1990 年度実績報告書

ヘテロ原子の特性を利用する分子設計

研究課題

研究課題/領域番号	02230101
研究機関	筑波大学
研究代表者	安藤亘筑波大学, 化学系, 教授 (30008429)
研究分担者	吉藤正明東北大学, 理学部, 教授 (90011676) 松本英之群馬大学, 工学部, 教授 (90008467) 廣田穣横浜国立大学, 工学部, 教授 (00017881) 秋葉欣哉広島大学, 理学部, 教授 (20011538)
キーワード	ゲルモ-ル / ジゲルミラン / 束縛回転 / 分子力学パラメ-タ- / 10ーSー3スルフラン / ジホスフェン / ホススファアレン / オクタシラキュバン
研究概要	1)無置換ゲルモ-ルは活性種、ゲルミレンをアセチレンとパラジュウム触媒を用いて反応させると、高収率でゲルモ-ルを生成する。3員環ゲルマニュウム化合物は光照射すると活性なジゲルメンを生成する。この中間体はジアゾメタン、アジドと反応し、ジゲルメラン及びアザジゲルミリジンを生成する。ジゲルミランは、ヘテロ原子と反応し、O、S、Se、がGeーGe結合に挿入した生成物を与える。(安藤)2)左右にピリミジン環が縮環した対称的な骨格をもつ10ー5ー3型スルフランを種々合成し、ピリミジン環の束縛回転の活性化エネルギ-をNMRスペクトル線形解析により求めた。置換基が同一の場合、活性化の自由エネルギ-は16.8kcal/molであった。置換基が非対称の場合、より電子求引力の強い置換基をもつピリミジン環の方のSーN総合エネルギ-(束縛回転の4Gで近似)が小さく(15.6kcal/mol)、H(水素)側のピリミジン環のエネルギ-が大きくなった。(秋葉)3)アミド類の窒素中心の立体化学は、置換ベンズアニリドの ^1H、 ^<13>C、 ^<15>N化学シフトに対する置換基効果について、重相関解析の手法を用いて置換基効果の性質を解明し、更にアミドのCーN結合の回転障壁と ^<15>N化学シフトとの間に直線関係を認め、分子力学パラメ-タ-の評価に応用した。振動分光学の経験則に基づいたヘテロ原子を含む系の新しい分子力学パラメ-タ-の設定法を開発する研究を行い、窒素・酸素を含む系の伸縮・変角の力の定数の決定に応用した。(廣田)4)オクタシラキュバン(RSi)_8(R=tーBuMe_2Si)をMcpbaで酸化すると、シルセスキオキサン(RSiO_<1.5>)_8が定量的に生成する。このものは光応答性を示し、光照射により高分子量化した。(松本)5)特異構造の2配位、1配位の有機リン化合物を安定化学種として単離・同定する目的で、2,4,6ートリーtーブチルフェニル基、2,4,6ートリーtーペンチルフェニル基、1,1,4,4,5,5,8,8ーオクタメチルー1,2,3,4,5,6,7,8ーオクタヒドロー9ーアントリル基,2,4ージーtーブチルー6ージメチルアミノフェニル基などの立体保護基について検討した。また、電子的にも興味ある2,4,6ートリス(ロリフルオロメチル)フェニル基についてもヘテロ原子多重結合化合物の安定化について検討した。1配位のホスファアルキンは、ジホスフェンとジクロロカルベンとの反応でジクロロホスファエチレンを合成し、リチオ化、光異性化を経由して転位反応でホスファアルキンを合成する。(吉藤)

研究成果
(26件)

すべてその他

すべて文献書誌 (26件)

