(ferrocenyl)CH2P(S)(CH2OH)2 | 180794-53-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: (ferrocenyl)CH2P(S)(CH2OH)2
• 英文别名: ferrocenylCH2P(S)(CH2OH)2；cyclopenta-1,3-diene;[cyclopenta-2,4-dien-1-ylmethyl(hydroxymethyl)phosphinothioyl]methanol;iron(2+)
• CAS: 180794-53-0
• 化学式: C₁₃H₁₇FeO₂PS
• 分子量: 324.164
• InChiKey: YGHLFVHEGDJZKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (ferrocenyl)CH2P(S)(CH2OH)2 、 7,7-dichloro-9-(4-chlorophenyl)-1,4-dimethyl-9λ6-thia-1,4,6,8,10-pentaza-5λ5,7λ5-diphosphaspiro[4.5]deca-5,7,9-triene 9-oxide 在 n-butyl lithium 作用下， 以 四氢呋喃 为溶剂， 以65%的产率得到
  参考文献：
  名称：

  二茂铁衍生的双（羟甲基）膦硫化物FcCH（R）P（S）（CH 2 OH）2（R = H，CH 3）与环状亚硫酰磷腈的反应：FcCH 2 P（S）（CH 2 O ）的晶体结构）2 PN（NPCl 2）[NS（O）Ph]和FcCH 2 P（S）（CH 2 O）2 PN 2 P [N（Me）CH 2 ] 2 [NS（O）Ph]（Fc =二茂铁基）

  摘要：

  环状六元thionylphosphazenes，（NPCL 2）2 [NS（O）X] X =氯（1）中，Ph（2）和4-ClC 6 ħ 4（3）以及所述monospirocyclic衍生物（NPCL 2）NP [N（Me）的CH 2 ] 2 [NS（O）PH]（4）和（NPCL 2）NP [N（Me）的CH 2 ] 2 [NS（O）4-ClC 6 ħ 4合成]（5）。这些化合物与二锂化二茂铁衍生的羟甲基膦硫化物FcCH 2 P（S）（CH 2OH）2（6）和FcCH（CH 3）P（S）（CH 2 OH）2（7）。1与6和7的反应未产生任何所需的产物。相反，2与6和7的1：1反应容易生成空气稳定的单螺环化合物FcCH 2 P（S）（CH 2 O）2 PN（NPCl 2）[NS（O）Ph]（8）和FcCH（CH 3）P（S）（CH 2 O）2 PN（NPCl 2）[NS（O）Ph]（9）分

  DOI：

  10.1016/s0022-328x(01)00939-1
• 作为产物：
  描述：

  (ferrocenylmethyl)bis(hydroxymethyl)phosphine 、 sulfur 以 not given 为溶剂， 生成 (ferrocenyl)CH2P(S)(CH2OH)2
  参考文献：
  名称：

  FcCH₂P(CH₂OH)₂: a new, reactive yet air-stable ferrocene-derived phosphine [Fc =(η-C₅H₅)FeC₅H₄]

  摘要：

  Reaction of FcCH(2)NMe(3)(+)I(-) with an excess of P(CH2OH)3 gives the air-stable ferrocenylphosphine FcCH(2)P(CH2OH)(2), characterised by an X-ray structure determination; reactivity towards reagents such as MeI, acrylonitrile and amines allows the synthesis of a range of new ferrocene-phosphine derivatives.

  DOI：

  10.1039/cc9960001551

文献信息

• Synthesis and reactivity of the ferrocene-derived phosphine [Fe(η-C5H5){η-C5H4CH2P(CH2OH)2}]
  作者：Nicholas J. Goodwin、William Henderson、Brian K. Nicholson、J. Kwabena Sarfo、John Fawcett、David R. Russell

