2,7,11-trimethyl-1,3,6,10-dodecatetraene | 1338547-97-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2,7,11-trimethyl-1,3,6,10-dodecatetraene
• 英文别名: 2,7,11-Trimethyldodeca-1,3,6,10-tetraene；2,7,11-trimethyldodeca-1,3,6,10-tetraene
• CAS: 1338547-97-9
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: FNHNUOYRYVDDPW-UHFFFAOYSA-N

物化性质

• 沸点：
  280.1±20.0 °C(Predicted)
• 密度：
  0.812±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  天然橡胶 在 CrCl₃(THF)₃ 、 {2-C6H4(OMe)}2PN(Me)N(Me)P(2-C6H4(OMe))2 作用下， 以 甲苯 为溶剂， 反应 1.0h， 生成 1,5,10-三甲基环十二碳-1,5,9-三烯 、 2,7,11-trimethyl-1,3,6,10-dodecatetraene
  参考文献：
  名称：

  Ligand effects in chromium diphosphine catalysed olefin co-trimerisation and diene trimerisation

  摘要：

  一系列对称和不对称的N,N-bis(diarylphosphino)胺（‘PNP’）配体（Ar2PN(R)PNAr′2: R = Me, Ar2 = o-甲氧基苯基, Ar′2 = 苯, 1; R = Me, Ar2 = o-甲苯基, Ar′2 = 苯, 2; R = Me, Ar2 = 苯（o-乙基）, Ar′2 = 苯, 3; R = Me, Ar2 = Ar′2 = o-甲氧基苯基, 4; R = iPr, Ar2 = Ar′2 = 苯, 5）和对称的N,N′-bis(diarylphosphino)二甲基肼（‘PNNP’）配体（Ar2PN(Me)N(Me)PAr2: Ar2 = o-甲苯基, 6; Ar2 = o-甲氧基苯基, 7）已被合成。通过原位与[CrCl3(THF)3]复合后激活的甲基铝氧烷（MAO）进行乙烯/苯乙烯共三聚化和异戊二烯三聚化的催化筛选。PNNP催化体系在异戊二烯三聚化中表现出了显著的活性和选择性的提高，相较于之前报道的PNP体系。在乙烯和苯乙烯共三聚化中，对称和不对称变体的比较导致选择性的转换，不对称催化（o-甲氧基苯基）2PN(Me)PPh2（1）配体体系在共三聚产物分布中独特地引入了两个苯乙烯单体，与熟悉的两个乙烯和一个苯乙烯的ω-取代烯烃有所不同。类型为[(双膦)Cr(CO)4]的配合物8-11也已合成，并报告了其单晶X射线衍射结果。我们提出了这些催化转化的机制，并深入探讨了配体系列对铬环催化中间体的影响。

  DOI：

  10.1039/b913302j

文献信息

• Ligand effects in chromium diphosphine catalysed olefin co-trimerisation and diene trimerisation
  作者：Lucy E. Bowen、Manutsavin Charernsuk、Thomas W. Hey、Claire L. McMullin、A. Guy Orpen、Duncan F. Wass

  DOI：10.1039/b913302j

  日期：——

  A series of symmetric and unsymmetric N,N-bis(diarylphosphino)amine (‘PNP’) ligands (Ar2PN(R)PNAr′2: R = Me, Ar2 = o-anisyl, Ar′2 = Ph, 1, R = Me, Ar2 = o-tolyl, Ar′2 = Ph, 2, R = Me, Ar2 = Ph(o-ethyl), Ar′2 = Ph, 3, R = Me, Ar2 = Ar′2 = o-anisyl, 4, R = iPr, Ar2 = Ar′2 = Ph, 5) and symmetric N,N′-bis(diarylphosphino)dimethylhydrazine (‘PNNP’) ligands (Ar2PN(Me)N(Me)PAr2: Ar2 = o-tolyl, 6, Ar2 = o-anisyl, 7) have been synthesised. Catalytic screening for ethene/styrene co-trimerisation and isoprene trimerisation was performed via the in situ complexation to [CrCl3(THF)3] followed by activation with methylaluminoxane (MAO). PNNP catalytic systems showed a significant increase in activity and selectivity over previously reported PNP systems in isoprene trimerisation. Comparing the symmetric and unsymmetric variants in ethene and styrene co-trimerisation resulted in a switch in selectivity, an unsymmetric catalytic (o-anisyl)2PN(Me)PPh2 (1) ligand system affording unique incorporation of two styrenic monomers into the co-trimer product distribution differing from the familiar two ethene and one styrene ω-substituted alkenes. Complexes of the type [(diphosphine)Cr(CO)4] 8–11 were also synthesised, the single-crystal X-ray diffraction of which are reported. We propose the mechanisms of these catalytic transformations and an insight into the effect of the ligand series on the chromacyclic catalytic intermediates.

  一系列对称和不对称的N,N-bis(diarylphosphino)胺（‘PNP’）配体（Ar2PN(R)PNAr′2: R = Me, Ar2 = o-甲氧基苯基, Ar′2 = 苯, 1; R = Me, Ar2 = o-甲苯基, Ar′2 = 苯, 2; R = Me, Ar2 = 苯（o-乙基）, Ar′2 = 苯, 3; R = Me, Ar2 = Ar′2 = o-甲氧基苯基, 4; R = iPr, Ar2 = Ar′2 = 苯, 5）和对称的N,N′-bis(diarylphosphino)二甲基肼（‘PNNP’）配体（Ar2PN(Me)N(Me)PAr2: Ar2 = o-甲苯基, 6; Ar2 = o-甲氧基苯基, 7）已被合成。通过原位与[CrCl3(THF)3]复合后激活的甲基铝氧烷（MAO）进行乙烯/苯乙烯共三聚化和异戊二烯三聚化的催化筛选。PNNP催化体系在异戊二烯三聚化中表现出了显著的活性和选择性的提高，相较于之前报道的PNP体系。在乙烯和苯乙烯共三聚化中，对称和不对称变体的比较导致选择性的转换，不对称催化（o-甲氧基苯基）2PN(Me)PPh2（1）配体体系在共三聚产物分布中独特地引入了两个苯乙烯单体，与熟悉的两个乙烯和一个苯乙烯的ω-取代烯烃有所不同。类型为[(双膦)Cr(CO)4]的配合物8-11也已合成，并报告了其单晶X射线衍射结果。我们提出了这些催化转化的机制，并深入探讨了配体系列对铬环催化中间体的影响。