高效液相色谱手性分离
摘要
随着科学技术的发展，人们对不同旋光性药物所表现出来的不同的生理活性这一现象认识更加深入。在生物化学、药物化学及有机化学中的不对称合成和催化技术中，旋光异构体的分离与分析显得越来越重要。在众多的旋光异构体的分离与分析方法中高效液相色谱手性固定相直接拆分是一种具有快速，有发展潜力的方法之一。本文重点研究了多糖类衍生物手性固定相。本论文共分四部分：
第一章综述了高效液相色谱手性固定相，重点评述了多糖类衍生物手性固定相的发展、手性固定相的类型、拆分机理、分离范围及应用的最新进展。
第二章合成了手性填料纤维素-三(4-甲基苯甲酸酯)，并涂敷于氨丙基硅胶上，制备成手性固定相。用高效液相色谱法，在此手性固定相上，对农药禾草灵外消旋体进行了拆分，考察了流动相组成，温度，醇效应对禾草灵对映体拆分及保留的影响，由实验结果对禾草灵对映体之间的-△_(R，S)△G~θ，△_(R，S)△H~θ，△_(R，A)△S~θ进行了计算，并对其在OJ柱上保留机理进行了讨论。
第三章近二十多年来，四面体原子簇化合物的合成方面研究已取得了很大的发展，但拆分四面体原子簇化合物来得到足够量的对映异构体是件很困难的事。我们用自制的纤维素-三(3，5-二甲基苯基氨基甲酸酯)手性固定相为手性填料，在正相条件首次成功地拆分了多种四面体金属簇化合物。系统地研究了以正己烷-醇为流动相，考察了流动相中醇的含量、醇链长度、醇的立体结构对手性拆分的影响。由实验结果提出了原子簇化合物与手性固定相的作用模式，解释了样品结构对手性拆分的影响。
第四章在OD柱和OJ柱上对外消旋体α-苯乙醇进行了拆分，选择了最佳的拆分条件，并将此方法应用于苯乙酮不对称催化还原产物的光学纯度的鉴定中，取得了较满意的结果。
With the development of science and technology , people deeply realize the distinguish between enantiomers for optically active compounds. It is becoming important to separate optical active compounds in the fields of biochemistry , organic chemistry, pharmaceutical chemistry as well as asymmetric synthesis and catalysis. There are many methods to separate optically active compounds. Among them, the high performance liquid chromatography (HPLC-CSP) is one of the rapid, most prospect methods in chiral separation. In the thesis, we emphasize on cellulose derivatives chiral stationary phase coated on silica gel.
This paper consists of four parts:
In the first part (chapter 1), the importance and methods of enantioseparation for chiral compounds have been reviewed systematically. It is given emphasis to development and types of cellulose chiral stationary phases . Especially application in enantioseparation and mechanism of chiral recognition of cellulose chiral stationary phases are mainly reviewed in detail.
In the second part (chapter 2), Cellulose tris (4-methylbenzoate) was synthesized by the reaction of microcrystalline cellulose with benzoyl chloride. A chiral stationary phase was prepared by coating cellulose tris (4-methylbenzoate) on the silica .On the cellulose tris (4-methylbenzoate ) chiral stationary phase (CTMB-CSP), diclofop-methyl was resolved in normal-phase system. The influence of the composition of the mobile phase and the column temperature was investigated. were calculated and retention mechanism was researched.
The third part (chapter 3 ) The asymmetric catalysis induced by metal framework chirality, instead of phosphine ligands, is alluring and difficult task in the field of catalysis. Today, there is rapid progress in synthesis of chiral metal clusters(l). It is very important to separate the metal clusters in order to gain adequate optical isomers, which can be used in catalysis. Unfortunately, separation of metal clusters is very difficult. Cellulose tris (3,5-dimethylphenylcarbamate) was prepared and used to chiral separation for five novel chiral metal clusters. The influence of alcohol such as the length of alkyl chain, steric bulk
and content of alcohol in mobile phases were systematically examined. Based on the experimental results, the mechanism of the chiral recognition was discussed.
