1985 Fiscal Year Final Research Report Summary
Synthesis of Optically Active Polyamides and Their Application as Stationary Phases for Optical Resolution
| Project/Area Number |
59850147
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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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 |
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| Project Period (FY) |
1984 – 1985
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| Keywords | Optically active anti head-to-head coumarin dimer / Optically active 1,2-diphenylethylenediamine / Optically active polyamides / Optical resolution / CD spectrum / Ordered conformation / Optically active stationary phases for optical resolution / 開環重付加 |
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| Research Abstract |
To obtain the useful components for the synthesis of optically active polyamides, we developed for the first time a method for the optical resolution of anti head-to-head coumarin dimer. Moreover, a new and efficient method for the optical resolution of 1,2-diphenylethylenediamine was achieved.
Optically active anti head-to-head coumarin dimer easily reacted with various kinds of diamines to give optically active polyamides by ring-opening polyaddition. On the basis of CD spectral studies, it was suggested that some of these polyamides exsist in an ordered conformation in a solution depending on the rigidity and conjugatability of the diamine components. For examples, optically active polyamide consisting of flexible hexamethylenediamine component exists in a random conformation in solutions although that consisting of rigid and conjugatable 1,4-phenylenediamine component exists in an ordered conformation in basic media.
These optically active polyamides were coated on the silica gel, pr
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etreated with diphenylsilane coupler, to prepare columns for high-performance liquid chromatographic resolution of racemates. The polyamide having hexamethylenediamine or 1,4-phenylenediamine component showed high ability for the optical resolution of racemates. The CD spectral sudies of the polyamides in film state indicated that the chiral recognition ability depends strongly on the simultanious interaction between the polyamide and the solute and/or on the ordered conformation of the polyamide.
The low temperature solution polymerization of 1,2-diphenylethylenediamine with dicarbonyl chlorides proceeded smoothly to give the corresponding optically active polyamides. The polyamides having aromatic dicarboxylic acid component showed higher ability for chiral recognition than those having aliphatic dicarboxylic acid component. The reason is considered as follows: The polyamides consisting of aromatic dicarboxylic acid component have a similar key structure to pirkle type, which is well-known to be effective as an optically active stationary phase, in the repeating units. Moreover, high-ordered comformation would contribute the high ability.
It is concluded that the results in this work offer important informations for the development of high-performance and wide-applicable optically active stationary phases for optical resolution. Less
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