含吡啶环系西佛碱大环配合物和氮杂大环自由配体的合成

2, 6-二羟甲基吡啶(1)经活性MnO~2氧化得到2, 6-二甲酰基吡啶(2)。邻硝基苯酚与N-取代的二(氯乙基)胺在DMF溶液中反应, 得到N-取代的1, 5-二(邻硝基苯氧基)-3-氮杂戊烷(3a～3c), 再经水合肼/Raney Ni还原, 获得N-取代的1, 5-二(邻氨基苯氧基)-3-氮杂戊烷(4a～4c)。利用Ba^2^+作为模板离子, (2)分别与(4a～4c)反应, 合成了一类新的含吡啶环系西佛碱大环配合物I-III, 配合物I、III与NaBH~4的乙醇溶液还原解络, 得到氮杂大环自由配体IV和V。所有西佛碱大环配合物和氮杂大环自由配体均经元素分析、IR、^1H NMR、MS等证实了它们的结构和组成。

Syntheses of Schiff''s base macrocyclic complexes and azamacrocyclic free ligands containing pyridine ring

2, 6-Di(hydroxymethyl)-pyridine(1) was oxidated with activated MnO~2 to afford 2, 6-pyridinedicarboxaldehyde(2). The rection of o-nitrophenol and N-substituted di(chloroethyl) amine in DMF/K~2CO~3 obtained N-substituted 1,5-di(o-nitrophenoxy)-3-azapentane (3a-c), which were reduced with hydrazine hydrate/Raney Ni to afford N-substituted 1,5-di(o-aminophenoxy)-3-azapentane (4a-c). Schiff's base macrocyclic complexes (I-III) were synthesized using Ba^2^+ as template ion by reaction of (2) with compounds (4a-c) respectively. Complexes I and III were reduced with NaBH~4 to azamacrocyclic free ligands (IV, V).