1,3-二碘金刚烷 | 23174-58-5

• 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: 1,3-二碘金刚烷
• 英文名称: 1,3-Diiodoadamantane
• 英文别名: 1,3-didodo-adamantane
• CAS: 23174-58-5
• 化学式: C₁₀H₁₄I₂
• 分子量: 388.03
• InChiKey: DVWQKZVSDOZRGC-UHFFFAOYSA-N

物化性质

• 熔点：
  110-111 °C
• 沸点：
  336.7±25.0 °C(Predicted)
• 密度：
  2.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 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：

  1,3-二碘金刚烷 在 trimethylstannylsodium 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以100%的产率得到1,3-脱氢金刚烷
  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
• 作为产物：
  描述：

  1-氯-3-羟基金刚烷 在 氢碘酸 作用下， 生成 1,3-二碘金刚烷
  参考文献：
  名称：

  1,3-二重氮基金刚烷与DMSO中碳的反应：通过S（RN）1机理与双环[3.3.1]壬烷衍生物的开环反应。

  摘要：

  研究了1，3-二重金刚烷与各种碳原子亲核试剂的反应。苯乙酮（2）和频哪酮（10b）的烯醇钾和硝基甲烷（10a）的阴离子在光刺激下通过自由基链过程在DMSO中与1,3-二碘十二金刚烷（1a）反应形成1-碘单取代产物中间体，该中间体经历一致的断裂以形成7-亚甲基双环[3.3.1]壬烯的衍生物（3和11）。该反应在25摄氏度的黑暗环境中不会发生，对光刺激的反应会被对二硝基苯部分抑制。1,3-二溴金刚烷（1b）和1-溴-3-氯金刚烷（1c）在2的照射下也发生了反应，尽管比1a慢得多，但也得到了7-亚甲基双环[3.3.1]壬烯衍生物3。当使用不带酸性氢原子的亲核试剂（例如异丁苯酮（16）的烯醇离子）时，为了抑制金刚烷的开环，它在1a的照射下反应生成金刚烷产物1-碘金刚烷，单取代的17、1-碘单取代的19和二取代的20。它们的分布取决于实验条件。在这些反应中，1-碘金刚烷和19是中间体。对于涉及1-碘

  DOI：

  10.1021/jo9620728

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 ...
• Radical Addition of Alkyl Halides to Formaldehyde in the Presence of Cyanoborohydride as a Radical Mediator. A New Protocol for Hydroxymethylation Reaction
  作者：Takuji Kawamoto、Takahide Fukuyama、Ilhyong Ryu

  DOI：10.1021/ja210585n

  日期：2012.1.18

  Hydroxymethylation of alkyl halides was achieved using paraformaldehyde as a radical C1 synthon in the presence of tetrabutylammonium cyanoborohydride as a hydrogen source. The reaction proceeds via a radical chain mechanism involving an alkyl radical addition to formaldehyde to form an alkoxy radical, which abstracts hydrogen from a hydroborate anion.

  在氰基硼氢化四丁基铵作为氢源存在下，使用多聚甲醛作为自由基 C1 合成子实现烷基卤化物的羟甲基化。该反应通过自由基链机制进行，包括烷基自由基加成到甲醛形成烷氧基自由基，烷氧基自由基从硼氢化物阴离子中提取氢。
• Organic electroluminescent compound and organic electroluminescent device containing the same
  申请人：INT TECH CO., LTD.

  公开号：US10651393B2

  公开（公告）日：2020-05-12

  The present disclosure provides an organic electroluminescent compound represented by the following formula (III): Wherein each of R1 to R4 is independently selected from the group consisting of hydrogen and the groups represented by formula (i), formula (ii), formula (iii), formula (iv), formula (v), formula (vi), formula (vii) and formula (viii), and at least two of the R1 to R4 are independently selected from the group consisting of the groups represented by formula (i), formula (ii), formula (iii), formula (iv), formula (v), formula (vi), formula (vii) and formula (viii): wherein R5, R6, R7, R8, R9, R10,R11, R12, R13,R14, R15, R16, p, q, r, s, t, u, v, A, B and D are each as defined in the description.

  本公开提供了由下式 (III) 表示的有机电致发光化合物： 其中 R1 至 R4 各自独立地选自氢和式 (i)、式 (ii)、式 (iii)、式 (iv)、式 (v)、式 (vi)、式 (vii) 和式 (viii) 所代表的基团组成的组，且 R1 至 R4 中至少有两个独立地选自式 (i)、式 (ii)、式 (iii)、式 (iv)、式 (v)、式 (vi)、式 (vii) 和式 (viii) 所代表的基团组成的组： 其中 R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、p、q、r、s、t、u、v、A、B 和 D 各如描述中所定义。
• The First Efficient Iodination of Unactivated Aliphatic Hydrocarbons
  作者：Peter R. Schreiner、Oliver Lauenstein、Ekaterina D. Butova、Andrey A. Fokin

  DOI：10.1002/(sici)1521-3773(19990917)38:18<2786::aid-anie2786>3.0.co;2-0

  日期：1999.9.17
• Dissociative Electron Transfer to Dihaloalkanes. Electrochemical Reduction of 1,3-Dihaloadamantanes, 1,4-Dihalobicyclo[2.2.2]octanes, and 1,3-Dihalobicyclo[1.1.1]pentanes
  作者：William Adcock、Christopher I. Clark、Abdelaziz Houmam、Alexander R. Krstic、Jean Pinson、Jean-Michel Saveant、Dennis K. Taylor、Julian F. Taylor

  DOI：10.1021/ja00090a013

  日期：1994.6

  The electrochemical reductive cleavage of the title compounds was investigated by means of cyclic voltammetry and electrolysis. The reaction is a two-electron process that yields competitively ring closure (or fragmentation) products and the monohalide resulting from the expulsion of the best leaving halide ion. Product selection occurs at the level of the carbanion resulting from the reduction of the one-electron reductive cleavage radical. In the formation of the latter, electron transfer and bond breaking are concerted; thus, the anion radical is not involved as an intermediate. The variations in the reduction potential observed in the three series of compounds can be rationalized, by application of the dissociative electron-transfer theory, as related variations of the bond dissociation energy of the first carbon-halogen bond to be cleaved. In the adamantane and bicyclopentane series, these are mainly the result of through-space-bonded interactions in the one-electron reductive cleavage radical and, to a lesser extent, in the starting dihalide itself, while through-bond interactions appear to prevail in the bicyclooctane series.