1,2,3,4-tetrapropyl-5-phenylcyclopenta-1,3-diene

• 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: 1,2,3,4-tetrapropyl-5-phenylcyclopenta-1,3-diene
• 英文别名: Cp^4PrPhH；(2,3,4,5-Tetrapropylcyclopenta-2,4-dien-1-yl)benzene
• 化学式: C₂₃H₃₄
• 分子量: 310.523
• InChiKey: SLRGALKUIWMLHC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  dysprosium(III) chloride 、 二苯甲酰基甲烷 、 1,2,3,4-tetrapropyl-5-phenylcyclopenta-1,3-diene 在 正丁基锂 、 benzoyl lithium 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 以37%的产率得到[(C₅Pr₄Ph)Dy(DBM)2(THF)]
  参考文献：
  名称：

  Half-Sandwich Complexes of Dy^III: A Janus-Motif with Facile Tunability of Magnetism

  摘要：

  Three half-sandwich organometallics [(Cp-R)Dy(DBM)(2)(THF)]center dot solvent [Cp-R = Cp* (1Dy, Cp* = C5Me5), Cp-4PrPh (2Dy, Cp-4PrPh = C5Pr4Ph), Cp' (3Dy, Cp' = C5Me4TMS, solvent = THF), DBM- = dibenzoylmethanoate anion, THF = tetrahydrofuran, TMS = trimethylsilyl] with a Janus structural motif, where the ligands of DBM- and [Cp-R](-) are widely used in Dy-III/beta-diketonate and Ln(III)/cyclopentadienyl systems, were synthesized, structurally and magnetically characterized, and theoretically investigated. Single-crystal structural analysis reveals that the three complexes crystallize in the same space group P2(1/c). All the molecules display slow magnetic relaxation in the absence of an applied magnetic field, and the magnetic hysteresis loops of 2Dy and 3Dy can be observed under a magnetic field sweep rate of 10 Oe/s, indicating all three complexes are single-ion magnets (SIMs). The modifications of the Cp-ring lead to the distinct increment of the energy barrier from 46 K (1Dy) to 76 K (2Dy) to 320 K (3Dy). Ab initio calculations show that the ground Kramers doublet is strongly axial with gz approaching the value of 20 expected for the pure M-J = +/- 15/2 state, and the magnetic anisotropy axes for three complexes share a similar orientation which is perpendicular to the molecular pseudosymmetric axis. Electrostatic analyses confirm the magnetic anisotropy orientations and reveal that proper charge distribution of the coordination sphere (including the first and second) around Dy-III ion enhances the magnetic anisotropy. Further investigation of the relaxation mechanisms suggests the energy barrier should be carefully used to evaluate single-ion magnets if Raman process is dominant in the low temperature range.

  DOI：

  10.1021/ic502734z
• 作为产物：
  描述：

  苯甲醛 、 5,6-dipropyl-4-iododeca-(4Z,6E)-4,6-diene 在 叔丁基锂 、 盐酸 作用下， 以 乙醚 、 正戊烷 、 水 为溶剂， 反应 1.5h， 生成 1,2,3,4-tetrapropyl-5-phenylcyclopenta-1,3-diene
  参考文献：
  名称：

  4-甲基，4-苯基和4-氢取代的1-硫代-1,3-丁二烯与醛的反应：多取代的环戊二烯的制备

  摘要：

  研究了醛与丁二烯基骨架第4位上具有甲基，苯基或氢取代基的1-lithio-1,3-丁二烯试剂的反应。使用强酸性溶液水解后，可以高收率获得多取代的环戊二烯衍生物。反应机理研究表明，这些环戊二烯是通过酸促进的共轭二烯醇环化反应形成的。因此，可以通过调节水解条件，从相同的1-硫代-1,3-丁二烯试剂和醛中获得立体定义的顺式取代的二烯醇或种类繁多的取代的环戊二烯。

  DOI：

  10.1016/j.tet.2006.04.083

文献信息

• Rare-Earth Metal Tris(trimethylsilylmethyl) Anionic Complexes Bearing One 1-Phenyl-2,3,4,5-tetrapropylcyclopentadienyl Ligand: Synthesis, Structural Characterization, and Application
  作者：Ling Xu、Zitao Wang、Wen-Xiong Zhang、Zhenfeng Xi

  DOI：10.1021/ic3018369

  日期：2012.11.5

  structural characterization of half-sandwich rare-earth metal tris(trimethylsilylmethyl) anionic complexes bearing one 1-phenyl-2,3,4,5-tetrapropylcyclopentadienyl ligand are achieved. These soluble anionic compounds show good reactivity in the stoichiometric reaction with dibenzoylmethane (DBM) to give the salt-free half-sandwich complex bearing two chelate DBM ligands. More importantly, they can serve as

