1-氯-3-碘金刚烷 | 60389-53-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 中文名称: 1-氯-3-碘金刚烷
• 英文名称: 1-Chloro-3-iodoadamantane
• 英文别名: 1-iodo-3-chloro-adamantane；1-Iod-3-chloradamantan
• CAS: 60389-53-9
• 化学式: C₁₀H₁₄ClI
• 分子量: 296.579
• InChiKey: FDSCHPGFDODYCQ-UHFFFAOYSA-N

物化性质

• 沸点：
  307.4±25.0 °C(Predicted)
• 密度：
  1.73±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  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-氯-3-碘金刚烷 在 四溴化碳 、 四丁基溴化铵 作用下， 以 氟苯 为溶剂， 以35%的产率得到1-bromo-3-chloro-5-iodoadamantane
  参考文献：
  名称：

  Pseudotetrahedral Polyhaloadamantanes as Chirality Probes:  Synthesis, Separation, and Absolute Configuration

  摘要：

  Pseudotetrahedral, conformationally as well as configurationally stable 1-bromo-3-chloro-5-fluoro- (4) and 1-bromo-3-chloro-5-fluoro-7-iodoadamantane (5) (and some related compounds) were prepared by our recently devised phase-transfer catalytic halogenation protocol; the optical antipodes of 4 were separated by HPLC on chiral phase in ee > 99%, and the absolute configurations were assigned by matching observed and computed circular dichroism spectra. Structure 5 is the first chiral aliphatic hydrocarbon containing all stable (nonradioactive) halogens; its structure was proven by NMR spectroscopy and by X-ray crystal data. We emphasize that the combination of experiment and theory is very powerful in assigning absolute configurations even for molecules without typical chromophors, with small values for the optical rotation, and without an atom at the stereogenic center.

  DOI：

  10.1021/ja0274195
• 作为产物：
  描述：

  在 2-碘-1,1,1-三氟乙烷 作用下， 以 苯 为溶剂， 以76%的产率得到1-氯-3-碘金刚烷
  参考文献：
  名称：

  Mechanistic definition of trimethylstannylation of 1,3-dihaloadamantanes: delocalized radical anions as possible intermediates

  摘要：

  A series of 1,3-dihaloadamantanes (3, X = Y = halogens) have been synthesized, characterized, and treated with (trimethylstannyl) alkali reagents (Me3SnM, M = Li or Na) in the absence and presence of tert-butylamine (TBA) and dicyclohexylphosphine (DCPH). The product distributions of these reactions have been established by C-13 and Sn-119 NMR spectroscopy and vapor-phase chromatographic analyses. Tin substitution via an S(RN)1-type pathway is shown to be a significant reaction for several of the derivatives of 3 (X = F, Y Br or I; X = Cl, Y = Br or I; X = Y = Br) but not for the bromo iodide or diiodide (3, X = Br, Y = I and X = Y = I). For the latter two compounds, the formation of 1,3-dehydroadamantane or propellane 8 is the predominant reaction product while tin substitution is insignificant. Propellane 8 formation is also a significant reaction product for some of the other dihalo derivatives of 3 (X = Cl, Y = I and X = Y = Br) but not for others (3, X = F, Y = Br or I and X = Cl, Y = Br). The mechanism of formation of 8 is perplexing in light of the trapping experiments in the presence of TBA and DCPH. A possible pathway is proposed in which the key intermediate is a delocalized radical anion.

  DOI：

  10.1021/jo00078a009

文献信息

• Oxidative Single-Electron Transfer Activation of σ-Bonds in Aliphatic Halogenation Reactions
  作者：Andrey A. Fokin、Peter R. Schreiner、Pavel A. Gunchenko、Sergey A. Peleshanko、Tat‘yana E. Shubina、Sergey D. Isaev、Pyotr V. Tarasenko、Natalya I. Kulik、Hans-Martin Schiebel、Alexander G. Yurchenko

  DOI：10.1021/ja000193q

  日期：2000.8.1

  experimentally and computationally. In the case of 1,3-dehydroadamantane (1) and [3.3.1]propellane (2) free-radical addition was observed. [3.3.2]Propellane (3) and 3,6-dehydrohomoadamantane (4), which are less prone to radical attack, selectively form products of formal double nucleophilic (oxidative) addition, e.g., dichloro (in ICl/CH2Cl2), dimethoxy (in ICl/CH3OH), and diacetamino (in ICl/CH3CN) derivatives

  通过实验和计算研究了一系列结构相关的大环推进器与一氯化碘的反应。在 1,3-脱氢金刚烷 (1) 和 [3.3.1] 推进烷 (2) 的情况下，观察到自由基加成。[3.3.2]推进烷 (3) 和 3,6-脱氢高金刚烷 (4) 不太容易受到自由基攻击，它们选择性地形成正式的双亲核（氧化）加成产物，例如二氯（在 ICl/CH2Cl2 中）、二甲氧基（在 ICl/CH3OH 中）和二乙酰氨基（在 ICl/CH3CN 中）衍生物在其他条件相同的情况下。涉及烷烃自由基阳离子的单电子转移途径被提议用于具有相对较低氧化电位的脂肪烃（例如笼烷烃）的活化步骤。基于 H/D 动力学同位素效应数据，假设了类似的机制用于激活金刚烷的叔 C-H 键。后者与来自金刚烷自由基阳离子的氢原子损失的 kH/kD 值相当（测量值为 2.78 ± 0.21 ...
• YURCHENKO, A. G.;KULIK, N. I.;KUCHAR, V. P.;DJAKOVSKAJA, V. M.;BAKLAN, V.+, TETRAHEDRON LETT., 1986, 27, N 12, 1399-1402
  作者：YURCHENKO, A. G.、KULIK, N. I.、KUCHAR, V. P.、DJAKOVSKAJA, V. M.、BAKLAN, V.+

  DOI：——

  日期：——