N-芳基马来海枞酸单甲酯二酰亚胺位阻异构化反应及其动力学特性  

Atropisomerism of Methyl Maleopimaric N-Arylimides and Their Kinetics Analysis

作　　者：陈华妮[1] 叶鳗仪[2] 姚贵阳[2] 李亚军[2] 朱永涛[2] 王恒山[2] 

机构地区：[1]百色学院化学与生命科学系,百色533000 [2]广西师范大学化学化工学院,药用资源化学与药物分子工程重点实验室,桂林541004

出　　处：《高等学校化学学报》2014年第4期839-846,共8页Chemical Journal of Chinese Universities

基　　金：国家"九七三"计划前期研究专项基金(批准号:2011CB512005);国家自然科学基金(批准号:20762001);广西自然科学基金重点项目(批准号:2011GXNSFD018010)资助~~

摘　　要：在合成松香基手性试剂(4a^4f)的过程中,首次发现N-(1-萘基)-马来海枞酸二酰亚胺(4f)的位阻异构现象,而与其结构类似的N-苯基-马来海枞酸二酰亚胺(4a)、N-(2-羧基苯基)-甲酯化马来海松酸二酰亚胺(4b)、N-(2-硝基苯基)-甲酯化马来海松酸二酰亚胺(4c)、N-(2-氯苯基)-甲酯化马来海松酸二酰亚胺(4d)和N-[1-(2-氨基)-苯基]-甲酯化马来海松酸二酰亚胺(4e)则没有该位阻异构现象.化合物4a^4f的结构通过核磁共振、质谱和红外光谱等方法进行了表征.采用变温条件下的1H NMR谱图研究了化合物4f的位阻异构化动力学特性.During the last few years, considerable interest has been focused on the atropisomerism of N-aryl bond contain compounds which belong to one of the most common classes with atropisomers. Six N-aryl methyl maleopimaric acid diimides （ 4 a-4 f ） were synthesized from aromatic amines andmaleopimaric acid trimethyl ester（3）. The structures of the compounds were characterized by 1H NMR,13C NMR and MS. The atropiso-merism and kinetics analyses of the N-（1-naphthyl） maleopimaric acid diimides were carried out by 1 H NMR. In the course of preparing resin-based chiralregent, atropisomerism was found in N-（1-naphthy） maleopimaric acid diimides（4f）. The N-（1-phenyl） maleopimaric acid diimide（4a）, N-（2-carboxy phenyl） methyl ma-leopimaric acid diimide （ 4 b ） , N-（ 2-nitrophenyl ）-methyl maleopimaric acid diimide （ 4 c ） , N-（ 2-chlorophe-nyl）-methyl maleopimaric acid diimide（4d） and N-[1-（2-amine）-phenyl]-methyl maleopimaric acid diimide （4e） did not exist atropisomerism due to the smaller steric effects. The results indicated that maleopimaric N-naphthylimide （ 4 f ） underwent slow trans-cis conversion and induced in a gradual change of different [ trans]/[ cis] ratio during dissolution in CDCl3 at ambient temperature.

关 键 词：马来海枞酸 二酰亚胺 位阻异构 动力学 核磁共振 

分 类 号：O643.1[理学—物理化学]