纤维素苯基氨基甲酸酯的均相合成及其手性拆分性能评价

doi:10.3724/SP.J.1123.2019.08044

摘要/Abstract

摘要：

认识多糖类手性拆分材料的结构性能关系对于构建新型高效手性固定相具有重要指导意义。该文中,以1-烯丙基-3-甲基咪唑氯离子液体为介质,合成了系列不同结构的纤维素苯基氨基甲酸酯,进而考察了取代度、取代基团种类和位置对产物手性拆分性能的影响。结果表明,随着取代度的增加,纤维素苯基氨基甲酸酯对于绝大部分手性分子的拆分效果提高;苯环上取代基团的种类和位置对纤维素苯基氨基甲酸酯手性拆分性能影响显著,弱吸电子基团氯基和给电子基团甲基在合适的位置能显著增强纤维素苯基氨基甲酸酯的手性拆分性能;纤维素3-甲基-4-氯苯基氨基甲酸酯、3,5-二氯苯基氨基甲酸酯和2-甲基-5-氯苯基氨基甲酸酯对一些手性分子的拆分效果优于纤维素3,5-二甲基苯基氨基甲酸酯。

关键词: 手性拆分, 纤维素, 纤维素苯基氨基甲酸酯, 均相合成

Abstract:

Understanding the structure-property relationship of polysaccharide derivatives is of great significance toward the development of novel chiral stationary phases. In this work, we used an ionic liquid, 1-allyl-3-methylimidazolium chloride (AmimCl), as the solvent and introduced phenyl isocyanates with various substituents into cellulose to obtain a series of cellulose phenylcarbamates. The effects of the degree of substitution (DS), as well as the type and position of the substituents, on the chiral separation capability of the cellulose phenylcarbamates were researched in detail. With an increase in the DS, the chiral recognition capability of the cellulose phenylcarbamates improved dramatically for most of the chiral analytes. Fully substituted cellulose phenylcarbamates showed the best enantioseparation capabilities. In addition, the type and position of the substituents on the benzene ring significantly influenced the chiral separation capabilities of the cellulose phenylcarbamates. Cellulose 3-methyl-4-chlorophenylcarbamate, 3,5-dichlorophenylcarbamate, and 2-methyl-5-chlorophenylcarbamate had better chiral recognition capabilities than cellulose 3,5-dimethylphenylcarbamate for some chiral analytes.

Key words: enantioseparation, cellulose, cellulose phenylcarbamates, homogeneous synthesis

中图分类号:

O658

尹春春, 杨田田, 张金明1, 张军. 纤维素苯基氨基甲酸酯的均相合成及其手性拆分性能评价[J]. 色谱, 2020, 38(4): 476-483.

YIN Chunchun, YANG Tiantian, ZHANG Jinming, ZHANG Jun. Homogeneous synthesis of cellulose phenylcarbamates and evaluation of their enantioseparation capabilities[J]. Chinese Journal of Chromatography, 2020, 38(4): 476-483.