[文献書誌] K.Ohkata,M.Ohsugi,T.Kuwaki,K.Yamamoto,and K.Akiba: "Restricted Rotation of Pyrimidine Ring in Synmmetrical 10ーSー3 Sulfuranes: Evaluation of Hypervalent NーSーN Bond" Tetrahedron Letters. 31. 1605-1608 (1990)
[文献書誌] K.Ohkata,T.Yano,T.Kuwaki and K.Akiba: "Synthesis of a New Dibenzobicyclic Stiborane by Way of 10ーSbー4 Hypervalent Intermediate.1,1ーDiarylー5ーazaー2,8ーdioxaー1ーstiba dibenzo(c,f)bicyclo(3.3)octadiene" Chemistry Letter. 1721-1724 (1990)
[文献書誌] T.Tsumuraya,W.Ando: "Carbon Unsaturated Germoles: Palladiumーcatalyzed Reactions of Germylenes with Acetylene" Organometallics. 9. 869-871 (1990)
[文献書誌] T.Tsumuraya,S.Sato,W.Ando: "Molecular Structures and Reactivities of Digermiranes and Azadigermiridienes" Organometallics. 9. 2061-2067 (1990)
[文献書誌] W.Ando,N.Nakayama,Y.Kabe,T.Shimizu: "Synthesis and Structure of Pentasilacycloheptyne" Tetrahedron Letters. 31. 3597-3598 (1990)
[文献書誌] A.Sakakibara,T.Tsumuraya,Y.Kabe,W.Ando: "Photoreactions of Cyclotetrasilane and Cyclotetragermane in the presence of Azobenzene" 日本化学会誌. 536-540 (1990)
[文献書誌] M.Yoshifuji,K.Toyota,Y.Okamoto and T.Asakura: "Separation of an Optically Active Phosphaallene of Pseudo Axial Dissymmetry" Tetrahedron Lett.31. 2311-2314 (1990)
[文献書誌] K.Hirotsu,A.Okamoto,K.Toyota,and M.Yoshifuji: "XーRay Structure of 3ーDiphenylmethyleneー2ー(2,4,6ーtriーtーbutylphenyl)ーthiaphosphirane 2ーSulfide.The First Thiaphosphirane with exoーMethylene" Heteroatom Chem.1. 251-254 (1990)
[文献書誌] K.Toyota,M.Yoshifuji,and K.Hirotsu: "Sulfurization Reaction of 1,3ーDiphosphaallene.XーRay Structure of cisー2,4ーBis(2,4,6ーtriーtーbutylphenyl)ー1,2,4ーthiadiphosphetane 2,4ーDisulfide" Chem.Lett.643-646 (1990)
[文献書誌] M.Yoshifuji,K.Toyota,T.Niitsu,N.Inamoto,and K.Hirotsu: "Preparation and Xーray Structure of Bis(pentacarbonyltungsten)Complexes of 1,3ーDiphosphaallene with η^1ーCoordination Mode" J.Organometal.Chem.389. C12-C15 (1990)
[文献書誌] T.Niitsu,N.Inamoto,K.Toyota,and M.Yoshifuji: "Preparation and Hydrolysis of Some Sterically Protected 3ーAzaー1ーphosphaallenes" Bull.Chem.Soc.Jpn.63. 2736-2738 (1990)
[文献書誌] M.Yoshifuji,K.Toyota,M.Murayama,H.Yoshimura,A.Okamoto,K.Hirotsu,and S.Nagase: "Preparation of Sterically Protected 3,4ーBis(phosphinidene)cyclobutenes and their Isomerism" Chem.Lett.2195-2198 (1990)
[文献書誌] H.Matsumoto,K.Kanuma,Y.Nagai,and M.Goto: "Molecular Structure and Photochemical Behavior of antiーDodecaisopropyltricyclo[4.2.0.0^<2,5>]octasilane" Chem.Lett.
[文献書誌] H.Matsumoto,M.Motegi,Y.Yagihashi,Y.Nagai,and M.Goto: "Synthesis and Molecular Structure of cisーcisーtransー1,2,3,4ーTetrakis(bis(trimethylsilyl)methyl]cyclotetrasilane" Bull.Chem.Soc.Jpn.
[文献書誌] H.Matsumoto,Y.Yagihashi,A.Sakamoto,Y.Nagai,and M.Goto: "Molecular Structure and Conformational Analysis of a Persilylcyclotetrasilane,Octakis(ethyldimethylsilyl)ーcyclotetrasilane" Chem.Lett.
[文献書誌] H.Matsumoto,K.Higuchi,Y.Nagai,and R.Akaba: "Electrochemical Properties of an Octasilacubane,Octakis(tーbutyldimethylsilyl)octasilacubane" Chem.Lett.
[文献書誌] H.Matsumoto,K.Higuchi,Y.Nagai,and M.Goto: "Oxidation of Octakis(tーbutyldimethylsilyl)octasilacubane with mーChloroperbenzoic Acid" Organometallics.
[文献書誌] H.Matsumoto,A.Matsushima,K.Higuchi,Y.Nagai,K.Kikuchi,I.Ikemoto: "Synthesis and Electric Properties of a Polysilylne,Polyー(Triethylsilylsilyne)" Appl.Organometallics.
[文献書誌] Hiroko Suezawa: "Substituent Effects on the ^1H, ^<13>C and ^<15>N NMR Spectra of Substituted Benzanilides." Bulletin of the Chemical Soiety of Japan. 63. 328-333 (1990)
[文献書誌] Masahiro Nakada: "Photooxidation of Alkylbenzenes in the Presence of Bromides." Bulletin of the Chemical Soiety of Japan. 63. 944-947 (1990)
[文献書誌] Tamiki Komatsuzaki: "A New Steric Substituent Parameter OmegaーS.Sophistication of Calculation and Correlation with the Kinetic Data of Several Reactions." Chemistry Letters. 1990. 1913-1916 (1990)
[文献書誌] Yukino Abe: "Spin Trapping of OxygenーCentered Radicals by Substituted NーBenzylideneーtーbutylamine Nーoxides." Journal of Chemical Society Perkin Trans.2. 1991. (1991)
[文献書誌] Tatsuji Chuman: "Conformational Analysis of Serricornin.Application of Molecular Mechanics Calculation to Stereochemical Assignment of Serricornin,the Sex Pheromone of Cigarette Beetle." Journal of Chemical Ecology.
[文献書誌] Minoru Hirota: "A New Steric Substituent Constant OmegaーS Based on Molecular Mechanics Calculations." Computer and Chemistry.
[文献書誌] M.Yoshifuji: "“Multiple Bonds and Low Coordination in Phosphorus Chemistry"Ed.M.Regitz and O.J.Scherer" Georg Thieme Verlag,Stuttgart, 21/478 (1990)
[文献書誌] Y.Nagai,H.Watanabe,and H.Matsumoto: "SiliconーBased Polymer Science Synthesis and Properties of SiliconーBranched Organoーsilicon Polymers" Am.Chem.Soc.,801(505-513) (1990)

