Synthesis and Properties of New Macrocyclic Conjugated Compounds

• Project/Area Number: 05453029
• Research Category: Grant-in-Aid for General Scientific Research (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Toyama University
• Principal Investigator: OJIMA Juro Department of Chemistry, Faculty of Science Toyama University Professor, 理学部, 教授 (00018988)
• Co-Investigator(Kenkyū-buntansha): HIGUCHI Hiroyuki Department of Chemistry, Faculty of Science Toyama University Associate Professo, 理学部, 助教授 (00165094)
• Project Period (FY): 1993 – 1994
• Project Status: Completed (Fiscal Year 1994)
• Budget Amount: ¥7,500,000 (Direct Cost: ¥7,500,000); Fiscal Year 1994: ¥2,000,000 (Direct Cost: ¥2,000,000); Fiscal Year 1993: ¥5,500,000 (Direct Cost: ¥5,500,000)
• Keywords: Nonbenzenoid Aromatics / Annulenedione / Ring Current Effect / Macrocycles / Conjugation

Research Abstract

Several new systems of macrocyclic conjugated compounds have been synthesized and their properties were examined.
In compounds (1) and (2) several annulenediones showed ring current effect under acidic conditions. Compounds (3) showed diatropicity under both neutral and acidic conditions, and their diatropicities proved to increase with increasing ring size.
In compound (4), the fused azulene ring reduecd the diatropicity of the 14pi-electron annulene of compound (4), but did not reduce the paratropicity of the 16pi-electron annulene of compound (5).