图/表 8

参考文献

[1]	Ward T J, Ward K D. Anal Chem, 2012, 84: 626
[2]	Scriba G K E. J Chromatogr A, 2016, 1467: 56
[3]	He Y J, Li K L, Li Q, et al. Chinese Journal of Chromatography, 2019, 37(4): 383
[3]	何义娟, 李克丽, 李倩, 等. 色谱, 2019, 37(4): 383
[4]	Okamoto Y, Yashima E. Angew Chem Int Ed, 1998, 37: 1020
[5]	Ikai T, Okamoto Y. Chem Rev, 2009, 109: 6077
[6]	Shen J, Okamoto Y. Chem Rev, 2016, 116: 1094
[7]	Cavazzini A, Pasti L, Massi A, et al. Anal Chim Acta, 2011, 706: 205
[8]	Teixeira J, Tiritan M E, Pinto M M M, et al. Molecules, 2019, 24: 865
[9]	Qian Z Y, Zhang M Y, Li S N, et al. Chinese Journal of Chromatography, 2018, 36(3): 261
[9]	钱哲元, 张明勇, 李升妮, 等. 色谱, 2018, 36(3): 261
[10]	Chen X X, Zhang P, He Y J, et al. Chinese Journal of Chromatography, 2019, 37(12): 1275
[10]	谌学先, 张鹏, 何义娟, 等. 色谱, 2019, 37(12): 1275
[11]	Toga Y, Hioki K, Namikoshi H, et al. Cellulose, 2004, 11: 65
[12]	Chang Y X, Zhou L L, Yuan L M. Chinese Journal of Chromatography, 2007, 25(2): 203
[12]	常银霞, 周玲玲, 袁黎明. 色谱, 2007, 25(2): 203
[13]	Ma C, Ai P, Zhang M, et al. Chemical Research and Application, 2010, 22(7): 907
[13]	马超, 艾萍, 张美, 等. 化学研究与应用, 2010, 22(7): 907
[14]	Chang L M, Zhang J M, Chen W W, et al. Anal Methods, 2018, 10: 2844
[15]	Chen W W, Ding M C, Zhang M, et al. Chinese J Polym Sci, 2015, 33: 1633
[16]	Chen W W, Zhang M, Feng Y, et al. Polym Int 2015, 64: 1037
[17]	Chankvetadze B. J Chromatogr A, 2012, 1269: 26
[18]	Weng X L, Bao Z B, Luo F, et al. Progress in Chemistry, 2014, 26(2/3): 415
[18]	翁西伦, 鲍宗必, 罗飞, 等. 化学进展, 2014, 26(2/3): 415
[19]	Cavazzini A, Pasti L, Massi A, et al. Anal Chim Acta, 2011, 706: 205
[20]	Kaida Y, Okamoto Y. Bull Chem Soc Jpn, 1993, 66: 2225
[21]	Yashima E, Fukaya H, Okamoto Y. J Chromatogr A, 1994, 672: 11
[22]	Acemoglu M, KüSters E, Baumann J, et al. Chirality, 1998, 10: 294
[23]	Shen J, Ikai T, Okamoto Y. J Chromatogr A, 2010, 1217: 1041
[24]	Shen J, Ikai T, Shen X D, et al. Chem Lett, 2010, 39: 442
[25]	Shen J, Li P F, Liu S Y, et al. Chirality, 2011, 23: 878
[26]	Kondo S, Yamamoto C, Kamigaito M, et al. Chem Lett, 2008, 37: 558
[27]	Katoh Y, Tsujimoto Y, Yamamoto C, et al. Polym J, 2011, 43: 84
[28]	Tang S W, Li X F, Wang F, et al. Chirality, 2012, 24: 167
[29]	Sun B S, Li X F, Jin Z L, et al. Chromatographia, 2012, 75: 1347
[30]	Shen J, Li G, Yang Z Z, et al. J Chromatogr A, 2016, 1467: 199
[31]	Shen J, Li G, Li P, et al. Chinese Journal of Chromatography, 2016, 34(1): 50
[31]	沈军, 李庚, 李平, 等. 色谱, 2016, 34(1): 50
[32]	Shen J, Wang F, Bi WY, et al. J Chromatogr A, 2018, 1572: 54
[33]	Dai X, Bi W Y, Sun M C, et al. Carbohydr Polym, 2019, 218: 30
[34]	Tang S, Bin Q, Chen W, et al. J Chromatogr A, 2016, 1440: 112
[35]	Zhang J, Wang X C, Chen W, et al. Analyst, 2016, 141: 4470
[36]	Tang S, Mei X M, Chen W, et al. Talanta, 2018, 185: 42
[37]	Yin C C, Zhang J M, Chang L M, et al. Anal Chim Acta, 2019, 1073: 90
[38]	Okada Y, Yamamoto C, Kamigaito M, et al. Molecules, 2016, 21: 1484
[39]	Rose M, Palkovits R. Macromol Rapid Commun, 2011, 32: 1299
[40]	El Seoud O A, Koschella A, Fidale L C, et al.Biomacromolecules, 2007, 8: 2629
[41]	Zhang J M, Chen W W, Feng Y, et al.Polym Int, 2015, 64: 963
[42]	Pinkert A, Marsh K N, Pang S, et al.Chem Rev, 2009, 109: 6712
[43]	Zhang J M, Wu J, Yu J, et al. Mater Chem Front, 2017, 1: 1273
[44]	Sun N, Rodríguez H, Rahman M, et al. Chem Commun, 2011, 47: 1405
[45]	Zhang J M, Chen W W, Feng Y, et al.Polym Int, 2015, 64: 963
[46]	Heinze T, Dorn S, Schöbitz M, et al. Macromol Symp, 2008, 262: 8
[47]	Yin C C, Chen W W, Zhang J M, et al. Sep Purif Technol, 2019, 210: 175
[48]	Jia R N, Tian W G, Bai H T, et al. Nat Commun, 2019, 10: 795
[49]	Yang T T, Xiao P, Zhang J M, et al. ACS Appl Mater Interfaces, 2019, 11: 4302
[50]	Chen Z Y, Xiao P, Zhang J M, et al.Chem Eng J, 2020, 379: 122270
[51]	Nawaz H, Tian W G, Zhang J M, et al. Anal Chem, 2019, 91: 3085

