bis-(bis-(trimethylsilyl)amino)thiophosphoryl chloride | 129732-18-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机硫代磷酸及其衍生物
• 英文名称: bis-(bis-(trimethylsilyl)amino)thiophosphoryl chloride
• 英文别名: N,N,N',N'-Tetrakis(trimethylsilyl)phosphorodiamidothioic chloride；[[[[bis(trimethylsilyl)amino]-chlorophosphinothioyl]-trimethylsilylamino]-dimethylsilyl]methane
• CAS: 129732-18-9
• 化学式: C₁₂H₃₆ClN₂PSSi₄
• 分子量: 419.266
• InChiKey: QYWTVJLHTWGVKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.39
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis-(bis-(trimethylsilyl)amino)thiophosphoryl chloride 在 (C₆H₅)3PO 作用下， 以 二氯甲烷 为溶剂， 生成 1,3-bis(trimethylsilyl)-2,2-dimethyl-4-thiodiazasilaphosphetidine-S-trichloroalluminum
  参考文献：
  名称：

  酸诱导的（甲硅烷基氨基）（亚氨基）（硫属元素基）正膦环化反应中的真正杂环，以及双（双（三甲基甲硅烷基）氨基]硫代磷酰氯中氯离子的提取结果

  摘要：

  The thio and seleno derivatives of the tricoordinate phosphorane P[NtBu(SiMe3)](NtBu)E 1 (E = S, Se) undergo a novel cyclization upon reaction with Lewis acids. A number of derivatives of the NSiEP framework have been isolated and characterized, including X-ray crystal structures of three derivatives, the neutral complexes NtBuSiMe2SP(Me)NtBu.AlCl3 (2a) and NtBuSiMe2SeP(Me)NtBu-GaCl3 (3), and the triflate salt of the protonated complex [NtBuSiMe2SP(Me)NtBu.H+] (2c). The new compounds are rare examples of ring systems which contain only one atom of each element in the heterocyclic framework, systems for which we introduce the terminology "genuine heterocycles". A similar cyclization process is observed for the new thiophosphoryl chloride P[N(SiMe3)2]2(S)Cl (4) in the presence of chloride ion acceptors to give salts of the cation [N(SiMe3)SiMe2SP(Me)N(SiMe3)2]+ (5), a direct analog of genuine heterocycles 2. Two salts of 5 have been structurally characterized. Both cyclization reactions have been examined by variable-temperature P-31 and H-1 NMR spectroscopy, and speculations are made as to the nature of the observed intermediates. The NSiSP(N) genuine heterocyclic unit is shown to be thermodynamically unstable with respect to the isomeric NSiNP(S) 1,3-diazasilaphosphetidine framework 6. The isomerization process is initiated by reaction with a base and can also be promoted thermally for salts of 5.

  DOI：

  10.1021/om00042a045

文献信息

• Syntheses and crystal structures for the first two examples of the four-membered PNSiS heterocycle
  作者：Neil Burford、Rupert E. H. Spence、J. Marc Whalen、Robin D. Rogers、John F. Richardson

  DOI：10.1021/om00161a002

  日期：1990.11
• Genuine heterocycles from the acid-induced cyclization of (silylamino)(imino)(chalcogeno)phosphoranes and as a result of chloride ion abstraction from bis[bis(trimethylsilyl)amino]thiophosphoryl chloride
  作者：Neil Burford、Simon Mason、Rupert E. H. Spence、J. Marc Whalen、John F. Richardson、Robin D. Rogers

  DOI：10.1021/om00042a045

  日期：1992.6

  The thio and seleno derivatives of the tricoordinate phosphorane P[NtBu(SiMe3)](NtBu)E 1 (E = S, Se) undergo a novel cyclization upon reaction with Lewis acids. A number of derivatives of the NSiEP framework have been isolated and characterized, including X-ray crystal structures of three derivatives, the neutral complexes NtBuSiMe2SP(Me)NtBu.AlCl3 (2a) and NtBuSiMe2SeP(Me)NtBu-GaCl3 (3), and the triflate salt of the protonated complex [NtBuSiMe2SP(Me)NtBu.H+] (2c). The new compounds are rare examples of ring systems which contain only one atom of each element in the heterocyclic framework, systems for which we introduce the terminology "genuine heterocycles". A similar cyclization process is observed for the new thiophosphoryl chloride P[N(SiMe3)2]2(S)Cl (4) in the presence of chloride ion acceptors to give salts of the cation [N(SiMe3)SiMe2SP(Me)N(SiMe3)2]+ (5), a direct analog of genuine heterocycles 2. Two salts of 5 have been structurally characterized. Both cyclization reactions have been examined by variable-temperature P-31 and H-1 NMR spectroscopy, and speculations are made as to the nature of the observed intermediates. The NSiSP(N) genuine heterocyclic unit is shown to be thermodynamically unstable with respect to the isomeric NSiNP(S) 1,3-diazasilaphosphetidine framework 6. The isomerization process is initiated by reaction with a base and can also be promoted thermally for salts of 5.