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

doi:10.7503/cjcu20130796

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (4): 839.doi: 10.7503/cjcu20130796

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

陈华妮¹, 叶鳗仪², 姚贵阳², 李亚军², 朱永涛², 王恒山²()

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

收稿日期:2013-08-16 出版日期:2014-04-10 发布日期:2013-10-23
作者简介:联系人简介: 王恒山, 男, 博士, 教授, 主要从事手性药物的研究. E-mail: whengshan@163.com
基金资助:
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)和广西自然科学基金重点项目(批准号: 2011GXNSFD018010)资助

Atropisomerism of Methyl Maleopimaric N-Arylimides and Their Kinetics Analysis^†

CHEN Huani¹, YE Manyi², YAO Guiyang², LI Yajun², ZHU Yongtao², WANG Hengshan^2,^*()

1. Department of Chemistry and Life Science, Baise University, Baise 533000, China
2. Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, Ministry of Education, School of Chemistry & Chemical Engineering, Guangxi Normal University, Guilin 541004, China

Received:2013-08-16 Online:2014-04-10 Published:2013-10-23
Contact: WANG Hengshan E-mail:whengshan@163.com
Supported by:
† Supported by the National Basic Research Program of China(No.2011CB512005), the National Natural Science Foundation of China(No.20762001) and the Natural Science Foundation of Guangxi Province, China(No.2011GXNSFD018010)

摘要/Abstract

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.

关键词: 马来海枞酸, 二酰亚胺, 位阻异构, 动力学, 核磁共振

Abstract:

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(4a—4f) 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 ¹H 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 maleopimaric acid diimide(4b), N-(2-nitrophenyl)-methyl maleopimaric acid diimide(4c), N-(2-chlorophenyl)-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(4f) underwent slow trans-cis conversion and induced in a gradual change of different [trans]/[cis] ratio during dissolution in CDCl₃ at ambient temperature.

Key words: Maleopimaric acid, Diimide, Atropisomerism, Kinetic, NMR

中图分类号:

O643.1

TrendMD:

陈华妮, 叶鳗仪, 姚贵阳, 李亚军, 朱永涛, 王恒山. 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. 高等学校化学学报, 2014, 35(4): 839.

CHEN Huani, YE Manyi, YAO Guiyang, LI Yajun, ZHU Yongtao, WANG Hengshan. Atropisomerism of Methyl Maleopimaric N-Arylimides and Their Kinetics Analysis^†. Chem. J. Chinese Universities, 2014, 35(4): 839.

