Studies on Preparation and Chiral Recognition of 2-<italic style="font-style: italic">N</italic>-phthaloyl Chitosan-based Chiral Stationary Phases

Li-li Zhang; Jun Shen; Yoshio Okamoto; Yu-long Li

doi:10.11777/j.issn1000-3304.2016.16072

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Studies on Preparation and Chiral Recognition of 2-N-phthaloyl Chitosan-based Chiral Stationary Phases

Research Article | 更新时间：2021-03-19

- Studies on Preparation and Chiral Recognition of 2-N-phthaloyl Chitosan-based Chiral Stationary Phases
- Acta Polymerica Sinica Issue 11, Pages: 1555-1562(2016)
- 作者机构：
  
  1.哈尔滨工程大学材料科学与化学工程学院超轻材料与表面技术教育部重点实验室哈尔滨 150001
  2.Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2016.16072
  CLC：
- Published：2016-11，
  
  Received：15 March 2016，
  
  Revised：28 April 2016，
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Li-li Zhang, Jun Shen, Yoshio Okamoto, Yu-long Li. Studies on Preparation and Chiral Recognition of 2-N-phthaloyl Chitosan-based Chiral Stationary Phases. [J]. Acta Polymerica Sinica (11):1555-1562(2016)
DOI：

Li-li Zhang, Jun Shen, Yoshio Okamoto, Yu-long Li. Studies on Preparation and Chiral Recognition of 2-N-phthaloyl Chitosan-based Chiral Stationary Phases. [J]. Acta Polymerica Sinica (11):1555-1562(2016) DOI： 10.11777/j.issn1000-3304.2016.16072.

摘要

为了开发具有高效手性识别能力的新型多糖类手性固定相，合成了5种糖单元2-位具有邻苯二甲酰亚胺，而3，6-位同时具有4种不同苯基氨基甲酸酯基团(2-氯、3-氯、4-氯和3，5二氯取代的苯基氨基甲酸酯)和一种无取代的苯基氨基甲酸酯基团的壳聚糖类衍生物，并将其涂覆在氨丙基硅胶表面制备成HPLC手性固定相.利用红外光谱和核磁氢谱对所合成的衍生物进行结构表征与分析，并应用HPLC法评价其对10种对映体的手性识别能力.研究结果表明：这些新型壳聚糖类手性固定相的手性识别能力受苯基氨基甲酸酯取代基中芳环上侧基的引入位置、数量和空间位阻的影响较大.同时色谱测试中所使用流动相的成分对该类手性固定相的识别能力也具有较大影响.进一步探讨了这些衍生物的氨基甲酸酯残基核磁氢谱中N—H质子的化学位移和红外光谱中N—H波数与手性识别能力之间的关系.

Abstract

To develop novel polysaccharide-based chiral stationary phases with high chiral recognition

five novel chitosan derivatives

bearing

-phthaloyl at 2-position of a glucose ring and four different phenylcarbamate substituents including 2-chloro

3-chloro

4-chloro and 3

5-dichloro

and one chitosan derivative bearing unsubstituted phenylcarbamate at 3- and 6-positions were synthesized by combination of a procedure on the regioselective acylation of 2-position.The structures of the obtained chitosan derivatives were characterized by FTIR and

H-NMR.They were then coated on the macroporous silica gel to be used as chiral stationary phases for high-performance liquid chromatography (HPLC).Their chiral recognition abilities were evaluated using ten racemates by HPLC.The results indicated that these coated-type chitosan CSPs exhibited characteristic chiral recognition ability

mainly depending on the position

number and steric hindrance of the substituents introduced on the aromatic moieties of the chitosan derivatives.Meanwhile

the eluent content in chromatographic tests had a great influence on the chiral recognition abilities of the chitosan-based CSPs.The racemates

were better resolved using a hexane/2-propanol (99/1) mixture as the eluent in comparison with the results obtained using hexane/2-propanol (90/10) mixture as the eluent on chitosan 2-phthaloyl-3

6-di(3

5-dichlorophenylcarbamate derivative (CSP-

).The correlations between the chiral recognition abilities and the chemical shifts of the N-H protons in the

H-NMR spectra and the N-H frequencies in the IR spectra of the carbamate moieties of these derivatives were also discussed further.Among the CSPs based on the chitosan derivatives bearing different substituents at 2 and 3

6-postions of the glucose unit

those based on the chitosan derivatives (CSP-

) bearing 3

5-dichlorophenylcarbamates at 3

6-positions showed higher chiral recognition abilities while those based on the derivatives bearing 2-chlorophenylcarbamates at 3

6-positions showed relatively lower recognition ability.Compared to chitosan 2-(3

5-dichlophenylurea)-3

6-di(3

5-dichlorophenylcarbamate) (CSP-ref) and chitosan 2-phthaloyl-3

6-(3

5-dichlorophenylcarbamate) (CSP-

-ref)

the chitosan derivative (CSP-

) showed complementary and similar chiral recognition abilities for some racemates.

关键词

壳聚糖2-N-邻苯二甲酰亚胺苯基氨基甲酸酯手性固定相手性识别能力

Keywords

ChitosanRegioselective substituentsPhenylcarbamateChiral stationary phasesChiral recognition

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College of Food Science and Technology, Nanjing Agricultural University

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Studies on Preparation and Chiral Recognition of 2-N-phthaloyl Chitosan-based Chiral Stationary Phases

DOI：10.11777/j.issn1000-3304.2016.16072

摘要

Abstract

关键词

Keywords

references