1,2-bis(3-methylinden-2-yl)ethane | 168640-23-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 1,2-bis(3-methylinden-2-yl)ethane
• 英文别名: 3-methyl-2-[2-(3-methyl-1H-inden-2-yl)ethyl]-1H-indene
• CAS: 168640-23-1
• 化学式: C₂₂H₂₂
• 分子量: 286.417
• InChiKey: BMJJAFUDQZRSCU-UHFFFAOYSA-N

物化性质

• 沸点：
  433.5±40.0 °C(Predicted)
• 密度：
  1.063±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  盐酸 、 四氢呋喃氯化钛 、 1,2-bis(3-methylinden-2-yl)ethane 在 n-BuLi 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 rac-[ethylenebis(1-methyl-η(5)-inden-2-yl)]titanium dichloride 、 rac-[ethylenebis(1-methyl-η(5)-inden-2-yl)]titanium dichloride
  参考文献：
  名称：

  Synthesis of ansa-Titanocenes from 1,2-Bis(2-indenyl)ethane and Structural Comparisons in the Catalytic Epoxidation of Unfunctionalized Alkenes

  摘要：

  Novel ansa-titanocene dichlorides have been prepared from 1,2-bis(2-indenyl)ethane (10). Treatment of the dilithio salt of 10 with either methyl iodide or benzyl bromide gives the corresponding dialkylated bis(indene) in high yield. Titanium complexation of the dimethyl and dibenzyl bis(indene) derivatives affords [ethylenebis[(eta(5)-1-methyl-2-indenyl)]titanium dichloride(14) and [ethylenebis[(eta 5-1-benzyl-2-indenyl)]titanium dichloride(15), respectively. In each case, the ansa-titanocene is obtained as a mixture of meso and racemic isomers. Treatment of the dilithio salt of 10 with trimethylsilyl chloride results in a mixture of bis(trimethylsilyl) derivatives. Attempted titanium complexation of the silylated bis(indene) mixture results in an intramolecular oxidative coupling of the C(3) and C(3') positions to yield a trans-6,7-dihydroindeno[2,1-c]fluorene derivative, 16. [Ethylenebis(eta(5)-2-indenyl)]titanium dichloride (9) is hydrogenated to yield tethylenebis(eta(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride (17). The crystal structures of rac-l4 and 17 were determined by X-ray crystallography and are presented. Examination of ethylene-bridged bis(2-indenyl) ansa-titanocenes as catalysts for the epoxidation of unfunctionalized alkenes was conducted using the representative titanocenes 9, 14, 15, and 17. The catalytic ability of this new class of. ansa-titanocenes in the epoxidation study was found in some cases to exceed the activity of existent titanocene complexes.

  DOI：

  10.1021/om00008a021

文献信息

• Synthesis of ansa-Titanocenes from 1,2-Bis(2-indenyl)ethane and Structural Comparisons in the Catalytic Epoxidation of Unfunctionalized Alkenes
  作者：Shawn R. Hitchcock、Janelle J. Situ、Jonathan A. Covel、Marilyn M. Olmstead、Michael H. Nantz

  DOI：10.1021/om00008a021

  日期：1995.8

  Novel ansa-titanocene dichlorides have been prepared from 1,2-bis(2-indenyl)ethane (10). Treatment of the dilithio salt of 10 with either methyl iodide or benzyl bromide gives the corresponding dialkylated bis(indene) in high yield. Titanium complexation of the dimethyl and dibenzyl bis(indene) derivatives affords [ethylenebis[(eta(5)-1-methyl-2-indenyl)]titanium dichloride(14) and [ethylenebis[(eta 5-1-benzyl-2-indenyl)]titanium dichloride(15), respectively. In each case, the ansa-titanocene is obtained as a mixture of meso and racemic isomers. Treatment of the dilithio salt of 10 with trimethylsilyl chloride results in a mixture of bis(trimethylsilyl) derivatives. Attempted titanium complexation of the silylated bis(indene) mixture results in an intramolecular oxidative coupling of the C(3) and C(3') positions to yield a trans-6,7-dihydroindeno[2,1-c]fluorene derivative, 16. [Ethylenebis(eta(5)-2-indenyl)]titanium dichloride (9) is hydrogenated to yield tethylenebis(eta(5)-4,5,6,7-tetrahydro-2-indenyl)]titanium dichloride (17). The crystal structures of rac-l4 and 17 were determined by X-ray crystallography and are presented. Examination of ethylene-bridged bis(2-indenyl) ansa-titanocenes as catalysts for the epoxidation of unfunctionalized alkenes was conducted using the representative titanocenes 9, 14, 15, and 17. The catalytic ability of this new class of. ansa-titanocenes in the epoxidation study was found in some cases to exceed the activity of existent titanocene complexes.