图/表 9

Scheme 1 Synthetic route of maleopimaric N-arylimides

Table 1 NMR and MS data of compounds 4a—4f

Compd.	¹H NMR(500 MHz, CDCl₃), δ	¹³C NMR(CDCl₃, 125 MHz), δ	MS(APCI), (M+H⁺), m/z
4a	7.411—7.365(m, 2H, J=7.5 Hz, 2'-H, 6'-H), 7.335(d, 1H, J=7.0 Hz, 4'-H), 7.116(d, 2H, J=8.0 Hz, 3'-H, 5'-H), 5.520(s, 1H, 14-H), 3.678(s, 3H, —CO₂CH₃), 3.163(s, 1H, 12-H), 2.970(dd, 1H, $J 1 =$ 3.0 Hz, J₂=7.5 Hz, 21-H), 2.604(d, 1H, J=8.0 Hz, 22-H ), 2.575(d, 1H, J=15.0 Hz, 7-H_a), 2.274(m, 1H, J=7.0 Hz, 15-H), 1.691—1.832(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.413—1.588(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.264—1.332(m, 1H, 11-H), 1.183—1.251(1H, 6-H_b), 1.165(s, 3H, 4-CH₃), 0.983—1.022(m, 6H, 15-2CH₃), 0.942—0.983(m, 1H, 1-H_b), 0.627(s, 3H, 10-CH₃)	179.34, 177.71, 176.53, 147.53, 132.21, 129.19, 128.55, 126.61, 124.74, 54.41, 52.65, 52.13, 49.76, 47.36, 45.29, 41.28, 38.38, 37.97, 36.94, 36.34, 35.51, 33.00, 27.81, 22.01, 20.99, 20.28, 17.25, 16.95, 15.86	490
4b	8.137(d, 1H, J=7.5 Hz, 3'-H), 7.629(t, 1H, J=7.5 Hz, 5'-H), 7.489(t, 1H, J=8.0 Hz, 4'-H), 7.021(d, 1H, J=6.5 Hz, 6'-H), 5.547(s, 1H, 14-H), 3.664(s, 3H, —COOCH₃), 3.162(s, 1H, 12-H), 3.034(d, 1H, J=7.5 Hz, 21-H), 2.671(d, 1H, J=8.0 Hz, 22-H ), 2.546(d, 1H, J=13.5 Hz, 7-H_a ), 2.302(d, 1H, J=7.0 Hz, 15-H), 1.690—1.827(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.410—1.593(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.240—1.324(m, 1H, 11-H), 1.176—1.237(m, 1H, 6-H_b), 1.164(s, 3H, 4-CH₃), 1.031(d, 6H, J=6.5 Hz, 15-2CH₃), 0.940—1.002(m, 1H, 1-H_b), 0.632(s, 3H, 10-CH₃)	179.30, 177.93, 176.74, 168.42, 147.57, 134.04, 133.13, 132.34, 129.65, 129.26, 126.78, 124.92, 54.40, 53.12, 52.07, 49.70, 47.34, 45.76, 41.14, 38.40, 37.93, 36.88, 36.09, 35.39, 32.96, 27.80, 21.96, 20.96, 20.34, 17.23, 16.93, 15. 84	534
4c	8.123(d, 1H, J=8.0 Hz, 3'-H), 7.682(t, 1H, J=7.5 Hz, 5'-H), 7.555(d, 1H, J=7.5 Hz, 4'-H), 7.27(d, 1H, J=8.0 Hz, 6'-H), 5.540(s, 1H, 14-H), 3.676(s, 3H, —COOCH₃), 3.165(s, 1H, 12-H), 3.075(d, 1H, J=7.5 Hz, 21-H), 2.715(d, 1H, J=8.5 Hz, 22-H ), 2.518(d, 1H, J=14.0 Hz, 7-H_a ), 2.279(m, 1H, J=6.0 Hz, 15-H), 1.672—1.821(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.400—1.584(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.243—1.324(m, 1H, 11-H), 1.176—1.235(m, 1H, 6-H_b), 1.161(s, 3H, 4-CH₃), 0.942—1.056(m, 7H, 15-2CH₃, 1-H_b), 0.619(s, 3H, 10-CH₃)	179.24, 176.78, 175.67, 147.72, 145.48, 134.16, 130.29, 129.91, 126.42, 125.89, 124.95, 54.36, 53.10, 52.10, 49.67, 47.34, 45.74, 41.27, 38.39, 37.96, 36.88, 36.16, 35.37, 32.97, 27.76, 21.95, 20.98, 20.37, 17.24, 16.95, 15.85	535
4d	7.446—7.512(m, 1H, 6'-H), 7.291—7.373(m, 2H, 3'-H, 5'-H), 6.925—7.134(m, 1H, 4'-H), 5.543(s, 1H, 14-H), 3.676(s, 3H, —COOCH₃), 3.153—3.212(m, 1H, 12-H), 3.014—3.080(1H, 21-H), 2.601(d, 1H, J=8.5 Hz, 22-H), 2.467—2.595(m, 1H, 7'-H), 2.289—2.270(m, 1H, 15-H), 1.663—1.824(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.411—1.560(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.244—1.330(m, 1H, 11-H_b), 1.182—1.442(m, 1H, 6-H_b), 1.162(s, 3H, 4-CH₃), 0.930—1.058(m, 7H, 15-2CH₃, 1-H_b), 0.625(s, 3H, 10-CH₃)	179.28, 176.81, 175.74, 147.57, 132.41, 130.59, 130.50, 129.82, 127.76, 125.00, 124.83, 54.43, 52.87, 52.09, 49.73, 47.33, 45.50, 41.24, 38.38, 37.94, 36.90, 36.14, 35.40, 32.94, 27.79, 21.96, 20.96, 20.32, 17.23, 16.90, 15.83	524
