Homogeneous synthesis of cellulose phenylcarbamates and evaluation of their enantioseparation capabilities

doi:10.3724/SP.J.1123.2019.08044

Abstract

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

CLC Number:

O658

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.

Figures/Tables 8

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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	-