9-triptycylthiol | 1160681-99-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 9-triptycylthiol
• 英文别名: 9-triptycylSH；9-Mercaptotriptycene；pentacyclo[6.6.6.02,7.09,14.015,20]icosa-2,4,6,9,11,13,15,17,19-nonaene-1-thiol
• CAS: 1160681-99-1
• 化学式: C₂₀H₁₄S
• 分子量: 286.397
• InChiKey: MCPCFIOBRDIXJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  9-triptycylthiol 、 对碘苯甲酸乙酯 在 sodium hydride 、 copper(l) iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 38.0h， 以47%的产率得到9-[p-(ethoxycarbonyl)phenylsulfanyl]triptycene
  参考文献：
  名称：

  Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations

  摘要：

  The p(Z)-pi(Ar) conjugations must operate fully in the ground states of 9-(arylchalcogenyl)triptycenes (p-YC(6)H(4)ZTpc:1 (Z = O), 2 (Z = S), 3 (Z = Se), and 4 (Z = Te)), where the p-YC6H4 group is placed in the bisected area between two phenyl planes of the triptycyl group with the parallel orientation. The ground-state geometries, which we call (A: pl), are confirmed by X-ray analysis. However, the conjugations never operate in the transition states between (A: pl) and/or the topomeric structures (A': pl'), where the Z-C-Tpc bond is perpendicular to the plane. The site-exchange processes correlate to the conjugations. Temperature-dependent H-1 NMR spectra are analyzed for 2 and 3 to demonstrate the effective p(Z)-pi(Ar) conjugations. The activation energies for the interconversion between (A: pl) and (A: pl) (GR: gear process) were obtained for 2 (Delta G(GR)(double dagger)(2)) and 3 (Delta G(GR)(double dagger)(3)). Delta G(GR)(double dagger)(3) correlate well with Delta G(GR)(double dagger)(2), and AG(GR)(double dagger)(2),ire well analyzed by the Hammett-type dual parameters. Delta G(GR)(double dagger)(2) and Delta G(GR)(double dagger)(3) are demonstrated to be controlled by the resonance interaction of the p(Z)-pi(C6H4)-p(Y) conjugations. QC calculations are performed on the ground and exited states of 1-4, which clarify the effective p(Z)-pi(C6H4)-p(Y) conjugations for Z of heavier atoms.

  DOI：

  10.1021/jo900488r

文献信息

• Synthesis and X-ray Structural Analysis of Hydrido(thiolato) Platinum(II) Complexes
  作者：Norio Nakata、Suzuka Yamamoto、Wataru Hashima、Akihiko Ishii

  DOI：10.1246/cl.2009.400

  日期：2009.5.5

  TripSH (4, Trip = 9-triptycyl) in toluene afforded cis-hydrido(thiolato) Pt II complex [PtH(STrip)(PPh 3 ) 2 ] (5), as thermally and moisture-stable colorless crystals in 91% yield. Complex 5 was fully characterized by 1 H, 13 C 1 H}, and 31 P 1 H} NMR and IR spectroscopies, and the molecular structure of 5 was determined by X-ray crystallography.

  [Pt(η 2 -nb)(PPh 3 ) 2 ] 与空间位阻硫醇 TripSH (4, Trip = 9-triptycyl) 在甲苯中的氧化加成得到顺式氢化（硫醇基）Pt II 复合物 [PtH(STrip )(PPh 3 ) 2 ] (5)，作为热和湿稳定的无色晶体，产率为 91%。配合物 5 被 1 H、 13 C 1 H} 和 31 P 1 H} NMR 和 IR 光谱完全表征，5 的分子结构由 X 射线晶体学确定。
• Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations
  作者：Satoko Hayashi、Takashi Nakamoto、Mao Minoura、Waro Nakanishi

  DOI：10.1021/jo900488r

  日期：2009.7.3

  The p(Z)-pi(Ar) conjugations must operate fully in the ground states of 9-(arylchalcogenyl)triptycenes (p-YC(6)H(4)ZTpc:1 (Z = O), 2 (Z = S), 3 (Z = Se), and 4 (Z = Te)), where the p-YC6H4 group is placed in the bisected area between two phenyl planes of the triptycyl group with the parallel orientation. The ground-state geometries, which we call (A: pl), are confirmed by X-ray analysis. However, the conjugations never operate in the transition states between (A: pl) and/or the topomeric structures (A': pl'), where the Z-C-Tpc bond is perpendicular to the plane. The site-exchange processes correlate to the conjugations. Temperature-dependent H-1 NMR spectra are analyzed for 2 and 3 to demonstrate the effective p(Z)-pi(Ar) conjugations. The activation energies for the interconversion between (A: pl) and (A: pl) (GR: gear process) were obtained for 2 (Delta G(GR)(double dagger)(2)) and 3 (Delta G(GR)(double dagger)(3)). Delta G(GR)(double dagger)(3) correlate well with Delta G(GR)(double dagger)(2), and AG(GR)(double dagger)(2),ire well analyzed by the Hammett-type dual parameters. Delta G(GR)(double dagger)(2) and Delta G(GR)(double dagger)(3) are demonstrated to be controlled by the resonance interaction of the p(Z)-pi(C6H4)-p(Y) conjugations. QC calculations are performed on the ground and exited states of 1-4, which clarify the effective p(Z)-pi(C6H4)-p(Y) conjugations for Z of heavier atoms.