tris(O-4-cyanophenyl)phosphorothionate | 107474-47-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tris(O-4-cyanophenyl)phosphorothionate
• 英文别名: Tris(4-cyanophenoxy)-sulfidophosphanium；tris(4-cyanophenoxy)-sulfidophosphanium
• CAS: 107474-47-5
• 化学式: C₂₁H₁₂N₃O₃PS
• 分子量: 417.384
• InChiKey: ZQJFKQXBXJTCNB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  100
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  4-羟基苯甲腈 在 sulfur 、 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 48.0h， 生成 tris(O-4-cyanophenyl)phosphorothionate
  参考文献：
  名称：

  Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates

  摘要：

  Six tris(aryloxy)phosphorothionates substituted in the para position of the aromatic rings were synthesized and studied by P-31 NMR, X-ray diffraction techniques and ab initio calculations at a RHF/6-31G** level of theory, in order to find the main structural factors associated with the delta P-31 in these compounds. As the electron-withdrawing (EW) ability of the substituents was increased, an 'abnormal' shielding effect on delta P-31 of the arylphosphorothionates was observed. The analyses of the geometrical properties obtained through both experimental and theoretical methods showed that a propeller-type conformation is preferred for the arylphosphorothionates, except in the case of the tris(O-4-methylphenyl)phosphorothionate, since one of the aromatic rings is not rotated in the same direction as the other two in the solid state. The main features associated with the delta P-31 NMR of compounds 1-6 were a decrease of the averaged O-P-O angle and mainly the shortening of the P=S bond length, which is consistent with an increase of the thiophosphoryl bond order as delta P-31 values go upfield. On the other hand, comparison of the experimental and calculated bond lengths and bond angles involving a bonded atoms to phosphorus of the six compounds suggested that stereoelectronic interactions of the type n(pi)O-sigma*(P=S), n(pi)O-sigma*(P-OAr) and n(pi)S-sigma*(P-OAr) could be present in the arylphosphorothionates 1-6. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.12.053

文献信息

• Phase-transfer-catalyzed preparation of triaryl phosphorothionates
  作者：John J. Talley、Carol B. Berman

  DOI：10.1021/je00048a038

  日期：1987.4
• Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates
  作者：Javier Hernández、Francisco M. Goycoolea、Denisse Zepeda-Rivera、Josué Juárez-Onofre、Karla Martínez、Jaime Lizardi、Magali Salas-Reyes、Bárbara Gordillo、Carlos Velázquez-Contreras、Oscar García-Barradas、Samuel Cruz-Sánchez、Zaira Domínguez

  DOI：10.1016/j.tet.2005.12.053

  日期：2006.3

  Six tris(aryloxy)phosphorothionates substituted in the para position of the aromatic rings were synthesized and studied by P-31 NMR, X-ray diffraction techniques and ab initio calculations at a RHF/6-31G** level of theory, in order to find the main structural factors associated with the delta P-31 in these compounds. As the electron-withdrawing (EW) ability of the substituents was increased, an 'abnormal' shielding effect on delta P-31 of the arylphosphorothionates was observed. The analyses of the geometrical properties obtained through both experimental and theoretical methods showed that a propeller-type conformation is preferred for the arylphosphorothionates, except in the case of the tris(O-4-methylphenyl)phosphorothionate, since one of the aromatic rings is not rotated in the same direction as the other two in the solid state. The main features associated with the delta P-31 NMR of compounds 1-6 were a decrease of the averaged O-P-O angle and mainly the shortening of the P=S bond length, which is consistent with an increase of the thiophosphoryl bond order as delta P-31 values go upfield. On the other hand, comparison of the experimental and calculated bond lengths and bond angles involving a bonded atoms to phosphorus of the six compounds suggested that stereoelectronic interactions of the type n(pi)O-sigma*(P=S), n(pi)O-sigma*(P-OAr) and n(pi)S-sigma*(P-OAr) could be present in the arylphosphorothionates 1-6. (c) 2005 Elsevier Ltd. All rights reserved.