| Project/Area Number |
12440181
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Osaka Prefecture University |
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Principal Investigator |
TAKATA Toshikazu Osaka Prefecture University, Graduate School of Engineering, Professor, 工学研究科, 教授 (40179445)
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| Co-Investigator(Kenkyū-buntansha) |
FURUSHO Yoshio Osaka Prefecture University, Graduate School of Engineering, Research Associate, 工学研究科, 助手 (00281270)
KIHARA Nobuhiro Osaka Prefecture University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (30214852)
NAKANISHI Saburo Osaka Prefecture University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (40081343)
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| Project Period (FY) |
2000 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥12,400,000 (Direct Cost: ¥12,400,000)
Fiscal Year 2002: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2001: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2000: ¥6,400,000 (Direct Cost: ¥6,400,000)
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| Keywords | disulfide bonding / rotaxane synthesis / crown ether / poly[3]rotaxane / entering method / topological bonding / secondary ammonium salt / thermodynamic control / [2]ロタキサン / [3]ロタキサン / 可逆的結合-再開裂 / 熱力学的安定性 / 全平衡 / 二官能性クラウンエーテル / ポリロタキサン / 可逆的開裂 再結合 |
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| Research Abstract |
This work was to synthesize rotaxanes by utilizing reversible cleavage of disulfide linkage. During these three years, many important findings have been done. In the synthetic method, dumbbell-shaped disulfide reacts with thiol to give rise to the reversible cleavage of the disulfid bond during which wheel molecule slips into the disulfide bond to yield the corresponding rotaxane. One of the purposes of this work was to complete the synthetic method and the method was actually useful in the syntheses of many [2] and [3]rotaxanes in high yields. The highest yield reached 95% via precise thermodynamic control. We have named mis method "entering method".
Meanwhile, in the case of [2]rotaxane obtained which has two annmonium groups one of which was covered with crown ether wheel, the wheel componet can move freely from one ammonium moiety to another one when some conditions are fulfilled, that is known as "shuttling". Effect of substituents on the crwon ether wheel was studied by ^1H NMR method, and the shuffling rate was enhanced as the electron-donating power of the substituents increased. As an application of the synthetic method to the synthesis of polyrotaxane, poly[3]rotaxane was synthesized with bifunctional ammonium salt and crwon ether. As a result, first ply[3]rotaxane with MW 30000 was obtained only by mixing the two bifunctional components in the presence of a catalytic amount of thiophenol. The poryrotaxane had topotogical lilnkages as the linking structure of the monomer units, while the poly[3]rotaxane thus prepared was the first topological polymer.
The novel synthetic method "entering method" was completed through the work which enabled the high yield syntheses of [2] and [3] rotaxanes, and the first topological polymer was obtained by applying die method to the bifunctional monomers.
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