9-((5'-Chloro-8'-hydroxy-7'-quinolinyl)methyl)-3,6,12,15-tetraoxa-9,21-diazabicyclo<15.3.1>heneicosa-1(21),17,19-triene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 9-((5'-Chloro-8'-hydroxy-7'-quinolinyl)methyl)-3,6,12,15-tetraoxa-9,21-diazabicyclo<15.3.1>heneicosa-1(21),17,19-triene
• 英文别名: 5-Chloro-7-(3,6,12,15-tetraoxa-9,21-diazabicyclo[15.3.1]henicosa-1(21),17,19-trien-9-ylmethyl)quinolin-8-ol
• 化学式: C₂₅H₃₀ClN₃O₅
• 分子量: 487.983
• InChiKey: KEZCFNHSLGGUMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  86.2
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  3,6,12,15-Tetraoxa-9,21-diazabicyclo<15.3.1>heneicosa-1(21),17,19-triene 以 苯 为溶剂， 反应 12.0h， 生成 9-((5'-Chloro-8'-hydroxy-7'-quinolinyl)methyl)-3,6,12,15-tetraoxa-9,21-diazabicyclo<15.3.1>heneicosa-1(21),17,19-triene
  参考文献：
  名称：

  Synthesis of New Pyridinoazacrown Ethers Containing Aromatic and Heteroaromatic Proton Ionizable Substituents

  摘要：

  Methods for the synthesis of pyridinocrowns functionalized with various proton ionizable groups have been elaborated. Sixteen new ligands containing pyridine rings as part of the macrocycle or as a side arm have been prepared. Different interactive abilities of the OH and NH functions of 3,9-dioxa-6-azaundecane-1,11-diol (3) in strong base allowed the synthesis of pyridinoazacrowns 1 and 2 by cyclization with 2,6-bis((tosyloxy)methyl)pyridine (4) and THP-protected 4-hydroxy-2,6-bis(tosyloxy)methyl)pyridine (5). Pyridinoazacrown 1 was functionalized with different proton ionizable side arms by treatment first with formaldehyde in methanol to form the N-methoxymethyl derivative 6 and then treating 6 with 5-chloro-8-hydroxyquinoline or the appropriate substituted phenol. Pyridinoaza-18-crown-6 ligands containing p-methylphenol (7), p-methoxyphenol (8), p-chlorophenol (9),p-fluorophenol (10),p-cyanophenol (11), 2-formyl-4-bromophenol (12), or 5-chloro-8-hydroxyquinoline (13) groups were prepared by this process. Pyridinoazacrowns 1 and 2 were alkylated with 2-hydroxy-5-nitrobenzyl chloride or 5-chloro-8-methoxy-2-(bromomethyl)quinol followed by removal of the protecting groups to form p-nitrophenol- and 5-chloro-8-hydroxy-2-quinolinyl-substituted ligands (16, 18, and 21). Macrocycles 22 and 23 containing proton ionizable triazole and phenol functions inside the macrocyclic cavity and a pyridine side arm were prepared by cyclization of the appropriate dihalide with 6-(2'-pyridylmethyl)-3,9-dioxa-6-azaundecane-1,11-diol followed by cleavage of the THP or methoxy protecting groups. Preliminary complexation data show that the phenol-substituted pyridinoaza-18-crown-6 ligands form strong complexes with various metal cations and exhibit high selectivity toward Ag+. Macrocycle 16 containing a p-nitrophenol substituent formed a complex with benzylamine. The crystal structures for 16 and its benzylamine complex are also given here.

  DOI：

  10.1021/jo00124a022

文献信息

• Synthesis of New Pyridinoazacrown Ethers Containing Aromatic and Heteroaromatic Proton Ionizable Substituents
  作者：Andrei V. Bordunov、Paul C. Hellier、Jerald S. Bradshaw、N. Kent Dalley、Xiaolan Kou、Xian Xin Zhang、Reed M. Izatt

  DOI：10.1021/jo00124a022

  日期：1995.9

  Methods for the synthesis of pyridinocrowns functionalized with various proton ionizable groups have been elaborated. Sixteen new ligands containing pyridine rings as part of the macrocycle or as a side arm have been prepared. Different interactive abilities of the OH and NH functions of 3,9-dioxa-6-azaundecane-1,11-diol (3) in strong base allowed the synthesis of pyridinoazacrowns 1 and 2 by cyclization with 2,6-bis((tosyloxy)methyl)pyridine (4) and THP-protected 4-hydroxy-2,6-bis(tosyloxy)methyl)pyridine (5). Pyridinoazacrown 1 was functionalized with different proton ionizable side arms by treatment first with formaldehyde in methanol to form the N-methoxymethyl derivative 6 and then treating 6 with 5-chloro-8-hydroxyquinoline or the appropriate substituted phenol. Pyridinoaza-18-crown-6 ligands containing p-methylphenol (7), p-methoxyphenol (8), p-chlorophenol (9),p-fluorophenol (10),p-cyanophenol (11), 2-formyl-4-bromophenol (12), or 5-chloro-8-hydroxyquinoline (13) groups were prepared by this process. Pyridinoazacrowns 1 and 2 were alkylated with 2-hydroxy-5-nitrobenzyl chloride or 5-chloro-8-methoxy-2-(bromomethyl)quinol followed by removal of the protecting groups to form p-nitrophenol- and 5-chloro-8-hydroxy-2-quinolinyl-substituted ligands (16, 18, and 21). Macrocycles 22 and 23 containing proton ionizable triazole and phenol functions inside the macrocyclic cavity and a pyridine side arm were prepared by cyclization of the appropriate dihalide with 6-(2'-pyridylmethyl)-3,9-dioxa-6-azaundecane-1,11-diol followed by cleavage of the THP or methoxy protecting groups. Preliminary complexation data show that the phenol-substituted pyridinoaza-18-crown-6 ligands form strong complexes with various metal cations and exhibit high selectivity toward Ag+. Macrocycle 16 containing a p-nitrophenol substituent formed a complex with benzylamine. The crystal structures for 16 and its benzylamine complex are also given here.