摘要
本文主要做了以下工作:
1.概述了β-环糊精类衍生物作为色谱固定相和添加剂的合成和应用,对分离机理及协同效应进行了初步的探讨。
2.依据β-环糊精类固定相和添加剂性质及分离作用机理,设计并最终合成了20种目标产物。它们分属以下四个大的类别:
a.亲油性烷基化β-环糊精五种,建立了全烷基β-环糊精的新的合成方法,大大缩短了合成的时间,取得了较高的纯度和产率。
b.亲水性β-环糊精二种,采用了较新报道的合成方法。
c.氨基酸衍生化β-环糊精八种。以β-环糊精为母体的一取代衍生物二种。以七(2,6-二-O-甲基)-β-环糊精物为母体的一取代衍生六种本系列衍生物在色谱应用方面的合成和应用未见报道。
d.二聚、交聚β-环糊精五种,本系列衍生物在色谱应用方面的合成和应用未见报道。
云南师范人学硕士研究生学位论丈6-环糊精类衍生物的合成及应用
一
注:SP为“色谱固定相”之代表缩写符号,MA为“色谱流动相添加剂”之缩写符号。
本文对所合成的目标产物用薄层层析、经典柱色谱、高效液相色谱、毛细管
电泳及红外等手段进行了提纯和表征,测定了它们的熔点。
3.所合成的目标产物分别在气相色谱、液相色谱及毛细管电泳上进行了应用,
经过初步的色谱性能研究,在己测试的部分衍生物中,各类都显示了良好的色
谱性能。能分离手性化合物包括全甲基p-环糊精、全戊基p-环糊精、磺酸化-
日.环糊精、竣甲基-日-环糊精、二酚氯聚p-环糊精,氨基酸衍生化类日-环糊精
在分离含苯环的位置异构体时初步显现了独特的分离能力,特别是在协同效应的
研究上取得了良好的效果,实现了合成的预期成果。
The main works of the thesis are as follows:
1. The development of P -cyclodextrin derivatives in chromatographic analysis was reviewed. Those chromatographic techniques included gas chromatograph,high performance liquid chromatography and capillary electrophoresis.
2. Four series of P -cyclodextrin derivaties were synthesizrd and confirmed. (l)Five alkylated P -cyclodextrins were synthesized included:
Heptakis (2,3,6-tri-O-methyl)- 3 -CD,
Heptakis (2,3,6-tri-O-ethyl)- P - CD,
Haptakis (2,3,6-tri-O-butyl)- P - CD,
Heptakis (2,3,6-tri-O-octyl)- P - CD,
Heptakis (2,6-di-O-methyl)- P - CD.
The peralkylated P - CDs were synthesized by single-step procedure.
(2) Two kinds of water-soluble P -cyclodextrin derivatives were Sulfonate P -CD and Heptakis (2,6-carboxyl)- P -CD .
(3) Eight P -cyclodextrin derivatives which were derivated with amino acids were:
Mono-O-(N-benzoyl-DL-lactamyl)- P -CD, Mono-O-(N-benzoyl-DL- valineyl)- P -CD,
3-mono-O-(N-benzoyl-DL-glycineyl)-heptakis(2,6-di-O-methyl)- P - CD, 3-mono-O-(N-benzoyl-DL-lactamyl)-heptakis(2,6-di-O-methyl)- P - CD, 3-mono-O-(N-benzoyl-DL-valineyl)-heptakis(2,6-di-O-methyl)- P - CD, 3-mono-O-(N-benzoyl-L-lactamyl)-heptakis(2,6-di-O-methyl)- P - CD, 3-mono-O-(N-benzoyl-L-valineyl)-heptakis(2,6-di-O-methyl)- P - CD, 3-mono-O-(N-benzoyl-DL- a -amino-butyl)-heptakis(2,6-di-O-methyl)- P -CD
(4) Five kinds of briadged and polymerized P -CD derivatives included: Oxalyl choride polymerized P -CD,
Oxalyl methyl choride polymerized 3 -CD, Oxalyl choride briadged heptakis(2,6-di-O-methyl)- 3 -CD, Tolylene 2,6-diisocyanate polymerized 3 -CD, Tolylene 2,6-diisocyanate briadged heptakis(2,6-di-O-methyl)- 3 -CD. S.Chromatographic character of 3 - CD derivatives were studied.
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