6-methyl-6-(p-chlorophenyl)fulvene | 13347-54-1

• 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-methyl-6-(p-chlorophenyl)fulvene
• 英文别名: 6-(4′-chlorophenyl)-6-methylfulvene；6-Methyl-6-p-chlorphenylfulven；6-(p-Chlorphenyl)fulven；6-methyl-6-(4'-chlorophenyl)fulvene；1-(4-chloro-phenyl)-1-cyclopentadienyliden-ethane；1-(4-Chlor-phenyl)-1-cyclopentadienyliden-aethan；1-Chloro-4-(1-cyclopenta-2,4-dien-1-ylideneethyl)benzene
• CAS: 13347-54-1
• 化学式: C₁₃H₁₁Cl
• 分子量: 202.683
• InChiKey: AWZIUBJMCGXHCW-UHFFFAOYSA-N

物化性质

• 沸点：
  328.3±11.0 °C(Predicted)
• 密度：
  1.158±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  14
• 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-乙酰氧基-2H-吡喃-3(6H)-酮 、 6-methyl-6-(p-chlorophenyl)fulvene 在 三乙胺 作用下， 以 氯仿 为溶剂， 反应 6.0h， 以50%的产率得到(1S,8S)-7-(4-Chloro-phenyl)-7-methyl-12-oxa-tricyclo[6.3.1.0^2,6]dodeca-2(6),4,9-trien-11-one
  参考文献：
  名称：

  [6+3] Cycloaddition of pentafulvenes with 3-oxidopyrylium betaine: a novel methodology toward the synthesis of 5–8 fused oxabridged cyclooctanoids

  摘要：

  Pentafulvenes undergo a facile [6+3] cycloaddition with 3-oxidopyrylium betaine, generated from the corresponding pyranulose acetate, leading to the formation of 5-8 fused oxabridged cyclooctanoids. The product is formed by a [6+3] cycloaddition, followed by a 1,5-hydrogen shift of the initially formed [6+3] adduct. The reaction was found to be general and a number of fulvenes with a wide range of substituents at the exocyclic double bond, that is, at the C6 position followed a similar reactivity pattern. The [6+3] adduct, a 5-8 fused oxabridged cyclooctanoid, is potentially amenable to a number of synthetic transformations due to the presence of an alpha, beta-unsaturated ketone and cyclopentadiene part. By selecting appropriately substituted fulvene and pyranulose acetates, it is possible to use this methodology for the synthesis of a wide range of 5-8 fused cyclooctanoids. The experimental results have been rationalized on the basis of theoretical calculations. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.04.017
• 作为产物：
  描述：

  对氯苯乙酮 、 环戊二烯 在 四氢吡咯 、 高氯酸吡咯烷 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以69%的产率得到6-methyl-6-(p-chlorophenyl)fulvene
  参考文献：
  名称：

  吡咯烷缓冲液催化的二甲苯形成动力学及机理

  摘要：

  使用无水乙腈中的吡咯烷鎓/吡咯烷缓冲液可实现富烯的快速合成。随时间变化的紫外可见吸收和NMR光谱分析表明，富勒烯形成的速率和产率在很大程度上取决于介质中酸的存在和溶剂的选择，并且它们受到水的负面影响。收集了各种底物的动力学数据，并展示了调整后的反应条件的综合优势。与文献方法相比，发现反应速率提高了。以前很难获得的α-不饱和富烯现在可以以高收率获得。

  DOI：

  10.1021/acs.joc.8b01660

文献信息

• A short route to cyclopentadienyltricarbonylrhenium substituted derivatives
  作者：F Le Bideau、J Hénique、P Pigeon、J.-M Joerger、S Top、G Jaouen

  DOI：10.1016/s0022-328x(02)02090-9

  日期：2003.2

  CpRe(CO)3 substituted derivatives were obtained in good yields (44–96%) from fulvenes and Re2(CO)10 in boiling mesitylene. This new methodology was applied to the synthesis of CpRe(CO)3 substituted steroids with success.

  CpRe（CO）3取代的衍生物从富烯和沸腾的均三甲苯中的Re 2（CO）10获得了良好的产率（44-96％）。此新方法已成功应用于CpRe（CO）3取代类固醇的合成。
• Nonalternant systems. 2. Electronic effects of substituents in 6-methyl-6-phenylfulvenes: carbon-13 NMR and theoretical studies
  作者：D. J. Sardella、C. M. Keane、P. Lemonias

  DOI：10.1021/ja00329a056

  日期：1984.8
• Kresze; Goetz, Chemische Berichte, 1957, vol. 90, p. 2161,2175
  作者：Kresze、Goetz

  DOI：——

  日期：——
• Can Remote Substituent Effects Influence Reactivity and Stereoselectivity in the Diels-Alder Cycloadditions of p-Substituted 6-Phenyl-6-methylfulvenes?
  作者：M. M. Gugelchuk、P. C.-M. Chan、T. J. Sprules

  DOI：10.1021/jo00104a031

  日期：1994.12

  The kinetics, activation parameters, and stereoselectivity in the Diels-Alder reaction of a series of p-substituted 6-phenyl-6-methylfulvenes with N-phenylmaleimide have been measured in benzene-d(6) to examine the consequence of remote electronic perturbation on the system. The variation in equilibrium endo:exo ratios as a function of substituent adheres very well to a LFER with sigma(+) (rho = 0.701) in contrast to the kinetic stereoselectivity which shows no linear relationship of the Hammett type. A reasonably good LFER with sigma(-) is observed for the reactivities, especially when the NMe(2) and OMe examples are excluded (rho = -0.684). Temperature and solvent effects on these properties have also been investigated. Substituent-induced changes in preferred conformation and pi-electron densities of the fulvenes have been studied by ab initio molecular orbital calculations. The optimum twist angle between the pi-subsystems remained relatively constant (54-55 degrees) across the series except in the case of p-NMe(2) substitution where it is substantially decreased (36 degrees). Relative reactivities and kinetic stereoselectivities are seen to have a connection with the calculated magnitude and direction of the fulvene molecular dipole moment. The importance of frontier MO energies was examined.
• US4264336A
  申请人：——

  公开号：US4264336A

  公开（公告）日：1981-04-28