Reaction and Electronic Properties of Novel Aromatic Seven-membered Heterocyclic Cation

• Project/Area Number: 20550044
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Okayama University
• Principal Investigator: SATAKE Kyousuke Okayama University, アドミッションセンター, 教授 (50033387)
• Project Period (FY): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000); Fiscal Year 2010: ¥520,000 (Direct Cost: ¥400,000、Indirect Cost: ¥120,000); Fiscal Year 2009: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2008: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 反応有機化学 / 2H-アゼピン / 3H-アゼピン / 非局在化陽イオン / π電子共役系 / 芳香族性 / 非ベンゼン系芳香族化合物 / アゼピニウムイオン / アザトロピリウムイオン / 芳香属性 / ab initio計算 / 開環加水分解反応 / フェニルナイトレン / アゼピニウム イオン / アザトロピリウム イオン / 芳香族陽イオン / 臭素化 / 非経験的分子軌道計算 / ab-initio計算

Research Abstract

Synthesis of hitherto unknown azepiniumu ion was obtained by demethoxylation of 2-methoxy-2H-azepine derivatives which are prepared from 3H-azepines. Theoretical calculations based on B3LYP/6-31G* levels and NMR spectroscopic data supported that the ion must be an delocalized aromatic cation. Additionally, the experimental data to confirm the mechanism of intramolecular ring-enlargement reaction of phenylnitrene were obtained.

