2-methyl-4-(2,3,5,6,8,9-hexahydro-1,4,7,10-tetraoxabenzocyclododecen-12-yl)but-3-yn-2-ol | 374565-20-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-4-(2,3,5,6,8,9-hexahydro-1,4,7,10-tetraoxabenzocyclododecen-12-yl)but-3-yn-2-ol
• 英文别名: 2-Methyl-4-(2,5,8,11-tetraoxabicyclo[10.4.0]hexadeca-1(12),13,15-trien-14-yl)but-3-yn-2-ol
• CAS: 374565-20-5
• 化学式: C₁₇H₂₂O₅
• 分子量: 306.359
• InChiKey: KIEAVNPBEVBNAX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-methyl-4-(2,3,5,6,8,9-hexahydro-1,4,7,10-tetraoxabenzocyclododecen-12-yl)but-3-yn-2-ol 在 氢氧化钾 作用下， 以 苯 为溶剂， 以50%的产率得到12-ethynyl-2,3,5,6,8,9-hexahydro-1,4,7,10-tetraoxabenzocyclododecene
  参考文献：
  名称：

  摘要：

  4 ' -Ethynylbenzo-12-crown-4 (8), 4 ' -ethynylbenzo-15-crown-5 (9), and 4 ' -ethynylbenzo-18-crown-6 (10) were synthesized by cross-coupling of the corresponding aryl iodides 1-3 with 2-methylbut-3-yn-2-ol (4a) followed by the retro-Favorsky cleavage of the resulting carbinols. Unlike the corresponding benzo-12-crown-4 derivative (5a), the cleavage of tertiary acetylenic, alcohols of benzo-15-crown-5 (6a) and benzo-18-crown-6 (7a) requires more than one molar equivalent of KOH. Aminoalkylation of crown ether 8 gives Mannich bases, independently of the reaction conditions and the nature of amine. The aminomethylation of acetylenic crown ethers 9 and 10 with paraform-piperidine (morpholine) in the presence of CuCl yields 1,4-disubstituted buta-1,3-diynes (19, 20) rather than Mannich bases.

  DOI：

  10.1023/a:1011367311643
• 作为产物：
  描述：

  2-甲基-3-丁炔-2-醇 、 12-iodo-2,3,5,6,8,9-hexahydro-1,4,7,10-tetraoxabenzocyclododecene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 苯 为溶剂， 反应 1.0h， 以91%的产率得到2-methyl-4-(2,3,5,6,8,9-hexahydro-1,4,7,10-tetraoxabenzocyclododecen-12-yl)but-3-yn-2-ol
  参考文献：
  名称：

  摘要：

  4 ' -Ethynylbenzo-12-crown-4 (8), 4 ' -ethynylbenzo-15-crown-5 (9), and 4 ' -ethynylbenzo-18-crown-6 (10) were synthesized by cross-coupling of the corresponding aryl iodides 1-3 with 2-methylbut-3-yn-2-ol (4a) followed by the retro-Favorsky cleavage of the resulting carbinols. Unlike the corresponding benzo-12-crown-4 derivative (5a), the cleavage of tertiary acetylenic, alcohols of benzo-15-crown-5 (6a) and benzo-18-crown-6 (7a) requires more than one molar equivalent of KOH. Aminoalkylation of crown ether 8 gives Mannich bases, independently of the reaction conditions and the nature of amine. The aminomethylation of acetylenic crown ethers 9 and 10 with paraform-piperidine (morpholine) in the presence of CuCl yields 1,4-disubstituted buta-1,3-diynes (19, 20) rather than Mannich bases.

  DOI：

  10.1023/a:1011367311643

文献信息

• ——
  作者：S. V. Klyatskaya、E. V. Tretyakov、S. F. Vasilevsky

  DOI：10.1023/a:1011367311643

  日期：——

  4 ' -Ethynylbenzo-12-crown-4 (8), 4 ' -ethynylbenzo-15-crown-5 (9), and 4 ' -ethynylbenzo-18-crown-6 (10) were synthesized by cross-coupling of the corresponding aryl iodides 1-3 with 2-methylbut-3-yn-2-ol (4a) followed by the retro-Favorsky cleavage of the resulting carbinols. Unlike the corresponding benzo-12-crown-4 derivative (5a), the cleavage of tertiary acetylenic, alcohols of benzo-15-crown-5 (6a) and benzo-18-crown-6 (7a) requires more than one molar equivalent of KOH. Aminoalkylation of crown ether 8 gives Mannich bases, independently of the reaction conditions and the nature of amine. The aminomethylation of acetylenic crown ethers 9 and 10 with paraform-piperidine (morpholine) in the presence of CuCl yields 1,4-disubstituted buta-1,3-diynes (19, 20) rather than Mannich bases.