1,1,2-Trimethylallylradikal | 42466-22-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,1,2-Trimethylallylradikal
• 英文别名: 2,3-Dimethylbutenyl-Radikal；2,3-dimethyl-but-1->3-enyl
• CAS: 42466-22-8
• 化学式: C₆H₁₁
• 分子量: 83.1533
• InChiKey: SKGROGHVUFLEJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  6
• 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

• 作为产物：
  描述：

  2,3-二甲基-2-丁烯 生成 1,1,2-Trimethylallylradikal
  参考文献：
  名称：

  Direct measurements of formation rate constants of allylic radical from hot olefins formed by internal conversion. I

  摘要：

  The photofragmentation of 2,3,3-trimethyl-1-butene (TMB), 2,3-dimethyl-2-pentene (DMP), and tetramethylethylene (TME) has been studied in the gas phase by ArF (193 nm) laser flash photolysis. For the first time, the formation rate constants to the common product of trimethylallyl (TMA) radical have been measured directly under collision free conditions. The C–C bond (the C–H bond for TME) at the position β to the double bond dissociates and TMA radical is formed. The formation rate constants of the TMA radical are found to be 5.6×107 s−1 for TMB, 2.7×107 s−1 for DMP, and 1.7×107 s−1 for TME. These rate constant values can be explained in terms of the RRKM theory by assuming that the absorbed photon energy is redistributed in all the vibrational modes. Formation of the TMA radical is reduced by adding a foreign gas, however, a small amount of the radical was still detected under a high pressure. The unquenched processes are interpreted in terms of predissociation.

  DOI：

  10.1063/1.452992

文献信息

• Thermal reaction of the isopropyl radical with 2,3-dimethylbut-2-ene
  作者：Tamás Körtvélyesi、László Seres

  DOI：10.1039/ft9928802445

  日期：——

  The CH3ĊHCH3 radical (iP˙) initiated homogeneous gas-phase thermal reaction of 2,3-dimethylbut-2-ene has been studied at 490–540 K by means of the thermal decomposition of azoisopropane (AIP). The products were identified using gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS).

  CH 3 isoHCH 3自由基（iP˙）引发了2,3-二甲基丁-2-烯的均相气相热反应，已经通过偶氮异丙烷（AIP）的热分解在490–540 K上进行了研究。使用气相色谱（GC）和气相色谱-质谱（GC-MS）鉴定产品。
• Pulse radiolysis and e.s.r. evidence for the formation of an alkene radical cation in aqueous solution
  作者：Klaus-Dieter Asmus、Peter S. Williams、Bruce C. Gilbert、Jeremy N. Winter

  DOI：10.1039/c39870000208

  日期：——

  Direct pulse radiolysis evidence, complemented by e.s.r. experiments, establishes that the radical cation Me2C–ĊMe2(λmax.ca. 290 nm) is formed by acid-catalysed elimination of OH– from ·CMe2CMe2OH; the radical cation deprotonates to give ·CH2CMeCMe2 with k 3.9 × 105 s–1.

  直接脉冲辐证据，通过ESR实验，建立了自由基阳离子我补充2 C-CME 2（λ最大大约290纳米）通过OH的酸催化的消除而形成-从·CME 2 CME 2 OH; 自由基阳离子去质子化，得到·CH 2 CME CME 2，k 3.9×10 5 s –1。
• Vibrationally resolved dynamics of the reaction of Cl atoms with 2,3-dimethylbut-2-ene in chlorinated solvents
  作者：Fawzi Abou-Chahine、Stuart J. Greaves、Greg T. Dunning、Andrew J. Orr-Ewing、Gregory M. Greetham、Ian P. Clark、Michael Towrie

  DOI：10.1039/c2sc21267f

  日期：——

  components gives bimolecular rate coefficients for formation of HCl of (1.7 ± 1.4) × 1010 M−1 s−1 in CDCl3 and (3.4 ± 1.2) × 1010 M−1 s−1 in CCl4. However, an additional transient absorption is observed ∼115 cm−1 lower in wavenumber than the fundamental HCl absorption band and is assigned to the v = 2 ← v = 1 hot band of HCl. The absorption by the nascent HCl(v = 1) peaks after ∼20 ps and subsequently decays

  据报道，宽带瞬态红外吸收测量结果对比了Cl原子与 2,3-二甲基丁-2-烯 和 正戊烷在氯化溶剂中。在这两种情况下，H原子转移都会产生HCl和一个烃基，但是在前一种反应中释放的能量更大，因为形成了一个共振稳定的烯丙基。Cl原子与正戊烷在CH 2中的溶液中，Cl 2仅在最低振动水平（v = 0）时形成HCl ，我们测得的速率系数与Sheps等人先前的报道一致。，J。Phys。化学 甲，2006，110，3087.在盐酸基本吸收带显示反应的两个结构域强度的生长的时间依赖性：提示上升与和光解产生的氯原子的反应相关正戊烷分子位于第一溶剂壳内，而进一步缓慢的上升归因于在溶液中扩散后的反应。对于Cl原子与2,3-二甲基丁-2-烯，还观察到了这两个反应域，对包含这些成分的动力学模型进行拟合可得出形成（1.7±1.4）×10 10 M -1 s -1的HCl的双分子速率系数。CDCl 3和（3.4±1.2）×10
• Sway, Mohammad I, Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1990, vol. 29, # 9, p. 900 - 902
  作者：Sway, Mohammad I

  DOI：——

  日期：——
• Direct measurements of formation rates of allylic radicals from vibrationally excited ethylene derivatives
  作者：Nobuaki Nakashima、Nobuo Shimo、Noriaki Ikeda、Keitaro Yoshihara

  DOI：10.1063/1.448125

  日期：1984.10.15

  Formation rates of allylic radicals have been observed directly for the first time to be 4×107 s−1 by photodissociation of 2,3,3-trimethyl-1-butene and to be 2×107 s−1 from 2,3-dimethyl-2-pentene at low pressure by excitation with an ArF laser.