Compd.	¹H NMR(500 MHz, CDCl₃), δ	¹³C NMR(CDCl₃, 125 MHz), δ	MS(APCI), (M+H⁺), m/z
4e	7.161—7.010(m, 1H, 6'-H), 6.734—6.915(m, 3H, 3'-H, 4-H, 5'-H), 5.530—5.579(m, 1H, 14-H), 3.678(s, 3H, —COOCH₃), 3.450—3.530(m, 2H, —NH₂), 3.188(d, 1H, J=15.0 Hz, 12-H), 3.016(dd, 1H, J₁=3.0 Hz, J₂=11.0 Hz, 21-H), 2.635(d, 1H, J=8.5 Hz, 22-H), 2.554—2.501(m, 1H, 7-H_a), 2.284—2.178(m, 1H, 15-H), 1.690—1.826(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.407—1.553(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.262—1.322(m, 1H, 11-H_b), 1.182—1.248(m, 1H, 6-H_b), 1.165(s, 3H, 4-CH₃), 0.994—1.049(m, 6H, 15-2CH₃), 0.941—0.994(m, 1H, 1-H_b), 0.621(s, 3H, 10-CH₃)	179.36, 177.68, 176.20, 147.52, 142.58, 130.22, 128.68, 128.50, 124.64, 119.00, 117.16, 54.78, 52.79, 52.14, 49.71, 47.33,45.96, 41.23, 38.33, 37.95, 36.91, 36.32, 35.36, 32.82, 27.64, 21.92, 20.93, 20.20, 17.22, 16.91, 15.86	504
4f-trans	7.897(d, 1H, J=8.5 Hz, 4'-H), 7.880(d, 1H, J=8.5 Hz, 5-H), 7.422—7.530(m, 4H, 8'-H, 3'-H, 7'-H, 6'-H), 7.062(d, 1H, J=7.0 Hz, 2'-H), 5.616(s, 1H, 14-H), 3.678(s, 3H, —COOCH₃), 3.228—3.218(m, 1H, 12-H), 3.159(dd, 1H, J₁=3.0 Hz, J₂=8.0 Hz, 21-H), 2.786(d, 1H, J=8.0 Hz, 22-H), 2.607(dt, 1H, J₁=3.2Hz, J₂=14.0 Hz, 7-H_eq), 2.345—2.200(m, 1H, J=7.0 Hz, 15-H), 1.721—1.833(m, 4H, 7-H_ax, 5-H, 11-H_ax, 3-H_ax), 1.454—1.600(m, 5H, 3-H_eq, 6-H, 9-H, 2-H), 1.440(dt, 1H, J=13 Hz, 1-H_eq), 1.306(ddd, 1H, J₁=3.0 Hz, J₂=5.4 Hz, J₃=13.0 Hz, 11-H_eq), 1.192—1.253(m, 1H, 6-H_eq), 1.178(s, 3H, 4-CH₃ ), 1.056(d, 3H, J=6.0 Hz, 15-CH₃), 1.086(d, 3H, J=6.0 Hz, 15-CH₃), 1.010(dt, 1H, J₁=5.0 Hz, J₂=13.0 Hz, 1-H_ax), 0.657(s, 3H, 10-CH₃)	179.24, 177.96, 176.63, 147.84, 134.50, 129.76, 129.59, 129.18, 128.60, 126.70, 126.49, 126.20, 125.46, 125.18, 122.92, 54.95, 53.02, 52.05, 49.72, 47.30, 46.30, 41.34, 38.33, 37.94, 36.90, 35.60, 35.36, 32.70, 27.67, 21.95, 20.46, 19.70, 17.22, 16.90, 15.90	540
4f-cis	7.890(d, 1H, J=8.5 Hz, 4'-H), 7.885(d, 1H, J=8.5 Hz, 5'-H), 7.422—7.530(m, 4H, 8-H, 3'-H, 7'-H, 6'-H), 7.232(d, 1H, J=7.5 Hz, 2'-H ), 5.780(s, 1H, 14-H), 3.681(s, 3H, —COOCH₃), 3.276—3.256(m, 1H, 12-H ), 3.128(dd, 1H, J₁=3.0 Hz, J₂=8.0 Hz, 21-H), 2.731(d, 1H, J=8.0 Hz, 22-H), 2.574(dt, 1H, J₁=3.2Hz, J₂=14.0 Hz, 7-H_eq), 2.392(d, 1H, J=7.0 Hz, 15-H), 1.726—1.860(m, 4H, 7-H_ax, 5-H, 11-H_ax, 3-H_ax), 1.472—1.615(m, 5H, 3-H_eq, 6-H_ax, 9-H, 2-H), 1.445(dt, 1H, J=13 Hz, 1-H_eq), 1.308(ddd, 1H, J₁=3.0 Hz, J₂=5.4 Hz, J₃=13.0 Hz, 11-H_eq), 1.190—1.250(m, 1H, 6-H_eq), 1.189(s, 3H, 4-CH₃), 1.062(d, 3H, J=6.0 Hz, 15-CH₃), 1.111(d, 3H, J=6.0 Hz, 15-CH₃), 1.010(dt, 1H, J₁=5.0 Hz, J₂=13.0 Hz, 1-H_ax), 0.678(s, 3H, 10-CH₃)	179.24, 177.96, 176.91, 147.52, 134.50, 129.86, 129.37, 129.18, 128.67, 127.04, 126.56, 126.06, 125.40, 124.78, 122.29, 54.45, 52.78, 52.05, 49.72, 47.30, 45.42, 41.36, 38.33, 37.94, 36.90, 36.21, 35.42, 32.93, 27.76, 21.95, 20.92, 20.27, 17.22, 16.90, 15.84	540

