Synthesis and Properties of Polycatenane, A Dream Polymer

理想聚合物聚链烯的合成与性能

• 批准号: 17550119
• 负责人: KIHARA Nobuhiro
• 金额: $ 2.37万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550119/
• 关键词: polycatenane; concerted cyclization; Diels-Alder reaction; ring-cleavage reaction; azo compounds; 6π pericyclic cyclization; McMurry reaction; isomerization; 協奏的環化付加重合; 高分子反応; α、β-不飽和ケトン; McMurryカップリング; トランス-シス異性化; トリエン

For the synthesis of polycatenane, the following three steps are essential : (i) the use of catenane as the monomer, (ii) cyclization by concerted reaction, and (iii) the quantitative cleavage of the bridging bonds. The utilization of 6π-pericyclic electron-cyclization reaction as the concerted cyclization reaction was investigated. McMurry coupling reaction of α,β-unsaturated ketones were carried out to prepare trienes. The trienes derived from aromatic ketones were very unstable while those derived from aliphatic ketones can be treated easily. The thermal cyclization of the resulting trienes was carried out. Although the triene in which the central double bond has the cis-configuration cyclized quantitatively, the trans-isomer remained unchanged. Therefore, the cyclization was carried out under the olefin-isomerization condition. However, irradiation by the high pressure mercury lamp or the addition of radical source caused the degradation of the triene system. The isomerization unde … More r the very mild condition is necessary to avoid the undesired reactions such as polymerization. The cleavage of the ring system obtained by the Diels-Alder reaction as the concerted cyclization reaction was investigated. The reductive cleavage of carbon-carbon single bond that has two vicinal ester groups was investigated although no cleavage was observed without the strain in the ring-system. Since the introduction of the strain to the ring-system may reduce the efficiency of the Diels-Alder reaction, such a system is unsuitable for the polycatenane synthesis. Thus, the cleavage of the ring-system obtained by the hetero Diels-Alder reaction of azo compounds as the dienophile was investigated. Although the cleavage of electron-rich nitrogen-nitrogen bonds underwent in low efficiency, the quantitative cleavage of electron-defficient nitrogen-nitrogen bond was possible. Therefore, catenane monomer must have the azodicarbonyl group that is reactive and rather unstable. To carry out the hetero Diels-Alder reaction of such catenane that can be oxidatively prepared in situ, the synthesis of macrocycle that has two 1,3-diene groups was carried out. Less

对于多产烯烷的合成，以下三个步骤至关重要：（i）将链苯二烷用作单体，（ii）通过协同反应环化，以及（iii）桥接键的定量裂解。研究了随着协同环化反应的使用，6π-周期性电子环化反应的利用。进行了α，β-不饱和酮的McMurry偶联反应，以制备Trienes。源自芳香酮的三角体非常不稳定，而从脂肪族酮衍生出的则可以轻松处理。进行了最终的三角体的热环化。尽管中央双键的三烯具有定量的顺式配置，但反异构体保持不变。因此，在烯烃异构体条件下进行环化。但是，高压汞灯的辐射或添加自由基源会导致三烯系统的降解。异构化unde…更温和的条件是避免不希望的反应，例如聚合。研究了随着协同环化反应的同时，通过Diels-Alder反应获得的环系统的裂解。研究了碳碳单键的裂解减少，该碳碳单键研究了两个阴道酯基团，尽管没有环形系统中没有菌株，但未观察到裂解。由于将应变引入环形系统可能会降低Diels-Alder反应的效率，因此这种系统不适合聚会烯烷合成。这是研究二氧化碳化合物的异氧化物alder反应获得的环形系统的裂解。尽管富含电子氮键的裂解在低效率下进行了，但电子 - 缺乏氮键的定量切割是可能的。因此，Catenane单体必须具有反应性且相当不稳定的偶氮骨基团。为了进行这种蛋白链烷的杂二烷 - alder反应，可以在原位氧化制备，将大环的合成具有两个1,3-二烯基团。较少的

项目成果

フラーレンを手術して水素を包み込む

富勒烯封闭氢气手术

• 发表时间: 2005
• 作者: Kei-ichiro Ikeshita;Nobuhiro Kihara;Akiya Ogawa;木原 伸浩;木原 伸浩;木原 伸浩;木原 伸浩;N.Kihara;木原 伸浩;N.Kihara et al.;木原 伸浩;高田 十志和 他;木原伸浩;木原 伸浩;落合 文吾;永井 大介;木原 伸浩
• 通讯作者: 木原 伸浩

ポリカテナン

多链聚糖

• 发表时间: 2006
• 作者: Kei-ichiro Ikeshita;Nobuhiro Kihara;Akiya Ogawa;木原 伸浩;木原 伸浩;木原 伸浩
• 通讯作者: 木原 伸浩

Photoinduced electron- and energy-transfer processes of [60]fullerene covalently bonded with one and …

[60]富勒烯与一个和……共价键合的光诱导电子和能量转移过程

• 发表时间: 2005
• 期刊: J. Mater. Chem. 15・23
• 作者: Hisahiro Sasabe;Nobuhiro Kihara;Kazuhiko Mizuno;Akiya Ogawa;Toshikazu Takata;N.Kihara;A.S.D.Sandanayaka
• 通讯作者: A.S.D.Sandanayaka

Photoinduced electron transfer processes in three component rotaxanes with porphyrins, [60]fullerene and triphenylamine

三组分轮烷与卟啉、[60]富勒烯和三苯胺的光诱导电子转移过程

• 发表时间: 2006
• 期刊: J. Porphyrins Phthalocyanines 10・12
• 作者: M;Sakomura;M. Sakomura;Masaru Sakomura;Y.Makita;Y.Makita;N.Kihara;N.Kihara;R.Liu;K.Ikeshita;Yoshimasa Makita;Yoshimasa Makita;Nobuhiro Kihara;Nobuhiro Kihara;Runtao Liu;Kei-ichiro Ikeshita;Y.Makita et al.;N.Kihara et al.;N.Kihara et al.;Y.Makita et al.;H.Sasabe;A.S.D.Sandanayaka;H.Sasabe et al.;M.Kajitani;Y.Tachibana;H.Sasabe
• 通讯作者: H.Sasabe

Photoinduced intramolecular electron-transfer processes in [60]fullerene-(spacer)-N,N-bis(biphenylyl)aniline dyad

[60]富勒烯-(间隔基)-N,N-双(联苯基)苯胺二元体中的光诱导分子内电子转移过程

• 发表时间: 2005
• 期刊: J. Phys. Chem. A 109・11
• 作者: Hisahiro Sasabe;Nobuhiro Kihara;Kazuhiko Mizuno;Akiya Ogawa;Toshikazu Takata;N.Kihara;A.S.D.Sandanayaka;A.S.D.Sandanayaka;N.Kihara;G.A.Rajkumar
• 通讯作者: G.A.Rajkumar