1990 年度 実績報告書

ヘテロ原子の特性を利用する分子設計

研究代表者

安藤 亘 筑波大学, 化学系, 教授 (30008429)

研究成果

[文献書誌] K.Ohkata,M.Ohsugi,T.Kuwaki,K.Yamamoto,and K.Akiba: "Restricted Rotation of Pyrimidine Ring in Synmmetrical 10ーSー3 Sulfuranes: Evaluation of Hypervalent NーSーN Bond" Tetrahedron Letters. 31. 1605-1608 (1990)

[文献書誌] K.Ohkata,T.Yano,T.Kuwaki and K.Akiba: "Synthesis of a New Dibenzobicyclic Stiborane by Way of 10ーSbー4 Hypervalent Intermediate.1,1ーDiarylー5ーazaー2,8ーdioxaー1ーstiba dibenzo(c,f)bicyclo(3.3)octadiene" Chemistry Letter. 1721-1724 (1990)

[文献書誌] T.Tsumuraya,W.Ando: "Carbon Unsaturated Germoles: Palladiumーcatalyzed Reactions of Germylenes with Acetylene" Organometallics. 9. 869-871 (1990)

[文献書誌] T.Tsumuraya,S.Sato,W.Ando: "Molecular Structures and Reactivities of Digermiranes and Azadigermiridienes" Organometallics. 9. 2061-2067 (1990)

[文献書誌] W.Ando,N.Nakayama,Y.Kabe,T.Shimizu: "Synthesis and Structure of Pentasilacycloheptyne" Tetrahedron Letters. 31. 3597-3598 (1990)

[文献書誌] A.Sakakibara,T.Tsumuraya,Y.Kabe,W.Ando: "Photoreactions of Cyclotetrasilane and Cyclotetragermane in the presence of Azobenzene" 日本化学会誌. 536-540 (1990)

[文献書誌] M.Yoshifuji,K.Toyota,Y.Okamoto and T.Asakura: "Separation of an Optically Active Phosphaallene of Pseudo Axial Dissymmetry" Tetrahedron Lett.31. 2311-2314 (1990)

[文献書誌] K.Hirotsu,A.Okamoto,K.Toyota,and M.Yoshifuji: "XーRay Structure of 3ーDiphenylmethyleneー2ー(2,4,6ーtriーtーbutylphenyl)ーthiaphosphirane 2ーSulfide.The First Thiaphosphirane with exoーMethylene" Heteroatom Chem.1. 251-254 (1990)

[文献書誌] K.Toyota,M.Yoshifuji,and K.Hirotsu: "Sulfurization Reaction of 1,3ーDiphosphaallene.XーRay Structure of cisー2,4ーBis(2,4,6ーtriーtーbutylphenyl)ー1,2,4ーthiadiphosphetane 2,4ーDisulfide" Chem.Lett.643-646 (1990)

