6,7,8,9,10,11,12,13,20,21,22,23,24,25,26,27-hexadecahydrodicyclohepta<1,4,12,15>tetraazacyclodocosine | 143285-55-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 6,7,8,9,10,11,12,13,20,21,22,23,24,25,26,27-hexadecahydrodicyclohepta<1,4,12,15>tetraazacyclodocosine
• CAS: 143285-55-6
• 化学式: C₂₈H₄₀N₄
• 分子量: 432.652
• InChiKey: RUJKWYHYWIPGTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.98
• 重原子数：
  32.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  48.78
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  甲醇 、 cobalt(II) diacetate tetrahydrate 、 6,7,8,9,10,11,12,13,20,21,22,23,24,25,26,27-hexadecahydrodicyclohepta<1,4,12,15>tetraazacyclodocosine 以 甲醇 为溶剂， 以58%的产率得到[Co2(μ-OAc)(μ-OH)(tropocoronand-7,7)]
  参考文献：
  名称：

  Synthesis, Tuning of the Stereochemistry, and Physical Properties of Cobalt(II) Tropocoronand Complexes

  摘要：

  A series of Co(II) complexes of the tropocoronand ligand system [TC-n,m](2-) (n,m = 3,3; 3,4; 4,4; 4,5; 5,5; 6,6; 7,7)have been prepared and fully characterized. X-ray structural analyses have been carried out on [Co(TC-3,3)], [Co(TC-4,4)], [Co(TC-4,5)], [Co(TC-5,5)], [Co(TC-6,6)], and the dinuclear complex [Co-2(mu-OAc)(mu-OH)(TC-7,7)]. In the mononuclear series, the coordination geometries vary from square-planar for [Co(TC-3,3)] to tetrahedral for [Co(TC-6,6)]. The twist angle, defined as the dihedral angle between the two five-membered aminotroponiminate chelate rings, increases from 9.0 to 84.5 degrees as a result of increasing torsional strain within the polymethylene linker chains of the tropocoronand macrocycle. The change in geometry from square-planar to tetrahedral, accompanied by a change in spin state from S = 1/2 to S = 3/2, occurs abruptly between [Co(TC-4,4)] and [Co(TC-4,5)] as determined by X-ray crystallographic and solid state magnetic studies. This dependence of geometry and spin state on ligand size is similar to that observed previously in the Ni(II) system, where the low spin to high spin transformation occurred at the [Ni(TC-4,5)]/[Ni(TC-5,5)] junction. The shift in the position of this transformation with metal ion is an indication of the greater preference of Co(n) for tetrahedral geometry compared with Ni(II). The dinuclear [Co-2(mu-OAc)(mu-OH)(TC-7,7)] compound was prepared from Co(OAc)(2) . 4H(2)O and H-2(TC-7,7) in refluxing MeOH. The complex contains two Co(II) atoms sitting in the plane of the macrocycle, bridged by an acetate group on one side of the ligand plane and a hydroxo group on the other. All of the complexes are air sensitive in solution to varying degree but stable in the solid state. Crystallographic data: [Co(TC-3,3)], monoclinic, P2(1), a = 10.187(4) Angstrom, b = 8.466(1) Angstrom, c = 10.227(1) Angstrom, beta = 97.80(3)degrees, Z = 2, R = 0.067, R(W) = 0.068; [Co(TC-4,4)], monoclinic, P2(1)/c, a = 11.109(3) Angstrom, b = 8.561(1) Angstrom, c = 20.088(6) Angstrom, beta = 90.53(2)degrees, Z = 4, R = 0.039, R(W) = 0.042; [Co(TC-4,5)], monoclinic, P2/c, a = 22.041(3) Angstrom, b = 9.351(2) Angstrom, c = 19.859(3) Angstrom, beta = 106.43(1)degrees, Z = 8, R = 0.048, R(W) = 0.054; [Co(TC-5,5)], hexagonal, P6(1)22, a = 10.965(2) Angstrom, c = 30.692(5) Angstrom, Z = 6, R = 0.038, R(W) = 0.048; [Co(TC-6,6)], orthorhombic, P2(1)2(1)2(1), a = 10.644(2) Angstrom, b = 11.426(2) Angstrom, c = 19.083(2) Angstrom, Z = 4, R = 0.047, R(W) = 0.051; [Co-2(mu-OAc)(mu-OH)(TC-7,7)]. Et(2)O, orthorhombic, Pbcn, a = 12.298(5) Angstrom, b = 16.128(4) Angstrom, c = 17.252(7) Angstrom, Z = 4, R = 0.036, R(W) = 0.042.