Cellulose phenylcarbamate	Reaction conditions			DS
Cellulose phenylcarbamate	Molar ratio of phenyl isocyanate/ anhydroglucose unit (AGU)	T/℃	Time/ h	DS
C-H-1	10∶1	80	3	3.0
C-H-2	5∶1	80	3	2.51
C-H-3	3∶1	80	3	1.83
3,5-Cl₂-1	5∶1	80	3	3.0
3,5-Cl₂-2	3∶1	80	3	2.63
3,5-Cl₂-3	2.5∶1	80	3	1.40
3-Cl-4-CH₃-1	7∶1	80	3	3.0
3-Cl-4-CH₃-2	4∶1	80	3	2.59
3-Cl-4-CH₃-3	2.5∶1	80	3	1.66
3,4-Cl₂	5∶1	80	3	3.0
2,3-Cl₂	7∶1	80	3	3.0
2,4-Cl₂	7∶1	80	3	3.0
2,6-Cl₂	7∶1	80	3	3.0
2,4,6-Cl₃	7∶1	80	3	3.0
3-CH₃-4-Cl	7∶1	80	3	3.0
2-CH₃-5-Cl	5∶1	80	3	3.0
3,5-(CH₃)₂	10∶1	80	4	3.0
1-N	4∶1	80	4	3.0

Cellulose phenylcarbamate	Reaction conditions			DS
Cellulose phenylcarbamate	Molar ratio of phenyl isocyanate/ anhydroglucose unit (AGU)	T/℃	Time/ h	DS
C-H-1	10∶1	80	3	3.0
C-H-2	5∶1	80	3	2.51
C-H-3	3∶1	80	3	1.83
3,5-Cl₂-1	5∶1	80	3	3.0
3,5-Cl₂-2	3∶1	80	3	2.63
3,5-Cl₂-3	2.5∶1	80	3	1.40
3-Cl-4-CH₃-1	7∶1	80	3	3.0
3-Cl-4-CH₃-2	4∶1	80	3	2.59
3-Cl-4-CH₃-3	2.5∶1	80	3	1.66
3,4-Cl₂	5∶1	80	3	3.0
2,3-Cl₂	7∶1	80	3	3.0
2,4-Cl₂	7∶1	80	3	3.0
2,6-Cl₂	7∶1	80	3	3.0
2,4,6-Cl₃	7∶1	80	3	3.0
3-CH₃-4-Cl	7∶1	80	3	3.0
2-CH₃-5-Cl	5∶1	80	3	3.0
3,5-(CH₃)₂	10∶1	80	4	3.0
1-N	4∶1	80	4	3.0

