6,9,12,15,18-Pentaoxa-3,21-dithiabicyclo[21.3.1]heptacosa-1(27),23,25-triene | 154264-31-0

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 6,9,12,15,18-Pentaoxa-3,21-dithiabicyclo[21.3.1]heptacosa-1(27),23,25-triene
• 英文别名: 6,9,12,15,18-pentaoxa-3,21-dithiabicyclo[21.3.1]heptacosa-1(27),23,25-triene
• CAS: 154264-31-0
• 化学式: C₂₀H₃₂O₅S₂
• 分子量: 416.603
• InChiKey: ANTIASYAFMDJBQ-UHFFFAOYSA-N

物化性质

• 沸点：
  601.2±55.0 °C(predicted)
• 密度：
  1.062±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  27
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  96.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  6,9,12,15,18-Pentaoxa-3,21-dithiabicyclo[21.3.1]heptacosa-1(27),23,25-triene 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Simultaneous First- and Second-Sphere Coordination. Organopalladium Metalloreceptors for Water, Ammonia, Amines, Hydrazine, and the Hydrazinium Ion

  摘要：

  The complexes [Pd(L)(CH3CN)][BF4] (L(3) = 5,8,11-trioxa-2,14-dithia[15]-m-cyclophane and L(5) = 5,8,11,14,17-pentaoxa-2,20-dithia[21]-m-cyclophane) were prepared by palladation of the respective thiacyclophane employing [Pd(CH3CN)(4)][BF4](2) These metalloreceptors were reacted with various small substrates (H2O, NH3, NH(2)R, NMR(2) NH2NH2, and NH2NH3+) capable of simultaneously coordinating to the Pd center and hydrogen-bonding with the peripheral ether oxygens. [Pd(L(3))(NH3)][BF4] crystallized in the space group Pbca with a = 21.377(4) Angstrom, b = 21.656(5) Angstrom, c = 9.437(6) Angstrom, V = 4368(2) Angstrom(3), and Z = 8. The structure refined to R = 6.41% and R(w) = 7.03% for 659 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(3))(NH2NH2)][BF4] crystallized in the space group P ($) over bar 1 with a = 11.652(3> Angstrom, b = 12.669(4) Angstrom, c = 8.355(1) Angstrom, a = 94.13(2)degrees, beta = 94.34(2)degrees, gamma = 117.21(1)degrees, V = 1090.3(5) Angstrom(3), and Z = 2. The structure refined to R = 2.81% and R(w) = 3.40% for 2709 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(5))(H2O)][BF4] crystallized in the space group P1 ($) over bar with a = 11.076(3) Angstrom, b = 15.147(5) Angstrom, c = 8.586(2) Angstrom, V = 1284(1) Angstrom(3), and Z = 2. The structure refined to R = 3.14% and R(w) = 4.06% for 2275 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(3))(NH2NH3)][CF3SO3](2) crystallized in the space group P2(1)/c with a = 11.906(4) Angstrom, b = 17.19(1) Angstrom, c = 15.313(4) Angstrom beta = 111.18(2)degrees, V = 2923(4) Angstrom(3), and Z = 4. The structure refined to R = 3.13% and R(w) = 4.25% for 2954 reflections with F-o(2)) > 3 sigma(F-o(2)). [Pd(L(5))(NH2NH3)][BF4](2) crystallized in the space group P ($) over bar 1 with a = 9.391(3) Angstrom, b = 18.292(5) Angstrom, c = 9.107(2) Angstrom, a = 94.45(3)degrees, beta = 102.02(2)degrees, gamma = 103.51(2)degrees, V = 1474.5(8) Angstrom(3), and Z = 2. The structure refined to R = 3.69% and R(w) = 4.58% for 3059 reflections with F-o(2) > 3 sigma(F-o(2)). Each complex shows evidence of hydrogen bonding between the Pd-bound substrate and the peripheral oxygen atoms. The major hydrogen-bonding sites are the oxygen atoms adjacent to the thioether atoms, while the extent of the hydrogen bonding is dependent on the size of the polyether ring and the orientation of the substrate. Controlling the number of hydrogen bonds formed results in selective binding of primary amines (two hydrogen bonds) over secondary amines (one hydrogen bond) and tertiary amines (no hydrogen bonds) as determined by competition reactions monitored by H-1 NMR spectroscopy.