The fourth part (chapter 4 ) a -phenylethanol was resolved on CDMPC and CTMB in normal-phase system. The influence of the composition and flow rate of the mobile phase was investigated. We choose the best experimental condition and determinate the excess value of the reaction.
第一章综述了高效液相色谱手性固定相，重点评述了多糖类衍生物手性固定相的发展、手性固定相的类型、拆分机理、分离范围及应用的最新进展。
第二章合成了手性填料纤维素-三(4-甲基苯甲酸酯)，并涂敷于氨丙基硅胶上，制备成手性固定相。用高效液相色谱法，在此手性固定相上，对农药禾草灵外消旋体进行了拆分，考察了流动相组成，温度，醇效应对禾草灵对映体拆分及保留的影响，由实验结果对禾草灵对映体之间的-△_(R，S)△G~θ，△_(R，S)△H~θ，△_(R，A)△S~θ进行了计算，并对其在OJ柱上保留机理进行了讨论。
第三章近二十多年来，四面体原子簇化合物的合成方面研究已取得了很大的发展，但拆分四面体原子簇化合物来得到足够量的对映异构体是件很困难的事。我们用自制的纤维素-三(3，5-二甲基苯基氨基甲酸酯)手性固定相为手性填料，在正相条件首次成功地拆分了多种四面体金属簇化合物。系统地研究了以正己烷-醇为流动相，考察了流动相中醇的含量、醇链长度、醇的立体结构对手性拆分的影响。由实验结果提出了原子簇化合物与手性固定相的作用模式，解释了样品结构对手性拆分的影响。
第四章在OD柱和OJ柱上对外消旋体α-苯乙醇进行了拆分，选择了最佳的拆分条件，并将此方法应用于苯乙酮不对称催化还原产物的光学纯度的鉴定中，取得了较满意的结果。
With the development of science and technology , people deeply realize the distinguish between enantiomers for optically active compounds. It is becoming important to separate optical active compounds in the fields of biochemistry , organic chemistry, pharmaceutical chemistry as well as asymmetric synthesis and catalysis. There are many methods to separate optically active compounds. Among them, the high performance liquid chromatography (HPLC-CSP) is one of the rapid, most prospect methods in chiral separation. In the thesis, we emphasize on cellulose derivatives chiral stationary phase coated on silica gel.
This paper consists of four parts:
In the first part (chapter 1), the importance and methods of enantioseparation for chiral compounds have been reviewed systematically. It is given emphasis to development and types of cellulose chiral stationary phases . Especially application in enantioseparation and mechanism of chiral recognition of cellulose chiral stationary phases are mainly reviewed in detail.
In the second part (chapter 2), Cellulose tris (4-methylbenzoate) was synthesized by the reaction of microcrystalline cellulose with benzoyl chloride. A chiral stationary phase was prepared by coating cellulose tris (4-methylbenzoate) on the silica .On the cellulose tris (4-methylbenzoate ) chiral stationary phase (CTMB-CSP), diclofop-methyl was resolved in normal-phase system. The influence of the composition of the mobile phase and the column temperature was investigated. were calculated and retention mechanism was researched.
The third part (chapter 3 ) The asymmetric catalysis induced by metal framework chirality, instead of phosphine ligands, is alluring and difficult task in the field of catalysis. Today, there is rapid progress in synthesis of chiral metal clusters(l). It is very important to separate the metal clusters in order to gain adequate optical isomers, which can be used in catalysis. Unfortunately, separation of metal clusters is very difficult. Cellulose tris (3,5-dimethylphenylcarbamate) was prepared and used to chiral separation for five novel chiral metal clusters. The influence of alcohol such as the length of alkyl chain, steric bulk
and content of alcohol in mobile phases were systematically examined. Based on the experimental results, the mechanism of the chiral recognition was discussed.
The fourth part (chapter 4 ) a -phenylethanol was resolved on CDMPC and CTMB in normal-phase system. The influence of the composition and flow rate of the mobile phase was investigated. We choose the best experimental condition and determinate the excess value of the reaction.
