[(ferrocenyl)CH2P(S)(CH2O)2PN](F2PN)2 | 301155-79-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [(ferrocenyl)CH2P(S)(CH2O)2PN](F2PN)2
• 英文别名: cyclopenta-1,3-diene;9-(cyclopenta-2,4-dien-1-ylmethyl)-2,2,4,4-tetrafluoro-9-sulfanylidene-7,11-dioxa-1,5-diaza-3-azanida-2λ5,4λ5,9λ5-triphospha-6-phosphoniaspiro[5.5]undeca-1,4-diene;iron(2+)
• CAS: 301155-79-3
• 化学式: C₁₃H₁₅F₄FeN₃O₂P₄S
• 分子量: 533.083
• InChiKey: DIPGFALPJGLUQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.59
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  76.3
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  正丁基锂 、 (ferrocenyl)CH2P(S)(CH2OH)2 、 [(ferrocenyl)CH2P(S)(CH2O)2PN](F2PN)2 以 四氢呋喃 为溶剂， 以36.8%的产率得到
  参考文献：
  名称：

  Preparation of the First Examples of Ansa−Spiro Substituted Fluorophosphazenes and Their Structural Studies:  Analysis of C−H···F−P Weak Interactions in Substituted Fluorophosphazenes

  摘要：

  The reactions of fluorophosphazenes, endo ansa FcCH(2)P(S)(CH2O)(2)[P(F)N](2)(F2PN) (1) (Fc = ferrocenyl) and spiro [RCH2P(S)(CH2O)(2)PN](F2PN)(2) (R = Fc (2), C6H5 (3)], with dilithiated diols have been explored. The study resulted in the formation of the first examples of ansa-spiro substituted fluorinated cyclophosphazenes as well as a bisansa substituted fluorophosphazene. The bisansa compound {1,3-[FcCH(2)P(S)(CH2O)(2)]}{5-[CH2(CH2O)(2)]}N3P3F2 (4) was found to be nongeminaly substituted with both the ansa rings in cis configuration, which is in stark contrast to the observations on cyclic chlorophosphazenes where geminal bisansa formation has been observed. The ansaspiro compounds (5-7) underwent the ansa to spiro transformation leading to dispiro compounds in the presence of catalytic amounts of CsF at room temperature. Two of the ansa-spiro compounds, endo-{3,5-[FcCH(2)P(S)(CH2O)(2)]}{1,1-[CH2(CH2O)(2)]}N3P3F2 (5) and endo, {3,5-[FcCH(2)P(S)(CH2O)(2)]}{1,1,-[FcCH(2)P(S)(CH2O)(2)]}N3P3F2 (6), were structurally characterized, and the crystal structures indicate boat-chair conformation as well as crown conformation for the eight-membered ansa rings. Weak C-(HF)-F-...-P interactions observed in the crystal structures of the ansa-spiro substituted fluorophosphazene derivatives have been analyzed and compared with C-(HF)-F-...-P interactions of other fluorinated phosphazenes and thionyl phosphazenes.

  DOI：

  10.1021/ic034712c
• 作为产物：
  描述：

  endo-FcCH2P(S)(CH2O)2[P(F)N]2(F2PN) 在 pyridine 作用下， 以 四氢呋喃 为溶剂， 以0%的产率得到[(ferrocenyl)CH2P(S)(CH2O)2PN](F2PN)2
  参考文献：
  名称：

  Ansa与环磷腈的螺取代：氟化反应对于ansa向环磷腈的螺转化是必不可少的吗？

  摘要：

  氟化ansa取代的环磷腈内-FcCH（2）P（S）（CH（2）O）（2）[P（F）N]（2）（F（2）PN）[Fc =二茂铁基]（1）和exo-FcCH（2）P（S）（CH（2）O）（2）[P（F）N]（2）（F（2）PN）（2）容易转化为螺环化合物[FcCH（2 ）P（S）（CH（2）O）（2）PN]（F（2）PN）（2）（3）不仅在存在CsF的情况下，而且还与非氟化碱（例如Cs（2））一起存在CO（3），K（2）CO（3），KOBu（t），Et（3）N，DABCO，DBN和DBU。但是，类似的四氯ansa化合物exo-FcCH（2）P（S）（CH（2）O）（2）[P（Cl）N]（2）（Cl（2）PN）（5）没有在这些碱的存在下转化为氯化螺化合物（6）。在过量的CsF下，发现5的P-Cl键发生氟化导致形成2，其转化为螺环化合物3。使用时间依赖性（31）P NMR光谱法监测该转化。

  DOI：

  10.1021/ic034119v

文献信息

• Syntheses of Novel Exo and Endo Isomers of Ansa-Substituted Fluorophosphazenes and Their Facile Transformations into Spiro Isomers in the Presence of Fluoride Ions
  作者：K. Muralidharan、N. Dastagiri Reddy、Anil J. Elias

  DOI：10.1021/ic0001863

  日期：2000.9.1

  Reactions of the dilithiated diols RCH2P(S)(CH2OLi)(2) [R = Fe (1), Ph (2) (Fc = ferrocenyl)] with N3P3F6 in equimolar ratios at -80 OC result exclusively in the formation of two structural isomers :of ansa-substituted compounds, endo-RCH2P(S)(CH2O)(2)[P(F)N](2)(F2PN) [R = Fe (3a), Ph (4a)] and exo-RCH2P(S)(CH2O)(2)[P(F)N](2)(F2PN) [R = Fe (3b), Ph (4b)], which are separated by column chromatography. Increasing the reaction temperature to -40 degrees C results in more of the exo isomers 3b and 4b at the expense of the endo isomers. The formation of the ansa-substituted compounds is found to depend on the dilithiation of the diols, as a reaction of the silylated phosphine sulfide FcCH(2)P(S)(CH2OSiMe3)(2) (5) With N3P3F6 in the presence of CsF does not yield either 3a or 3b but instead fives the spiro isomer [FcCH(2)P(S)(CH2O)(2)PN](F2PN)(2) (6) as the disubstitution product of N3P3F6. The ansa isomers 3a and 3b an transformed into the spiro compound 6 in the presence of catalytic amounts of CsF at room temperature in THF, while 4a and 4b are transformed into the spiro compound [PhCH2P(S)(CH2O)(2)PN](F2PN)(2) (7) under similar conditions. The novel conversions of ansa-substituted phosphazenes into spirocyclic phosphazenes Were monitored by time-dependent P-31 NMR spectroscopy. The effect of temperature on a transformation was studied by carrying out reactions at various temperatures in the range from -60 to +33 degrees C for 3b. In addition, compounds 3a, 3b, 4a, and 6 were structurally characterized. In the case of the ansa compounds, the nitrogen atom flanked by the bridging phosphorus sites was found to deviate significantly from the plane defined by the five remaining atoms of the phosphazene ring.