
  参考文献：
  名称：

  Synthesis of trioxatricornan and derivatives. Useful keystones for the construction of rigid molecular cavities

  摘要：

  The synthesis of a new class of organic keystones for the development of macrocage structures is presented. These represent some of the most versatile building blocks for macrocage construction. The keystone structure developed herein can be interpreted as either a centrally alkylated [cd,mn]dibenzopyrene or a tris ortho-bridged triphenylmethane. We call this basic skeleton tricornan. Routes into both chiral (C3 and C1 symmetry) and achiral (C3-upsilon symmetry) derivatives are reported. The synthesis of derivatives of the trioxatricornan keystone, leading to two macrocage structures, is presented. The X-ray structures of cent-methyltrioxatricornan 7 and 2,6,10-tris(dimethylamino)-cent-methyltrioxatricornan (20) are discussed and compared to that of 1,1,1-triphenylethane. Empirical force field and AM1 calculations are compared to the X-ray structures and discussed. A general discussion on the keystone analogy is presented.

  DOI：

  10.1021/jo00027a015
• 作为产物：
  描述：

  1,7,9-tribromo-12c-methyl-4,8,12-trioxatricornan 在 吡啶 、 氨 、 sodium amide 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 生成 2,6,10-tris(tosylamino)-12c-methyl-4,8,12-trioxatricornan
  参考文献：
  名称：

  Synthesis of trioxatricornan and derivatives. Useful keystones for the construction of rigid molecular cavities

  摘要：

  The synthesis of a new class of organic keystones for the development of macrocage structures is presented. These represent some of the most versatile building blocks for macrocage construction. The keystone structure developed herein can be interpreted as either a centrally alkylated [cd,mn]dibenzopyrene or a tris ortho-bridged triphenylmethane. We call this basic skeleton tricornan. Routes into both chiral (C3 and C1 symmetry) and achiral (C3-upsilon symmetry) derivatives are reported. The synthesis of derivatives of the trioxatricornan keystone, leading to two macrocage structures, is presented. The X-ray structures of cent-methyltrioxatricornan 7 and 2,6,10-tris(dimethylamino)-cent-methyltrioxatricornan (20) are discussed and compared to that of 1,1,1-triphenylethane. Empirical force field and AM1 calculations are compared to the X-ray structures and discussed. A general discussion on the keystone analogy is presented.

  DOI：

  10.1021/jo00027a015

文献信息

• Lofthagen, Michael; Chadha, Raj; Siegel, Jay S., Journal of the American Chemical Society, 1991, vol. 113, # 23, p. 8785 - 8790
  作者：Lofthagen, Michael、Chadha, Raj、Siegel, Jay S.

  DOI：——

  日期：——
• Synthesis of metallomacrocyclophanes: Deduction of structure from electrospray ionization mass spectroscopy and molecular mechanics computations
  作者：Michael Lofthagen、Jay S Siegel、Murray Hackett

  DOI：10.1016/0040-4020(95)00287-i

  日期：1995.5

  The synthesis of metallomacrocyclophanes 7-tos and 8, in which environmentally tunable ferric-catecholamide coordination bonds hold the cyclophane together, is described. W-vis spectroscopic studies of 7-tos and 8 display characteristics of ferric-tris(catecholamide) complexes, i.e. burgundy color (lambda(max) = ca. 490 nm)and high stability, at high pH, and 1:1 stoichiometry. Electrospray ionization mass spectra of 8 show prominent ions due to a monomeric 1:1 (ligand/metal) complex. Molecular mechanics calculations on 7 and 8 indicate that oar-isomeric configurations predominate, leaving a void in the metallomacrocyclophane interiors.
• Synthesis and Conformational Analysis of Trioxatricornan-Based Macrocyclophanes
  作者：Michael Lofthagen、Jay S. Siegel

  DOI：10.1021/jo00114a045

  日期：1995.5

  The synthesis of macrocyclophanes 7 and 8 is described. The constructions are composed of one phloroglucinol and one 2,6,10-triaminotrioxatricornan subunit. The subunits are linked by tri- and hexamethylene (7 and 8, respectively) chains. Conformational analysis by empirical force field calculations and H-1 NMR techniques demonstrates that 7 has adopted a collapsed conformation, leaving no space between the two aromatic subunits. Macrocyclophane 1, in which the phloroglucinol oxygens have been replaced by methylenes, has instead adopted an open conformation, leaving a void in the macrocyclophane interior. The conformational preference of the side chains is shown to be the dominant factor in determining the overall conformation of 7 and its a-methylene analog 1. With the use of low-temperature H-1 NMR, the barrier for the process of equivalencing all exchangeable sites in 7 is estimated at 8.6 kcal/mol.