引文
[1] 叶秀林，立体化学p：52，高教出版社，1982。
[2] 戴立信 陆熙炎 朱光美，手性技术的兴起，化学通报，1995，6：15—23
[3] NorberM.Maier,Pilar F.,Wolfgang L. Seperation of enantiomers: need, challeng, perspectives. Joural of chromatongraphy A, 2001, 906:3-33
[4] 周志强等，高效液相色谱法对外滴旋药物的拆分，分析测试技术与仪器1998，
Vol4：1-6
[5] USA. Food and Drug Administration. chirality, 1992, 4:338
[6] 林国强，陈耀全 陈新兹 手性合成 北京科学出版社2001年
[7] Dalgliesh C.E., J.Chem.Soc.1952, 47, 39-40
[8] 刘国诠 余兆楼 色谱柱技术P：240 化学工业出版社 2001年7月第1版
[9] Hesse G., Hagel R., Chromatographia.1973, 6: 227
[10] Yashima E. and Okamoto Y. Chiral Discrimination on Polysaccharides Derivatives. Bull.Chem.Soc.Jpn. 1995, 68:3289—3307
[11] Chankvetadze B, Yishima E., Okamoto Y. J. Chromatogr.A,1994,670(1):39-54
[12] Yashima E. Polysacchadde- based chiral stationary phases for high-performance liquid chromatographic enantioseparation. J. Chromatogr.A, 2001,906:105-125
[13] Okamoto.Y, Kawashima M., and Hatada K. The CDMPC column has been commercialized by Daicel Chemical Industries. The ADMPC column is scheduled to be commercialized. J. Chromatogr. 1956, 363:173-186
[14] Okamoto Y, Kaide Y., Review: Resolution by HIPLC using polysaccharide carbamates and benzoates as chiral stationary phases. J.Chromatogr.A, 1994, 666(2): 403-419
[15] Norbert M. Maier, Pilar F.Wolfgang Lindner, Separation of enantiomers: needs, challengers, perspectives. Joural of Chromatgraphy A,2001,9063-33
[16] Yashima E.Polysaccharide-based chiral stationary phases for high-performance liquid chromatographic enantioseperation.Journal of chromatography A, 2001, 906: 105-125
[17] KustersE., Loux V. and Schmid E. Enantiomeric separation of chiral sulphoxides. Journal of chromatography A, 1994, 666, 421-432
[18] Chankvetadze B., Yashima E., Okamoto Yoshio. J. Chromatogr. A, 1994, 670(1): 39-45
[19] Westhoff F, Blaschke G. High performance liquid Chromatographic determination of the stereoselective biotrnsformation of the chiral clrug praziquantel. J. Chromatogr. 1992,578:265
[20] Cottfriecl Blaschke Chromatographic resolution of chiral drug on polyamides and cellulose triacetate. Joural of Liquid Chromatography, 1986, 9: 341-368
[21] Sybilska D Z.Resolution of mephenytoin and some chiral barbiturates into enantiomers by reversed HPLC via β-cyclodextrin inclusion complexes. J. Liq.chromatogr., 1986,9:591-599
[22] 中科院化学部编写组 展望21世纪的化学 化学工业出版社2000年
[23] Hou J.G., Wang Y.L. Reversed-phase separation on cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase. Chromatographia 1999,50(1/2):89-97
[24] Okamoto Y., Kawashima Y. and Hatade K. Chromatographic resolution: controlled chiral recognition of cellulose triphenglcarbamate derivatives supported on dilica gel. Journal of chrornatography, 1986, 363: 173-186
[25] Shibata T., Okamoto land Ishii K., Chromatographic optical resolution on polysaceharides and their derivatives. Journal of liquid chromatography 1956, 9 (2and3): 313-340
[26] Hassan Y. Aboul Enein and Vince Serignese Roie of solventa in the resolution of some beta-adrenergic blockers on cellose 3, 5-dimethylphenyl earbamate chiral stationary phase. Journal of liquid chromatography 1993, 16(1): 197-207
[27] Vanessal L, Herring Y, Direct HPLC determination in urine of the enantiomers of propranolol and its major metabolite 4-hytrixy propranolol.J.Chromatogr.B, 1993, 612: 215
[28] Hailang Z, James T, VTEWART. Y. High performace liquid chromatographic analysis of pindolol enantiomers in human serum and urine using a reversed-phase cellulose-based chiral column. J.Chromatogr.B, 1995, 668: 309
[29] Flesh G, Francotte E, Hell F, Determination of the R- (-) and S- (+) enantiomers of the monohydroxylated metabolite of oxcarbazepine in human plasma by enantio selective HPLC. J.Chromatogr. B.1992, 581: 147
[30] Terete H, Blaschke G, A chiral HPLC determination of tramadol and its major mertabolites in unine after oral administration of racemic tramadol. J.Chromatogr.B, 1993, 612: 223
[31] Westhoff F, Blaschke G.high performance liquid Chromatographic determintion of the stereoselective biotransformation of the chiral drug praziquantel., J.
