1996 Fiscal Year Annual Research Report

第13回IUPAC物理有機化学国際会議部会「反応中間体の化学」に関する研究

Research Project

Project/Area Number	08354013
Research Institution	University of Tsukuba
Principal Investigator	安藤亘筑波大学, 化学系, 教授 (30008429)
Co-Investigator(Kenkyū-buntansha)	小田雅司大阪大学, 理学部, 教授 (60004438) 奥彬東京工芸繊維大学, 工芸学部, 教授 (50027885) 伊與田正彦東京都立大学, 理学部, 教授 (50115995) 井畑敏一大阪大学, 理学部, 教授 (80029644) 古川尚道筑波大学, 化学系, 教授 (80015966)
Keywords	反応中間体 / 2価活性種 / イリド / 電子移動 / ケテン / ヘテロ原子多重結合
Research Abstract	「反応中間体の化学」をテーマとした物理有機化学の国際会議が、筑波大学、大学会館で、招待外国人14人、招待日本人15人と一般参加者69人の参加を得て開催された。講演は(1)新しい異常原子価反応活性種の創製とその物理化学的性質、(2)反応中間体の生成とその化学的挙動、(3)異常な電荷やπ-共役系を有する反応中間体の生成を中心として、特別講演10件、口頭発表21件、ポスター発表42件あった。この会議では、反応中間体の生成として、極限条件下、特に真空超高温、極低温マトリックス中での光反応を利用してのカルベン、シリレン、ゲルミレン、セルニレン等の原子欠損型の中間体についての研究から論じられ、その構造や反応性に興味ある報告がなされた。また反応中間体の速度論的研究が検討され、その結合状態に新しい知見を与えている。一方、ラジカルイオン種の生成が電子移動の反応を通して検討され、ヘテロ原子の特性を利用した新しいπ-電子系の構築による、新規機能材料の開発で興味ある結果が報告された。現在活性分子には高歪みや反芳香族性、原子欠損型分子などいろいろあるが、なかでも14属元素を含む活性種は最も注目され、そのせいかもめざましいものがる。ジシラシクロペンの光、および熱によるジシラベンズヴァレンへの異性化、ケイ素の3重結合の理論的考察、またフラーレンを中心とするケイ素化合物の生成など、新しい活性種がみられている。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] H.Ohgaki, W.Ando: "Stereospecific Insertion of Germylene into the Vinyl Chloride bond" J.Organomet.Chem.521. 387-389 (1996)
[Publications] N.Furukawa, T.Nakahodo, H.Fujihara: "Preparation and crystal structure of a new tetracordinated cyclic selenurane with two unsymmetrieal anicl ligands of oxygen" Chem.Commun.311-312 (1996)
[Publications] K.Kobayashi, S.Nagase,T.Akasaka: "Endohedral Dimetallofullerenes Sc2@C84and La2@C80.Are the Metal atoms Still inside the Fullrerene cages?" Chem.Phys.Lett.261. 502-506 (1996)
[Publications] T.Suzuki,J.Nishida,T.Tsuji: "Hexaphenylethane Derivatives Exhibiting Novel Electrochromic Behavior" Angew.Chem.Int.Ed.Engl.36(in press). (1997)
[Publications] K.Isgiguro,et al.: "Redox Reaction of Belzyl Radicals with Aromatic Radical Ions.Photogenerated" J.Am.Chem.Soc.118.31. 7255-7264 (1996)
[Publications] J.Nakayama: "Reactions of Benzyne with 1,3-Benzodithiole-2-thione and Related Compounds:Formation of Novel Tetracvclic Sulfonium Salts" Bull.Chem.Soc.Jpn.69.8. 2349-2354 (1996)
