1,2,3,4,7,8,9,10-Octachlorobenzo[c][1,2,5,6]benzotetrathiocine

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 1,2,3,4,7,8,9,10-Octachlorobenzo[c][1,2,5,6]benzotetrathiocine
• 化学式: C₁₂Cl₈S₄
• 分子量: 556.02
• InChiKey: PXBTZXSZZCGMOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3,4,5,6-四氯-1,2-苯二硫醇 在 磺酰氯 作用下， 以 苯 为溶剂， 反应 1.0h， 以90%的产率得到1,2,3,4,7,8,9,10-Octachlorobenzo[c][1,2,5,6]benzotetrathiocine
  参考文献：
  名称：

  Conformational isomers of 1,2,5,6-tetrathiocins and the photoisomerization of a 1,2,5,6-tetrathiocin into a 1,2,3,6-tetrathiocin: X-ray structures of (C₆X₄S₂)₂ (X = F, Cl) and C₆F₄SSSC₆F₄S

  摘要：

  1,2,5,6-四硫杂环己烷(C6X4S2)2 (3a，X = F; 3b，X = Cl)通过将1,2-C6X4(SH)2 (X = F，Cl)与I2或SO2Cl2氧化反应，高产得到。在固态下，3a具有C2h (椅形)构象，并结晶为两个不同的相：α-(C6F4S2)2，单斜晶系，P21/a，a = 9.351(2)，b = 6.465(2)，c = 11.546(2) Å，ß = 95.60(1)°，V = 694.6(2) Å3，Z = 2；ß-(C6F4S2)2，单斜晶系，P21/c，a = 4.825(2)，b = 11.302(2)，c = 12.453(2) Å，ß = 91.45(3)°，V = 678.8(3) Å3，Z = 2。相比之下，3b显示出D2 (扭船)结构，并在C2/c空间群中结晶，其a = 15.243(3)，b = 8.703(2)，c = 27.010(14) Å，ß = 92.81(4)°，V = 3578(1) Å3，Z = 8。衍生物3a在甲苯溶液中存在两种构象异构体的平衡混合物。VT 19F NMR数据提供了热力学参数H° = 9.9 ± 0.4 kJ mol-1和S° = 14 ± 1 J K-1 mol-1。对于3a的密度泛函理论计算表明，D2构象比C2h异构体低4.6 kJ mol-1的能量。3a在苯中的光解促进了硫的跨环迁移，得到1,2,3,6-四硫杂环己烷，C6F4SSSC6F4S (6)，其相对于反极硫原子存在椅形构象。6的晶体结构：正交晶系，空间群Pnma，a = 8.652(6)，b = 19.084(4)，c = 8.301(6) Å，V = 1370.6(14) Å3，Z = 4。异构体3a和6还通过EI质谱，19F NMR，FTIR和拉曼光谱进行了表征。关键词：四硫杂环己烷，构象异构体，光异构化。

  DOI：

  10.1139/v98-106

文献信息

• Conformational isomers of 1,2,5,6-tetrathiocins and the photoisomerization of a 1,2,5,6-tetrathiocin into a 1,2,3,6-tetrathiocin: X-ray structures of (C₆X₄S₂)₂ (X = F, Cl) and C₆F₄SSSC₆F₄S
  作者：Tristram Chivers、Masood Parvez、Ignacio Vargas-Baca、Gabriele Schatte

  DOI：10.1139/v98-106

  日期：1998.7.1

  The 1,2,5,6-tetrathiocins (C₆X₄S₂)₂ (3a, X = F; 3b, X = Cl) are obtained in high yields by the oxidation of the dithiols 1,2-C₆X₄(SH)₂ (X = F, Cl) with I₂ or SO₂Cl₂, respectively. In the solid state 3a has the C_2h (chair) conformation and crystallizes in two different phases: alpha-(C₆F₄S₂)₂, monoclinic, P2₁/a, a = 9.351(2), b = 6.465(2), and c = 11.546(2) Å, ß = 95.60(1)°, V = 694.6(2) ų, Z = 2; and ß-(C₆F₄S₂)₂, monoclinic, P2₁/c, a = 4.825(2), b = 11.302(2), and c = 12.453(2) Å, ß = 91.45(3)°, V = 678.8(3) ų, Z = 2. By contrast, 3b displays a D₂ (twist-boat) structure and crystallizes in the C2/c space group with a = 15.243(3), b = 8.703(2), and c = 27.010(14) Å, ß = 92.81(4)°, V = 3578(1) ų, and Z = 8. The derivative 3a exists as an equilibrium mixture of two conformational isomers in toluene solution. The VT ¹⁹F NMR data afford the thermodynamic parameters H° = 9.9 ± 0.4 kJ mol^-1 and S° = 14 ± 1 J K^-1 mol^-1. Density functional theory calculations for 3a indicate that the D₂ conformation is lower in energy than the C_2h isomer by 4.6 kJ mol^-1. The photolysis of 3a in benzene promotes a transannular sulfur migration to give the 1,2,3,6-tetrathiocin, C₆F₄SSSC₆F₄S (6), which exists in a chair conformation with respect to antipodal sulfur atoms. Crystal structure of 6: orthorhombic, space group Pnma, a = 8.652(6), b = 19.084(4), and c = 8.301(6) Å, V = 1370.6(14) ų, and Z = 4. The isomers 3a and 6 were also characterized by EI mass spectrometry, ¹⁹F NMR, FTIR, and Raman spectroscopies.Key words: tetrathiocins, conformational isomers, photoisomerization.

  1,2,5,6-四硫杂环己烷(C6X4S2)2 (3a，X = F; 3b，X = Cl)通过将1,2-C6X4(SH)2 (X = F，Cl)与I2或SO2Cl2氧化反应，高产得到。在固态下，3a具有C2h (椅形)构象，并结晶为两个不同的相：α-(C6F4S2)2，单斜晶系，P21/a，a = 9.351(2)，b = 6.465(2)，c = 11.546(2) Å，ß = 95.60(1)°，V = 694.6(2) Å3，Z = 2；ß-(C6F4S2)2，单斜晶系，P21/c，a = 4.825(2)，b = 11.302(2)，c = 12.453(2) Å，ß = 91.45(3)°，V = 678.8(3) Å3，Z = 2。相比之下，3b显示出D2 (扭船)结构，并在C2/c空间群中结晶，其a = 15.243(3)，b = 8.703(2)，c = 27.010(14) Å，ß = 92.81(4)°，V = 3578(1) Å3，Z = 8。衍生物3a在甲苯溶液中存在两种构象异构体的平衡混合物。VT 19F NMR数据提供了热力学参数H° = 9.9 ± 0.4 kJ mol-1和S° = 14 ± 1 J K-1 mol-1。对于3a的密度泛函理论计算表明，D2构象比C2h异构体低4.6 kJ mol-1的能量。3a在苯中的光解促进了硫的跨环迁移，得到1,2,3,6-四硫杂环己烷，C6F4SSSC6F4S (6)，其相对于反极硫原子存在椅形构象。6的晶体结构：正交晶系，空间群Pnma，a = 8.652(6)，b = 19.084(4)，c = 8.301(6) Å，V = 1370.6(14) Å3，Z = 4。异构体3a和6还通过EI质谱，19F NMR，FTIR和拉曼光谱进行了表征。关键词：四硫杂环己烷，构象异构体，光异构化。