5-methyl-1-nonene

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 5-methyl-1-nonene
• 英文别名: 1-Nonene, 5-methyl；5-methylnon-1-ene
• 化学式: C₁₀H₂₀
• 分子量: 140.269
• InChiKey: LGYIQPOLYWEIQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  10
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  乙烯 在 (η5-C5H4CMe2Ph)TiCl3 作用下， 以 甲苯 为溶剂， 30.0 ℃ 、200.0 kPa 条件下， 反应 0.5h， 生成 辛烯 、 5-methyl-1-nonene
  参考文献：
  名称：

  OLEFIN OLIGOMERIZATION METHOD INVOLVING A CATALYTIC SYSTEM BASED ON ORGANOMETALLIC COMPLEXES AND A POROUS SOLID

  摘要：

  本发明涉及一种将烯烃M选择性地寡聚为寡聚物Mn的方法，涉及一个催化系统，该系统包括至少一个含有周期表第4至第10族金属的有机金属配合物和一个平均微孔直径Φ大于或等于Φmin的微孔或介孔固体，其中Φmin定义为分子体积(Vmo+nVmM)的函数，其中n是在获得金属环中间体时串联在一起的单体烯烃的数量，VmM为单体烯烃的分子体积。

  公开号：

  US20110137100A1

文献信息

• Mechanistic Studies of Ethylene and α-Olefin Co-Oligomerization Catalyzed by Chromium–PNP Complexes
  作者：Loi H. Do、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/om300492r

  日期：2012.7.23

  chromatographic and mass spectrometric analyses, strongly support a mechanism that involves five- and seven-membered metallacyclic intermediates comprised of ethylene and LAO units. Using 1-heptene as a mechanistic probe, it was established that 1-hexene formation from ethylene is competitive with formation of ethylene/LAO cotrimers and that cotrimers derived from one ethylene and two LAO molecules

  为了探索从乙烯作为化学原料生产窄分布的中长链烃的可能性，使用先前报道的铬络合物 [CrCl 3 (PNP OMe )]( 1，其中 PNP OMe = N，N-双(双(邻-甲氧基苯基)膦基)甲胺)。在乙烯和 1-己烯存在下，通过用改性甲基铝氧烷 (MMAO) 处理活化1，主要提供 C 6和 C 10烯烃产物。C 10的身份通过详细的气相色谱和质谱分析指定的异构体强烈支持涉及由乙烯和 LAO 单元组成的五元和七元金属环中间体的机制。使用 1-庚烯作为机制探针，确定由乙烯形成的 1-己烯与乙烯/LAO 共三聚体的形成具有竞争性，并且还生成了衍生自一个乙烯和两个 LAO 分子的共三聚体。Complex 1/ MMAO 也能够将 1-己烯转化为 C 12二聚体和 C 18三聚体，尽管效率很低。讨论了这些研究的机械意义，并与之前的烯烃共三聚报道进行了比较。
• Effect of an additional donor on decene formation in ethylene oligomerization catalyzed by a Cr/PCCP system: a combined experimental and DFT study
  作者：Zhichao Wang、Lin Liu、Xufeng Ma、Yao Liu、Puke Mi、Zhen Liu、Jun Zhang

  DOI：10.1039/d1cy00423a

  日期：——

  Cr catalyst based on a PCCP ligand shows high activity in ethylene oligomerization, giving 1-hexene and considerable C₁₀ fraction. DFT calculation results are consistent with the experimental observations on the distribution of C₁₀ isomers.

