4-bromo-4-homoadamantene | 762245-92-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-bromo-4-homoadamantene
• 英文别名: 4-Bromotricyclo[4.3.1.13,8]undec-4-ene
• CAS: 762245-92-1
• 化学式: C₁₁H₁₅Br
• 分子量: 227.144
• InChiKey: YTVMKCZQKVRIMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  4-bromo-4-homoadamantene 在 叔丁基锂 、 potassium hydride 、 对甲苯磺酸 作用下， 以 氘代四氢呋喃 、 乙醚 、 正戊烷 为溶剂， 反应 35.33h， 生成
  参考文献：
  名称：

  Spin-Localized Cyclopentadienyl Radical Annelated with Homoadamantene Frameworks:  Isolation, X-ray Crystal Structure, and ESR Characterization

  摘要：

  A cyclopentadienyl radical annelated with two homoadamantene frameworks 1 was synthesized and isolated in stable, crystalline form by the single-electron oxidation of the corresponding cyclopentadienyl anion. The X-ray structure clearly demonstrated distinct bond alternation in the cyclopentadienyl ring, suggesting that radical 1 has the characteristics of a spin-localized 2,4-cyclopentadien-1-yl radical. The two homoadamantene frameworks are nonequivalent in crystals at 100 K, while ESR spectra indicated that they are equivalent in toluene at room temperature due to rapid changes in conformation.

  DOI：

  10.1021/ja046617o
• 作为产物：
  描述：

  trans-4,5-dibromohomoadamantane 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以69%的产率得到4-bromo-4-homoadamantene
  参考文献：
  名称：

  Spin-Localized Cyclopentadienyl Radical Annelated with Homoadamantene Frameworks:  Isolation, X-ray Crystal Structure, and ESR Characterization

  摘要：

  A cyclopentadienyl radical annelated with two homoadamantene frameworks 1 was synthesized and isolated in stable, crystalline form by the single-electron oxidation of the corresponding cyclopentadienyl anion. The X-ray structure clearly demonstrated distinct bond alternation in the cyclopentadienyl ring, suggesting that radical 1 has the characteristics of a spin-localized 2,4-cyclopentadien-1-yl radical. The two homoadamantene frameworks are nonequivalent in crystals at 100 K, while ESR spectra indicated that they are equivalent in toluene at room temperature due to rapid changes in conformation.

  DOI：

  10.1021/ja046617o

文献信息

• Generation and Reaction of a Phenyl-Substituted Cyclopentadienyl Cation Annelated with Two Homoadamantene Frameworks
  作者：Kohei Ogawa、Shinya Minegishi、Koichi Komatsu、Toshikazu Kitagawa

  DOI：10.1021/jo800340g

  日期：2008.7.1

  persists without any rearrangement of the homoadamantane frameworks, at least during the period before capture by the nucleophile. On the other hand, the abstraction of a chloride ion from 5 by Ag+ in the absence of a nucleophile at −78 °C resulted in the quantitative formation of allyl cation 8+, incorporated in a bicyclo[3.1.0]hexane framework, via the Wagner−Meerwein rearrangement of a homoadamantane

  研究了溶剂分解和非亲核条件下标题阳离子2 +的生成及其反应。当使前体氯环戊二烯5与含有水的硅胶或与无水MeOH反应时，相应的5-羟基和5-甲氧基环戊二烯（7和6）的产率分别为68％和81％。这表明2 +在溶剂分解条件下作为中间体形成，并且至少在亲核试剂捕获之前的时间内持续存在而没有高金刚烷骨架的任何重排。另一方面，Ag +从5中提取氯离子在-78°C时不存在亲核试剂的情况下，通过高金刚烷骨架的Wagner-Meerwein重排，定量形成了烯丙基阳离子8 +，并引入了双环[3.1.0]己烷骨架中。阳离子8 +分离为的SbF 6 -的盐，其结构通过X-射线晶体学测定。用MeOH淬灭该阳离子，得到的甲醚14保留了环戊二烯结构，但其中一个高金刚烷骨架由于进一步的Wagner-Meerwein重排而发生了结构变化。