Cellulose phenylcarbamate	DS	1			2			3			4			5
Cellulose phenylcarbamate	DS	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s
C-H	3.0	2.94	1.13	1.95	2.05	1.22	2.41	3.44	1.08	1.34	7.56	1.14	2.84	9.12	1.05	1.09
	2.51	2.28	1.07	0.99	1.54	1.17	1.57	2.79	1.0	-	6.94	1.14	3.03	7.87	1.08	1.13
	1.83	0.97	1.0	-	0.70	1.0	-	0.70	1.0	-	6.87	1.10	1.53	2.89	1.0	-
3,5-Cl₂	3.0	2.01	1.23	3.29	0.98	1.17	1.90	1.40	1.07	1.00	3.76	1.06	1.20	5.32	1.12	2.34
	2.63	2.01	1.0	-	1.37	1.0	-	0.78	1.0	-	4.12	1.08	1.04	5.95	1.06	0.92
	1.40	2.43	1.0	-	1.93	1.0	-	2.22	1.0	-	5.10	1.07	1.08	8.01	1.03	0.66
3-Cl-4-CH₃	3.0	3.15	1.21	1.99	1.87	1.06	0.72	2.89	1.08	1.07	5.22	1.06	0.87	11.5	2.24	6.81
	2.59	1.76	1.13	1.03	1.24	1.10	0.96	1.70	1.08	0.87	5.01	1.09	0.87	6.16	1.0	-
	1.66	1.42	1.0	-	1.29	1.0	-	1.59	1.0	-	5.01	1.08	1.15	2.08	1.0	-
Cellulose phenylcarbamate	DS	6			7			8			9			10
Cellulose phenylcarbamate	DS	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s
C-H	3.0	5.97	1.59	3.74	0.79	1.26	2.90	1.88	1.33	2.11	0.76	1.0	-	0.75	1.0	-
	2.51	5.08	1.44	2.29	0.63	1.15	1.38	2.75	1.24	1.49	0.72	1.0	-	0.71	1.0	-
	1.83	5.50	1.33	0.81	0.35	1.0	-	2.49	1.15	0.89	0.70	1.0	-	0.68	1.0	-
3,5-Cl₂	3.0	3.82	1.40	3.65	0.36	1.48	2.45	0.94	1.09	0.68	0.49	1.0	-	0.49	1.0	-
	2.63	6.22	1.30	2.34	0.36	1.11	0.69	1.08	1.07	0.53	0.55	1.0	-	0.56	1.0	-
	1.40	7.74	2.73	1.36	0.45	1.09	0.73	1.72	1.06	0.52	0.89	1.0	-	0.87	1.0	-
3-Cl-4-CH₃	3.0	4.84	2.24	6.81	0.56	1.82	4.88	1.19	1.12	0.82	2.32	1.0	-	2.37	1.0	-
	2.59	3.27	1.44	3.76	0.41	1.34	1.33	1.69	1.13	0.82	0.48	1.0	-	0.50	1.0	-
	1.66	3.18	1.31	2.10	0.39	1.0	-	2.30	1.0	-	0.57	1.0	-	0.56	1.0	-

