Covalent Organic Framework Material Derivative of Chiral Camphor Used as High Performance Liquid Chromatography Stationary Phase for Resolution of Racemates

doi:10.19894/j.issn.1000-0518.210329

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (9): 1371-1381.DOI: 10.19894/j.issn.1000-0518.210329

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Covalent Organic Framework Material Derivative of Chiral Camphor Used as High Performance Liquid Chromatography Stationary Phase for Resolution of Racemates

Hao FU, Wan-Qi XIONG, Zhen WANG, Ai-Hong DUAN, Li-Ming YUAN()

School of Chemistry and Chemical Engineering，Yunnan Normal University，Kunming 650500，China

Received:2021-07-05 Accepted:2021-10-21 Published:2022-09-01 Online:2022-09-08
Contact: Li-Ming YUAN
About author:yuan_limingpd@126.com
Supported by:
the National Natural Science Foundation of China(91856123)

Abstract

Abstract:

Covalent organic framework materials （COFs） are a new type of crystalline porous materials， and their chiral materials have good application prospects in various fields. In this paper， TpBD（NH₂）₂ synthesized by the reaction of 1，3，5-trialdehyde phloroglucinol （Tp） and 3，3'-dinitrobenzidine （BD） was used as the covalent organic skeleton， and reacts with （1S）-（+）-10-camphorsulfonyl chloride （Cam） to prepare （1S）-（+）-10-camphorsulfonyl chloride derivative TpBD-1S-（+）-Cam. The derivative is a newly synthesized chiral covalent organic framework material. TpBD-1S-（+）-Cam was immobilized on silica gel to prepare a chiral column for high performance liquid chromatography to separate racemates. The experimental results show that the prepared COF， TpBD-1S-（+）-Cam， can separate warfarin， chlorpheniramine maleate， atenolol， metoprolol， zopiclone， 10-（9-anthryl）-2，2，2-trifluoroethanol， 1，2-benzophenone， ketoprofen， mexiletine hydrochloride， timolol 10 kinds of racemates and o，m，p-bromoaniline， o，m，p-iodoaniline are two kinds of positional isomers of benzene series. This material has potential as the stationary phase of high performance liquid chromatography.

Key words: Covalent organic frameworks, Stationary phase, High performance liquid chromatography, Chiral resolution

CLC Number:

O657.7

Hao FU, Wan-Qi XIONG, Zhen WANG, Ai-Hong DUAN, Li-Ming YUAN. Covalent Organic Framework Material Derivative of Chiral Camphor Used as High Performance Liquid Chromatography Stationary Phase for Resolution of Racemates[J]. Chinese Journal of Applied Chemistry, 2022, 39(9): 1371-1381.

Figures/Tables 14

Fig.1 Synthetic route of TpBD（NH2）2

Fig.2 Synthetic route of TpBD-1S-（+）-Cam

Fig.3 PXRD patterns of TpBD-1S-（+）-Cam （a）， TpBD（NH2）2 （b） and TpBD（NH2）2 （c）

Fig.4 FT-IR spectra of TpBD（NO2）2 （a）， TpBD（NH2）2 （b） and TpBD-1S-（+）-Cam （c）

Fig.5 Nitrogen adsorption desorption isotherm and pore size distribution curve of TpBD-1S-（+）-Cam

Fig.6 SEM images of the stationary phases prepared by pure silica gel （A） and the TpBD-1S-（+）-Cam （B）

Table 1 Resolution results of 11 kinds of chiral racemates by chromatographic column

流动相 Mobile phase	样品名称 Sample	保留因子 k₁	保留因子 k₂	分离因子 α	分离度 R_s
V（CH₃OH）∶V（H₂O）=9∶1	华法林 Warfarin	0.15	0.42	2.88	1.02
	马来酸氯苯那敏 Chlorpheniramine maleate	0.20	0.35	1.77	0.42
	阿替洛尔 Atenolol	0.15	0.45	3.10	0.68
	美托洛尔 Metoprolol	0.13	0.44	3.43	0.84
	佐匹克隆 Zopiclone	0.47	0.64	1.35	0.40
V（CH₃（CH₂）₄CH₃）∶V（（CH₃）₂CHOH）=9∶1	1?（9?蒽基）?2，2，2?三氟乙醇 1?（9?Anthracenyl）?2，2，2?trifluoroethanol	0.58	2.98	5.12	5.29
	1，2?二苯乙醇酮 1，2?Benzophenone	0.14	1.75	12.79	3.51
	华法林 Warfarin	1.21	1.84	1.51	1.54
	酮洛芬 Ketoprofen	1.03	3.63	3.53	4.23
	盐酸美西律 Mexiletine hydrochloride	0.12	1.13	9.50	4.48
	噻吗洛尔 Timolol	0.15	1.09	7.16	2.97