  DOI：10.1039/a703666c

  日期：——

  The air-stable compound [Fe(η-C5H5)η-C5H4CH2P(CH2OH)2}] 1 has been prepared by the reaction of [Fe(η-C5H5)(η-C5H4CH2NMe3)]I with an excess of P(CH2OH)3. Compound 1 has been used to produce a range of other new compounds, thus demonstrating its versatility as a starting material; the phosphine oxide [Fe(η-C5H5)η-C5H4CH2P(O)(CH2OH)2}] 2, phosphine sulfide [Fe(η-C5H5)η-C5H4CH2P(S)(CH2OH)2}] 3, and other derivatives [Fe(η-C5H5)η-C5H4CH2P(CH2CH2CN)2}] 4, [Fe(η-C5H5)η-C5H4CH2P(CH2NEt2)2}] 5, [Fe(η-C5H5)η-C5H4CH2P(O)(CH2NEt2)2}] 6, [Fe(η-C5H5)η-C5H4CH2P(Me)(CH2OH)2}]I 7 and [Fe(η-C5H5)η-C5H4CH2P(Me)CH2OH}] 8. Crystal structure determinations for 1, 3 and 7 are reported and the hydrogen bonding of each structure described.

  空气稳定化合物 [Fe(η-C5H5)η-C5H4CH2P(CH2OH)2}] 1 通过 [Fe(η- )(η-C5H4CH2NMe3)]I 与过量 P(CH2OH)3 反应制备。化合物 1 已被用于合成一系列其他新化合物，从而展示了其作为起始材料的多样性；包括膦氧化物 [Fe(η- )η-C5H4CH2P(O)(CH2OH)2}] 2，膦硫化物 [Fe(η- )η-C5H4CH2P(S)(CH2OH)2}] 3，以及其他衍生物 [Fe(η- )η-C5H4CH2P(CH2CH2CN)2}] 4，[Fe(η- )η-C5H4CH2P(CH2NEt2)2}] 5，[Fe(η- )η-C5H4CH2P(O)(CH2NEt2)2}] 6，[Fe(η- )η-C5H4CH2P(Me)(CH2OH)2}]I 7 和 [Fe(η- )η-C5H4CH2P(Me)CH2OH}] 8。报道了 1、3 和 7 的晶体结构测定，并描述了每种结构的氢键。
• Ansa versus Spiro Substitution of Cyclophosphazenes:  Is Fluorination Essential for Ansa to Spiro Transformation of Cyclophosphazenes?
  作者：K. Muralidharan、P. Venugopalan、Anil J. Elias

  DOI：10.1021/ic034119v

  日期：2003.5.1

  analogous tetrachloro ansa compound exo-FcCH(2)P(S)(CH(2)O)(2)[P(Cl)N](2)(Cl(2)PN) (5), however, did not transform to the chlorinated spiro compound (6) in the presence of these bases. With excess of CsF, P-Cl bonds of 5 were found to undergo fluorination leading to the formation of 2, which transformed to spirocyclic compound 3. Time dependent (31)P NMR spectroscopy was used to monitor this transformation

  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。
• 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.
• 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
  作者：K. Muralidharan、Anil J. Elias

  DOI：10.1021/ic034712c

  日期：2003.11.1

  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.
• Synthesis and ansa substitution of novel examples of aryl hydrido fluorophosphazenes
  作者：Anil J Elias、K Muralidharan

  DOI：10.1016/s1387-7003(03)00045-5

  日期：2003.5

  The first examples of uncharged aryl substituted fluorinated hydridophosphazenes, N3P3F4(Ar)H [Ar = C6H5 (1), p-ClC6H4 (2)] were obtained in an unprecedented manner upon fluorination of diaryloctachlorobi(cyclophosphazenes) (N6P6Cl8(Ar)(2)) [Ar = C6H5, p-ClC6H4] using KF in acetonitrile. The compounds (1) and (2) were stable to air and moisture, and were characterized by spectral and analytical methods. Compound (1) on reaction with FcCHP(S)(CH2OLi)(2) (Fc=Ferrorcenyl) gave endo (3) and exo (4) isomers of ansa. substituted hydridophosphazenes. The crystal structure of (4) was determined and the structure shows the ansa substitution on the phosphazene ring, trans to the phenyl group with the hydridophosphazene ring puckered to a partial chair configuration. (C) 2003 Elsevier Science B.V. All rights reserved.