  基于PCCP配体的Cr催化剂在乙烯寡聚化中表现出高活性，产生1-己烯和相当数量的C₁₀分数。密度泛函理论计算结果与实验观察到的C₁₀异构体分布一致。
• Decene formation in ethylene trimerization reaction catalyzed by Cr–pyrrole system
  作者：Timur M. Zilbershtein、Vladislav A. Kardash、Vladlena V. Suvorova、Anatoly K. Golovko

  DOI：10.1016/j.apcata.2014.01.051

  日期：2014.4

  Decene formation in the ethylene trimerization reaction was studied using a chromium(III) 2-ethylhexanoate/2,5-dimethylpyrrole/triethylaluminum/diethylaluminum chloride catalyst system. Kinetic investigations revealed that some decene formation reactions did not depend on 1-hexene concentration, because 1-hexene and catalyst may react with ethylene before dissociation of 1-hexene-catalyst complex after 1-hexene formation. The results demonstrated that decene formation is an intrinsic part of the trimerization reaction mechanism. It was also shown that a stepwise elimination mechanism for the decomposition of the chromacycloheptane intermediate cannot explain the observed product distribution. The dependencies found allow selection of appropriate conditions for low or high decene formation in the ethylene trimerization reaction. (C) 2014 Elsevier B.V. All rights reserved.
• Lewis Acid Promoted Titanium Alkylidene Formation: Off-Cycle Intermediates Relevant to Olefin Trimerization Catalysis
  作者：Aaron Sattler、David G. VanderVelde、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/ja5055687

  日期：2014.7.30

  Two new precatalysts for ethylene and a-olefin trimerization, (FI)Ti(CH2SiMe3)(2)Me and (FI)Ti(CH2CMe3)(2)Me (FI = phenoxy-imine), have been synthesized and structurally characterized by X-ray diffraction. (FI)Ti(CH2SiMe3)(2)Me can be activated with 1 equiv of B(C6F5)(3) at room temperature to give the solvent-separated ion pair [(FI)Ti(CH2SiMe3)(2)][MeB(C6F5)(3)], which catalytically trimerizes ethylene or 1-pentene to produce 1-hexene or C-15 olefins, respectively. The neopentyl analogue (FI)Ti(CH2CMe3)(2)Me is unstable toward activation with B(C6F5)(3) at room temperature, giving no discernible diamagnetic titanium complexes, but at -30 degrees C the following can be observed by NMR spectroscopy: (i) formation of the bis-neopentyl cation [(FI)Ti(CH2CMe3)(+), (ii) alpha-elimination of neopentane to give the neopentylidene complex [(FI)Ti(=CHCMe3)](+), and (iii) subsequent conversion to the imido-olefin complex [(MeOAr2N=)-Ti(OArHC=CHCMe3)](+) via an intramolecular metathesis reaction with the imine fragment of the (FI) ligand. If the reaction is carried out at low temperature in the presence of ethylene, catalytic production of 1-hexene is observed, in addition to the titanacyclobutane complex [(FI)Ti(CH(CMe3)CH2CH2)](+), resulting from addition of ethylene to the neopentylidene [(FI)Ti(=CHCMe3)](+). None of the complexes observed spectroscopically subsequent to [(FI)Ti(CH2CMe3)(2)](+) is an intermediate or precursor for ethylene trimerization, but notwithstanding these off-cycle pathways, [(FI)Ti(CH2CMe3)(+) is a precatalyst that undergoes rapid initiation to generate a catalyst for trimerizing ethylene or 1-pentene.
• Highly Selective Olefin Trimerization Catalysis by a Borane-Activated Titanium Trimethyl Complex
  作者：Aaron Sattler、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/om401098m

  日期：2013.12.9

  Reaction of a trimethyl titanium complex, (FI)TiMe3 (FI = phenoxy-imine), with 1 equiv of B(C6F5)(3) gives [(FI)TiMe2][MeB(C6F5)(3)], an effective precatalyst for the selective trimerization of ethylene. Mechanistic studies indicate that catalyst initiation involves generation of an active Ti-II species by olefin insertion into a Ti-Me bond, followed by beta-H elimination and reductive elimination of methane, and that initiation is slow relative to trimerization. (FI)TiMe3/B(C6F5)(3) also leads to a competent catalyst for the oligomerization of alpha-olefins, displaying high selectivity for trimers (>95%), approximately 85% of which are one regioisomer. This catalyst system thus shows promise for selectively converting light a-olefins into transportation fuels and lubricants.