Chromatogr. 1992, 578:265
[32] Kaiming C, Shyming S., Enantiomeric separation of a carcdiotonic agent pimobendan and its major active meablol:te, UD-CG212BS, by copied achiral-chiral normal-phase HPLC, J.Chromatogr.Sci. 1992,30:171
[33] Jens E, Auja van Arkens, Chiral Separation of β-blocking drug substances using chiral stationary phases., J. Chromatogr. A, 1995,708:253
[34] Ishikawa A. and Shibate T., Cellulose chiral stationary phase under reversed-phase condition J.liq. Chromatogra..1993,16(4):859-878
[35] Gubitz G, Jellenz W and Schonleber. High performance liquid chromatographic resolution of the optical isomers of D, L-tryptophane, D, L-5-hydroxytryptophan and D, L-dopa on cellulose column, J.high Res chromatogr.1980, 3: 31
[36] Dhanesar S C., Chiral separations by HPLC 11:188
[37] C.Chassaing, A, Thienpont,G.Felix Regioselective carbamoylated and benzoylated cellulose for the sparation of enantiomers in high-performance liquid chromatography Journal of chromatography A, 1996, 738:157-167
[38] Yashima E., Sahavattana P.and Okamoto Y. HPLC enantiosepartion on cellulose tris(3,5-dimethylphenylcarbamate) as a chiral stationary phase:influences of pore size of silica gel, coating amount, coating solvent, and column temperature on chiral discrimination. Chirality, 1996, 8:446-451
[39] 王亚丽 候经国 高锦章 高效液相色谱手性固定相拆分 a-氨基酸衍生物对映体分析化学 1998，26：1447-1450
[40] Yashima E.Polysaccharide-based chiral stationary phases for high-performance liquid chromatographic enantioseparation. J. chromatogr. A, 2001,906:105-125
[41] Karin Balmer, Per-olof Lagerstrom, Direction chiral separation of almokalant on chiral OD and chiral AD for liquid chromatographic essay of biological samples J. Chromatogr.A, 1993, 631:191-196
[42] Pilaf Franco,Cristina MinguiIIon, Laureano Olivers Bonded cellulose-derived high-performance liquid chromatography chiral stationary phases J. Chromatogr. A, 1997, 791: 37-44
[43] 夏立均等 用高效液相色谱手性固定相法拆分芳香仲醇及芳香乙二醇类手性化
合物 有机化学 2002，22：60-63
[44] 侯经国等 纤维素-三(3，5-二甲基苯基氨基甲酸酯)涂敷手性固定相的制备、表征及评价 色谱 2001，19：154-156
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[49] Hou J.G., Wang Y.L. Reversed-phase separation on cellulose tris (3,5-dimethylphenylcarbamate) chiral stationary phase. Chromatographia 1999,50(1/2):89-97
[50] Yashima E. Polysaceharide-based chiral stationary phases for high performance liquid chromatographic enantioseparation. J.Chromatogr.A, 2001,906:105-125
[51] Tristan D. Booth, Irving W. wainer, Mechanistic investigation into the enantioselective separation of mexiletine and related compounds, chromatographyed on an amylose tris(3,5-dimethylphenylcarbamate) chiral stationary phase. Journal of Chromatgraphy A, 1996,741:205-211
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[56] Okamoto Y. and Kaida Y., Resolution by high-performance liquid chromatography using polysaccharide carbamates and benzoates as chiral stationary phases. J.Chromatogr.A, 1994,666:403-419.