Table 1 NMR and MS data of compounds 4a—4f

Compd.	¹H NMR(500 MHz, CDCl₃), δ	¹³C NMR(CDCl₃, 125 MHz), δ	MS(APCI), (M+H⁺), m/z
4a	7.411—7.365(m, 2H, J=7.5 Hz, 2'-H, 6'-H), 7.335(d, 1H, J=7.0 Hz, 4'-H), 7.116(d, 2H, J=8.0 Hz, 3'-H, 5'-H), 5.520(s, 1H, 14-H), 3.678(s, 3H, —CO₂CH₃), 3.163(s, 1H, 12-H), 2.970(dd, 1H, $J 1 =$ 3.0 Hz, J₂=7.5 Hz, 21-H), 2.604(d, 1H, J=8.0 Hz, 22-H ), 2.575(d, 1H, J=15.0 Hz, 7-H_a), 2.274(m, 1H, J=7.0 Hz, 15-H), 1.691—1.832(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.413—1.588(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.264—1.332(m, 1H, 11-H), 1.183—1.251(1H, 6-H_b), 1.165(s, 3H, 4-CH₃), 0.983—1.022(m, 6H, 15-2CH₃), 0.942—0.983(m, 1H, 1-H_b), 0.627(s, 3H, 10-CH₃)	179.34, 177.71, 176.53, 147.53, 132.21, 129.19, 128.55, 126.61, 124.74, 54.41, 52.65, 52.13, 49.76, 47.36, 45.29, 41.28, 38.38, 37.97, 36.94, 36.34, 35.51, 33.00, 27.81, 22.01, 20.99, 20.28, 17.25, 16.95, 15.86	490
4b	8.137(d, 1H, J=7.5 Hz, 3'-H), 7.629(t, 1H, J=7.5 Hz, 5'-H), 7.489(t, 1H, J=8.0 Hz, 4'-H), 7.021(d, 1H, J=6.5 Hz, 6'-H), 5.547(s, 1H, 14-H), 3.664(s, 3H, —COOCH₃), 3.162(s, 1H, 12-H), 3.034(d, 1H, J=7.5 Hz, 21-H), 2.671(d, 1H, J=8.0 Hz, 22-H ), 2.546(d, 1H, J=13.5 Hz, 7-H_a ), 2.302(d, 1H, J=7.0 Hz, 15-H), 1.690—1.827(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.410—1.593(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.240—1.324(m, 1H, 11-H), 1.176—1.237(m, 1H, 6-H_b), 1.164(s, 3H, 4-CH₃), 1.031(d, 6H, J=6.5 Hz, 15-2CH₃), 0.940—1.002(m, 1H, 1-H_b), 0.632(s, 3H, 10-CH₃)	179.30, 177.93, 176.74, 168.42, 147.57, 134.04, 133.13, 132.34, 129.65, 129.26, 126.78, 124.92, 54.40, 53.12, 52.07, 49.70, 47.34, 45.76, 41.14, 38.40, 37.93, 36.88, 36.09, 35.39, 32.96, 27.80, 21.96, 20.96, 20.34, 17.23, 16.93, 15. 84	534
