1-溴-3-氯金刚烷 | 35537-98-5

• 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-氯金刚烷
• 英文名称: 1-bromo-3-chloroadamantane
• 英文别名: 1-bromo-3-chloro-adamantane
• CAS: 35537-98-5
• 化学式: C₁₀H₁₄BrCl
• 分子量: 249.578
• InChiKey: VDEFNJAPDNJBCH-UHFFFAOYSA-N

物化性质

• 沸点：
  283.4±23.0 °C(Predicted)
• 密度：
  1.51±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 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-溴-3-氯金刚烷 在 (trimethylstannyl)lithium 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以77%的产率得到1-氯金刚烷
  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-溴金刚烷 在 四氯化碳 作用下， 生成 1-溴-3-氯金刚烷
  参考文献：
  名称：

  Perkins,R.R.; Pincock,R.E., Canadian Journal of Chemistry, 1978, vol. 56, p. 1269 - 1272

  摘要：

  DOI：

文献信息

• Reactions of 1,3-Dihaloadamantanes with Carbanions in DMSO:  Ring-Opening Reactions to Bicyclo[3.3.1]nonane Derivatives by the S_RN1 Mechanism
  作者：Andrés E. Lukach、Ana N. Santiago、Roberto A. Rossi

  DOI：10.1021/jo9620728

  日期：1997.6.1

  The reactions of 1,3-dihaloadamantanes with various carbanionic nucleophiles were studied. Potassium enolates of acetophenone (2) and pinacolone (10b) and the anion of nitromethane (10a) reacted with 1,3-diiodoadamantane (1a) in DMSO under photostimulation by a free radical chain process to form a 1-iodo monosubstitution product as an intermediate, which undergoes concerted fragmentation to form derivatives

  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
• Reactions of 1,3-dihaloadamantanes with diphenylphosphide ions by theSRN1 mechanism. Competition between intermolecular and intramolecular electron transfer reactions
  作者：Andres E. Lukach、Ana. N. Santiago、Roberto A. Rossi

  DOI：10.1002/poc.610071104

  日期：1994.11

  under photostimulation by the SRN1 mechanism. Irradiation of 1c without Ph2P− ions gave no reaction (<5%). Three products were found: 1,3-bis(diphenyphosphinyl)adamantane (2), (3-X-1-adamantyl)diphenylphosphine (X = Cl, 3a; X = Br, 3b) and 1-adamantyldiphenylphosphine (4). Compounds 2 and 4 were formed by intramolecular electron transfer (ET) of the radical anion 3a−· (3b−·); whereas 3a (3b) were formed

  1,3- dihaloadamantanes与二苯基磷化物离子（pH下反应2 P - ）在液氨中进行了研究。1,3- Dichloroadamantane（1A），1-溴-3- chloroadamantane（1b）和1,3-二溴金刚烷（1c）中的Ph反应2 P -下光刺激由S离子RN 1机构。1c的照射不进行pH 2 P -离子没有给出反应（<5％）。发现三种产物：1，3-双（二苯膦基）金刚烷（2），（3-X-1-金刚烷基）二苯基膦（X ＝ Cl，3a； X ＝ Br，3b）和1-金刚烷基二苯基膦（4）。化合物2和4是通过自由基阴离子3a- ·（3b- ·）; 而3a（3b）是由该自由基阴离子在底物上的分子间ET形成的。观察到产物分布取决于底物和反应条件。
• Khusnutdinov; Shchadneva; Baiguzina, Petroleum Chemistry, 2004, vol. 44, # 2, p. 126 - 133
  作者：Khusnutdinov、Shchadneva、Baiguzina、Lavrent'eva、Burangulova、Dzhemilev

  DOI：——

  日期：——
• Yagrushkina, I. N.; Zemtsova, M. N.; Moiseev, I. K., Russian Journal of Organic Chemistry, 1995, vol. 31, # 4, p. 579
  作者：Yagrushkina, I. N.、Zemtsova, M. N.、Moiseev, I. K.

  DOI：——

  日期：——