Cellulose phenylcarbamate	DS	1			2			3			4			5
Cellulose phenylcarbamate	DS	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s
C-H	3.0	2.94	1.13	1.95	2.05	1.22	2.41	3.44	1.08	1.34	7.56	1.14	2.84	9.12	1.05	1.09
	2.51	2.28	1.07	0.99	1.54	1.17	1.57	2.79	1.0	-	6.94	1.14	3.03	7.87	1.08	1.13
	1.83	0.97	1.0	-	0.70	1.0	-	0.70	1.0	-	6.87	1.10	1.53	2.89	1.0	-
3,5-Cl₂	3.0	2.01	1.23	3.29	0.98	1.17	1.90	1.40	1.07	1.00	3.76	1.06	1.20	5.32	1.12	2.34
	2.63	2.01	1.0	-	1.37	1.0	-	0.78	1.0	-	4.12	1.08	1.04	5.95	1.06	0.92
	1.40	2.43	1.0	-	1.93	1.0	-	2.22	1.0	-	5.10	1.07	1.08	8.01	1.03	0.66
3-Cl-4-CH₃	3.0	3.15	1.21	1.99	1.87	1.06	0.72	2.89	1.08	1.07	5.22	1.06	0.87	11.5	2.24	6.81
	2.59	1.76	1.13	1.03	1.24	1.10	0.96	1.70	1.08	0.87	5.01	1.09	0.87	6.16	1.0	-
	1.66	1.42	1.0	-	1.29	1.0	-	1.59	1.0	-	5.01	1.08	1.15	2.08	1.0	-
Cellulose phenylcarbamate	DS	6			7			8			9			10
Cellulose phenylcarbamate	DS	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s
C-H	3.0	5.97	1.59	3.74	0.79	1.26	2.90	1.88	1.33	2.11	0.76	1.0	-	0.75	1.0	-
	2.51	5.08	1.44	2.29	0.63	1.15	1.38	2.75	1.24	1.49	0.72	1.0	-	0.71	1.0	-
	1.83	5.50	1.33	0.81	0.35	1.0	-	2.49	1.15	0.89	0.70	1.0	-	0.68	1.0	-
3,5-Cl₂	3.0	3.82	1.40	3.65	0.36	1.48	2.45	0.94	1.09	0.68	0.49	1.0	-	0.49	1.0	-
	2.63	6.22	1.30	2.34	0.36	1.11	0.69	1.08	1.07	0.53	0.55	1.0	-	0.56	1.0	-
	1.40	7.74	2.73	1.36	0.45	1.09	0.73	1.72	1.06	0.52	0.89	1.0	-	0.87	1.0	-
3-Cl-4-CH₃	3.0	4.84	2.24	6.81	0.56	1.82	4.88	1.19	1.12	0.82	2.32	1.0	-	2.37	1.0	-
	2.59	3.27	1.44	3.76	0.41	1.34	1.33	1.69	1.13	0.82	0.48	1.0	-	0.50	1.0	-
	1.66	3.18	1.31	2.10	0.39	1.0	-	2.30	1.0	-	0.57	1.0	-	0.56	1.0	-

Cellulose phenylcarbamate	1			2			3			4			5
Cellulose phenylcarbamate	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s
C-H	2.94	1.13	1.95	2.05	1.22	2.41	3.44	1.08	1.34	7.56	1.14	2.84	9.12	1.05	1.09
3,5-Cl₂	2.01	1.23	3.29	0.98	1.17	1.90	1.40	1.07	1.00	3.76	1.06	1.20	5.32	1.12	2.34
3,4-Cl₂	3.63	1.15	1.82	2.18	1.0	-	2.79	1.06	0.84	5.53	1.08	1.09	11.5	1.05	0.78
2,4-Cl₂	2.33	1.0	-	1.33	1.0	-	2.79	1.07	0.70	4.54	1.23	1.75	6.17	1.07	0.85
2,3-Cl₂	2.40	1.0	-	1.40	1.0	-	3.46	1.0	-	5.02	1.0	-	2.67	1.0	-
2,6-Cl₂	1.56	1.0	-	2.99	1.0	-	2.35	1.0	-	5.55	1.0	-	7.35	1.0	-
2,4,6-Cl₃	0.68	1.0	-	1.51	1.0	-	1.08	1.0	-	1.13	1.0	-	2.05	1.0	-
Cellulose phenylcarbamate	6			7			8			9			10
Cellulose phenylcarbamate	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s	k₁	α	R_s
C-H	5.97	1.59	3.74	0.79	1.26	2.90	1.88	1.33	2.11	0.76	1.0	-	0.75	1.0	-
3,5-Cl₂	3.82	1.40	3.65	0.36	1.48	2.45	0.94	1.09	0.68	0.49	1.0	-	0.49	1.0	-
3,4-Cl₂	8.90	1.56	3.40	0.54	1.59	3.93	1.29	1.11	0.73	0.65	1.0	-	0.54	1.0	-
2,4-Cl₂	1.05	1.09	0.69	0.67	1.0	-	1.67	1.0	-	2.05	1.0	-	2.07	1.0	-
2,3-Cl₂	2.33	1.0	-	0.77	1.0	-	2.01	1.0	-	1.93	1.0	-	1.94	1.0	-
2,6-Cl₂	4.16	1.0	-	0.53	1.0	-	2.42	1.0	-	2.35	1.0	-	2.47	1.0	-
2,4,6-Cl₃	1.11	1.0	-	0.29	1.0	-	1.21	1.0	-	0.59	1.0	-	0.55	1.0	-