6-p-Tolyl-fulven | 32884-55-2

• 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: 6-p-Tolyl-fulven
• 英文别名: 1-(Cyclopenta-2,4-dien-1-ylidenemethyl)-4-methylbenzene
• CAS: 32884-55-2
• 化学式: C₁₃H₁₂
• 分子量: 168.238
• InChiKey: OXPLXIAZICUMFQ-UHFFFAOYSA-N

物化性质

• 熔点：
  60-61 °C
• 沸点：
  117.5 °C(Press: 0.4 Torr)
• 密度：
  1.0011 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  6-p-Tolyl-fulven 在 sodium hydroxide 作用下， 以 乙醇 、 甲苯 、 苯 为溶剂， 反应 10.0h， 生成
  参考文献：
  名称：

  cis–trans Enantiomerism in the Diels–Alder cycloadducts of 6-arylfulvenes with maleic anhydride: resolution of the exo adducts via the N-((1S)-1-(naphth-1-yl)ethyl)imide derivatives: assignment of the absolute configurations based on the crystal structure of an imide diastereomer

  摘要：

  A new case of the uncommon cis-trans enantiomerism is presented. The titled anhydride adducts were prepared in good yields by the known reaction of three 6-arylfulvenes with maleic anhydride (aryl = phenyl, p-tolyl and p-anisyl). The exo adducts were converted to the corresponding imides by reaction with (1S)-1-(naphth-1-yl)ethylamine in similar to 80% yields, and the resulting diastereomeric imides separated by silica gel column chromatography. They were hydrolysed and recyclised to the chiral anhydrides, in 'one-pot' with 10% NaOH-EtOH, followed by treatment with 2 M HCl, in similar to 40% yields. The titled anhydrides were thus obtained in homochiral form, in enantiomeric purities (generally) of similar to 90% as indicated by chiral HPLC. The chiral anhydrides were also converted to the corresponding imides (presumably stereospecifically), by treatment with ammonia solution in excellent yields. The crystal structure of one of the above diastereomeric imides (derived from 6-phenylfulvene) was determined, and based on the known (S)-configuration of the naphthylethylamine moiety, the 'configurations' of the original anhydride adducts were assigned. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.11.015
• 作为产物：
  描述：

  对甲基苯甲醛 、 环戊二烯 在 四氢吡咯 作用下， 以 甲醇 、 水 为溶剂， 以98%的产率得到6-p-Tolyl-fulven
  参考文献：
  名称：

  富烯合成的高效催化方法

  摘要：

  研究了碱的性质和用量、底物结构、加水量和溶剂对仲胺存在下羰基化合物与环戊二烯缩合反应的影响。基于这些研究，开发了一种新的高效绿色合成富烯。

  DOI：

  10.1016/j.tet.2011.09.036

文献信息

• Improving cytotoxic properties of ferrocenes by incorporation of saturated N-heterocycles
  作者：Tomáš Hodík、Martin Lamač、Lucie Červenková Šťastná、Petra Cuřínová、Jindřich Karban、Hana Skoupilová、Roman Hrstka、Ivana Císařová、Róbert Gyepes、Jiří Pinkas

  DOI：10.1016/j.jorganchem.2017.06.005

  日期：2017.10

  selected ferrocene derivatives were determined by X-ray diffraction analysis. The ferrocene derivatives and the ruthenium complexes were tested in vitro for their cytotoxic properties against three cell lines derived from ovarian cancer (A2780, A2780cis, and SK-OV-3) and against non-tumour embryonic cell line HEK293 (human kidney cells). The most active ferrocene derivatives displayed cytotoxicity in submicromolar

  通式的二茂铁衍生物的家族的[Fe（η 5 -C 5 H ^ 4 CH 2（p -C 6 H ^ 4）CH 2（N-HET））2 ]轴承饱和六元和五元N-杂环（N-het）已准备好。所选择的配合物与酸（HCl，乙酸）的反应提供相应的盐酸盐或导致官能化的侧链N-杂环的脱保护。的[茹（η反应6 - p氯-cymene）2 } 2与相应的环戊二烯衍生物，得到的阳离子钌络合物的[Ru（η] 6- p -cymene）（η 5 -C 5 H ^ 4 CH 2（p -C 6 H ^ 4）CH 2（N-HET））]氯而ruthenocenes的[Ru（η 5 -C 5 H ^ 4 CH 2（p - C 6 H 4）CH 2（N-het））2形成副产物。通过元素分析，熔点，NMR和ESI-MS对制备的配合物（20个实施例）进行表征，并通过X射线衍射分析确定所选择的二茂铁衍生物的分子结构。二茂铁衍生物和钌配
• General Enantioselective C−H Activation with Efficiently Tunable Cyclopentadienyl Ligands
  作者：Zhi-Jun Jia、Christian Merten、Rajesh Gontla、Constantin G. Daniliuc、Andrey P. Antonchick、Herbert Waldmann

  DOI：10.1002/anie.201611981

  日期：2017.2.20

  applicable chiral Cp ligand collection (JasCp ligands) with highly variable and adjustable structures. Their modular nature and their amenability to rapid structure variation enabled the efficient discovery of ligands for three enantioselective RhIII‐catalyzed C−H activation reactions, including one unprecedented transformation. This novel approach should enable the discovery of efficient chiral Cp ligands

