四甲基乙基自由基 | 24436-98-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 饱和烃
• 中文名称: 四甲基乙基自由基
• 英文名称: Tetramethylethyl radical
• 英文别名: Dimethyl-isopropylcarbinyl-Radikal；2,3-Dimethylbutylradikal；2.3-Dimethyl-2-butyl-Radikal；1,2-Dimethylbutyl-Radikal；1,1,2-trimethylpropyl radical；1,1,2-trimethyl-propyl；tert-isohexyl
• CAS: 24436-98-4
• 化学式: C₆H₁₃
• 分子量: 85.1692
• InChiKey: UHYDNELGDYZAEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  四甲基乙基自由基 生成 2,3-二甲基-1-丁烯
  参考文献：
  名称：

  Homolytic Bond Dissociation Enthalpies of the C−H Bonds Adjacent to Radical Centers

  摘要：

  Homolytic bond dissociation enthalpies (BDEs) at 0 and 298 K of the C-H bonds adjacent to various radical centers have been obtained from ab initio CBS-4 (complete basis set) model calculations and experimental data available in the literature. The BDEs of the C-H bonds adjacent to the radical centers derived from 11 saturated hydrocarbons were found to be 33.5 +/- 3 kcal/mol at 298 K. The BDEs of the C-H bonds adjacent to nine allylic and benzylic radical centers were found to be 48 +/- 3 kcal/mol at 298 K, but the benzylic C-H BDE of the PhCH2CH2. radical was found to be only 29.7 and 30.5 kcal/mol at 0 and 298 K, respectively. The BDEs of the vinylic C-H bonds adjacent to four vinylic radical centers were found to be 35.5 +/- 3.5 kcal/mol at 298 K. The BDEs of the vinylic C-H bonds adjacent to three allylic radical centers were found to be 56.5 +/- 3 kcal/mol at 298 K. These results suggest that the radical centers weaken the adjacent C-H bond strengths by about 50-70 kcal/mol. The calculated BDEs agree within +/-2 kcal/mol with most of the available experimental results. Isomerization enthalpies of butenes and pentenes have been obtained. Substituent effects on BDEs have also been examined.

  DOI：

  10.1021/jo971768d
• 作为产物：
  描述：

  2,3-二甲基丁烷 在 ϖ-C6H6Cl 作用下， 以 四氯化碳 为溶剂， 生成 四甲基乙基自由基
  参考文献：
  名称：

  Kinetic study of the photochlorination of 2,3-dimethylbutane and other alkanes in solution in the presence of benzene. First measurements of the absolute rate constants for hydrogen abstraction by the "free" chlorine atom and the chlorine atom-benzene .pi.-complex. Identification of these two species as the only hydrogen abstractors in these systems

  摘要：

  DOI：

  10.1021/ja00305a023

文献信息

• Thermal reaction of 2-methyl-2-butene in the presence of azomethane: enthalpy of formation of the radicals (CH3)2ĊCH(CH3)2 and tert-Ċ4H9
  作者：Zoltán Király、Tamás Körtve´lyesi、László Seres

  DOI：10.1039/a907433c

  日期：——

  The reaction of ĊH3 and 2-methyl-2-butene (2MB2) was investigated in the temperature range 540610 K. Azomethane was used as the source of ĊH3. The addition of ĊH3 to 2MB2 was concluded to be an equilibrium process: ĊH3+(CH3)2C2CHCH3(CH3)2ĊCH(CH3)2. The equilibrium constant of this reaction was determined from the rates of formation of the combination products (E)- and (Z)-CH3CH2C(CH3)2CHCH3 and (E)-

  在540610 K的温度范围内研究了ĊH3和2-甲基-2-丁烯（2MB2）的反应。偶氮甲烷被用作ĊH3的来源。ĊH3 加入 2MB2 被认为是一个平衡过程：ĊH3+(CH3)2C2CH ( )2ĊCH( )2。该反应的平衡常数由组合产物 (E)- 和 (Z)- CH2C( )2CH 和 (E)- 和 (Z)-( )2CHC( )2CH2C( )2CH 。最后，从平衡常数的温度依赖性得到加合物自由基的形成焓ΔfH298°[( )2ĊCH( )2] = (3±10) kJ mol-1。假设基团可加性规则对加合物自由基有效，得到以下基团值：ΔfH298°[Ċ–(C)3] = (179±12) kJ mol-1。通过使用这个数据 ΔfH298°(tert-Ċ4H9) = (53±12) kJ mol−1。
• Spectroscopic detection and reactivity of the chlorine atom-carbon disulfide molecular complex
  作者：John E. Chateauneuf

  DOI：10.1021/ja00058a042

  日期：1993.3

  Pulse radiolysis and laser flash photolysis techniques have been used to generate and kinetically characterize the chlorine atom-carbon disulfide molecular complex (Cl . /CS 2 ) in CCl 4 solution. The transient absorption spectrum of Cl . /CS 2 has been generated from three independent Cl . sources: pulse radiolysis of CCl 4 , 266-nm photodecomposition of CCl 4 , and photodissociation of Cl 2

  脉冲辐射分解和激光闪光光解技术已用于在 CCl 4 溶液中生成氯原子-二硫化碳分子复合物 (Cl . /CS 2 ) 并对其进行动力学表征。Cl 的瞬态吸收光谱。/CS 2 已由三个独立的 Cl 生成。来源：CCl 4 的脉冲辐射分解、CCl 4 的 266 nm 光分解和 Cl 2 的光解
• Kirwan, J. Nicolas; Roberts, Brian P., Journal of the Chemical Society. Perkin transactions II, 1989, p. 539 - 550
  作者：Kirwan, J. Nicolas、Roberts, Brian P.

  DOI：——

  日期：——
• Clocking Tertiary Cyclopropylcarbinyl Radical Rearrangements¹
  作者：Paul S. Engel、Shu-Lin He、J. T. Banks、K. U. Ingold、J. Lusztyk

  DOI：10.1021/jo961685h

  日期：1997.3.1

  Three independent methods have been employed to estimate the rate constant, k(1), for ring-opening of the 2-cyclopropyl-2-propyl radical, 1, at room temperature. These three estimates are based on chemical trapping of 1 and the ring-opened 4-methylpent-3-ene-1-yl radical by thiophenol (k(1) = (1.6(5) +/- 0.4(1)) x 10(7) M(-1) s(-1)), 9-azabicyclo[3.3.1]nonane-N-oxyl (k(1) = (1.7(6) +/- 0.3(4)) x 10(7) M(-1) s(-1)) and 2,2,6,6-tetramethylpiperidine-N-oxyl (k(1) = (2.1 +/- 0.4) x 10(7) M(-1) s(-1)) and absolute rate constants for nonrearranging radicals structurally related to 1. The mean value for k(1) ((1.8(4) +/- 0.4) x 10(7) M(-1) s(-1)) should be used when 1 is employed as a tertiary alkyl free radical clock at ambient temperatures.
• Complexation effects in the photochlorination of 2,3-dimethylbutane in the presence of fluorinated benzenes
  作者：Nigel J. Bunce、R. Bruce Joy、James P. Landers、Jamie S. Nakai

  DOI：10.1021/jo00382a037

  日期：1987.3