4c	8.123(d, 1H, J=8.0 Hz, 3'-H), 7.682(t, 1H, J=7.5 Hz, 5'-H), 7.555(d, 1H, J=7.5 Hz, 4'-H), 7.27(d, 1H, J=8.0 Hz, 6'-H), 5.540(s, 1H, 14-H), 3.676(s, 3H, —COOCH₃), 3.165(s, 1H, 12-H), 3.075(d, 1H, J=7.5 Hz, 21-H), 2.715(d, 1H, J=8.5 Hz, 22-H ), 2.518(d, 1H, J=14.0 Hz, 7-H_a ), 2.279(m, 1H, J=6.0 Hz, 15-H), 1.672—1.821(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.400—1.584(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.243—1.324(m, 1H, 11-H), 1.176—1.235(m, 1H, 6-H_b), 1.161(s, 3H, 4-CH₃), 0.942—1.056(m, 7H, 15-2CH₃, 1-H_b), 0.619(s, 3H, 10-CH₃)	179.24, 176.78, 175.67, 147.72, 145.48, 134.16, 130.29, 129.91, 126.42, 125.89, 124.95, 54.36, 53.10, 52.10, 49.67, 47.34, 45.74, 41.27, 38.39, 37.96, 36.88, 36.16, 35.37, 32.97, 27.76, 21.95, 20.98, 20.37, 17.24, 16.95, 15.85	535
4d	7.446—7.512(m, 1H, 6'-H), 7.291—7.373(m, 2H, 3'-H, 5'-H), 6.925—7.134(m, 1H, 4'-H), 5.543(s, 1H, 14-H), 3.676(s, 3H, —COOCH₃), 3.153—3.212(m, 1H, 12-H), 3.014—3.080(1H, 21-H), 2.601(d, 1H, J=8.5 Hz, 22-H), 2.467—2.595(m, 1H, 7'-H), 2.289—2.270(m, 1H, 15-H), 1.663—1.824(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.411—1.560(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.244—1.330(m, 1H, 11-H_b), 1.182—1.442(m, 1H, 6-H_b), 1.162(s, 3H, 4-CH₃), 0.930—1.058(m, 7H, 15-2CH₃, 1-H_b), 0.625(s, 3H, 10-CH₃)	179.28, 176.81, 175.74, 147.57, 132.41, 130.59, 130.50, 129.82, 127.76, 125.00, 124.83, 54.43, 52.87, 52.09, 49.73, 47.33, 45.50, 41.24, 38.38, 37.94, 36.90, 36.14, 35.40, 32.94, 27.79, 21.96, 20.96, 20.32, 17.23, 16.90, 15.83	524
Compd.	¹H NMR(500 MHz, CDCl₃), δ	¹³C NMR(CDCl₃, 125 MHz), δ	MS(APCI), (M+H⁺), m/z
4e	7.161—7.010(m, 1H, 6'-H), 6.734—6.915(m, 3H, 3'-H, 4-H, 5'-H), 5.530—5.579(m, 1H, 14-H), 3.678(s, 3H, —COOCH₃), 3.450—3.530(m, 2H, —NH₂), 3.188(d, 1H, J=15.0 Hz, 12-H), 3.016(dd, 1H, J₁=3.0 Hz, J₂=11.0 Hz, 21-H), 2.635(d, 1H, J=8.5 Hz, 22-H), 2.554—2.501(m, 1H, 7-H_a), 2.284—2.178(m, 1H, 15-H), 1.690—1.826(m, 4H, 3-H_a, 5-H, 11-H_a, 7-H_b), 1.407—1.553(m, 6H, 1-H_a, 2-H_a, 2-H_b, 3-H_b, 6-H_a, 9-H), 1.262—1.322(m, 1H, 11-H_b), 1.182—1.248(m, 1H, 6-H_b), 1.165(s, 3H, 4-CH₃), 0.994—1.049(m, 6H, 15-2CH₃), 0.941—0.994(m, 1H, 1-H_b), 0.621(s, 3H, 10-CH₃)	179.36, 177.68, 176.20, 147.52, 142.58, 130.22, 128.68, 128.50, 124.64, 119.00, 117.16, 54.78, 52.79, 52.14, 49.71, 47.33,45.96, 41.23, 38.33, 37.95, 36.91, 36.32, 35.36, 32.82, 27.64, 21.92, 20.93, 20.20, 17.22, 16.91, 15.86	504