  环戊二烯基（Cp）配体可有效控制各种过渡金属催化的转化，特别是对映选择性的CH活化。目前只有几种手性Cp配体可用。因此，用于手性Cp配体发现的概念上通用的方法将是无价的，因为它将使得能够发现适用的Cp配体并有效且快速地改变和调节其结构。在这里，我们描述了具有高度可变和可调节结构的结构多样且广泛适用的手性Cp配体集合（JasCp配体）的三步克级合成。它们的模块性质和对快速结构变化的适应性使得能够有效发现三种对映选择性Rh III的配体催化的CH活化反应，包括一种前所未有的转化。这种新颖的方法应该能够发现用于各种进一步对映选择性转化的有效手性Cp配体。
• Titanium-Catalyzed Hydroalumination of Conjugated Dienes: Access to Fulvene-Derived Allylaluminium Reagents and Their Diastereoselective Reactions with Carbonyl Compounds
  作者：Jomy Joseph、Florian Jaroschik、Dominique Harakat、K. V. Radhakrishnan、Jean-Luc Vasse、Jan Szymoniak

  DOI：10.1002/chem.201304775

  日期：2014.4.25

  The described titanium‐catalyzed hydroalumination of conjugated dienes opens up a new way to allylaluminium reagents. The reaction is carried out by using diisobutylaluminium hydride (DIBAL‐H) and a catalytic amount of [Cp2TiCl2] (Cp=cyclopentadienyl). When applied to mono‐ and disubstitued pentafulvenes, this reaction proceeds in a highly endocyclic manner. The formed allylaluminium compounds react

  钛催化的共轭二烯加氢铝化为烯丙基铝试剂开辟了一条新途径。通过使用氢化二异丁基铝（DIBAL-H）和催化量的[Cp 2 TiCl 2]（Cp ＝环戊二烯基）。当将其用于单和五元五联戊酸酯时，该反应会以高度内环的方式进行。形成的烯丙基铝化合物与醛和酮发生区域和立体选择性反应，生成均聚烯丙醇，适合作为功能化环戊酮的合成子。还研究了这种方法对简单二烯的扩展。在提出的机理中，最初形成的双金属物种（Ti / Al）参与了两个可能的催化循环，这些循环包括直接加氢铝化或/和加氢钛化，然后进行钛到铝的金属转移。
• Substituted Cyclopentadienyl Osmium Complexes from the Reactions of OsH₃Cl(PPh₃)₃ with Fulvenes and Cyclopentadienes
  作者：Sunny Kai San Tse、Wei Bai、Herman Ho-Yung Sung、Ian Duncan Williams、Guochen Jia

  DOI：10.1021/om1005066

  日期：2010.8.23

  methodologies were developed for the preparation of half-sandwich osmium complexes with the general formula (η5-cyclopentadienyl)OsCl(PPh3)2. The first approach involves the reactions of OsH3Cl(PPh3)3 with cyclopentadienes. Treatment of OsH3Cl(PPh3)3 with cyclopentadienes gives (η5-cyclopentadienyl)OsCl(PPh3)2 via C−H oxidative addition of cyclopentadienes followed by reductive elimination of hydrogen. The

  两种方法被用于制备半夹心络合物锇与通式显影（η 5 -环戊二烯基）OSCL（PPH 3）2。第一种方法涉及OSH 3 Cl（PPh 3）3与环戊二烯的反应。职业安全与卫生的治疗3氯（PPH 3）3与环戊二烯，得到（η 5 -环戊二烯基）OSCL（PPH 3）2通过C-H氧化加成环戊二烯，随后还原消除氢。该方法使我们能够合成一系列包含Cp，Cp *，茚基和C的半三明治络合物5 Me 4 R（R = H，Et，n -Pr）。第二种方法涉及OSH 3 Cl（PPh 3）3与富烯的插入反应。职业安全与卫生的治疗3氯（PPH 3）3与C 6 -C取代的富烯产生干净地单取代的环戊二烯基配合物锇（η 5 -C 5 H ^ 4 CHRR'）OSCL（PPH 3）2（R = H，R'= p -C 6 H 4 CH 3，p -C 6 H 4 OCH 3，CMe 3 ; R = R'= Ph）通过氢化物转移到富
• Catalytic asymmetric [2+2] cycloaddition between quinones and fulvenes and a subsequent stereoselective isomerization to 2,3-dihydrobenzofurans
  作者：Haifeng Zheng、Chaoran Xu、Yan Wang、Tengfei Kang、Xiaohua Liu、Lili Lin、Xiaoming Feng

  DOI：10.1039/c7cc03211k

  日期：——

  The catalytic enantioselective [2+2] cycloaddition between quinones and fulvenes was achieved, for the first time, by the use of a chiral copper(II) complex catalyst. The transformation afforded a series of enantiomerically enriched [6,4,5]-tricyclic cyclobutane derivatives in good yields with excellent regio- and stereoselectivities. Furthermore, the [2+2] adducts could be easily converted into formal

  通过使用手性铜（II）络合物催化剂，首次实现了醌与富烯之间的催化对映选择性[2 + 2]环加成反应。该转化以良好的产率提供了一系列对映异构体富集的[6,4,5]-三环环丁烷衍生物，具有优异的区域选择性和立体选择性。此外，[2 + 2]加合物可以轻松有效地和立体选择性地转化为正式的[3 + 2]加合物。