8-hydroxy-N-tosyl-4,5-benzoazacyclodeca-2,6-diyne | 953818-89-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 8-hydroxy-N-tosyl-4,5-benzoazacyclodeca-2,6-diyne
• 英文别名: 4-(4-Methylphenyl)sulfonyl-4-azabicyclo[8.4.0]tetradeca-1(14),10,12-trien-2,8-diyn-7-ol
• CAS: 953818-89-8
• 化学式: C₂₀H₁₇NO₃S
• 分子量: 351.426
• InChiKey: IIQHPYDTAPASPP-UHFFFAOYSA-N

物化性质

• 沸点：
  558.6±60.0 °C(predicted)
• 密度：
  1.39±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  甲醇 、 8-hydroxy-N-tosyl-4,5-benzoazacyclodeca-2,6-diyne 以49%的产率得到4,5-dimethoxy-N-tosyl-1,2,3,4-tetrhydrobenzo[g]quinoline
  参考文献：
  名称：

  Synthesis and Unusual Reactivity of N-Tosyl-4,5-benzoazacyclodeca-2,6-diyne, Yneamino-Containing Enediyne

  摘要：

  Substitution of the propargylic carbon for nitrogen in cyclic 10-membered ring enediynes results in at least 2 orders of magnitude enhancement of reactivity. The mechanism of cycloaromatization of aza-enediynes, however, switches from radical (Bergman) to polar, which proceeds by initial protonation of a reactive yneamine moiety. Ketenimmonium cation produced on this step undergoes intramolecular nucleophilic cyclization. Reaction is strongly catalyzed by acids and exhibits substantial kinetic isotope effect.

  DOI：

  10.1021/ja073614d
• 作为产物：
  描述：

  N-(2-iodoethynylphenylethynyl)-N-(3-oxopropyl)-4-methylbenzenesulfonamide 在 nickel dichloride chromium dichloride 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以61%的产率得到8-hydroxy-N-tosyl-4,5-benzoazacyclodeca-2,6-diyne
  参考文献：
  名称：

  Synthesis and Unusual Reactivity of N-Tosyl-4,5-benzoazacyclodeca-2,6-diyne, Yneamino-Containing Enediyne

  摘要：

  Substitution of the propargylic carbon for nitrogen in cyclic 10-membered ring enediynes results in at least 2 orders of magnitude enhancement of reactivity. The mechanism of cycloaromatization of aza-enediynes, however, switches from radical (Bergman) to polar, which proceeds by initial protonation of a reactive yneamine moiety. Ketenimmonium cation produced on this step undergoes intramolecular nucleophilic cyclization. Reaction is strongly catalyzed by acids and exhibits substantial kinetic isotope effect.

  DOI：

  10.1021/ja073614d

文献信息

• Nucleophilic Cycloaromatization of Ynamide-Terminated Enediynes
  作者：Andrei Poloukhtine、Valentin Rassadin、Alexander Kuzmin、Vladimir V. Popik

  DOI：10.1021/jo101238x

  日期：2010.9.3

  ynamide fragment. The resulting ketenimmonium cation then cyclizes to produce naphthyl cation, which rapidly reacts with nucleophiles or undergoes Friedel−Crafts addition to aromatic compounds. In alcohols, addition of the nucleophilic solvent across the activated triple bond competes with the cyclization reaction. The ratio of cyclized to solvolysis products decreases with the increase in ring size.

  在10元，11元，12元和13元苯环式环烯二炔的炔基末端之一处引入氮原子导致完全抑制常规自由基Bergman反应，有利于极性环芳化。后者的反应由酸催化，并通过乙酰胺片段的初始质子化进行。然后，生成的酮亚胺阳离子环化以生成萘阳离子，该萘阳离子与亲核试剂快速反应或经历芳族化合物的Friedel-Crafts加成反应。在醇中，通过活化的三键添加亲核溶剂会与环化反应竞争。环化产物与溶剂分解产物的比率随着环尺寸的增加而降低。