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[2] 戴立信 陆熙炎 朱光美，手性技术的兴起，化学通报，1995，6：15—23
[3] NorberM.Maier,Pilar F.,Wolfgang L. Seperation of enantiomers: need, challeng, perspectives. Joural of chromatongraphy A, 2001, 906:3-33
[4] 周志强等，高效液相色谱法对外滴旋药物的拆分，分析测试技术与仪器1998，
Vol4：1-6
[5] USA. Food and Drug Administration. chirality, 1992, 4:338
[6] 林国强，陈耀全 陈新兹 手性合成 北京科学出版社2001年
[7] Dalgliesh C.E., J.Chem.Soc.1952, 47, 39-40
[8] 刘国诠 余兆楼 色谱柱技术P：240 化学工业出版社 2001年7月第1版
[9] Hesse G., Hagel R., Chromatographia.1973, 6: 227
[10] Yashima E. and Okamoto Y. Chiral Discrimination on Polysaccharides Derivatives. Bull.Chem.Soc.Jpn. 1995, 68:3289—3307
[11] Chankvetadze B, Yishima E., Okamoto Y. J. Chromatogr.A,1994,670(1):39-54
[12] Yashima E. Polysacchadde- based chiral stationary phases for high-performance liquid chromatographic enantioseparation. J. Chromatogr.A, 2001,906:105-125
[13] Okamoto.Y, Kawashima M., and Hatada K. The CDMPC column has been commercialized by Daicel Chemical Industries. The ADMPC column is scheduled to be commercialized. J. Chromatogr. 1956, 363:173-186
[14] Okamoto Y, Kaide Y., Review: Resolution by HIPLC using polysaccharide carbamates and benzoates as chiral stationary phases. J.Chromatogr.A, 1994, 666(2): 403-419
[15] Norbert M. Maier, Pilar F.Wolfgang Lindner, Separation of enantiomers: needs, challengers, perspectives. Joural of Chromatgraphy A,2001,9063-33
[16] Yashima E.Polysaccharide-based chiral stationary phases for high-performance liquid chromatographic enantioseperation.Journal of chromatography A, 2001, 906: 105-125
[17] KustersE., Loux V. and Schmid E. Enantiomeric separation of chiral sulphoxides. Journal of chromatography A, 1994, 666, 421-432
[18] Chankvetadze B., Yashima E., Okamoto Yoshio. J. Chromatogr. A, 1994, 670(1): 39-45
[19] Westhoff F, Blaschke G. High performance liquid Chromatographic determination of the stereoselective biotrnsformation of the chiral clrug praziquantel. J. Chromatogr. 1992,578:265
[20] Cottfriecl Blaschke Chromatographic resolution of chiral drug on polyamides and cellulose triacetate. Joural of Liquid Chromatography, 1986, 9: 341-368
[21] Sybilska D Z.Resolution of mephenytoin and some chiral barbiturates into enantiomers by reversed HPLC via β-cyclodextrin inclusion complexes. J. Liq.chromatogr., 1986,9:591-599
[22] 中科院化学部编写组 展望21世纪的化学 化学工业出版社2000年
[23] Hou J.G., Wang Y.L. Reversed-phase separation on cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase. Chromatographia 1999,50(1/2):89-97
[24] Okamoto Y., Kawashima Y. and Hatade K. Chromatographic resolution: controlled chiral recognition of cellulose triphenglcarbamate derivatives supported on dilica gel. Journal of chrornatography, 1986, 363: 173-186
[25] Shibata T., Okamoto land Ishii K., Chromatographic optical resolution on polysaceharides and their derivatives. Journal of liquid chromatography 1956, 9 (2and3): 313-340
[26] Hassan Y. Aboul Enein and Vince Serignese Roie of solventa in the resolution of some beta-adrenergic blockers on cellose 3, 5-dimethylphenyl earbamate chiral stationary phase. Journal of liquid chromatography 1993, 16(1): 197-207