Fig.7 Chromatographic resolution of 5 racemates by TpBD-1S-（+）-Cam stationary phaseA.Warfarin； B.Chlorpheniramine maleate； C.Atenolol； D.Metoprolol； E.Zopiclone

Fig.8 Chromatographic resolution of 6 racemates by TpBD-1S-（+）-Cam stationary phaseA.1?（9?Anthracenyl）?2，2，2?trifluoroethanol； B.1，2?Benzophenone； C.Warfarin； D.Ketoprofen； E.Mexiletine hydrochloride； F.Timolol

Fig.9 Resolution of two positional isomers of benzene series of bromoaniline （A） and iodoaniline （B） by TpBD-1S-（+）-Cam stationary phase

Table 2 Resolution of the two positional isomers by the chromatographic column

流动相

Mobile phase

样品名称

Sample

保留因子

k₁

保留因子

k₂

保留因子k₃

分离因子

α_1，2

分离因子

α_2，3

分离度

R_{s 1，2}

分离度

R_{s 2，3}

V（CH₃（CH₂）₄CH₃）∶V（（CH₃）₂CHOH）=9∶1

o，m，p?溴苯胺

o，m，p?Bromoaniline

o，m，p?碘苯胺

o，m，p?Iodoaniline

Fig.10 Separation spectra of different injection volumes of ketoprofen （2，4，6，8，10 μL） on the TpBD-1S-（+）-Cam

Fig.11 Chromatographs of ketoprofen at different temperatures （20，25，30，35，40 ℃） on the column of TpBD-1S-（+）-Cam

Fig.12 Reproducibility of separation of ketoprofen on the TpBD-1S-（+）-Cam （Repeat injection 5 times）