Research Products

• [Journal Article] Steric Effect on the Formation of 3H-Azepine Derivatives from o-Alkyl- phenylnitrene and Alcohol as a Nucleophilic Media (2011)
  • Author(s): Siti Mariyah Ulfa, Hideki Okamoto, Kyosuke Satake
  • Journal Title: Heterocycles 83(6) Pages: 1259-1265
  • Peer Reviewed
• [Journal Article] Facile Synthesis of Picene from 1,2-Di-(1-naphthyl)ethane by 9-Fluorenone-Sensitized Photolysis (2011)
  • Author(s): Hideki Okamoto, Minoru Yamaji, Shin Gohda, Yoshihiro Kubozono, Noriko Komura, Kaori Sato, Hisako Sugino, Kyosuke Satake
  • Journal Title: Org.Lett. 13(10) Pages: 2758-2761
  • Peer Reviewed
• [Journal Article] Facile Synthesis of Picene from 1,2-Di (1-naphthyl)ethane by 9-Fluorenone-Sensitized Photolysis (2011)
  • Author(s): Hideki Okamoto, 他
  • Journal Title: Organic Letters Volume: 13 Pages: 2758-2761
  • Peer Reviewed
• [Journal Article] Fluorescence Response of a 4-Trifluoro- acetylaminophthalimide to Iodide Ions upon 254 nm Irradiation in MeCN (2008)
  • Author(s): Hideki Okamoto, Hhiroyuki Konishi, Mami Kohno, Kyosuke Satake
  • Journal Title: Org. Lett. 10 Pages: 3125-3128
  • Peer Reviewed
• [Journal Article] Photochemistry of nitrogen-bridged cyclophanes : 2, 11-diaza[32]anthra-cenoparacyclophane and 2, 11-diaza[32]paracyclophane systems (2008)
  • Author(s): H. Okamoto, M. Yamaji, K. Satake
  • Journal Title: Synlett Pages: 1931-1945
  • Peer Reviewed
• [Journal Article] Fluorescence Response of a 4-Trifluoroacetylaminophthalimide to Iodide Ions upon 254 nm Irradiation in MeCN (2008)
  • Author(s): H. Okamoto, H. Konishi, M. Kohno, K. Satake
  • Journal Title: Organic Letters 10 Pages: 3125-3128
  • Peer Reviewed
• [Journal Article] A convenient synthesis of trifluoroacetamide derivatives of diaza[32]cyclophanes and triaza[33]cyclophanes (2008)
  • Author(s): H. Okamoto, H. Takemura, K. Satake
  • Journal Title: Synthesis Pages: 39-44
  • Peer Reviewed
• [Presentation] アミンおよびアルコール存在下でのo-アルキルフェニルナイトレンの反応における温度依存性 (2011)
  • Author(s): Siti Mariyah Ulfa, 他
  • Organizer: 第91日本化学会春季年会
  • Place of Presentation: 神奈川大学横浜キャンパス
  • Year and Date: 2011-03-28
• [Presentation] ジピコリルアミノレセプターで修飾されたアントラセンジカルボン酸類緑体をルミノフォアとして用いるPETプローブの構築と発光特性 (2011)
  • Author(s): 岡本秀毅, 他
  • Organizer: 第91日本化学会春季年会
  • Place of Presentation: 神奈川大学横浜キャンパス
  • Year and Date: 2011-03-28
• [Presentation] Photo- and thermal reaction of 2-alkoxy and 2-alkylthio 2H-azepines (2010)
  • Author(s): 安達希美, 他
  • Organizer: 環太平洋化学会議(PACIFICHEM2010)
  • Place of Presentation: Honolulu
  • Year and Date: 2010-12-17
• [Presentation] Steric Effect on the Formation of 3H-Azepine Derivatives from o-Phenylnitrene and Alcohol as a Nucleophic Media (2010)
  • Author(s): Siti Mariyah Ulfa, 他
  • Organizer: 環太平洋化学会議(PACIFICHEM2010)
  • Place of Presentation: Honolulu
  • Year and Date: 2010-12-17
• [Presentation] Photo- and thermal reaction of 2-alkoxy and 2-alkylthio 2H-azepines (2010)
  • Author(s): Nozomi Adachi, 他
  • Organizer: 環太平洋化学会議(PACIFICHEM2010)
  • Place of Presentation: Honolulu(米・ハワイ州)
  • Year and Date: 2010-12-17
• [Presentation] Steric Effect on the Formation of 3H-Azepine Derivatives from o-Phenylnitrene and Alcohol as a Nucleophic Media (2010)
  • Author(s): Siti Mariyah Ulfa, 他
  • Organizer: 環太平洋化学会議(PACIFICHEM2010)
  • Place of Presentation: Honolulu(米・ハワイ州)
  • Year and Date: 2010-12-17
• [Presentation] Synthesis and Conformational Analysis of 3-Methyl-3H- Azepine Derivatives Based on NMR Spectra and An Initio Calculation (2010)
  • Author(s): Siti Mariyah Ulfa, 他
  • Organizer: 2010年日本化学会西日本大会
  • Place of Presentation: 熊本大学(黒髪キャンパス)
  • Year and Date: 2010-11-07
• [Presentation] Synthesis and Conformational Analysis of 3-Methyl-3H-Azepine Derivatives Based on NMR Spectra and An Initio Calculation (2010)
  • Author(s): Siti Mariyah Ulfa, 他
  • Organizer: 2010年 日本化学会西日本大会
  • Place of Presentation: 熊本大学(黒髪キャンパス)
  • Year and Date: 2010-11-07
• [Presentation] 2-置換-2H-アゼピン誘導体の光および熱反応性 (2010)
  • Author(s): 安達希美, 他
  • Organizer: 2010年 日本化学会西日本大会
  • Place of Presentation: 熊本大学(黒髪キャンパス)
  • Year and Date: 2010-11-06
• [Presentation] ニトロベンゼン誘導体から5-ホルミルペンタジエン酸の簡便合成法の開発 (2010)
  • Author(s): 菊池恭兵, 他
  • Organizer: 2010年日本化学会西日本大会
  • Place of Presentation: 熊本大学(黒髪キャンパス)
  • Year and Date: 2010-11-06
• [Presentation] ニトロベンゼン誘導体から5-ホルミルペンタジエン酸の簡便合成法の開発 (2010)
  • Author(s): 菊池恭兵, 他
  • Organizer: 2010年 日本化学会西日本大会
  • Place of Presentation: 熊本大学(黒髪キャンパス)
  • Year and Date: 2010-11-06
• [Presentation] フェニルニトレンから誘導されるデヒドロアゼピンとアルコールの反応の立体効果 (2009)
  • Author(s): 佐竹恭介, 他
  • Organizer: 第39回複素環化学討論会
  • Place of Presentation: 千葉県柏市
  • Year and Date: 2009-10-15
• [Presentation] FRIEDEL-CRAFTS REACTION of DELOCALIZED AZEPINIUM IONS WITH BENZENE AND FIVE-MEMBERED AROMATIC HETEROCYCLES (2008)
  • Author(s): 佐竹恭介, 他
  • Organizer: 23th European Colloquium on Heterocyclic Chemistry
  • Place of Presentation: アントワープ(ベルギー)
  • Year and Date: 2008-09-11
• [Presentation] FRIEDEL-CRAFTS REACTION of DELOCALIZED AZEPINIUM IONS WITH BENZENE AND FIVE-MEMBERED AROMATIC HETEROCYCLES (2008)
  • Author(s): K. Satake, C. Cordonier, Y. Kubota, Y. Sasaki, H. Okamoto
  • Organizer: 23th European Colloquium on Heterocyolio Chemistry
  • Place of Presentation: アントワープ(ベルギー)
  • Year and Date: 2008-09-11
• [Remarks] ホームページ等
  • URL: http://chem.okayama-u.ac.jp/staff/detail/kyosuke-satake.html