[27] Vanessal L, Herring Y, Direct HPLC determination in urine of the enantiomers of propranolol and its major metabolite 4-hytrixy propranolol.J.Chromatogr.B, 1993, 612: 215
[28] Hailang Z, James T, VTEWART. Y. High performace liquid chromatographic analysis of pindolol enantiomers in human serum and urine using a reversed-phase cellulose-based chiral column. J.Chromatogr.B, 1995, 668: 309
[29] Flesh G, Francotte E, Hell F, Determination of the R- (-) and S- (+) enantiomers of the monohydroxylated metabolite of oxcarbazepine in human plasma by enantio selective HPLC. J.Chromatogr. B.1992, 581: 147
[30] Terete H, Blaschke G, A chiral HPLC determination of tramadol and its major mertabolites in unine after oral administration of racemic tramadol. J.Chromatogr.B, 1993, 612: 223
[31] Westhoff F, Blaschke G.high performance liquid Chromatographic determintion of the stereoselective biotransformation of the chiral drug praziquantel., J.
Chromatogr. 1992, 578:265
[32] Kaiming C, Shyming S., Enantiomeric separation of a carcdiotonic agent pimobendan and its major active meablol:te, UD-CG212BS, by copied achiral-chiral normal-phase HPLC, J.Chromatogr.Sci. 1992,30:171
[33] Jens E, Auja van Arkens, Chiral Separation of β-blocking drug substances using chiral stationary phases., J. Chromatogr. A, 1995,708:253
[34] Ishikawa A. and Shibate T., Cellulose chiral stationary phase under reversed-phase condition J.liq. Chromatogra..1993,16(4):859-878
[35] Gubitz G, Jellenz W and Schonleber. High performance liquid chromatographic resolution of the optical isomers of D, L-tryptophane, D, L-5-hydroxytryptophan and D, L-dopa on cellulose column, J.high Res chromatogr.1980, 3: 31
[36] Dhanesar S C., Chiral separations by HPLC 11:188
[37] C.Chassaing, A, Thienpont,G.Felix Regioselective carbamoylated and benzoylated cellulose for the sparation of enantiomers in high-performance liquid chromatography Journal of chromatography A, 1996, 738:157-167
[38] Yashima E., Sahavattana P.and Okamoto Y. HPLC enantiosepartion on cellulose tris(3,5-dimethylphenylcarbamate) as a chiral stationary phase:influences of pore size of silica gel, coating amount, coating solvent, and column temperature on chiral discrimination. Chirality, 1996, 8:446-451
[39] 王亚丽 候经国 高锦章 高效液相色谱手性固定相拆分 a-氨基酸衍生物对映体分析化学 1998，26：1447-1450
[40] Yashima E.Polysaccharide-based chiral stationary phases for high-performance liquid chromatographic enantioseparation. J. chromatogr. A, 2001,906:105-125
[41] Karin Balmer, Per-olof Lagerstrom, Direction chiral separation of almokalant on chiral OD and chiral AD for liquid chromatographic essay of biological samples J. Chromatogr.A, 1993, 631:191-196
[42] Pilaf Franco,Cristina MinguiIIon, Laureano Olivers Bonded cellulose-derived high-performance liquid chromatography chiral stationary phases J. Chromatogr. A, 1997, 791: 37-44
[43] 夏立均等 用高效液相色谱手性固定相法拆分芳香仲醇及芳香乙二醇类手性化
合物 有机化学 2002，22：60-63
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