Elongation and Contraction of Molecular Springs. Synthesis, Structures, and Properties of Bridged [7]Thiaheterohelicenes

分子弹簧的伸长和收缩。

• 批准号: 12440179
• 负责人: TANAKA Kazuhiko
• 金额: $ 8.83万
• 依托单位: Wakayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12440179/
• 关键词: thiaheterohelicene; helical pitch; X-ray crystallography; inclusion; circular dichroism; absorption spectra; bridged helicene; unbridged helicene; ジリチオ化; 光学分割; 不斉配位子; ビス(ジフェニルホスフィノ)ヘリセン; 架橋ヘリセン; X線結晶構造解析; 超分子構造

A series of bridged [7]thiaheterohelicenes 3a-c and 4 with a variety of helical pitches have been prepared from racemic and optical pure 2, 13-bis(hydroxymethyl)dithieno[3, 2-e: 3', 2'-e']benzo[1, 2-b: 4, 3-b']bis[1]benzothiophene (1) in order to investigate the helical structures in solution. Recrystallizations of (PM)-3a, (PM)-3b, (PM)-3c, and (P)-4 from hexane-dichloromethane gave crystals suitable for X-ray crystallography, while recrystallization of (PM)-4 with benzene gave an inclusion complex with a stoichiometry of (PM-4)_4【O!R】 (C_6H_6). X-ray analyses of (PM)-3a-c, (PM-4)_4【O!R】 (C_6H_6), and (P)-4 indicate that the dihedral angles between terminal thiophene rings of the helical framework significantly vary from 22^o for 4 to 59^o for 3c. This represents as increase of 37^o or 168%. Although the ^<13>C-NMR and UV absorption spectra of bridged helicenes 3a-c and unbridged helicene 5 are essentially the same, the molar rotation of 5 is very large compared with those of 3a-c and 4. A red-shift (15nm) in the circular dichroism (CD) spectrum is observed for 4, suggesting that this compound is more planar than 3a-c in solution. In the series of [7]thiaheterohelicenes studied, the minimum helical pitch is 2.70 A^^o for 4.

由种族和光学纯2, 13-双(羟甲基)二噻吩[3, 2-e: 3', 2'-e制备了一系列具有各种螺距的桥联[7]硫杂螺烯3a-c和4 ']苯并[1, 2-b: 4, 3-b']双[1]苯并噻吩 (1) 以研究螺旋结构从己烷-二氯甲烷中重结晶(PM)-3a、(PM)-3b、(PM)-3c和(P)-4得到适合X射线晶体学的晶体，而(PM)-4重结晶。与苯生成包合物，其化学计量为(PM-4)_4【O!R】(C_6H_6)。 (PM)-3a-c、(PM-4)_4【O!R】 (C_6H_6) 和 (P)-4 表明螺旋框架末端噻吩环之间的二面角显着变化，从 22^o 到 4对于3c，这表示增加了37％或168％，尽管桥联的13C-NMR和UV吸收光谱。螺旋烯3a-c和未桥联的螺旋烯5本质上是相同的，与3a-c和4相比，5的摩尔旋转非常大。在4的圆二色性(CD)光谱中观察到红移(15nm) ，表明该化合物在溶液中比 3a-c 更平坦。在研究的 [7] 硫杂螺旋烯系列中，最小螺距为 2.70。 A^^o 为 4。

项目成果

Kazuhiko Tanaka: "Elongation and Contraction of Molecular Springs. Synthesis, Structures, and Properties of Bridged [7]Thiaheterohelicenes"Journal of Organic Chemistry. 67-6. 1795-1801 (2002)

Kazuhiko Tanaka：“分子弹簧的伸长和收缩。桥联[7]硫杂螺旋烯的合成、结构和性质”有机化学杂志。

Kazuhiko Tanaka: "Synthesis and electroluminescent applications of ortho-fused heterocyclic Compounds"Bulletin of the Chemical Society of Japan. 75. 551-557 (2002)

田中和彦：“邻位稠合杂环化合物的合成和电致发光应用”日本化学会会刊。

Kazuhiko Tanaka: "Elongation and Contraction of Molecular Springs. Synthesis, Structures, and Properties of Bridged [7] Thiaheterohelicenes"Journal of Organic Chemistry. 67. 932-933 (2002)

Kazuhiko Tanaka：“分子弹簧的伸长和收缩。桥联[7]硫杂螺烯的合成、结构和性质”有机化学杂志。

Kazuhiko Tanaka: "Synthesis and electroluminescent applications of ortho-fused heterocyclic compounds"Bulletin of the Chemical Society of Japan. 75(in press). (2002)

田中和彦：“邻位稠合杂环化合物的合成和电致发光应用”日本化学会会刊。

Kazuhiko Tanaka: "Synthesis and electroluminescent applications of ortho-fused heterocyclic Compounds"Bulletin of the Chemical Society of Japan. 75-3. 551-557 (2002)

田中和彦：“邻位稠合杂环化合物的合成和电致发光应用”日本化学会会刊。