6-methyl-6-(p-tolyl)fulvene | 38069-02-2

• 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-methyl-6-(p-tolyl)fulvene
• 英文别名: 6-(4′-methylphenyl)-6-methylfulvene；6-Methyl-6-(p-methylphenyl)fulven；6-Methyl-6-p-tolylfulven；1-(1-(cyclopenta-2,4-dien-1-ylidene)ethyl)-4-methylbenzene；1-cyclopentadienylidene-1-p-tolyl-ethane；1-Cyclopentadienyliden-1-p-tolyl-aethan；6-methyl-6-(4-tolyl)-fulvene；1-(1-cyclopenta-2,4-dien-1-ylideneethyl)-4-methylbenzene
• CAS: 38069-02-2
• 化学式: C₁₄H₁₄
• 分子量: 182.265
• InChiKey: BMCJYAHQPGJNCO-UHFFFAOYSA-N

物化性质

• 沸点：
  309.0±12.0 °C(Predicted)
• 密度：
  1.016±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  马来酸酐 、 6-methyl-6-(p-tolyl)fulvene 在 苯 作用下， 生成 (+-)(1Ξ,2Ξ)-7-(1-p-tolyl-ethylidene)-norborn-5-ene-2r,3c-dicarboxylic acid-anhydride
  参考文献：
  名称：

  Kresze; Goetz, Chemische Berichte, 1957, vol. 90, p. 2161,2175

  摘要：

  DOI：
• 作为产物：
  描述：

  环戊二烯 、 对甲基苯乙酮 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88%的产率得到6-methyl-6-(p-tolyl)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

• An efficient catalytic method for fulvene synthesis
  作者：Necdet Coşkun、Ihsan Erden

  DOI：10.1016/j.tet.2011.09.036

  日期：2011.11

  added water and solvent on the condensation of carbonyl compounds with cyclopentadiene in the presence of secondary amines were investigated. Based on these studies, a new efficient and green synthesis of fulvenes was developed.

  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。
• METHOD FOR PRODUCING OLEFIN POLYMER
  申请人：Mitsui Chemicals, Inc.

  公开号：US20150045523A1

  公开（公告）日：2015-02-12

  [Object] There is provided a method which enables an olefin polymer having high melting point and high molecular weight to be produced even at high temperature proper in an industrial production process. [Solution] A method for producing an olefin polymer is provided, the method including polymerizing an olefin having two or more carbon atoms in the presence of a catalyst for olefin polymerization, wherein the catalyst for olefin polymerization includes (A) a bridged metallocene compound represented by Formula [1] and (B) at least one compound selected from, for example, an organoaluminum oxy-compound and an organoaluminum compound: [where R 1 to R 4 each represent, for example, a hydrocarbon group; R 5 to R 9 each represent, for example, a hydrogen atom or a halogen atom; R 10 and R 11 each represent, for example, a hydrogen atom; and R 12 represents, for example, a hydrocarbon group. Y represents, for example, a carbon atom. M represents, for example, Zr; Y represents, for example, a carbon atom; and Q represents, for example, a halogen atom. j is an integer from 1 to 4].

  [目标] 提供一种方法，使得在工业生产过程中，即使在高温条件下，也能生产出具有高熔点和高分子量的烯烃聚合物。 [解决方案] 提供了一种生产烯烃聚合物的方法，包括在烯烃聚合催化剂的存在下聚合具有两个或多个碳原子的烯烃。其中，烯烃聚合催化剂包括（A）由式[1]表示的桥联金属茂化合物和（B）至少一种从以下化合物中选择的化合物，例如，有机铝氧化合物和有机铝化合物：[其中，R1到R4分别表示例如一个碳氢基团；R5到R9分别表示例如一个氢原子或卤素原子；R10和R11分别表示例如一个氢原子；R12表示例如一个碳氢基团。Y表示例如一个碳原子。M表示例如Zr；Y表示例如一个碳原子；Q表示例如一个卤素原子。j是1到4的整数。]
• Method for producing olefin polymer
  申请人：Mitsui Chemicals, Inc.

  公开号：US09315602B2

  公开（公告）日：2016-04-19

  [Object] There is provided a method which enables an olefin polymer having high melting point and high molecular weight to be produced even at high temperature proper in an industrial production process. [Solution] A method for producing an olefin polymer is provided, the method including polymerizing an olefin having two or more carbon atoms in the presence of a catalyst for olefin polymerization, wherein the catalyst for olefin polymerization includes (A) a bridged metallocene compound represented by Formula [1] and (B) at least one compound selected from, for example, an organoaluminum oxy-compound and an organoaluminum compound: [where R1 to R4 each represent, for example, a hydrocarbon group; R5 to R9 each represent, for example, a hydrogen atom or a halogen atom; R10 and R11 each represent, for example, a hydrogen atom; and R12 represents, for example, a hydrocarbon group. Y represents, for example, a carbon atom. M represents, for example, Zr; Y represents, for example, a carbon atom; and Q represents, for example, a halogen atom. j is an integer from 1 to 4].

  【目标】提供一种方法，使得即使在工业生产过程中适当的高温下，也能生产出具有高熔点和高分子量的烯烃聚合物。 【解决方案】提供一种生产烯烃聚合物的方法，包括在烯烃聚合催化剂的存在下聚合具有两个或更多碳原子的烯烃，其中烯烃聚合催化剂包括(A)由公式[1]表示的桥联金属茂化合物和(B)至少一种选择自例如有机铝氧化合物和有机铝化合物的化合物。[其中R1至R4分别表示例如一个烃基；R5至R9分别表示例如氢原子或卤素原子；R10和R11分别表示例如一个氢原子；R12表示例如一个烃基。Y表示例如一个碳原子。M表示例如Zr；Y表示例如一个碳原子；Q表示例如一个卤素原子。j是1到4的整数]。
• 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
• 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.