(2S)-2-bromo-4-methylpentanenitrile | 28659-90-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (2S)-2-bromo-4-methylpentanenitrile
• 英文别名: 5-α-Bromisocapronitril；2-(S)-bromo-4-methyl-pentanenitrile
• CAS: 28659-90-7
• 化学式: C₆H₁₀BrN
• 分子量: 176.056
• InChiKey: GPNVFADTULBZGG-LURJTMIESA-N

物化性质

• 沸点：
  185.0±13.0 °C(Predicted)
• 密度：
  1.305±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  (2S)-2-bromo-4-methylpentanenitrile 在 lithium aluminium tetrahydride 作用下， 生成 4-甲基戊-1-胺
  参考文献：
  名称：

  Umwandlung von Aldehyden in 2-monosubstituierte Aziridine。还原 von α-Chlor, Brom- und Sulfonyloxynitilen mit Lithiumaluminiumhydrid

  摘要：

  描述了 α-氯、溴和磺酰氧基腈的还原环化。α-氯代腈被氢化铝锂还原，得到足够产率的氮丙啶。发现瓦尔登反转发生在 S-α-氯异己腈的还原环化过程中。我们发现了醛向 2-单取代氮丙啶的两步转化，其中包括用苯磺酰氯和碱金属氰化物处理醛以形成 α-苯磺酰氧基腈，后者被氢化铝锂还原为相应的氮丙啶。用氢化物还原 α-溴代腈产生 prim。胺与氮丙啶。

  DOI：

  10.1246/bcsj.43.1443
• 作为产物：
  描述：

  5-α-Bromisocapronsaeurechlorid 在 ammonium hydroxide 、 phosphorus pentoxide 作用下， 生成 (2S)-2-bromo-4-methylpentanenitrile
  参考文献：
  名称：

  Umwandlung von Aldehyden in 2-monosubstituierte Aziridine。还原 von α-Chlor, Brom- und Sulfonyloxynitilen mit Lithiumaluminiumhydrid

  摘要：

  描述了 α-氯、溴和磺酰氧基腈的还原环化。α-氯代腈被氢化铝锂还原，得到足够产率的氮丙啶。发现瓦尔登反转发生在 S-α-氯异己腈的还原环化过程中。我们发现了醛向 2-单取代氮丙啶的两步转化，其中包括用苯磺酰氯和碱金属氰化物处理醛以形成 α-苯磺酰氧基腈，后者被氢化铝锂还原为相应的氮丙啶。用氢化物还原 α-溴代腈产生 prim。胺与氮丙啶。

  DOI：

  10.1246/bcsj.43.1443
• 作为试剂：
  描述：

  (S)-N-(4-methoxybenzylidene)-α-methylbenzylamine 在 双氧水 、 碳酸氢钠 、 (2S)-2-bromo-4-methylpentanenitrile 作用下， 以 二氯甲烷 为溶剂， 生成 2-(1'-phenylethyl)-3-paramethoxyphenyloxaziridine 、 (3R)-3-(4-methoxyphenyl)-2-[(1S)-1-phenylethyl]oxaziridine
  参考文献：
  名称：

  Enantio- and Diastereoselective Oxidation of N-Alkylimines Using Chiral α-Bromonitriles and Hydrogen Peroxide System

  摘要：

  Chiral alpha-bromonitriles were prepared with good chemical and optical yields starting from natural alpha-amino acids by dehydrating the corresponding alpha-bromoamides with thionyl chloride. The combined system alpha-bromonitriles/hydrogen peroxide was examined for the enantio- and diastereoselective oxidation of N-alkylimines in basic media at room temperature. The oxidation of N-tertiobutylarylimines leads to optically active oxaziridines with moderate enantiomeric excess. However, the oxidation of (S)-1-phenylethylarylimines affords the corresponding oxaziridines with good diasteromeric excess up to 97/3 as proved by gaseous-phase chromatography.

  DOI：

  10.1080/00397911.2011.573611

文献信息

• [EN] IMPROVED SYNTHESIS OF OPTICALLY PURE (S) - 3-CYANO-5-METHYL-HEXANOIC ACID ALKYL ESTER, AN INTERMEDIATE OF (S)- PREGABALIN<br/>[FR] SYNTHÈSE AMÉLIORÉE D'UN ESTER ALKYLIQUE OPTIQUEMENT PUR DE L'ACIDE (S) - 3-CYANO-5-MÉTHYL-HEXANOÏQUE, INTERMÉDIAIRE DE LA (S)-PRÉGABALINE
  申请人：LUPIN LTD

  公开号：WO2011141923A3

  公开（公告）日：2012-01-19
• Umwandlung von Aldehyden in 2-monosubstituierte Aziridine. Reduktion von α-Chlor, Brom- und Sulfonyloxynitilen mit Lithiumaluminiumhydrid
  作者：Kunihiro Ichimura、Masaki Ohta

  DOI：10.1246/bcsj.43.1443

  日期：1970.5

  The reductive cyclization of α-chloro, bromo- and sulfonyloxycarbonitriles are described. α-Chlorocarbonitriles were reduced by lithium aluminum hydride to afford aziridines in sufficient yields. The Walden inversion was found to take place in the cource of the reductive cyclization of S-α-chloroisocapronitrile. We have found the two-step conversion of aldehydes to 2-mono-substituted aziridines which

  描述了 α-氯、溴和磺酰氧基腈的还原环化。α-氯代腈被氢化铝锂还原，得到足够产率的氮丙啶。发现瓦尔登反转发生在 S-α-氯异己腈的还原环化过程中。我们发现了醛向 2-单取代氮丙啶的两步转化，其中包括用苯磺酰氯和碱金属氰化物处理醛以形成 α-苯磺酰氧基腈，后者被氢化铝锂还原为相应的氮丙啶。用氢化物还原 α-溴代腈产生 prim。胺与氮丙啶。
• Synthesis of Enantiomerically Enriched <font>α</font>-Bromonitriles from Amino Acids
  作者：Najeh Tka、Jamil Kraïem、Béchir Ben Hassine

  DOI：10.1080/00397911.2011.608142

  日期：2013.1.1

  Two methods were investigated for the preparation of six chiral alpha-bromonitriles with different optic purities. The nitrous deamination of amino acids gives alpha-bromoacids, which react with chlorosulfonyl isocyanate followed by triethylamine to afford alpha-bromonitriles with moderate enantiomeric excess. However, the dehydration of corresponding alpha-bromoamids using thionyl chloride gives alpha-bromonitriles with good enantiomeric excess up to 94%. The use of phosphoryl chloride instead of thionyl chloride results in more than 30% racemization as determined by high-performance liquid chromatograpic analysis.
• Enantio- and Diastereoselective Oxidation of <i>N</i>-Alkylimines Using Chiral <font>α</font>-Bromonitriles and Hydrogen Peroxide System
  作者：Najeh Tka、Jamil Kraïem、Béchir Ben Hassine

  DOI：10.1080/00397911.2011.573611

  日期：2012.10.15

  Chiral alpha-bromonitriles were prepared with good chemical and optical yields starting from natural alpha-amino acids by dehydrating the corresponding alpha-bromoamides with thionyl chloride. The combined system alpha-bromonitriles/hydrogen peroxide was examined for the enantio- and diastereoselective oxidation of N-alkylimines in basic media at room temperature. The oxidation of N-tertiobutylarylimines leads to optically active oxaziridines with moderate enantiomeric excess. However, the oxidation of (S)-1-phenylethylarylimines affords the corresponding oxaziridines with good diasteromeric excess up to 97/3 as proved by gaseous-phase chromatography.