  DOI：

  10.1021/ic00127a010
• 作为产物：
  描述：

  cyclohepta<1,4>benzoxazine 、 1,7-二氨基庚烷 以 乙醇 为溶剂， 反应 30.0h， 以86%的产率得到6,7,8,9,10,11,12,13,20,21,22,23,24,25,26,27-hexadecahydrodicyclohepta<1,4,12,15>tetraazacyclodocosine
  参考文献：
  名称：

  One-Pot Synthesis of Tetraazabis(tropocoronand)s and Podands from Benzo[b]cyclohept[e][1,4]oxazine andα,ω-Polymethylenediamines

  摘要：

  苯并[b]环庚烷并[e][1,4]恶嗪（9）与 1.2当量的α,ω-烷二胺（2，n = 4-12）在乙醇中于80 °C下进行反应，以一锅法和高产率得到了托硼烷（5，n,n′ = 4,4-12,12），而9与过量的2反应主要得到了托硼烷12（n,n′ = 4,4-6,6）。9 与短链二胺 2（n = 2,3）反应的主要产物是双环吡嗪或二氮杂卓化合物。9 与ω-氨基醇反应得到相应的二羟基荚膜 23。实验证实了 9 与 2 反应的预测途径。

  DOI：

  10.1246/bcsj.66.2941

文献信息

• Nozoe, Tetsuo; Shindo, Kimio; Wakabayashi, Hidetsugu, Heterocycles, 1992, vol. 34, # 5, p. 881 - 884
  作者：Nozoe, Tetsuo、Shindo, Kimio、Wakabayashi, Hidetsugu、Ishikawa, Sumio

  DOI：——

  日期：——
• One-Pot Synthesis of Tetraazabis(tropocoronand)s and Podands from Benzo[<i>b</i>]cyclohept[<i>e</i>][1,4]oxazine and<i>α</i>,<i>ω</i>-Polymethylenediamines
  作者：Kimio Shindo、Hidetsugu Wakabayashi、Sumio Ishikawa、Tetsuo Nozoe

  DOI：10.1246/bcsj.66.2941

  日期：1993.10

  The reactions of benzo[b]cyclohept[e][1,4]oxazine (9) with a 1.2 equivalent of α,ω-alkanediamines (2, n = 4—12) in ethanol at 80 °C afforded tropocoronands (5, n,n′ = 4,4—12,12) in a one-pot procedure and in high yields, while the reaction of 9 with an excess of 2 mainly gave tropopodands 12 (n,n′ = 4,4—6,6). The reactions of 9 with short-chain diamines 2 (n = 2,3) yielded bicyclic pyrazino or diazepino compounds as the main products. The reaction of 9 with ω-amino alcohol afforded the corresponding dihydroxy podands 23. The predicted pathways of the reaction of 9 with 2 were experimentally confirmed.

