2''-hydroxy-5''-nitro-14,15:17,19:21,22-tribenzo-1,4,7,10,13-pentaoxacyclodocosa-14,17,21-triene | 137794-12-8

• 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: 2''-hydroxy-5''-nitro-14,15:17,19:21,22-tribenzo-1,4,7,10,13-pentaoxacyclodocosa-14,17,21-triene
• 英文别名: 31-nitro-9,12,15,18,21-pentaoxatetracyclo[27.3.1.03,8.022,27]tritriaconta-1(32),3,5,7,22,24,26,29(33),30-nonaen-33-ol
• CAS: 137794-12-8
• 化学式: C₂₈H₃₁NO₈
• 分子量: 509.556
• InChiKey: KGFXCGUGBAWBBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  37.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  109.52
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 2''-hydroxy-5''-nitro-14,15:17,19:21,22-tribenzo-1,4,7,10,13-pentaoxacyclodocosa-14,17,21-triene 在 吡啶 作用下， 以99%的产率得到5''-nitro-14,15:17,19:21,22-tribenzo-1,4,7,10,13-pentaoxacyclodocosa-14,17,21-trien-18-yl acetate
  参考文献：
  名称：

  New crown ether-like macrocycles containing a nitrophenol unit. Synthesis and metal ion effects on the reactivity of their acetates in transacylation reactions

  摘要：

  A series of crown ether-like macrocyclic compounds 3 containing the 2,6-dibenzyl-4-nitrophenol substructure have been prepared by cyclization reactions of disalicylideneacetone 4 with ditosylates 7 of oligoethylene glycols, followed by hydrogenation and double aldol condensation with nitromalondialdehyde. These compounds may be regarded as possessing a section of a 1,3-crowned calix[4]arene. X-ray analysis of two examples shows, however, that the three phenolic units linked via o-methylene groups adopt a conformation different to the all-cis conformation found in calix[4]arenes. The reaction of the nitrophenyl acetates derived from 3 and from suitable model compounds with ethoxide in ethanol was studied kinetically. This reaction is accelerated by the addition of SrBr2 and BaBr2 in all cases, indicating that the metal ion is bound more strongly to the transition state than to the initial state. Especially high acceleration factors (up to 700 in the case of 10e) were observed for cyclic and open-chain compounds with longer flexible oligoethylene oxide chains, which means that only in these cases do the ether oxygens contribute effectively to the binding of the metal ion in the transition state.

  DOI：

  10.1021/jo00029a009
• 作为产物：
  描述：

  14,15:21,22-dibenzo-1,4,7,10,13-pentaoxacyclodocosa-14,16,19,21-tetraen-18-one 在 镍 氢气 、 sodium ethanolate 作用下， 以 甲醇 为溶剂， 反应 20.0h， 生成 2''-hydroxy-5''-nitro-14,15:17,19:21,22-tribenzo-1,4,7,10,13-pentaoxacyclodocosa-14,17,21-triene
  参考文献：
  名称：

  New crown ether-like macrocycles containing a nitrophenol unit. Synthesis and metal ion effects on the reactivity of their acetates in transacylation reactions

  摘要：

  A series of crown ether-like macrocyclic compounds 3 containing the 2,6-dibenzyl-4-nitrophenol substructure have been prepared by cyclization reactions of disalicylideneacetone 4 with ditosylates 7 of oligoethylene glycols, followed by hydrogenation and double aldol condensation with nitromalondialdehyde. These compounds may be regarded as possessing a section of a 1,3-crowned calix[4]arene. X-ray analysis of two examples shows, however, that the three phenolic units linked via o-methylene groups adopt a conformation different to the all-cis conformation found in calix[4]arenes. The reaction of the nitrophenyl acetates derived from 3 and from suitable model compounds with ethoxide in ethanol was studied kinetically. This reaction is accelerated by the addition of SrBr2 and BaBr2 in all cases, indicating that the metal ion is bound more strongly to the transition state than to the initial state. Especially high acceleration factors (up to 700 in the case of 10e) were observed for cyclic and open-chain compounds with longer flexible oligoethylene oxide chains, which means that only in these cases do the ether oxygens contribute effectively to the binding of the metal ion in the transition state.

  DOI：

  10.1021/jo00029a009