bis(di-(4-thiophenyl)phosphino)ethane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: bis(di-(4-thiophenyl)phosphino)ethane
• 英文别名: 4-[2-Bis(4-sulfanylphenyl)phosphanylethyl-(4-sulfanylphenyl)phosphanyl]benzenethiol；4-[2-bis(4-sulfanylphenyl)phosphanylethyl-(4-sulfanylphenyl)phosphanyl]benzenethiol
• 化学式: C₂₆H₂₄P₂S₄
• 分子量: 526.688
• InChiKey: WFHWRMHDCVXQPA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  4
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  4-溴茴香硫醚 在 正丁基锂 、 sodium 作用下， 以 乙醚 、 正己烷 、 氨 为溶剂， 反应 1.5h， 生成 bis(di-(4-thiophenyl)phosphino)ethane
  参考文献：
  名称：

  Synthesis of triarylphosphines having para –SH and –SMe groups

  摘要：

  The phosphines P(C6H4-4-SR)(3) (R = H, Me, 2-C5H9O) and (C6H4-4-SR)(2)PCH2CH2P(C6H4-4-SR)(2) (R = H, Me) have been synthesized. The phosphines with -SMe groups can be prepared by reaction of 4-BrC6H4SMe with either BuLi or magnesium (to generate the corresponding Grignard compound) followed by reaction with PCl3 or Cl2PCH2CH2PCl2, respectively. The methyl group can be eliminated by reaction with sodium in liquid NH3. Other methods of protection/deprotection of the thiol group failed to afford the desired compounds. Reaction of 4-BrC6H4SH with dihydropyrane afforded the protected thiol 4-BrC6H4S-2-C5H9O from which the corresponding phosphine was successfully synthesized. However, attempts to remove the tetrahydropyranyl group by reaction with AgNO3-HCl, gave an insoluble polymer as product. Reaction of P(C6H4SR)(3) (R = H, Me) with Ni(CO)(4) affords the corresponding mono phosphine complex quantitatively. The complex with the unprotected thiol group can be absorbed on a gold surface and the corresponding v(CO) bands were detected by grazing angle Fourier transform infrared reflection absorption spectroscopy (grazing angle FTIR-RAS). Reaction of Rh(acac)(CO)(2) with P(C6H4SR)(3) (R = Me) affords the complex Rh(acac) (CO)(P(C6H4SR)(3)) (R = Me), but if R = H a polymer insoluble in any solvent was obtained. The same occurs in the case of PtCl2(CO)(DMSO). Apparently, once P(C6H4SH)(3) is coordinated to a metal not in the zero oxidation state, oxidation of the thiol group to disulphide becomes very easy even in a dinitrogen atmosphere. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2004.08.031

文献信息

• Synthesis of triarylphosphines having para –SH and –SMe groups
  作者：Fabio Ragaini、Luca Lunardi、Diego Tomasoni、Vittoria Guglielmi

  DOI：10.1016/j.jorganchem.2004.08.031

  日期：2004.11

  The phosphines P(C6H4-4-SR)(3) (R = H, Me, 2-C5H9O) and (C6H4-4-SR)(2)PCH2CH2P(C6H4-4-SR)(2) (R = H, Me) have been synthesized. The phosphines with -SMe groups can be prepared by reaction of 4-BrC6H4SMe with either BuLi or magnesium (to generate the corresponding Grignard compound) followed by reaction with PCl3 or Cl2PCH2CH2PCl2, respectively. The methyl group can be eliminated by reaction with sodium in liquid NH3. Other methods of protection/deprotection of the thiol group failed to afford the desired compounds. Reaction of 4-BrC6H4SH with dihydropyrane afforded the protected thiol 4-BrC6H4S-2-C5H9O from which the corresponding phosphine was successfully synthesized. However, attempts to remove the tetrahydropyranyl group by reaction with AgNO3-HCl, gave an insoluble polymer as product. Reaction of P(C6H4SR)(3) (R = H, Me) with Ni(CO)(4) affords the corresponding mono phosphine complex quantitatively. The complex with the unprotected thiol group can be absorbed on a gold surface and the corresponding v(CO) bands were detected by grazing angle Fourier transform infrared reflection absorption spectroscopy (grazing angle FTIR-RAS). Reaction of Rh(acac)(CO)(2) with P(C6H4SR)(3) (R = Me) affords the complex Rh(acac) (CO)(P(C6H4SR)(3)) (R = Me), but if R = H a polymer insoluble in any solvent was obtained. The same occurs in the case of PtCl2(CO)(DMSO). Apparently, once P(C6H4SH)(3) is coordinated to a metal not in the zero oxidation state, oxidation of the thiol group to disulphide becomes very easy even in a dinitrogen atmosphere. (C) 2004 Elsevier B.V. All rights reserved.