4f-trans	7.897(d, 1H, J=8.5 Hz, 4'-H), 7.880(d, 1H, J=8.5 Hz, 5-H), 7.422—7.530(m, 4H, 8'-H, 3'-H, 7'-H, 6'-H), 7.062(d, 1H, J=7.0 Hz, 2'-H), 5.616(s, 1H, 14-H), 3.678(s, 3H, —COOCH₃), 3.228—3.218(m, 1H, 12-H), 3.159(dd, 1H, J₁=3.0 Hz, J₂=8.0 Hz, 21-H), 2.786(d, 1H, J=8.0 Hz, 22-H), 2.607(dt, 1H, J₁=3.2Hz, J₂=14.0 Hz, 7-H_eq), 2.345—2.200(m, 1H, J=7.0 Hz, 15-H), 1.721—1.833(m, 4H, 7-H_ax, 5-H, 11-H_ax, 3-H_ax), 1.454—1.600(m, 5H, 3-H_eq, 6-H, 9-H, 2-H), 1.440(dt, 1H, J=13 Hz, 1-H_eq), 1.306(ddd, 1H, J₁=3.0 Hz, J₂=5.4 Hz, J₃=13.0 Hz, 11-H_eq), 1.192—1.253(m, 1H, 6-H_eq), 1.178(s, 3H, 4-CH₃ ), 1.056(d, 3H, J=6.0 Hz, 15-CH₃), 1.086(d, 3H, J=6.0 Hz, 15-CH₃), 1.010(dt, 1H, J₁=5.0 Hz, J₂=13.0 Hz, 1-H_ax), 0.657(s, 3H, 10-CH₃)	179.24, 177.96, 176.63, 147.84, 134.50, 129.76, 129.59, 129.18, 128.60, 126.70, 126.49, 126.20, 125.46, 125.18, 122.92, 54.95, 53.02, 52.05, 49.72, 47.30, 46.30, 41.34, 38.33, 37.94, 36.90, 35.60, 35.36, 32.70, 27.67, 21.95, 20.46, 19.70, 17.22, 16.90, 15.90	540
4f-cis	7.890(d, 1H, J=8.5 Hz, 4'-H), 7.885(d, 1H, J=8.5 Hz, 5'-H), 7.422—7.530(m, 4H, 8-H, 3'-H, 7'-H, 6'-H), 7.232(d, 1H, J=7.5 Hz, 2'-H ), 5.780(s, 1H, 14-H), 3.681(s, 3H, —COOCH₃), 3.276—3.256(m, 1H, 12-H ), 3.128(dd, 1H, J₁=3.0 Hz, J₂=8.0 Hz, 21-H), 2.731(d, 1H, J=8.0 Hz, 22-H), 2.574(dt, 1H, J₁=3.2Hz, J₂=14.0 Hz, 7-H_eq), 2.392(d, 1H, J=7.0 Hz, 15-H), 1.726—1.860(m, 4H, 7-H_ax, 5-H, 11-H_ax, 3-H_ax), 1.472—1.615(m, 5H, 3-H_eq, 6-H_ax, 9-H, 2-H), 1.445(dt, 1H, J=13 Hz, 1-H_eq), 1.308(ddd, 1H, J₁=3.0 Hz, J₂=5.4 Hz, J₃=13.0 Hz, 11-H_eq), 1.190—1.250(m, 1H, 6-H_eq), 1.189(s, 3H, 4-CH₃), 1.062(d, 3H, J=6.0 Hz, 15-CH₃), 1.111(d, 3H, J=6.0 Hz, 15-CH₃), 1.010(dt, 1H, J₁=5.0 Hz, J₂=13.0 Hz, 1-H_ax), 0.678(s, 3H, 10-CH₃)	179.24, 177.96, 176.91, 147.52, 134.50, 129.86, 129.37, 129.18, 128.67, 127.04, 126.56, 126.06, 125.40, 124.78, 122.29, 54.45, 52.78, 52.05, 49.72, 47.30, 45.42, 41.36, 38.33, 37.94, 36.90, 36.21, 35.42, 32.93, 27.76, 21.95, 20.92, 20.27, 17.22, 16.90, 15.84	540

