Application of Artificial Polyamides, Having Cyclobutane Rings in the Main Chain, as Chiral Stationary Phases for Hplc
| Project/Area Number |
01850200
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| Research Category |
Grant-in-Aid for Developmental Scientific Research (B).
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| Allocation Type | Single-year Grants |
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| Research Field |
高分子合成
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| Research Institution | The University of Tokyo |
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Principal Investigator |
SAIGO Kazuhiko The University of Tokyo, Faculty of Engineering, Associate Professor, 工学部, 助教授 (80016154)
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| Co-Investigator(Kenkyū-buntansha) |
TACHIBANA Kouzou Daicel Chemical Industries, LTD., Research Associate, セパレーションシステム, 研究員
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| Project Period (FY) |
1989 – 1990
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| Project Status |
Completed (Fiscal Year 1990)
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| Budget Amount *help |
¥4,800,000 (Direct Cost: ¥4,800,000)
Fiscal Year 1990: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1989: ¥2,700,000 (Direct Cost: ¥2,700,000)
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| Keywords | Photodimerization / Optical Resolution / Ring-Opening Polyaddition / Alkaline Depolymerization / Optically Active Polyamides / Chiral Stationary Phases for HPLC / Odd-Even Discrimination / Odered Conformation |
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| Research Abstract |
The phenolic hydroxyl groups in optically active polyamides, which consist of anti head-to-head coumarin dimer, were easily carbamoylated with several kinds of isocyanates in high yield and conversion. HPLC coumns were prepared by coating the polyamides on silica gel surface. The carbamoylated polyamides showed a chiral recognition ability for the racemates, which could not be recognized by the parent polyamides. Consequently, the carbamoylated and parent polyamides showed complementary recognition ability.
The chiral recognition ability of polyamides, consisting of anti head-to-head coumarin dimer and alpha, omega-alkanediamine, depended on the methylene number of the diamine component and showed odd-even dscrimination. The X-ray diffraction and DSC analyses revealed that the chiral recognition ability appeared only for the polyamides, which could crystallize on the surface of silica gel and that the higher crystallinity resulted in the higher chiral recognition ability. This result is
… More
the first example for the elucidation of the correlation between chiral recognition ability, crystallinity, and odd-even discrimination.
Polyamides, derived from anti head-to-head umbelliferone dimer, showed steep decrease of their viscosity in an alkaline solution, whereas polyamides consisting of anti head-to-head coumarin dimer were rather stable in an alkaline solution. This phenomenon was found to result from the scission of the main chian via a quinoid from of dihydroxyphenyl groups in the side chain.
Anti head-to-head umbelliferone dimer was successfully resolved into enantiomers with high optical purities. The ring-opening polyaddition reaction of the optically active dimer with diamines proceeded very smoothly to give the corresponding, optically active polyamides. Some of them existed in ordered conformation in a solution and/or film state. The polyamides, however, unfortunately showed no chiral recognition ability, which would come from the strong hidrogen bonding between the hydroxyl group at C7 and a solute. Less
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Report
(3 results)
Research Products
(15 results)
