1989 Fiscal Year Annual Research Report

ヘテロ原子の特性を利用する分子設計

Research Project

Project/Area Number	01648001
Research Institution	University of Tsukuba
Principal Investigator	安藤亘筑波大学, 化学系, 教授 (30008429)
Co-Investigator(Kenkyū-buntansha)	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, 助教授 (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)
Keywords	トリチアペンタレン / オクタシラキュバン / スピントラップ / オクタシルセスキオキサン / ジゲルメン / シリラン / ジホスファアレン / ジホスフェン
Research Abstract	1)1,2,3ーセレナ及びチアジアゾールは熱及び光反応による高い反応活性種を生成し、セレニレンのDiels-Alder付加体を得る。シリランは種々の求核試薬と反応し環拡大生成物を、ジゲルメンは安定なヘテロジゲルミランの無色(C,N,S,Se)および黄色(Te)の結晶を生成する。(安藤) 2)ピリジン環とピリミジン環が縮環したトリチアペンタレン型化合物は、2個のメチル基が40ー60℃でコアレスする。これはピリミジン側のNーS結合の開裂、回転による。左右にピリジンが縮環したチアペンタレン型化合物は、NーS(IV)ーN結合開裂による環の束縛回転に対する置換基(X,Y)の電子的効果を検討した。(秋葉) 3)ラジカルのPBNへの付加の遷移状態に関して新しいスピントラップ剤を合成し、その選択性を検討した。^<15>Nの測定を各種の置換アミドに対し、ρ値の符号が逆転していることを認めた。ヘテロ原子を含む分子力学パラメーターの設定法を開発し、これらの系の伸縮・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(1)の電化電位(0.48V)は、塩化アルミニニウムにより容易に一電子酸化を受けた。テトラシアノエチレンとの混合物は、820nmにCTバンドを与えた。環状ポリシランのCTバンドの中で最も長波長の値であり、半導体レーザーの波長範囲内である。過酸で酸化したところオクタシルセスキオキサンがほぼ定量的に生成した。1が高電子性有機ポリシランであることが示された。(松本) 5)特異構造をもつ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、立体保護基として2,4,6ートリーtーペンチルフェニル基をはじめとして、2,6ージー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1,2,3,4,5,6,7,8ーオクタヒドロー9ーアントラセニル基などの有用性について検討し、ジホスフェン(ーP=Pー)、1,3ージホスファレン(ーP=C=Pー)、ホスファアルキン(ーC=P)類の合成を試みた。(吉藤)

Research Products
(29 results)

All Other

All Publications (29 results)

[Publications] W.Ando,: "3-Alkylidenethiagermiranes" Organometallics. 8. 1467-1472 (1989)
[Publications] W.Ando,: "Thermolysis of Cyclotrigermane:Simple Preparation of Digermetanes containing Germanium-Germanium Bond" Chemical Communications. 770-772 (1989)
[Publications] H.Saso: "Novel Si-C Bond Cleavages of Alkylidenesiliranes in the Reaction with Nucleophiles" Tetrahedron. 45. 1929-1940 (1989)
[Publications] T.Tsumuraya: "synthesis and Chemistry of Thiagermiranes" Organometallics. 8. 161-167 (1989)
[Publications] AT.Akasaka: "Reaction of singlet Oxygen with-Unsaturated Aldimines:Novel Formation of 3-Amino-4-methylene-1,2-dioxolanes" Heterocycles. 28. 445-451 (1989)
[Publications] T.Akasaka: "3-Methylene-1,2-dioxetane as a Possible Chemiluminescent Intermediate in Singlet Oxgenation of Allene" Bull.Chem.Soc.Jpn. 62. 1367-1369 (1989)
[Publications] T.Akasaka,: "Singlet Oxygen and Triazolinedione Additions to-Unsaturated Sulfoxides" Tetrahedron Letters. 45. 6657-6666 (1989)
[Publications] W.Ando,: "Active Oxygen Species in Oxidation of Organic Sulfur Compounds" Medical,Biochemical and Chemical Aspects of Free Radicals Ed.O.Hayaishi,E.Niki,M.Kondo,T.Yoshikawa. 141-145 (1989)
[Publications] W.Ando,: "New Aspects of Dye-Sensitized Photooxidation" Chemistry of functional Dye Ed.Z.Yoshida,T.Kitao. 157-163 (1989)
[Publications] 赤坂健: "低温酸素マトリックス中での光化学反応による過酸化物中間体の生成と構造" 日本化学会誌. 8. 1440-1446 (1989)
[Publications] T.Tsumuraya,: "A Palladagermetane:Palladium-Catalyzed Insertion Reactions of Digermiranes" Organometallics. 8. 2286-2288 (1989)
[Publications] T.Tsumuraya: "Photolysis of an Azidogermane.Observation of a Germanimine in Hydrocarbon Matrices" Chemistry Letters. 1043-1046 (1989)
[Publications] Katsuo Ohkata: "Synthesis and Chemical Behaviors of 12-substituted Dibenz〔c,f〕〔1,5〕azastibocine and Dibenz〔c,f〕〔1,5〕azabismocine Derivatives:Evidences of 10-pn-4 Type Hypervalent Interaction" Tetrahedron Letters. 30. 4841-4844 (1989)
[Publications] Katsuo Ohkata: "Restricted Rotation of Pyrimidine Ring in symmetrical 10-S-3 Sulfuranes:Evaluation of Hypervalent N-S-N Bond Energy" Tetrahedron Letters(accepted). 31. (1990)
[Publications] Kazuhisa Sakakibara: "Can Hydrogen Atoms in Alkyl Group Interact with π-electrons of Double Bond?Theoretical Study for the CH/π Interaction of Organic Molecules." Chemistry Letters. 1989. 921-924 (1989)
[Publications] Tamiki Komatsuzaki: "A New Method for Evaluating the Steric Hindrance by Substituent." Tetrahedron Letters. 30. 3309-3312 (1989)
[Publications] Yasunori Hase: "How to Determine the Force Constants of MM2 Force Field in a Consistent Way." Chemistry Letters. 1989. 1507-1510 (1989)
[Publications] Motohiro Nishio: "CH/π Interaction:Implications in Organic Chemistry." Tetrahedron. 45. 7201-7245 (1989)
[Publications] Masahiro Nakada: "Photoreactions of Polyhalobenzenes in Benzene.Formation of Terphenyls." Bulletin of the Chemical Society of Japan. 62. 3122-3126 (1989)
[Publications] Hiroko Suezawa: "Substituent Effects on the ^1H,^<18>C and ^<15>N NMR Spectra of Substituted Benzanilides." Bulletin of the Chemical society of Japan. 63. 328-333 (1990)
[Publications] H.Shizuka,: "Photolysis of Cyclotetrasilanes,Remarkable Dependence on Molecular Structure" J.Chem.Soc.,Faraday Trans.I. 85. 2369-2379 (1989)
[Publications] H.Shizuka,: "Fluorescene of Cyclotetrasilanes in Rigd Glass at 77 K,a Remarkably Large Stokes Shift" J.Chem.Soc.,Farasu Trans.I. 85. 2809-2817 (1989)
[Publications] M.Yoshifuji: "A Convenient New Route from Diphosphene to 1,3-diphospha-allene and Dynamic NMR Studies of the 2,4,6-Tri-t-butylphenyl Derivative" Tetrahedron Lett.30. 187-188 (1989)
[Publications] M.Yoshifuji: "A New Direct Method for Introducing 2-(2,4,6-Tri-t-butylphenyl)-2-phosphavinylidene Group.Formation of 1-phospha-and 1,3-diphospha-allenes" Terahedron Lett.30. 839-842 (1989)
[Publications] M.Yoshifuji: "A Versatile Preparation of 2,6-Di-t-butylbromobenzene.Application for Organophosphorus Compounds in Low Coordination" Tetrahedron Lett.30. 5433-5436 (1989)
[Publications] M.Yoshifuji: "The First Preparation of an Unsymmetrical 1,3-Diphospha-allene Carrying 2,4,6-Tri-t-butylphenyl and 2,4,6-tri-t-pentyl as Protecting Groups" J.Chem.Soc.,Chem.Commun.1732-1733 (1989)
[Publications] M.Yoshifuji: "Separation of an Optically Active Phosphaallene of Pseudo Axial Dissymmetry" Tetrahedron Lett.31. (1990)
[Publications] M.Yoshifuji: "Preparation of 2,4,6-Tri-t-pentylbromobenzene and Its Application as a New Protecting Group for Phosphorus Compounds.in Low Coordination State" Science Reports,Tohoku University,Ser.I. 72. (1989)
[Publications] H.Matsumoto: "Silicon-Branched Polysilances in New Aspects of Organic Chemistry" Kodansha,VCH, 303-326 (1989)

