1-azido-3-(Z)-hexene | 127611-41-0

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 1-azido-3-(Z)-hexene
• 英文别名: (3Z)-1-azido-3-hexene；(Z)-1-azidohex-3-ene
• CAS: 127611-41-0
• 化学式: C₆H₁₁N₃
• 分子量: 125.173
• InChiKey: SOPDEWGLVZVLCL-ARJAWSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  14.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-azido-3-(Z)-hexene 在 吡啶 、 4-二甲氨基吡啶 、 水 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 57.0h， 生成 acetoxyacetic acid methyl ester
  参考文献：
  名称：

  Tin tetrachloride-induced π-cyclizations of glycine cation equivalents to substituted pipecolic acid derivatives

  摘要：

  Cationic pi-cyclization reactions of N-(3-alkenyl)-N-(methoxycarbonyl)acetoxyglycine esters induced by tin tetrachloride in dichloromethane are described. Reactions started and quenched with water at -78-degrees-C mainly yield cis-4-hydroxypipecolic esters, whereas reactions quenched after warm-up to room temperature provide trans-4-chloropipecolic esters as major products. A mechanistic scheme is advanced which adequately explains these results. The essentials are a rapid cationic aza-Cope equilibrium of the incipient iminium cation, and participation of the ester moiety through formation of a relatively stable bicyclic dioxycarbenium cation as pivotal intermediate.

  DOI：

  10.1016/s0040-4020(01)86443-7
• 作为产物：
  描述：

  叶醇 在 sodium azide 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.25h， 生成 1-azido-3-(Z)-hexene
  参考文献：
  名称：

  Tin tetrachloride-induced π-cyclizations of glycine cation equivalents to substituted pipecolic acid derivatives

  摘要：

  Cationic pi-cyclization reactions of N-(3-alkenyl)-N-(methoxycarbonyl)acetoxyglycine esters induced by tin tetrachloride in dichloromethane are described. Reactions started and quenched with water at -78-degrees-C mainly yield cis-4-hydroxypipecolic esters, whereas reactions quenched after warm-up to room temperature provide trans-4-chloropipecolic esters as major products. A mechanistic scheme is advanced which adequately explains these results. The essentials are a rapid cationic aza-Cope equilibrium of the incipient iminium cation, and participation of the ester moiety through formation of a relatively stable bicyclic dioxycarbenium cation as pivotal intermediate.

  DOI：

  10.1016/s0040-4020(01)86443-7

文献信息

• Stereospecific synthesis of Z olefins bearing an ω-azido group
  作者：A. Chhen、M. Vaultier、R. Carrié

  DOI：10.1016/s0040-4039(01)80552-9

  日期：1989.1

  Ylides derived from ω-azidoalkyltriphenylphosphonium salts were generated at low temperature. They are stable at −80°C for several hours and react smoothly and stereospecifically with typical aldehydes to form Z-ω-azido olefins which are the precursors of ω-unsaturated primary and secondary amines.

  ω-叠氮基烷基三苯基phosph盐衍生的叶立德在低温下生成。它们在-80°C稳定数小时，并且与典型的醛平稳且立体定向反应，形成Z-ω-叠氮基烯烃，它们是ω-不饱和伯胺和仲胺的前体。
• A straightforward preparation of benz[f]indoles by an intramolecular diels-alder cycloaddition of unsaturated ketenimines.
  作者：Pedro Molina、Carmen López-Leonardo、Julián Alcántara

  DOI：10.1016/s0040-4020(01)90414-4

  日期：1994.4

  An intramolecular Diels-Alder cycloaddition of de ketenimines 3, available by aza Wittig reaction between iminophosphoranes 2, derived from azido olefins 1, and diaryl ketenes followed by an oxidative aromatization of the cycloadduct provided benz[f]indoles 5. Attempts to apply this process either with ethylphenylketene, 5-aryl-4-pentenylazides or with the related carbodiimides failed.

  酮亚胺3的分子内Diels-Alder环加成反应可通过衍生自叠氮烯烃1的亚氨基膦2与二芳基烯酮通过aza Wittig反应获得，然后对环加合物进行氧化芳构化得到苯并[ f ]吲哚5。尝试将这种方法与乙基苯基乙烯酮，5-芳基-4-戊烯叠氮化物或相关的碳二亚胺一起应用的尝试失败了。