[文献書誌] M.Yoshifuji,K.Toyota,T.Niitsu,N.Inamoto,and K.Hirotsu: "Preparation and Xーray Structure of Bis(pentacarbonyltungsten)Complexes of 1,3ーDiphosphaallene with η^1ーCoordination Mode" J.Organometal.Chem.389. C12-C15 (1990)

[文献書誌] T.Niitsu,N.Inamoto,K.Toyota,and M.Yoshifuji: "Preparation and Hydrolysis of Some Sterically Protected 3ーAzaー1ーphosphaallenes" Bull.Chem.Soc.Jpn.63. 2736-2738 (1990)

[文献書誌] M.Yoshifuji,K.Toyota,M.Murayama,H.Yoshimura,A.Okamoto,K.Hirotsu,and S.Nagase: "Preparation of Sterically Protected 3,4ーBis(phosphinidene)cyclobutenes and their Isomerism" Chem.Lett.2195-2198 (1990)

[文献書誌] H.Matsumoto,K.Kanuma,Y.Nagai,and M.Goto: "Molecular Structure and Photochemical Behavior of antiーDodecaisopropyltricyclo[4.2.0.0^<2,5>]octasilane" Chem.Lett.

[文献書誌] H.Matsumoto,M.Motegi,Y.Yagihashi,Y.Nagai,and M.Goto: "Synthesis and Molecular Structure of cisーcisーtransー1,2,3,4ーTetrakis(bis(trimethylsilyl)methyl]cyclotetrasilane" Bull.Chem.Soc.Jpn.

[文献書誌] H.Matsumoto,Y.Yagihashi,A.Sakamoto,Y.Nagai,and M.Goto: "Molecular Structure and Conformational Analysis of a Persilylcyclotetrasilane,Octakis(ethyldimethylsilyl)ーcyclotetrasilane" Chem.Lett.

[文献書誌] H.Matsumoto,K.Higuchi,Y.Nagai,and R.Akaba: "Electrochemical Properties of an Octasilacubane,Octakis(tーbutyldimethylsilyl)octasilacubane" Chem.Lett.

[文献書誌] H.Matsumoto,K.Higuchi,Y.Nagai,and M.Goto: "Oxidation of Octakis(tーbutyldimethylsilyl)octasilacubane with mーChloroperbenzoic Acid" Organometallics.

[文献書誌] H.Matsumoto,A.Matsushima,K.Higuchi,Y.Nagai,K.Kikuchi,I.Ikemoto: "Synthesis and Electric Properties of a Polysilylne,Polyー(Triethylsilylsilyne)" Appl.Organometallics.

[文献書誌] Hiroko Suezawa: "Substituent Effects on the ^1H, ^<13>C and ^<15>N NMR Spectra of Substituted Benzanilides." Bulletin of the Chemical Soiety of Japan. 63. 328-333 (1990)

[文献書誌] Masahiro Nakada: "Photooxidation of Alkylbenzenes in the Presence of Bromides." Bulletin of the Chemical Soiety of Japan. 63. 944-947 (1990)

[文献書誌] Tamiki Komatsuzaki: "A New Steric Substituent Parameter OmegaーS.Sophistication of Calculation and Correlation with the Kinetic Data of Several Reactions." Chemistry Letters. 1990. 1913-1916 (1990)

[文献書誌] Yukino Abe: "Spin Trapping of OxygenーCentered Radicals by Substituted NーBenzylideneーtーbutylamine Nーoxides." Journal of Chemical Society Perkin Trans.2. 1991. (1991)

[文献書誌] Tatsuji Chuman: "Conformational Analysis of Serricornin.Application of Molecular Mechanics Calculation to Stereochemical Assignment of Serricornin,the Sex Pheromone of Cigarette Beetle." Journal of Chemical Ecology.

[文献書誌] Minoru Hirota: "A New Steric Substituent Constant OmegaーS Based on Molecular Mechanics Calculations." Computer and Chemistry.

[文献書誌] M.Yoshifuji: "“Multiple Bonds and Low Coordination in Phosphorus Chemistry"Ed.M.Regitz and O.J.Scherer" Georg Thieme Verlag,Stuttgart, 21/478 (1990)

[文献書誌] Y.Nagai,H.Watanabe,and H.Matsumoto: "SiliconーBased Polymer Science Synthesis and Properties of SiliconーBranched Organoーsilicon Polymers" Am.Chem.Soc.,801(505-513) (1990)

1990 年度実績報告書

安藤亘筑波大学, 化学系, 教授 (30008429)