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

• Project/Area Number: 03453030
• Research Category: Grant-in-Aid for General Scientific Research (B)
• Allocation Type: Single-year Grants
• Research Field: 有機化学一般
• Research Institution: KYUSHU UNIVERSITY
• Principal Investigator: INAZU Takahiko Kyushu University Faculty of Science Department of Chemistry Professor, 理学部, 教授 (60037207)
• Co-Investigator(Kenkyū-buntansha): TAKEMURA Hiroyuki Kyushu University College of General Education Research Associate, 教養部, 助手 (60183456) ; SUENAGA Masahiko Kyushu University Faculty of Science Department of Chemistry Research Associate, 理学部, 助手 (70216274) ; SHINMYOZU Teruo Kyushu University Institute for Molecular Science Associate Professor, 助教授 (90037292)
• Project Period (FY): 1991 – 1992
• Project Status: Completed (Fiscal Year 1992)
• Budget Amount: ¥7,000,000 (Direct Cost: ¥7,000,000); Fiscal Year 1992: ¥900,000 (Direct Cost: ¥900,000); Fiscal Year 1991: ¥6,100,000 (Direct Cost: ¥6,100,000)
• Keywords: 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

Research Abstract

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.

Research Products

• [Publications] 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)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 新名主 輝男: "Synthesis of[3.3.3.3](1,2,3,5)-and(1,2,4,5)Cyclophanes" Chem.Ber.
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 新名主 輝男: "A Simple Synthetic Method of Tetraaza[3.3.3.3]meta-and para-cyclophanes by Alkylation of N-Substituted Trifluoroacetamide" Synthesis.
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 新名主 輝男: "Synthesis and Transannular π-π Interaction of[3.3]Cyclophanes Containing 1,6-Methano[10]annulene" J.Org.Chem.
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] 新名主 輝男: "Synthesis and X-ray Structure Determination of anti-[3.3]Meta-cyclophane Quihydrone Dimethyl Ether" J.Org.Chem.
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Katsuya Sako, Hiroyuki Takemura, Masahiko Suenaga, Teruo Shinmyozu, and Takahiko Inazu: "A Conformational Study of [3.3]Metacyclophane through Variable Temperature 'H NMR and Optical Rotation" J.Org.Chem.57. 6536-6541 (1992)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 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.
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Teruo Shinmyozu, Nobihiko Shibakawa, Kenichi Sugimoto, Hiroko Sakane, Hiroyuki Takemura, and Takahiko Inazu: "A Simple Synthetic Method of Tetraaza[3.3.3.3]meta-and para-cyclophanes by Alkylation of N-Substituted Trifluoroacetamide" Synthesis.
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 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.
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Teruo Shinmyozu, Takafumi Hirakawa, and Takahiko Inazu: "Synthesis and X-ray Structure Determination of anti-[3.3]Meta-cyclophane Quihydrone Dimethyl Ether" J.Org.Chem.
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] 迫 克也: "A Conformational Study of[3.3]Metacyclophanes through Variable-Temperature ^1HNMR and Optical Rotation" J.Org.Chem.57. 6536-6541 (1992)
• [Publications] 新名主 輝男: "Synthesis of [3_4](1,2,3,5)-and(1,2,4,5)Cyclophanes" Chem.Ber.
• [Publications] 新名主 輝男: "A Simple Synthetic Method of Tetraaza[3.3.3.3]meta- and para-cyclophanes by Alkylation of N-Substituted Trifluoroacetamide" Synthesis.
• [Publications] 迫 克也: "A Conformational Study of[3.3]Metacyclophane through Variable Temperature ^1H NMR Method and Optical Rotation" J.Org.Chem.
• [Publications] 迫 克也: "A Conformational Study of[3.3](2,6)Pyridinophanes by Dynamic NMR Method" J.Org.Chem.
• [Publications] 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.
• [Publications] 新名主 輝男: "Synthesis of 2,16ーDiaza[3.3](2,7)(1,6ーmethano[10]annuleno)phanes" Angew,Chem,Int.Ed.Engl.
• [Publications] 新名主 輝男: "Synthesis and Transannular piーpi Interaction of[3.3]Cyclopanes Containing 1,6ーMethano[10]annulenes"
• [Publications] 新名主 輝男: "Synthesis of Novel cyclophane Host Molecules Constructed with[3.3]Metacyclophane Units"