1-bromo-3-tert-butylbicyclo<1.1.1>pentane | 127321-07-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: 1-bromo-3-tert-butylbicyclo<1.1.1>pentane
• 英文别名: 1-Bromo-3-tert-butylbicyclo[1.1.1]pentane
• CAS: 127321-07-7
• 化学式: C₉H₁₅Br
• 分子量: 203.122
• InChiKey: NUUOEAOZIDPAKA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  10
• 可旋转键数：
  1
• 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：

  1-bromo-3-tert-butylbicyclo<1.1.1>pentane 在 水 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以83%的产率得到1-tert-butyl-3-methylene-1-cyclobutanol
  参考文献：
  名称：

  Bridgehead Carbocations: A Solvolytic Study of 1-Bromobicyclo[1.1.1]pentane and Its Bridgehead-Substituted Derivatives

  摘要：

  The rate constants (k) for solvolysis of a range of 3-X-substituted bicyclo[1.1.1]pentyl bromides in 80% aqueous ethanol have been measured and a linear relationship found to exist between log k and the inductive/field constant sigma(I). These observations, together with the results of isotope and solvent effect studies described below, have been interpreted as evidence for the formation of 1-bicyclo[1.1.1]pentyl cations in the ionization step in preference to mechanisms in which either ring-opening is concerted with ionization to give 3-methylenecyclobutyl cations or ionization is accompanied by ring-contraction to give bicyclo[1.1.0]butyl-1-carbinyl cations. The latter mechanisms would have been expected to show the effects of strong pi-donor substituent participation, a phenomenon which was not observed. A comparison of the rates of solvolysis of the parent bromide and its 3-deuterated analog is characterized by a large deuterium-isotope effect (k(H)/k(D) = 1.30) which, combined with the observation that 1-bromobicyclo[1.1.1]pentane solvolyses with enhanced rates in solvents which are strong hydrogen bonding accepters, lends support to the view that the 1-bicyclo[1.1.1]pentyl cation derives substantial stabilization from sigma-hyperconjugative interactions.

  DOI：

  10.1021/ja00093a014
• 作为产物：
  描述：

  1,3-二碘双环[1.1.1]戊烷 在 氟烷 、 N,N'-二环己基碳二亚胺 作用下， 反应 0.17h， 生成 1-bromo-3-tert-butylbicyclo<1.1.1>pentane
  参考文献：
  名称：

  Synthesis of Some Bridgehead-Bridgehead-Disubstituted Bicyclo[1.1.1]pentanes

  摘要：

  The synthesis of a wide variety of 1,3-disubstituted bicyclo[1.1.1]pentanes is described, with particular emphasis on the generation of a series of S-X-substituted bicyclo[1.1.1]pentyl bromides required for solvolytic studies. Functional group manipulation at the bridgehead was readily accomplished in the majority of cases by radical processes in some instances, transformations were effected via carbanionic-type intermediates.

  DOI：

  10.1021/jo00090a015

文献信息

• Toward a molecular-size tinkertoy construction set. Preparation of terminally functionalized [n]staffanes from [1.1.1]propellane
  作者：Piotr Kaszynski、Andrienne C. Friedli、Josef Michl

  DOI：10.1021/ja00028a029

  日期：1992.1

  of [n]staffanes (the oligomers of [1.1.1]propellane n=1-5) functionalized on one or both ends is described,and their properties are summarized. The substituents are -COOCH 3 ,-n-C 4 H 9 ,-C 6 H 5 ,-Br,-I and -SCOCH 3 , and their conversion to others,such as -COOH, -COCH 3 and -SH,is demonstrated. it is proposed that these rod-shaped molecules will be useful in the development of a molecular-size civil

  描述了一种在一端或两端官能化的 [n]staffanes（[1.1.1]propellane 的低聚物 n=1-5）的简便但低场合成，并总结了它们的性质。取代基为-COOCH 3 、-nC 4 H 9 、-C 6 H 5 、-Br、-I 和-SCOCH 3 ，并证明了它们向其他取代基如-COOH、-COCH 3 和-SH 的转化。建议这些棒状分子将有助于开发类似于儿童玩具建筑套装的分子大小的土木工程建筑套装
• Gleiter, Rolf; Pfeifer, Karl-Heinz; Szeimies, Guenter, Angewandte Chemie, 1990, vol. 102, # 4, p. 418 - 420
  作者：Gleiter, Rolf、Pfeifer, Karl-Heinz、Szeimies, Guenter、Bunz, Uwe

  DOI：——

  日期：——
• US5405550A
  申请人：——

  公开号：US5405550A

  公开（公告）日：1995-04-11
• Bridgehead Carbocations: A Solvolytic Study of 1-Bromobicyclo[1.1.1]pentane and Its Bridgehead-Substituted Derivatives
  作者：Ernest W. Della、Cyril A. Grob、Dennis K. Taylor

  DOI：10.1021/ja00093a014

  日期：1994.7

  The rate constants (k) for solvolysis of a range of 3-X-substituted bicyclo[1.1.1]pentyl bromides in 80% aqueous ethanol have been measured and a linear relationship found to exist between log k and the inductive/field constant sigma(I). These observations, together with the results of isotope and solvent effect studies described below, have been interpreted as evidence for the formation of 1-bicyclo[1.1.1]pentyl cations in the ionization step in preference to mechanisms in which either ring-opening is concerted with ionization to give 3-methylenecyclobutyl cations or ionization is accompanied by ring-contraction to give bicyclo[1.1.0]butyl-1-carbinyl cations. The latter mechanisms would have been expected to show the effects of strong pi-donor substituent participation, a phenomenon which was not observed. A comparison of the rates of solvolysis of the parent bromide and its 3-deuterated analog is characterized by a large deuterium-isotope effect (k(H)/k(D) = 1.30) which, combined with the observation that 1-bromobicyclo[1.1.1]pentane solvolyses with enhanced rates in solvents which are strong hydrogen bonding accepters, lends support to the view that the 1-bicyclo[1.1.1]pentyl cation derives substantial stabilization from sigma-hyperconjugative interactions.
• Synthesis of Some Bridgehead-Bridgehead-Disubstituted Bicyclo[1.1.1]pentanes
  作者：Ernest W. Della、Dennis K. Taylor

  DOI：10.1021/jo00090a015

  日期：1994.6

  The synthesis of a wide variety of 1,3-disubstituted bicyclo[1.1.1]pentanes is described, with particular emphasis on the generation of a series of S-X-substituted bicyclo[1.1.1]pentyl bromides required for solvolytic studies. Functional group manipulation at the bridgehead was readily accomplished in the majority of cases by radical processes in some instances, transformations were effected via carbanionic-type intermediates.