Fig.1 Specific rotation curve(A) and circular dichroism spectra(B) of compound 4f

Table 2 Specific rotation of compound 4f in CHCl3(293 K)

Determination number	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15
t/min	5	10	15	20	25	30	35	40	45	50	55	60	65	70	75
[α $] D 20$ /(°)	-7.5	-12.7	-17.9	-22.2	-26.6	-29.8	-33.7	-36.5	-39.3	-41.7	-43.9	-45.6	-47.2	-47.6	-47.6
(c=0.084,CHCl₃)

Table 2 Specific rotation of compound 4f in CHCl3(293 K)

Determination number	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15
t/min	5	10	15	20	25	30	35	40	45	50	55	60	65	70	75
[α $] D 20$ /(°)	-7.5	-12.7	-17.9	-22.2	-26.6	-29.8	-33.7	-36.5	-39.3	-41.7	-43.9	-45.6	-47.2	-47.6	-47.6
(c=0.084,CHCl₃)

Fig.2 Rate of 1H NMR peak area of atropisomer at different time(40 ℃, CDCl3) a. trans; b. cis.

Table 3 Relationship of -ln([A]-[A]eq) with t(s) of 14-H and 22-H in compound 4f

H atom	T/K	Linear equation	k₁+ $k 2 *$	H atom	T/K	Linear equation	k₁+ $k 2 *$
14-H	293	y=1.931×10^-4x +0.5666	1.931×10^-4	22-H	293	y=1.833×10^-4x +0.5652	1.833×10^-4
	303	y=4.452×10^-4x +0.4760	4.452×10^-4		303	y=4.830×10^-4x +0.47757	4.830×10^-4
	313	y=1.000×10^-3x +0.4176	1.000×10^-3		313	y=1.050×10^-3x +0.47797	1.050×10^-3
	323	y=2.310×10^-3x +0.5229	2.310×10^-3		323	y=1.740×10^-3x +0.74405	1.740×10^-3
	333	y=3.930×10^-3x +0.6046	3.930×10^-3		333	y=3.260×10^-3x +0.74935	3.260×10^-3

Table 3 Relationship of -ln([A]-[A]eq) with t(s) of 14-H and 22-H in compound 4f

H atom	T/K	Linear equation	k₁+ $k 2 *$	H atom	T/K	Linear equation	k₁+ $k 2 *$
14-H	293	y=1.931×10^-4x +0.5666	1.931×10^-4	22-H	293	y=1.833×10^-4x +0.5652	1.833×10^-4
	303	y=4.452×10^-4x +0.4760	4.452×10^-4		303	y=4.830×10^-4x +0.47757	4.830×10^-4
	313	y=1.000×10^-3x +0.4176	1.000×10^-3		313	y=1.050×10^-3x +0.47797	1.050×10^-3
	323	y=2.310×10^-3x +0.5229	2.310×10^-3		323	y=1.740×10^-3x +0.74405	1.740×10^-3
	333	y=3.930×10^-3x +0.6046	3.930×10^-3		333	y=3.260×10^-3x +0.74935	3.260×10^-3

Fig.3 Linear regressions during the kinetically transformation of two atropisomer(trans and cis) at different temperatures (A) 14-H; (B) 22-H.

Table 4 Thermodynamic and kinetic parameters for transformation of two isomers at different temperatures(CDCl3)

T/K	Percentage of cis-isomer(%)	$K eq *$	k₁/s^-1	k₂/s^-1
293	38.22	1.671	1.177×10^-4	0.704×10^-4
303	38.69	1.574	2.838×10^-4	1.803×10^-4
313	39.67	1.521	6.183×10^-4	4. 067×10^-4
323	40.31	1.481	1.209×10^-3	8.163×10^-4
333	38.74	1.584	2.20×10^-3	1.391×10^-3

Table 4 Thermodynamic and kinetic parameters for transformation of two isomers at different temperatures(CDCl3)

T/K	Percentage of cis-isomer(%)	$K eq *$	k₁/s^-1	k₂/s^-1
293	38.22	1.671	1.177×10^-4	0.704×10^-4
303	38.69	1.574	2.838×10^-4	1.803×10^-4
313	39.67	1.521	6.183×10^-4	4. 067×10^-4
323	40.31	1.481	1.209×10^-3	8.163×10^-4
333	38.74	1.584	2.20×10^-3	1.391×10^-3

Fig.4 Linear rehression equations between temperature(T) and the observed rate constant(k) during the kinetic transformation of two atropisomera. lnk1 vs. 1/T; b. lnk2 vs. 1/T.

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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^†

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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†

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Atropisomerism of Methyl Maleopimaric N-Arylimides and Their Kinetics Analysis^†