[Publications] T.Kawase,H.R.Darabi,M.Oda: "Cyclic 6- and 8 Paraphenylacetylenes." Angew.Chem.108. 2803-2805 (1996)
[Publications] Y.Kohno,K.Narasaka: "Synthesis of (±)-Stemonamide by the Application of Oxidative Coupling Reaction of Stannyl Compounds with Silyl Enol Ethers" Bull.Chem.Soc.Jpn. 69. 2063-2070 (1996)
[Publications] L.Zhao,H.Matsuyama,M.Iyoda: "N,N-Dialkylation of Aminocarbene Complexes under Phse-Transfer Conditions" Chem.Lett.827-828 (1996)
[Publications] T.Ibata,M.Himori,K.Fukushima,H.Suga,H.Nakano: "Regioselectivity and Relativity of Ylide Formation in the Reaction of Ketocarbenoid with Hetero-cumulenes" Heterocyclic Comm.2. 87-90 (1996)
[Publications] M.Kira,T.Iwamoto,C.Kabuto: "The first stable cyclic disilene:hexakis(trialkylsilyl)tetrasilacyclobutene" J.Am.Chem.Soc.118.42. 10303-10304 (1996)
[Publications] N.Komiya,T.Naota,Y.Oda,S.Murahashi: "Aerobic Oxidations of Alkanes and Alkenes in the Presence of Aldehydes Catalysed by Copper and Copper-Crown Ether" J.Mol.Catal A:Chemical. (in press).
[Publications] K.Goto,M.Holler,R.Okazaki: "Synthesis,Structure,and Reactions of a Sulfenic Acid Bearing a Novel Bowl-type Substituent:The First Synthesis of a Stable" J.Am.Chem.Soc.119(in press). (1997)
[Publications] N.Takeda,H.Suzuki,N.Tokitoh,R.Okazaki,S.Nagase: "Reaction of a Sterically Hindered Silylene with Isocyanides:The First Stable Silylene-Lewis Base Complex" J.Am.Chem.Soc.119(in press). (1997)
[Publications] T.Okazaki,H.Isobe,T.Kitagawa,K.Takeuchi: "Generation and Reactions of 2-(1-Adamantyl)admantene.Rearrangement to 3-(1-Adamantyl)-4-protoadamantylendene" Bull.Chem.Soc.Jpn.69.7. 2053-2062 (1996)
[Publications] H.Tomioka,M.Hattori,K.Hirai,S.Murata: "Anomalous Effects of Para Substituents on the Stability of Sterically Congested Triplet Diarylcarbenes" J.Am.Chem.Soc.118.36. 8723-8724 (1996)
[Publications] A.Sekiguchi,M.Nanjo,C.Kabuto,H.Sakurai: "[Me(PhMe_2Si)_2SiLi]and[Ph(Me_3Si)_2Li]:Preparation,Characterization and Evidence for an Intramolecular Li-Ph Interaction" Amgew.Chem.Int.Ed.Engl.36. 113-115 (1997)
[Publications] A.Oku,T.Harada,T.Katsuhira,H.Wada,A.Osada: "Design of[1,n]-ambiphiles based on zincate carbenoid chmistry" Pure & Appl.Chem.68.3. 649-652 (1996)

