2-甲基-1-丙烯-1-13C | 71910-43-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 中文名称: 2-甲基-1-丙烯-1-13C
• 英文名称: 1-¹³C-2-methylpropene
• 英文别名: [1-(13)C]2-methylpropene；2-methylpropene-1-(13)C；1-(13)C-isobutene；1-13C-isobutylene；isobutylene-1-13C；2-methyl-[1-¹³C]propene；2-Methyl(113C)prop-1-ene
• CAS: 71910-43-5
• 化学式: C₄H₈
• 分子量: 57.0965
• InChiKey: VQTUBCCKSQIDNK-OUBTZVSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  Tebbe's reagent 、 2-甲基-1-丙烯-1-13C 在 THF 作用下， 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Titanacyclobutenes

  摘要：

  DOI：

  10.1021/ja00539a033
• 作为产物：
  描述：

  甲基-13C-三苯基碘化膦 、 丙酮 在 dimsylsodium 作用下， 以 二甲基亚砜 为溶剂， 反应 1.25h， 生成 2-甲基-1-丙烯-1-13C
  参考文献：
  名称：

  End-Group-Confined Chain Walking within a Group 4 Living Polyolefin and Well-Defined Cationic Zirconium Alkyl Complexes for Modeling This Behavior

  摘要：

  Living polymers derived from the polymerization of 1-butene using the cationic zirconium initiator, {Cp*ZrMe[N(Et)C(Me)-N(tBu)]}[B(C6F5)4] (Cp* = eta5-C5Me5) (1), have been shown to undergo end-group-confined chain walking that is competitive with direct beta-hydride elimination and chain release at -10 degrees C. The well-defined complexes, {Cp*Zr(iBu)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (2) and {Cp*Zr(2-ethylbutyl)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (3), were prepared, and each was found to possess a strong beta-hydrogen agostic interaction that is absent in the living polymer. The isotopically single- and double-labeled derivatives, {Cp*Zr(2-d-2-methylpropyl)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (2') and {Cp*Zr(1-13C-2-d-2-methylpropyl)[N(Et)C(Me)N(tBu)]}[B(C6F5)4] (2' '), were also prepared and found to undergo isotopic label scrambling at 0 degrees C. For 2' ', the observation that after scrambling each deuterium label is located on a 13C-labeled carbon atom is consistent with the Busico mechanism for chain-end epimerization rather than the Resconi mechanism. Decomposition of 3 yielded olefinic products also consistent with chain walking prior to beta-hydride elimination and chain release. Finally, the unexpected decrease in stability of the living polymer relative to that of the model complexes reveals the importance of subtle differences in steric and electronic factors in controlling beta-hydride elimination and chain release.

  DOI：

  10.1021/ja0496975

文献信息

• Living Ziegler−Natta Polymerization by Early Transition Metals:  Synthesis and Evaluation of Cationic Zirconium Alkyl Complexes Bearing β-Hydrogens as Models for Propagating Centers
  作者：Matthew B. Harney、Richard J. Keaton、James C. Fettinger、Lawrence R. Sita

  DOI：10.1021/ja057866v

  日期：2006.3.1

  zirconium and hafnium complexes with alkyl substituents bearing beta-hydrogens of general formula (eta(5)-C5Me5)MR[N(Et)C(Me)N(t-Bu)]}[B(C6F5)4] [M = Zr; R = Et, n-Pr, i-Pr, n-Bu, i-Bu, and 2-ethylbutyl (5a-f) and M = Hf; R = i-Bu and t-Bu (6 and 7, respectively)] is described, including several isotopically labeled derivatives. The ability of these complexes to serve as model complexes for the living Ziegler-Natta

  一系列带有通式 (eta(5)-C5Me5)MR[N(Et)C(Me)N(t-Bu)]} 的带有 β-氢的烷基取代基的阳离子锆和铪配合物的合成和表征[B(C6F5)4] [M = Zr; R = Et、n-Pr、i-Pr、n-Bu、i-Bu 和 2-乙基丁基 (5a-f)，M = Hf；描述了 R = i-Bu 和 t-Bu（分别为 6 和 7）]，包括几种同位素标记的衍生物。这些配合物作为烯烃的活性齐格勒-纳塔聚合反应的模型配合物的能力已经得到解决，该聚合反应可以使用引发剂 2a (R = Me in 5) 进行。获得的结果进一步阐明了空间和电子因素，这些因素可能有助于基于早期过渡金属引发剂的齐格勒-纳塔聚合的活性特性。