  DOI：

  10.1021/ic00126a040

文献信息

• Receptors for the hydrazinium ion. Simultaneous first- and second-sphere coordination inside organopalladium crown ether complexes
  作者：James E. Kickham、Stephen J. Loeb

  DOI：10.1039/c39930001848

  日期：——

  Organopalladium crown ether complexes are employed to bind the hydrazinium ion, [NH2NH3]+, via simultaneous first- and second-sphere coordination featuring σ-donation to Pd and hydrogen bonding to aliphatic ether oxygen atoms.

  有机钯冠醚配合物用于将肼离子，[NH结合2 NH 3 ] +，通过同时第一代和第二球协调设有σ-捐赠Pd和氢键合到脂族醚氧原子。
• Simultaneous First- and Second-Sphere Coordination. Organopalladium Metalloreceptors for Water, Ammonia, Amines, Hydrazine, and the Hydrazinium Ion
  作者：James E. Kickham、Stephen J. Loeb

  DOI：10.1021/ic00126a040

  日期：1995.10

  The complexes [Pd(L)(CH3CN)][BF4] (L(3) = 5,8,11-trioxa-2,14-dithia[15]-m-cyclophane and L(5) = 5,8,11,14,17-pentaoxa-2,20-dithia[21]-m-cyclophane) were prepared by palladation of the respective thiacyclophane employing [Pd(CH3CN)(4)][BF4](2) These metalloreceptors were reacted with various small substrates (H2O, NH3, NH(2)R, NMR(2) NH2NH2, and NH2NH3+) capable of simultaneously coordinating to the Pd center and hydrogen-bonding with the peripheral ether oxygens. [Pd(L(3))(NH3)][BF4] crystallized in the space group Pbca with a = 21.377(4) Angstrom, b = 21.656(5) Angstrom, c = 9.437(6) Angstrom, V = 4368(2) Angstrom(3), and Z = 8. The structure refined to R = 6.41% and R(w) = 7.03% for 659 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(3))(NH2NH2)][BF4] crystallized in the space group P ($) over bar 1 with a = 11.652(3> Angstrom, b = 12.669(4) Angstrom, c = 8.355(1) Angstrom, a = 94.13(2)degrees, beta = 94.34(2)degrees, gamma = 117.21(1)degrees, V = 1090.3(5) Angstrom(3), and Z = 2. The structure refined to R = 2.81% and R(w) = 3.40% for 2709 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(5))(H2O)][BF4] crystallized in the space group P1 ($) over bar with a = 11.076(3) Angstrom, b = 15.147(5) Angstrom, c = 8.586(2) Angstrom, V = 1284(1) Angstrom(3), and Z = 2. The structure refined to R = 3.14% and R(w) = 4.06% for 2275 reflections with F-o(2) > 3 sigma(F-o(2)). [Pd(L(3))(NH2NH3)][CF3SO3](2) crystallized in the space group P2(1)/c with a = 11.906(4) Angstrom, b = 17.19(1) Angstrom, c = 15.313(4) Angstrom beta = 111.18(2)degrees, V = 2923(4) Angstrom(3), and Z = 4. The structure refined to R = 3.13% and R(w) = 4.25% for 2954 reflections with F-o(2)) > 3 sigma(F-o(2)). [Pd(L(5))(NH2NH3)][BF4](2) crystallized in the space group P ($) over bar 1 with a = 9.391(3) Angstrom, b = 18.292(5) Angstrom, c = 9.107(2) Angstrom, a = 94.45(3)degrees, beta = 102.02(2)degrees, gamma = 103.51(2)degrees, V = 1474.5(8) Angstrom(3), and Z = 2. The structure refined to R = 3.69% and R(w) = 4.58% for 3059 reflections with F-o(2) > 3 sigma(F-o(2)). Each complex shows evidence of hydrogen bonding between the Pd-bound substrate and the peripheral oxygen atoms. The major hydrogen-bonding sites are the oxygen atoms adjacent to the thioether atoms, while the extent of the hydrogen bonding is dependent on the size of the polyether ring and the orientation of the substrate. Controlling the number of hydrogen bonds formed results in selective binding of primary amines (two hydrogen bonds) over secondary amines (one hydrogen bond) and tertiary amines (no hydrogen bonds) as determined by competition reactions monitored by H-1 NMR spectroscopy.