  苯并[b]环庚烷并[e][1,4]恶嗪（9）与 1.2当量的α,ω-烷二胺（2，n = 4-12）在乙醇中于80 °C下进行反应，以一锅法和高产率得到了托硼烷（5，n,n′ = 4,4-12,12），而9与过量的2反应主要得到了托硼烷12（n,n′ = 4,4-6,6）。9 与短链二胺 2（n = 2,3）反应的主要产物是双环吡嗪或二氮杂卓化合物。9 与ω-氨基醇反应得到相应的二羟基荚膜 23。实验证实了 9 与 2 反应的预测途径。
• Synthesis, Tuning of the Stereochemistry, and Physical Properties of Cobalt(II) Tropocoronand Complexes
  作者：B. Scott Jaynes、Linda H. Doerrer、Shuncheng Liu、Stephen J. Lippard

  DOI：10.1021/ic00127a010

  日期：1995.11

  A series of Co(II) complexes of the tropocoronand ligand system [TC-n,m](2-) (n,m = 3,3; 3,4; 4,4; 4,5; 5,5; 6,6; 7,7)have been prepared and fully characterized. X-ray structural analyses have been carried out on [Co(TC-3,3)], [Co(TC-4,4)], [Co(TC-4,5)], [Co(TC-5,5)], [Co(TC-6,6)], and the dinuclear complex [Co-2(mu-OAc)(mu-OH)(TC-7,7)]. In the mononuclear series, the coordination geometries vary from square-planar for [Co(TC-3,3)] to tetrahedral for [Co(TC-6,6)]. The twist angle, defined as the dihedral angle between the two five-membered aminotroponiminate chelate rings, increases from 9.0 to 84.5 degrees as a result of increasing torsional strain within the polymethylene linker chains of the tropocoronand macrocycle. The change in geometry from square-planar to tetrahedral, accompanied by a change in spin state from S = 1/2 to S = 3/2, occurs abruptly between [Co(TC-4,4)] and [Co(TC-4,5)] as determined by X-ray crystallographic and solid state magnetic studies. This dependence of geometry and spin state on ligand size is similar to that observed previously in the Ni(II) system, where the low spin to high spin transformation occurred at the [Ni(TC-4,5)]/[Ni(TC-5,5)] junction. The shift in the position of this transformation with metal ion is an indication of the greater preference of Co(n) for tetrahedral geometry compared with Ni(II). The dinuclear [Co-2(mu-OAc)(mu-OH)(TC-7,7)] compound was prepared from Co(OAc)(2) . 4H(2)O and H-2(TC-7,7) in refluxing MeOH. The complex contains two Co(II) atoms sitting in the plane of the macrocycle, bridged by an acetate group on one side of the ligand plane and a hydroxo group on the other. All of the complexes are air sensitive in solution to varying degree but stable in the solid state. Crystallographic data: [Co(TC-3,3)], monoclinic, P2(1), a = 10.187(4) Angstrom, b = 8.466(1) Angstrom, c = 10.227(1) Angstrom, beta = 97.80(3)degrees, Z = 2, R = 0.067, R(W) = 0.068; [Co(TC-4,4)], monoclinic, P2(1)/c, a = 11.109(3) Angstrom, b = 8.561(1) Angstrom, c = 20.088(6) Angstrom, beta = 90.53(2)degrees, Z = 4, R = 0.039, R(W) = 0.042; [Co(TC-4,5)], monoclinic, P2/c, a = 22.041(3) Angstrom, b = 9.351(2) Angstrom, c = 19.859(3) Angstrom, beta = 106.43(1)degrees, Z = 8, R = 0.048, R(W) = 0.054; [Co(TC-5,5)], hexagonal, P6(1)22, a = 10.965(2) Angstrom, c = 30.692(5) Angstrom, Z = 6, R = 0.038, R(W) = 0.048; [Co(TC-6,6)], orthorhombic, P2(1)2(1)2(1), a = 10.644(2) Angstrom, b = 11.426(2) Angstrom, c = 19.083(2) Angstrom, Z = 4, R = 0.047, R(W) = 0.051; [Co-2(mu-OAc)(mu-OH)(TC-7,7)]. Et(2)O, orthorhombic, Pbcn, a = 12.298(5) Angstrom, b = 16.128(4) Angstrom, c = 17.252(7) Angstrom, Z = 4, R = 0.036, R(W) = 0.042.