1996 Fiscal Year Annual Research Report

第13回IUPAC物理有機化学国際会議部会「反応中間体の化学」に関する研究

Principal Investigator

安藤 亘 筑波大学, 化学系, 教授 (30008429)

Research Products

[Publications] H.Ohgaki, W.Ando: "Stereospecific Insertion of Germylene into the Vinyl Chloride bond" J.Organomet.Chem.521. 387-389 (1996)

[Publications] N.Furukawa, T.Nakahodo, H.Fujihara: "Preparation and crystal structure of a new tetracordinated cyclic selenurane with two unsymmetrieal anicl ligands of oxygen" Chem.Commun.311-312 (1996)

[Publications] K.Kobayashi, S.Nagase,T.Akasaka: "Endohedral Dimetallofullerenes Sc2@C84and La2@C80.Are the Metal atoms Still inside the Fullrerene cages?" Chem.Phys.Lett.261. 502-506 (1996)

[Publications] T.Suzuki,J.Nishida,T.Tsuji: "Hexaphenylethane Derivatives Exhibiting Novel Electrochromic Behavior" Angew.Chem.Int.Ed.Engl.36(in press). (1997)

[Publications] K.Isgiguro,et al.: "Redox Reaction of Belzyl Radicals with Aromatic Radical Ions.Photogenerated" J.Am.Chem.Soc.118.31. 7255-7264 (1996)

[Publications] J.Nakayama: "Reactions of Benzyne with 1,3-Benzodithiole-2-thione and Related Compounds:Formation of Novel Tetracvclic Sulfonium Salts" Bull.Chem.Soc.Jpn.69.8. 2349-2354 (1996)

[Publications] T.Kawase,H.R.Darabi,M.Oda: "Cyclic 6- and 8 Paraphenylacetylenes." Angew.Chem.108. 2803-2805 (1996)

[Publications] Y.Kohno,K.Narasaka: "Synthesis of (±)-Stemonamide by the Application of Oxidative Coupling Reaction of Stannyl Compounds with Silyl Enol Ethers" Bull.Chem.Soc.Jpn. 69. 2063-2070 (1996)

[Publications] L.Zhao,H.Matsuyama,M.Iyoda: "N,N-Dialkylation of Aminocarbene Complexes under Phse-Transfer Conditions" Chem.Lett.827-828 (1996)

[Publications] T.Ibata,M.Himori,K.Fukushima,H.Suga,H.Nakano: "Regioselectivity and Relativity of Ylide Formation in the Reaction of Ketocarbenoid with Hetero-cumulenes" Heterocyclic Comm.2. 87-90 (1996)

[Publications] M.Kira,T.Iwamoto,C.Kabuto: "The first stable cyclic disilene:hexakis(trialkylsilyl)tetrasilacyclobutene" J.Am.Chem.Soc.118.42. 10303-10304 (1996)

[Publications] N.Komiya,T.Naota,Y.Oda,S.Murahashi: "Aerobic Oxidations of Alkanes and Alkenes in the Presence of Aldehydes Catalysed by Copper and Copper-Crown Ether" J.Mol.Catal A:Chemical. (in press).

[Publications] K.Goto,M.Holler,R.Okazaki: "Synthesis,Structure,and Reactions of a Sulfenic Acid Bearing a Novel Bowl-type Substituent:The First Synthesis of a Stable" J.Am.Chem.Soc.119(in press). (1997)

[Publications] N.Takeda,H.Suzuki,N.Tokitoh,R.Okazaki,S.Nagase: "Reaction of a Sterically Hindered Silylene with Isocyanides:The First Stable Silylene-Lewis Base Complex" J.Am.Chem.Soc.119(in press). (1997)

[Publications] T.Okazaki,H.Isobe,T.Kitagawa,K.Takeuchi: "Generation and Reactions of 2-(1-Adamantyl)admantene.Rearrangement to 3-(1-Adamantyl)-4-protoadamantylendene" Bull.Chem.Soc.Jpn.69.7. 2053-2062 (1996)

[Publications] H.Tomioka,M.Hattori,K.Hirai,S.Murata: "Anomalous Effects of Para Substituents on the Stability of Sterically Congested Triplet Diarylcarbenes" J.Am.Chem.Soc.118.36. 8723-8724 (1996)

[Publications] A.Sekiguchi,M.Nanjo,C.Kabuto,H.Sakurai: "[Me(PhMe_2Si)_2SiLi]and[Ph(Me_3Si)_2Li]:Preparation,Characterization and Evidence for an Intramolecular Li-Ph Interaction" Amgew.Chem.Int.Ed.Engl.36. 113-115 (1997)

[Publications] A.Oku,T.Harada,T.Katsuhira,H.Wada,A.Osada: "Design of[1,n]-ambiphiles based on zincate carbenoid chmistry" Pure & Appl.Chem.68.3. 649-652 (1996)

安藤亘筑波大学, 化学系, 教授 (30008429)