References 29

1	YANG H S， DU Y， WAN S， et al. Mesoporous 2D covalent organic frameworks based on shape-persistent arylene-ethynylene macrocycles［J］. Chem Sci， 2015， 6（7）： 4049-4053.
2	CÔTÉ A P， BENIN A I， OCKWIG N W， et al. Porous， crystalline， covalent organic frameworks［J］. Science， 2005， 310（5751）： 1166-1170.
3	李路路，刘帅，章琴，等. 共价有机框架材料研究进展［J］.物理化学学报， 2017， 33（10）： 1960-1977.
	LI L L， LIU S， ZHANG Q， et al. Research progress of covalent organic framework materials［J］. J Phys Chem， 2017， 33（10）： 1960-1977.
4	王禹婷，杨天怡，章应辉. 卟啉框架材料在光催化领域的应用［J］. 应用化学， 2020， 37（6）： 611-619.
	WANG Y T， YANG T Y， ZHANG Y H. Application of porphyrin framework materials in the field of photocatalysis［J］. Chinese J Appl Chem， 2020， 37（6）： 611-619.
5	LI Z P， FENG X， ZOU Y C， et al. A 2D azine-linked covalent organic framework for gas storage applications［J］. Chem Commun （Cambridge， Eng）， 2014， 50（89）： 13825-13828.
6	PACHFULE P， ACHARJYA A， ROESER J， et al. Diacetylene functionalized covalent organic framework （COF） for photocatalytic hydrogen generation［J］. J Am Chem Soc， 2017， 140（4）： 1423-1427.
7	CÔTÉ A P， EL-KADERI H M， FURUKAWA H， et al. Reticular synthesis of microporous and mesoporous 2D covalent organic frameworks［J］. J Am Chem Soc， 2007， 129（43）： 12914-12915.
8	符嫦娥，陈婉，戴朝霞，等. 磁性共价有机框架材料吸附甲基橙和茜素绿两种阴离子有机染料［J］. 应用化学， 2018， 35（5）： 594-599.
	FU C E， CHEN W， DAI Z X， et al. Adsorption of two anionic organic dyes， methyl orange and alizarin green on magnetic covalent organic framework materials［J］. Chinese J Appl Chem， 2018， 35（5）： 594-599.
9	LI Z， ZHANG Y， HONG X， et al. A robust and luminescent covalent organic framework as a highly sensitive and selective sensor for the detection of Cu²⁺ ions［J］. Chem Commun， 2016， 52（39）： 6613-6616.
10	LIU X， ZHANG Y， SHEN X， et al. Covalent organic frameworks as pH responsive signaling scaffolds［J］. Chem Commun， 2016， 52（74）： 11088.
11	SHINDE D B， KANDAMBETH S， PACHFULE P， et al. Bifunctional covalent organic frameworks with two dimensional organocatalytic micropores［J］. Chem Commun， 2014， 51（2）： 310-313.
12	DING S Y， GAO J， WANG Q， et al. Construction of covalent organic framework for catalysis： Pd/COF-LZU1 in Suzuki-Miyaura coupling reaction［J］. J Am Chem Soc， 2011， 133（49）： 19816-19822.
13	WANG X， HAN X， JIE Z， et al. Homochiral 2D porous covalent organic frameworks for heterogeneous asymmetric catalysis［J］. J Am Chem Soc， 2016， 138（38）： 12332-12335.
14	VAZQUEZ-MOLINA D A， MOHAMMAD-POUR G S， LEE C， et al. Mechanically shaped two-dimensional covalent organic frameworks reveal crystallographic alignment and fast Li-ion conductivity［J］. J Am Chem Soc， 2016， 138（31）： 9767-9770.
15	YOO J T， CHO S J， JUNG G Y， et al. COF-net on CNT-net as a molecularly designed， hierarchical porous chemical trap for polysulfides in lithium-sulfur batteries［J］. Nano Lett， 2016， 16（5）： 3292-3300.
16	LIN G Q， DING H M， YUAN D Q， et al. A pyrene-based， fluorescent three-dimensional covalent organic framework［J］. J Am Chem Soc， 2016， 138（10）： 3302-3305.
17	CHANDRA S， CHOWDHURY D R， ADDICOAT M， et al. Molecular level control of the capacitance of two-dimensional covalent organic frameworks： role of hydrogen bonding in energy storage materials［J］. Chem Mater， 2017， 29（5）： 2074-2080.
18	ABDUL K M， VIDYANAND V， SUVENDU K， et al. Convergent covalent organic framework thin sheets as flexible supercapacitor electrodes［J］. ACS Appl Mater Interfaces， 2018， 10（33）： 28139-28146.
19	QIAN H L， YANG C X， YAN X P. Bottom-up synthesis of chiral covalent organic frameworks and their bound capillaries for chiral separation［J］. Nat Commun， 2016， 7（10）： 12104-12111.
20	ZHANG K， CAI S L， YAN Y L， et al. Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography［J］. J Chromatogr A， 2017， 1519（2017）： 100-109.
21	XING H， HUANG J， CHEN Y， et al. Chiral 3D covalent organic frameworks for high performance liquid chromatographic enantioseparation［J］. J Am Chem Soc， 2018， 140（3）： 892.
22	HUANG J， HAN X， YANG S， et al. Microporous 3D covalent organic frameworks for liquid chromatographic separation of xylene isomers and ethylbenzene［J］. J Am Chem Soc， 2019， 141（22）： 8996-9003.
23	CHEN J， HUANG Y， WEI X， et al. Covalent organic nanospheres： facile preparation and application in high-resolution gas chromatographic separation［J］. Chem Commun， 2019， 55（73）： 10908-10911.
24	SEGURA J L， ROYUELA S， RAMOS M. Post-synthetic modification of covalent organic frameworks［J］. Chem Soc Rev， 2019， 48 （14）： 3903-3945.
25	XU H， GAO J， JIANG D L. Stable， crystalline， porous， covalent organic frameworks as a platform for chiral organocatalysts［J］. Nat Chem， 2015， 7（11）： 905-912.
26	LOHSE M S， STASSIN T， NAUDIN G， et al. Sequential pore wall modification in a covalent organic framework for application in lactic acid adsorption［J］. Chem Mater， 2016， 28（2）： 626-631.
27	何义娟，李克丽，李倩，等. 利用“网包法”制备高效液相色谱大环抗生素类手性固定相［J］. 色谱， 2019， 37（4）： 383-391.
	HE Y J， LI K L， LI Q， et al. Preparation of chiral stationary phases of macrocyclic antibiotics for high performance liquid chromatography by “Net-pack method”［J］. Chromatography， 2019， 37（4）： 383-391.
28	冯国政. 液相色谱柱高压匀浆填充装置［J］. 分析仪器， 1987： 36-37.
	FENG G Z. High-pressure homogenate filling device for liquid chromatography column［J］. Anal Instrum， 1987： 36-37.
29	CHANDRA S， KANDAMBETH S， BISWAL B P， et al. Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination［J］. J Am Chem Soc， 2013， 135（47）： 17853-17861.

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Covalent Organic Framework Material Derivative of Chiral Camphor Used as High Performance Liquid Chromatography Stationary Phase for Resolution of Racemates

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