鈀金屬催化2,3-雙(乙炔基苯基)-1,1’-聯苯環化反應合成醋菲烯衍生物之結構分析與性質探討

Palladium-Catalyzed Annulation of 2,3-Bis(phenylethynyl)-1,1’-biphenyl: Synthesis, Structural Analysis and Properties of Acephenanthrylene Derivatives

陳柏廷(Po-Ting Chen)

指導教授 ： 徐秀福

淡江大學/理學院/化學學系碩士班/碩士(2021年)

https://doi.org/10.6846/TKU.2021.00792

摘要

本論文提出了新的合成方法，演示了鈀金屬催化2,3-雙(乙炔基苯基)-1,1’-聯苯進行環化反應，製備稠五環多環芳香烴碳氫化合物，並置備了在過去難以得到的多取代醋菲烯衍生物及其π系統延伸衍生物，其中一個雙環戊烯[cd,mn]芘為主結構之衍伸物，是第一次在溫和的反應條件下被置備，並且帶有官能基。接著我們透過晶體結構分析乙炔基的位置對於醋菲烯結構與分子堆疊的影響，並且量測其光物理性質；此外我們也合成了具有醋菲烯骨架之液晶分子，藉著醋菲烯具有π系統的平面結構作為中心硬核，外圍苯環引入氟原子與氧烷鏈作為擾動基團，得到具有作為有機半導體潛力的筒形液晶分子。

關鍵字

稠五環多環芳香烴碳氫化合物 ； 鈀催化 ； 醋菲烯 ； 液晶

並列摘要

We demonstrate the new synthetic route of cyclopentene-fused polycyclic aromatic hydrocarbons(CP-PAHs) via palladium-catalyzed annulation of bis(phenylethynyl)-1,1’-biphenyl. And prepared polysubstituted acephenanthyrlene (AP) derivatives and their π-conjugated system extended derivatives, which were difficult to obtain in the past. Notably, functionalized dicyclopenta[cd,mn]pyrene-based derivatives were synthesized under mild reaction conditions for the first time. Then, the substituent effect on crystal structure, molecule packing, and their photophysical properties were investigated. In addition, one of AP derivatives containing fluorine and alkoxy group was designed as a columnar liquid crystalline material successfully synthesized.

並列關鍵字

cyclopentene-fused polycyclic aromatic hydrocarbons ； palladium-catalyzed ； Acephenanthrylene ； liquid crystal

參考文獻

1. Necula, A.; Scott, L. T. High Temperature Behavior of Alternant and Nonalternant Polycyclic Aromatic Hydrocarbons. J. Anal. Appl. Pyrolysis 2000, 54, 65−87.

2. Lafleur, A. L.; Howard, J. B.; Plummer, E.; Taghizadeh, K.; Necula, A.; Scott, L. T.; Swallow, K. C. Identification of Some Novel Cyclopenta-Fused Polycyclic Aromatic Hydrocarbons in Ethylene Flames. Polycycl. Aromat. Compd. 1998, 12, 223−237.

3. Radenkovic, S.; Durdevic, J.; Bultinck, P. Local aromaticity of the five-membered rings in acenaphthylene derivatives. Phys. Chem. Chem. Phys. 2012, 14, 14067−14078.

4. Sarobe, M.; Jenneskens, L. W.; Kleij, A.; Petroutsa, M. Migration of Redundant Ethynyl Substituents Along Polycyclic Aromatic Hydrocarbon Peripheries. Consequences for Polycyclic Aromatic Hydrocarbon Build Up. Tetrahedron Lett. 1997, 38, 7255−7258.

5. Anthony, J. E.; Scott, J. L.; Parkin, S. R. Radical-Induced Cycloaromatization: Routes to Fluoranthenes and Acephenanthrylenes. Synlett 2004, 1, 161−164.