Transannular pi-pi Interaction of (4n)pi Systems

(4n)pi 系统的跨环 pi-pi 相互作用

• 批准号: 03453030
• 负责人: INAZU Takahiko
• 金额: $ 4.48万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453030/
• 关键词: Transannular pi-pi Interaction; annulenophane; anti-aromatic compound; cyclophane; annulene; aromatic compound; semi-empirical molecular orbital calculation; MOPAC; 渡環πーπ相互作用; シアナミド; 1,6ーメタノ[10]アヌレン

It is our interest to study how two pi-systems mutually interact when they overlap each other in a close proximity. According to the frontier molecular orbital calculations, Greenberg et al. predicted a destabilizing pi-pi interaction in a (4n+2)pi-(4n+2)pi system, a stabilizing interaction in a (4n+2)pi-(4n)pi system, and greater stabilization in a (4n)pi-(4n)pi system than in the (4n+2)pi-(4n)pi system. To verify this interesting prediction experimentally, we considered that [3.3]annulenophanes must be the most suitable models since [3.3]cyclophane permits exact evaluation of pi-pi interaction without interference of the strain effect.As model compounds for the study of (4n+2)(4n+2)interaction (n*2), we synthesized [3.3]cyclophanes containing Vogel's 1,6-methano[10]annulene, which are the first example of [m.n]cyclophanes containing two annulene rings. The synthesis of double-layered annulenophanes containing trans-15,16-dimethyl-dihydropyrene units (14pi) and Paudler's 8b,8c-diazacyclopent[fg]acenaphthylene (12pi) is in progress. The structures and transannular pi-pi interactions of annuleno-phanes were studies based on the spectral properties and theoretical calculations by the MNDO-PM3 method.

我们的兴趣是研究两个 pi 系统在彼此靠近重叠时如何相互作用。根据前沿分子轨道计算，Greenberg 等人。预测了 (4n+2)pi-(4n+2)pi 系统中的不稳定 pi-pi 相互作用、(4n+2)pi-(4n)pi 系统中的稳定相互作用以及 (4n)pi-(4n)pi 系统中比 (4n+2)pi-(4n)pi 系统中更高的稳定性。为了通过实验验证这一有趣的预测，我们认为[3.3]环烷一定是最合适的模型，因为[3.3]环烷可以在不干扰应变效应的情况下精确评估π-π相互作用。作为研究(4n+2)(4n+2)相互作用(n*2)的模型化合物，我们合成了含有Vogel's的[3.3]环烷 1,6-亚甲基[10]轮烯，这是含有两个轮烯环的[m.n]环烷的第一个例子。含有反式 15,16-二甲基-二氢芘单元 (14pi) 和 Paudler 的 8b,8c-二氮杂环戊二烯[fg]苊 (12pi) 的双层环烷的合成正在进行中。基于MNDO-PM3方法的光谱特性和理论计算，研究了环烯的结构和跨环pi-pi相互作用。

项目成果

Teruo Shinmyozu, Shirou Kusumoto, Sachiyo Nomura, Haruo Kawase, and Takahiko Inazu: "Synthesis of [3.3.3.3](1,2,3,5)-and(1,2,4,5)Cyclophanes" Chem.Ber.

Teruo Shinmyozu、Shirou Kusumoto、Sachiyo Nomura、Haruo Kawase 和 Takahiko Inazu：“[3.3.3.3](1,2,3,5)-和(1,2,4,5)Cyclophanes 的合成”Chem.Ber。

新名主 輝男: "Synthesis of[3_4](1,2,3,5)ーand(1,2,4,5)Cyclophanes" Angew.Chem.Int.Ed.Engl.

Teruo Shinmeishu：“[3_4](1,2,3,5)ー和(1,2,4,5)Cyclophanes的合成” Angew.Chem.Int.Ed.Engl。

Teruo Shinmyozu, Tomonori Matsunaga, Takahiko Inazu, Jerzy M.Rudzinski, and Mayumi Matsushita: "Synthesis and Transannular pi-pi Interaction of [3.3]Cyclophanes Containing 1,6-Methano[10]annulene" J.Org.Chem., submitted.

Teruo Shinmyozu、Tomonori Matsunaga、Takahiko Inazu、Jerzy M.Rudzinski 和 Mayumi Matsushita：“含有 1,6-Methano[10]annulene 的 [3.3]Cyclophanes 的合成和跨环 pi-pi 相互作用”，提交给 J.Org.Chem.

迫 克也: "A Conformational Study of [3.3]Metacyclophane through Variable Temperature ^1H NMR and Optical Rotation" J.Org Chem.57. 6536-6541 (1992)

Katsuya Sako：“通过变温 ^1H NMR 和旋光进行 [3.3]Metacyclophane 的构象研究”J.Org Chem.57 (1992)。

新名主 輝男: "Synthesis of[3.3.3.3](1,2,3,5)-and(1,2,4,5)Cyclophanes" Chem.Ber.

Teruo Shinmeishu：“[3.3.3.3](1,2,3,5)-和(1,2,4,5)环芳烃的合成”Chem.Ber。