1-溴-3-(三氯甲基)二环<1.1.1>戊烷 | 105542-91-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 中文名称: 1-溴-3-(三氯甲基)二环<1.1.1>戊烷
• 英文名称: 1-bromo-3-(trichloromethyl)bicyclo<1.1.1>pentane
• 英文别名: 1-Bromo-3-trichloromethylbicyclo<1.1.1>pentane；1-Bromo-3-(trichloromethyl)bicyclo[1.1.1]pentane
• CAS: 105542-91-4
• 化学式: C₆H₆BrCl₃
• 分子量: 264.377
• InChiKey: XQJLDQVQZOAMTH-UHFFFAOYSA-N

物化性质

• 沸点：
  242.9±20.0 °C(Predicted)
• 密度：
  2.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  α-methylstyrene-methyl-d3 、 1-溴-3-(三氯甲基)二环<1.1.1>戊烷 在 甲基锂 作用下， 以 乙醚 为溶剂， 反应 12.0h， 以8%的产率得到
  参考文献：
  名称：

  Trapping of 4-Halo-2-chlorobicyclo[2.1.1]hex-1-ene: DFT Calculations on This and Related Molecules

  摘要：

  The reaction of 1-chloro-3-trichloromethylbicyclo[1.1.1]pentane 5a with an excess of MeLi leads to 1,3-dichloro-3,4-dimethylbicyclo[2.1.1]hexane (7a) as the major product in 33% yield, as well as to the bicyclo[2,1.1]hexane derivatives 6a and 8a. C-13 labeling shows that 7a is formed through two routes, the minor one constituting a trapping reaction of the elusive bicyclo[2.1.1]hex-1-ene (3) by MeLi. This bridgehead olefin is also trapped in an ene reaction with alpha-methylstyrene leading to 18 in 8 % yield, DFT calculations at the B3LYP/6-311G(d,p)//B3LYP/6-31G(d) level of theory show that 3-chlorobicyclo[1.1.1]pent-1-yl-chlorocarbene (2a) in its singlet electronic state is local minimum on the corresponding energy hypersurface, It rearranges over a barrier of only 7.9 kcal mol(-1) to the strongly pyramidalized bridgehead olefin 3 a, which shows a high propensity for a second rearrangement (barrier 8.4 kcal mol(-1)) to give carbene 4a. Hydrogen migration of 4a to afford 1,3-dichlorobicyclo[2.1.1]hex-2-ene (20a) needs a somewhat higher barrier of 13.2 kcal mol(-1) and is not observed under the experimental conditions employed in this work.

  DOI：

  10.1002/(sici)1521-3765(19990503)5:5<1422::aid-chem1422>3.0.co;2-e
• 作为产物：
  描述：

  三氯溴甲烷 、 bicyclo[1.1.1]pentane 以 乙醚 为溶剂， 反应 48.0h， 以76%的产率得到1-溴-3-(三氯甲基)二环<1.1.1>戊烷
  参考文献：
  名称：

  Trapping of 4-Halo-2-chlorobicyclo[2.1.1]hex-1-ene: DFT Calculations on This and Related Molecules

  摘要：

  The reaction of 1-chloro-3-trichloromethylbicyclo[1.1.1]pentane 5a with an excess of MeLi leads to 1,3-dichloro-3,4-dimethylbicyclo[2.1.1]hexane (7a) as the major product in 33% yield, as well as to the bicyclo[2,1.1]hexane derivatives 6a and 8a. C-13 labeling shows that 7a is formed through two routes, the minor one constituting a trapping reaction of the elusive bicyclo[2.1.1]hex-1-ene (3) by MeLi. This bridgehead olefin is also trapped in an ene reaction with alpha-methylstyrene leading to 18 in 8 % yield, DFT calculations at the B3LYP/6-311G(d,p)//B3LYP/6-31G(d) level of theory show that 3-chlorobicyclo[1.1.1]pent-1-yl-chlorocarbene (2a) in its singlet electronic state is local minimum on the corresponding energy hypersurface, It rearranges over a barrier of only 7.9 kcal mol(-1) to the strongly pyramidalized bridgehead olefin 3 a, which shows a high propensity for a second rearrangement (barrier 8.4 kcal mol(-1)) to give carbene 4a. Hydrogen migration of 4a to afford 1,3-dichlorobicyclo[2.1.1]hex-2-ene (20a) needs a somewhat higher barrier of 13.2 kcal mol(-1) and is not observed under the experimental conditions employed in this work.

  DOI：

  10.1002/(sici)1521-3765(19990503)5:5<1422::aid-chem1422>3.0.co;2-e

文献信息

• Reactions of [1.1.1]propellane
  作者：Kenneth B. Wiberg、Sherman T. Waddell

  DOI：10.1021/ja00162a022

  日期：1990.3

  The free radical addition reactions of [1.1.1] propellane (1) are described in some detail and allowed the preparation of a wide variety of 1,3-disubstituted bicyclo [1.1.1.] pentanes. The reaction of 1 with free radicals was more rapid than that of bicyclo [1.1.0] butane (2), whereas bicyclo [2.1.0] pentane (3) was relatively inert

  [1.1.1] 推进烷 (1) 的自由基加成反应进行了一些详细的描述，并允许制备各种 1,3-二取代双环 [1.1.1.] 戊烷。1 与自由基的反应比双环 [1.1.0] 丁烷 (2) 更快，而双环 [2.1.0] 戊烷 (3) 相对惰性
• [1.1.1]Propellane: Reaction with free radicals
  作者：Kenneth B. Wiberg、Shennan T. Waddell、Keith Laidig

  DOI：10.1016/s0040-4039(00)84310-5

  日期：1986.1

  [1.1.1]Propellane is more reactive towards free radicals than bicyclo[1.1.0]butane, and much more reactive than bicyclo[2.1.0]pentane. Therefore, the reactivity is not determined by strain energy relief or the HOMO energy. The addition of acetaldehyde is unique in that a 1:2 adduct is formed. A number of other additions are described, and provide convenient routes to 1,3-disubstituted bicyclo[1.1.1]pentanes

  [1.1.1]螺旋桨比双环[1.1.0]丁烷对自由基的反应性更高，并且比双环[2.1.0]戊烷更具反应性。因此，反应性不是由应变能释放或HOMO能决定的。乙醛的添加是独特的，因为会形成1：2的加合物。描述了许多其他的加成，并提供了通往1，3-二取代的双环[1.1.1]戊烷的便利途径。