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将前体N,N’-(3-胺基苯基)-2,6-二甲酰胺吡啶(1)和5,5-二甲基-1,9-二甲酰基二吡咯甲烷(2)进行缩合作用得到[1+1]Schiff碱大环3.进一步将Schiff碱大环3还原得到饱和大环4.采用~1H NMR,FT-IR,FABMS和元素分析等对大环的组成进行了表征,通过X射线单晶衍射技术解析了大环4的晶体结构.采用紫外-可见吸收光谱、核磁和等温量热滴定等技术对大环3和4分别与AcO~-阴离子的键合作用进行了考察,获得了反应的键合比、键合常数(K)及Δ_(r)H_m,Δ_(r)S_m,Δ_(r)G_m等热力学参数信息.结果表明,大环3与AcO~-氢键作用的键合比为1∶1,键合常数K_a≈10~5 L·mol~(-1),具有更柔性的环状骨架大环4与AcO~-作用的键合比为1∶2,K_(a1)≈10~3 L·mol~(-1),K_(a2)≈10~5 L·mol~(-1).
The precursor N, N ’- (3-aminophenyl) -2,6-dicarboxamide pyridine (1) and 5,5-dimethyl-1,9- diformyl dipyrromethane (2) The condensation was carried out to give [1 + 1] Schiff base macrocycles 3. Further reduction of the Schiff base macrocycles 3 gave saturated macrocycles 4. The macrocycle composition was characterized by ~ 1H NMR, FT-IR, FABMS and elemental analysis The crystal structure of macrocycle 4 was analyzed by X-ray single crystal diffraction technique.The bonding of macrocycles 3 and 4 to AcO ~ - anions were carried out by UV-Vis absorption spectroscopy, nuclear magnetic resonance and isothermal calorimetry, respectively (K) and Δ_ (r) H_m, Δ_ (r) S_m, Δ_ (r) G_m and other thermodynamic parameters were obtained.The results showed that the reaction parameters of macrocyclic ring 3 and AcO ~ The bonding ratio of hydrogen bonding is 1: 1, the bonding constant K_a≈10 ~ 5 L · mol ~ (-1), the bonding ratio of the more flexible ring skeleton macrocycle 4 to AcO ~ - is 1 : 2, K a1 ≈10 ~ 3 L · mol -1, K a2 ≈10 ~ 5 L · mol -1.