  获得了具有一个1-苯基-2,3,4,5-四丙基环戊二烯基配体的半三明治稀土金属三（三甲基硅烷基甲基）阴离子配合物的合成和结构表征。这些可溶的阴离子化合物在与二苯甲酰甲烷（DBM）的化学计量反应中显示出良好的反应活性，从而得到带有两个螯合DBM配体的无盐半三明治复合物。更重要的是，它们可以用作添加常规胺（ArNH 2），无环（RR'NH，ArRNH和ArAr'NH; R，R'=烷基，Ar，Ar'=芳香族基团）或环状仲脂族胺形成碳二亚胺，可有效生成胍。以前的稀土催化剂不能有效地获得通式为ArAr'NH和ArRNH的无环仲胺，因为它们的弱亲核性和位阻。我们的结果清楚地表明，在化学计量反应中，阴离子三烷基前体的反应性与相应的中性烷基络合物相当，但与已知的催化剂相比，具有更好的催化活性。
• Concise synthesis of stereodefined dienols and cyclopentadienes via direct addition of 1-bromomagnesiobutadienes and 1-lithiobutadienes to carbonyl compounds
  作者：Hongyun Fang、Qiuling Song、Zhihui Wang、Zhenfeng Xi

  DOI：10.1016/j.tetlet.2004.04.156

  日期：2004.6

  Stereodefined all-cis substituted dienols could be readily prepared in excellent yields by the direct addition of 1-bromomagnesiobutadiene or 1-lithiobutadiene derivatives with aldehydes and ketones. Depending on the nature of substituents and workup procedures. multi-substituted cyclopentadienes could be also formed in high yields from these dienols. It is interesting to note that, unlike normal alkenyl magnesium bromides, these conjugated butadienyl magnesiumbromide reagents do not react with ketones. (C) 2004 Elsevier Ltd. All rights reserved.
• Formation of cyclopentadiene derivatives by reaction of zirconacyclopentadienes with 1,1-dihalo compounds
  作者：Zheng Duan、Wen-Hua Sun、Yuanhong Liu、Tamotsu Takahashi

  DOI：10.1016/s0040-4039(00)01277-6

  日期：2000.9

  Zirconacyclopentadienes reacted with benzal halides in the presence of CuCl and dimethylpropyleneurea to give pentasubstituted cyclopentadienes in moderate to good yields. Treatment of zirconacyclopentadienes with 1,1-dibromo-1-alken-3-yne and 1,1-dibromo-1,3-alkadiene afforded fulvene derivatives in good yields. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Half-Sandwich Complexes of Dy^III: A Janus-Motif with Facile Tunability of Magnetism
  作者：Shan-Shan Liu、Ling Xu、Shang-Da Jiang、Yi-Quan Zhang、Yin-Shan Meng、Zitao Wang、Bing-Wu Wang、Wen-Xiong Zhang、Zhenfeng Xi、Song Gao

  DOI：10.1021/ic502734z

  日期：2015.6.1

  Three half-sandwich organometallics [(Cp-R)Dy(DBM)(2)(THF)]center dot solvent [Cp-R = Cp* (1Dy, Cp* = C5Me5), Cp-4PrPh (2Dy, Cp-4PrPh = C5Pr4Ph), Cp' (3Dy, Cp' = C5Me4TMS, solvent = THF), DBM- = dibenzoylmethanoate anion, THF = tetrahydrofuran, TMS = trimethylsilyl] with a Janus structural motif, where the ligands of DBM- and [Cp-R](-) are widely used in Dy-III/beta-diketonate and Ln(III)/cyclopentadienyl systems, were synthesized, structurally and magnetically characterized, and theoretically investigated. Single-crystal structural analysis reveals that the three complexes crystallize in the same space group P2(1/c). All the molecules display slow magnetic relaxation in the absence of an applied magnetic field, and the magnetic hysteresis loops of 2Dy and 3Dy can be observed under a magnetic field sweep rate of 10 Oe/s, indicating all three complexes are single-ion magnets (SIMs). The modifications of the Cp-ring lead to the distinct increment of the energy barrier from 46 K (1Dy) to 76 K (2Dy) to 320 K (3Dy). Ab initio calculations show that the ground Kramers doublet is strongly axial with gz approaching the value of 20 expected for the pure M-J = +/- 15/2 state, and the magnetic anisotropy axes for three complexes share a similar orientation which is perpendicular to the molecular pseudosymmetric axis. Electrostatic analyses confirm the magnetic anisotropy orientations and reveal that proper charge distribution of the coordination sphere (including the first and second) around Dy-III ion enhances the magnetic anisotropy. Further investigation of the relaxation mechanisms suggests the energy barrier should be carefully used to evaluate single-ion magnets if Raman process is dominant in the low temperature range.
• Reaction of 4-methyl, 4-phenyl, and 4-hydrogen substituted 1-lithio-1,3-butadienes with aldehydes: preparation of multiply substituted cyclopentadienes
  作者：Zhihui Wang、Hongyun Fang、Zhenfeng Xi

  DOI：10.1016/j.tet.2006.04.083

  日期：2006.7

  acidic solution. Reaction mechanism study revealed that these cyclopentadienes were formed via an acid-promoted cyclization of conjugated dienols. Thus, stereodefined all-cis substituted dienols or a wide diversity of substituted cyclopentadienes can be obtained from the same 1-lithio-1,3-butadiene reagent and aldehyde by adjusting the hydrolysis conditions.

  研究了醛与丁二烯基骨架第4位上具有甲基，苯基或氢取代基的1-lithio-1,3-丁二烯试剂的反应。使用强酸性溶液水解后，可以高收率获得多取代的环戊二烯衍生物。反应机理研究表明，这些环戊二烯是通过酸促进的共轭二烯醇环化反应形成的。因此，可以通过调节水解条件，从相同的1-硫代-1,3-丁二烯试剂和醛中获得立体定义的顺式取代的二烯醇或种类繁多的取代的环戊二烯。