Research Products

• [Publications] Hiroyuki Higuchi: "Annelated Dehydroannulenes Fused with Azulene Ring.The Synthesie of Bisdehydro[14]-and-[16]annuleno[a]azulene" Tetrahedron Lett.35. 1259-1262 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masahiko Iyoda: "Synthesis and Properties of a Bisdehydro[14]annuleno[c]furan and an Ortho-Annelated Tetrakisdehydro[14]annuleno[14]annulene" Bull.Chem.Soc.Jpn.67. 778-791 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Annelated Dehydroannulenes Fused with Azulene.Synthesis and Properties of Tetradehydro[14]-and-[16]annuleno[a]azulenes" J.Chem.Soc.,Perkin Trans.I. 1167-1177 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Formation of a Paratropic,Dicationic 24π-Electron System in D_2SO_4" J.Chem.Soc.,Chem.Commun.877-878 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Syntheses and Properties of Methano Bridged Dichlorodidehydro-[16]-,-[20]-and-[24]annulenediones" J.Chem.Soc.,Perkin Trans.I. 1453-1468 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of Methano-bridged Tetradehydro[22]annulenedione21GC06:J.Chem.Soc.,Perkin Trans.I" 1579-1587 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of Tetramethyloctadehydro-[26]-,-[28]-,-[30]-,-[32]-and-[34]annulenediones" J.Chem.Soc.,Perkin Trans.I. 1957-1968 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Unusual Formation of Tricyclic Annulenediones.Diatropic Cationic 10π-Electron Species in D_2SO_4" J.Chem.Soc.,Perkin Trans.I. 2915-2920 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Gaku Yamamoto: "Stereodynamics of N-Benzyl-N-methyl-9-aminotriptycene" Chem.Lett.1911-1914 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of a Bismethano-bridged Bisdehydro[21]-annulenone.Conformation in Solution and in the Crystalline State" Chem.Lett.2291-2294 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hiroyuki Higuchi: "Annelated Dehydroannulenes Fused with Azulene Ring. The Synthesis of Bisdehydro [14] - and - [16] annuleno [a] azulene" Tetrahedron Lett.35. 1259-1262 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Masahiko Iyoda: "Synthesis and Properties of a Bisdehydro [14] annuleno [c] furan and an Ortho-Annelated Tetrakisdehydro [14] annuleno [14] annulene" Bull.Chem.Soc.Jpn.67. 778-791 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Annelated Dehydroannulenes Fused with Azulene. Synthesis and Properties of Tetradehydro [14] - and - [16] annuleno [a] azulenes" J.Chem.Soc., Perkin Trans.I. 1167-1177 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Formation of a Paratropic, Dicationic 24pi-Electron System in D_2SO_4" J.Chem.Soc., Chem.Commun.877-878 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Syntheses and Properties of Methano Bridged Dichlorodidehydro- [16] -, - [20] - and - [24] annulenediones" J.Chem.Soc., Perkin Trans.I. 1453-1468 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of Methano-bridged Tetradehydro [22] - annulenedione" J.Chem.Soc., Perkin Trans.I. 1579-1587 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of Tetramethyloctadehydro- [26] -, - [28] -, - [30] -, - [32] - and - [34] annulenediones" J.Chem.Soc., Perkin Trans.I. 1957-1968 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Unusual Formation of Tricyclic Annulenediones. Diatropic Cationic 10pi-Electron Species in D_2SO_4" J.Chem.Soc., Perkin Trans.I. 2915-2920 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Gaku Yamamoto: "Stereodynamics of N-Benzyl-N-methyl-9-aminotriptycene" Chem.Lett.1911-1914 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of a Bismethano-bridged Bisdehydro - [21] annulenone. Conformation in Solution and in the Crystalline State" Chem.Lett.2291-2294 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi: "Annelated Dehydroannulenes Fused with Azulene Ring.The Synthesis of Bisdehydro[14]-and-[16]annuleno[a]azulene" Tetrahedron Lett.35. 1259-1262 (1994)
• [Publications] Masahiko Iyoda: "Synthesis and Properties of a Bisdchydro[14]annulcno[c]furan and an Ortho-Annelated Tetrakisdchydro[14]annuleno[14]annulene" Bull.Chem.Soc.Jpn.67. 778-791 (1994)
• [Publications] Hiroyuki Higuchi: "Annelated Dchydroannulenes Fused with Azulcne.Synthcsis and Properties of Tetrasdehydro[14]-and-[16]annulcno[a]azulcnes" J.Chem.Soc.,Perkin Trans.I. 1167-1177 (1994)
• [Publications] Hiroyuki Higuchi: "Formation of a Paratropic,Dicationic 24π-Electron System in D_2SO_4" J.Chem.Soc.,Chem.Commun.877-878 (1994)
• [Publications] Hiroyuki Higuchi: "Syntheses and Properties of Methano Bridged Dichlorodidehydro-[16]-,[20]-and-[24]-annulenediones" J.Chem.Soc.,Perkin Trans.I. 1453-1468 (1994)
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of Methano-bridged Tetradchydro[22]annulenedione" J.Chem.Soc.,Perkin Trans.I. 1579-1587 (1994)
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of Tetramethyloctadehydro-[26]-,-[28]-,-[30]-,-[32]-and-[34]-annulenediones" J.Chem.Soc.,Perkin Trans.I. 1957-1968 (1994)
• [Publications] Hiroyuki Higuchi: "Unusual Formation of Tricyclic Annulenediones.Diatropic Cationic 10π-Electron Species in D_2SO_4" J.Chem.Soc.,Perkin Trans.I. 2915-2920 (1994)
• [Publications] Caku Yamamoto: "Stereodynamics of N-Benzyl-N-methy1-9-aminotriptycene" Chem.Lett.1911-1914 (1994)
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of a Bismethano-bridged Bisdehydro[21]annulenone.Conformation in Solution and in the Crystalline State" Chem.Lett.2291-2294 (1994)
• [Publications] Hiroyuki Higuchi: "Synthesis of Methano-Bridged Tetradehydroaza[22]annulene and the Related Compounds" J.Chem.Soc.,Perkin Trans.I. 975-982 (1993)
• [Publications] Hiroyuki Higuchi: "Synthesis of Methano-bridged Tetradehydro[36]annulene" J.Chem.Soc.,Perkin Trans.I. 983-986 (1993)
• [Publications] Gaku Yamamoto: "Unusual Formation of a Methano-Bridged Didehydro[20]annulenedione.A Highly Diatropic,Dicationic 18π-Electron Species in D_2SO_4." J.Chem.Soc.,Chem.Commun.698-699 (1993)
• [Publications] Hiroyuki Higuchi: "Synthesis of Dibenzotrisdehydro[16]annulene-1,4-dione and the Related Compounds." Bull.Chem.Soc.Jpn.66. 2323-2329 (1993)
• [Publications] Hiroyuki Higuchi: "Annelated Dehydroannulenes with Azulene Ring.The Synthesis of Bisdehydro[14]-and-[16]annuleno[a]azulene." Tetrahedron Lett.35(印刷中). (1994)
• [Publications] Masahiko Iyoda: "Synthesis and Properties of a Bisdehydro[14]annuleno[c]furan and Ortho-Annelated Tetrakisdehydro[14]annuleno[14]annulene." Bull.Chem.Soc.Jpn.67(印刷中). (1994)
• [Publications] Hiroyuki Higuchi: "Annelated Dehydroannulenes Fused with Azulene.Synthesis and Properties of Tetrakisdehydro[14]-and-[16]annuleno[a]azulene." J.Chem.Soc.,Perkin Trans.I. (印刷中). (1994)
• [Publications] Hiroyuki Higuchi: "Synthesis and Properties of Methano-Bridged Dichlorodidehydro[16]-,-[20]-,and-[26]annulenediones." J.Chem.Soc.,Perkin Trans.I. (印刷中). (1994)