2-chlorobicyclo[2.2.1]hept-5-ene-exo-2-carbonitrile

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-chlorobicyclo[2.2.1]hept-5-ene-exo-2-carbonitrile
• 英文别名: 2-chlorobicyclo<2.2.1>hept-5-ene-2-carbonitriles；(1R*,2R*,4R*)-2-chlorobicyclo[2.2.1]hept-5-ene-2-carbonitrile；Rel-(1S,2S,4S)-2-chlorobicyclo[2.2.1]hept-5-ene-2-carbonitrile；(1S,2S,4S)-2-chlorobicyclo[2.2.1]hept-5-ene-2-carbonitrile
• 化学式: C₈H₈ClN
• 分子量: 153.611
• InChiKey: UCYKNDOOVFKJKU-XLPZGREQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  苯基氯化硒 、 2-chlorobicyclo[2.2.1]hept-5-ene-exo-2-carbonitrile 以 氯仿 为溶剂， 反应 48.0h， 生成 6-exo-benzeneselenenyl-2-endo,5-endo-dichlorobicyclo<2.2.1>heptane-2-exo-carbonitrile
  参考文献：
  名称：

  亲电子体对烯烃的区域选择性加成受到远程干扰。羰基作为均共给电子的取代基。

  摘要：

  亲电试剂优先攻击2-norborn-5-enone和2-双环[2.2.2] oct-5-enone的C（5）位置，而C（6）位置更适合2-chloronorborn-5-ene- 2-腈和2-氯双环[2.2.2]辛-5-烯-2-腈。

  DOI：

  10.1016/s0040-4039(00)87396-7
• 作为产物：
  描述：

  5-norbornene-2-carbonitrile 在 lithium diisopropyl amide 、 2-chloro-2-fluoro-2-phenylacetonitrile 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 2-chlorobicyclo[2.2.1]hept-5-ene-exo-2-carbonitrile 、 二环[2.2.1]庚-5-烯-2-甲腈,2-氯-,外-
  参考文献：
  名称：

  Metalated Nitrile and Enolate Chlorinations

  摘要：

  Metalated nitriles and enolates rapidly and efficiently abstract chlorine from 2-chloro-2-fluoro-2-phenylacetonitrile to afford a diverse range of chloronitriles and chloroesters. The method provides the first general anionic chlorination of alkylnitriles, tolerates numerous functional groups, and addresses the challenge of synthesizing alpha-chloronitriles under mild conditions.

  DOI：

  10.1021/ol100897y

文献信息

• Microwave-Assisted Solvent-Free Diels-Alder Reaction - A Fast and Simple Route to Various 5,6-Substituted Norbornenes and Polychlorinated Norbornenes
  作者：Radim Nencka、Milan Dejmek、Hubert Hřebabecký、Michal Šála、Martin Dračínský

  DOI：10.1055/s-0031-1289610

  日期：2011.12

  Diels-Alder reaction. This procedure proved very versatile, fast, and with an easy workup step, and therefore suitable even for large-scale synthesis. Diels-Alder reactions - bicyclic compounds - cyclo­additions - norbornene - microwave - polychlorinated norbornanes

  通过使用微波辅助的Diels-Alder反应，制备了一系列的5，6-取代的降冰片烯和5，6-取代的多氯降冰片烯。事实证明，该方法非常通用，快速并且具有易于完成的步骤，因此甚至适用于大规模合成。 Diels-Alder反应-双环化合物-环加成-降冰片烯-微波-多氯降冰片烷
• 2-Chlorobicyclo[2.2.1]hept-5-ene-2-carboxamide and 2-chlorobicyclo[2.2.1]heptane-2-carboxamide as precursors of bicyclo[2.2.1]hept-5-en-2-one and bicyclo[2.2.1]heptan-2-one: resolution, absolute configuration and hydrogen-bonding properties
  作者：Erika Plettner、Ashley Mohle、Martin T. Mwangi、Johanna Griscti、Brian O. Patrick、Ranjeet Nair、Raymond J. Batchelor、Fredrick Einstein

  DOI：10.1016/j.tetasy.2005.07.016

  日期：2005.8

  We found the absolute configuration (1R,2R,4R) for the (+)-enantiomer of the α-chloroamide. This compound was converted to (+)-bicyclo[2.2.1]hept-5-ene-2-one by base hydrolysis, and the 5,6-unsaturated compounds converted to the saturated congeners. This is the first unambiguous experimental determination of the absolute configuration of bicyclo[2.2.1]heptan-2-one and of bicyclo[2.2.1]hept-5-ene-2-one

  双环[2.2.1]庚-2--2-酮的绝对构型尚未与化学前体的晶体结构相关。唯一可用的化学相关性含糊不清，这可能会颠倒分配。在此，我们报道了三乙酸纤维素色谱柱上2-氯双环[2.2.1]庚-5-烯-2-外-羧酰胺的分离度以及对映体纯的和外消旋的α-氯酰胺的晶体结构。我们找到了绝对配置（1 R，2 R，4 R）表示α-氯酰胺的（+）对映体。通过碱水解将该化合物转化为（+）-双环[2.2.1]庚-5-烯-2-酮，并且5，6-不饱和化合物转化为饱和同类物。这是对双环[2.2.1]庚-2-酮和双环[2.2.1]庚-5-烯-2-酮的绝对构型的第一个明确实验确定。2-氯双环[2.2.1] hept-5-en-2- exo的三种晶体结构本文报道的β-羧酰胺显示出H键合的二聚体，双环部分相对于羧酰胺二聚体具有两个不同的取向。在外消旋晶体中，每个二聚体均由两个对映体组成，双环部分的H键合羧酰胺二聚体部分的相对侧
• Yates, Peter; Kronis, John David, Canadian Journal of Chemistry, 1984, vol. 62, p. 1751 - 1766
  作者：Yates, Peter、Kronis, John David

  DOI：——

  日期：——
• Metalated Nitrile and Enolate Chlorinations
  作者：Bhaskar Reddy Pitta、Fraser F. Fleming

  DOI：10.1021/ol100897y

  日期：2010.6.18

  Metalated nitriles and enolates rapidly and efficiently abstract chlorine from 2-chloro-2-fluoro-2-phenylacetonitrile to afford a diverse range of chloronitriles and chloroesters. The method provides the first general anionic chlorination of alkylnitriles, tolerates numerous functional groups, and addresses the challenge of synthesizing alpha-chloronitriles under mild conditions.
• Regioselective additions of electrophiles to olefins remotely perturbed. The carbonyl group as a homoconjugated electron donating substituent.
  作者：Pierre-Alain Carrupt、Pierre Vogel

  DOI：10.1016/s0040-4039(00)87396-7

  日期：1982.1

  Electrophiles attack preferentially at the C(5) position of 2-norborn-5-enone and 2-bicyclo[2.2.2]oct-5-enone whereas the C(6) position is preferred for 2-chloronorborn-5-ene-2-carbonitriles and 2-chlorobicyclo[2.2.2]oct-5-ene-2-carbonitriles.

  亲电试剂优先攻击2-norborn-5-enone和2-双环[2.2.2] oct-5-enone的C（5）位置，而C（6）位置更适合2-chloronorborn-5-ene- 2-腈和2-氯双环[2.2.2]辛-5-烯-2-腈。