含2,6-吡啶二甲酰胺基和二甲基双吡咯甲烷单元的大环合成及其与醋酸根的键合性质

发布时间：2018-06-20 20:53

  本文选题：-二甲酰胺吡啶 + 二甲基双吡咯甲烷　； 参考：《有机化学》2017年11期

【摘要】：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).
[Abstract]:[1] Schiff base macrocyclic 3 was obtained by the condensation of the precursors Nu Nu (3-aminophenyl) -2n (6-diformamide pyridyl) and 5 (5) -dimethyl-1-dimethyl-9-dipyrrolidine (dipyrrolidine) 2). The saturated macrocyclic 4 was obtained by further reduction of Schiff base macrocyclic 3. The composition of macroring was characterized by 1H NMRFT-IRFBMS and elemental analysis. The crystal structure of macroring 4 was analyzed by X-ray single crystal diffraction technique. UV-Vis absorption spectra, NMR and isothermal calorimetric titration techniques were used to investigate the interaction of macrocyclic 3 and 4 with AcON-anions, respectively. The thermodynamic parameter information, such as the bonding ratio, the bonding constant K) and the structure of the reaction were obtained. The results show that the bonding ratio of macrocyclic 3 to AcOO-H bond is 1: 1, the bonding constant K _ a 鈮，

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