1989 Fiscal Year Annual Research Report

ヘテロ原子の特性を利用する分子設計

Principal Investigator

安藤 亘 筑波大学, 化学系, 教授 (30008429)

Research Products

[Publications] W.Ando,: "3-Alkylidenethiagermiranes" Organometallics. 8. 1467-1472 (1989)

[Publications] W.Ando,: "Thermolysis of Cyclotrigermane:Simple Preparation of Digermetanes containing Germanium-Germanium Bond" Chemical Communications. 770-772 (1989)

[Publications] H.Saso: "Novel Si-C Bond Cleavages of Alkylidenesiliranes in the Reaction with Nucleophiles" Tetrahedron. 45. 1929-1940 (1989)

[Publications] T.Tsumuraya: "synthesis and Chemistry of Thiagermiranes" Organometallics. 8. 161-167 (1989)

[Publications] AT.Akasaka: "Reaction of singlet Oxygen with-Unsaturated Aldimines:Novel Formation of 3-Amino-4-methylene-1,2-dioxolanes" Heterocycles. 28. 445-451 (1989)

[Publications] T.Akasaka: "3-Methylene-1,2-dioxetane as a Possible Chemiluminescent Intermediate in Singlet Oxgenation of Allene" Bull.Chem.Soc.Jpn. 62. 1367-1369 (1989)

[Publications] T.Akasaka,: "Singlet Oxygen and Triazolinedione Additions to-Unsaturated Sulfoxides" Tetrahedron Letters. 45. 6657-6666 (1989)

[Publications] W.Ando,: "Active Oxygen Species in Oxidation of Organic Sulfur Compounds" Medical,Biochemical and Chemical Aspects of Free Radicals Ed.O.Hayaishi,E.Niki,M.Kondo,T.Yoshikawa. 141-145 (1989)

[Publications] W.Ando,: "New Aspects of Dye-Sensitized Photooxidation" Chemistry of functional Dye Ed.Z.Yoshida,T.Kitao. 157-163 (1989)

[Publications] 赤坂健: "低温酸素マトリックス中での光化学反応による過酸化物中間体の生成と構造" 日本化学会誌. 8. 1440-1446 (1989)

[Publications] T.Tsumuraya,: "A Palladagermetane:Palladium-Catalyzed Insertion Reactions of Digermiranes" Organometallics. 8. 2286-2288 (1989)

[Publications] T.Tsumuraya: "Photolysis of an Azidogermane.Observation of a Germanimine in Hydrocarbon Matrices" Chemistry Letters. 1043-1046 (1989)

[Publications] Katsuo Ohkata: "Synthesis and Chemical Behaviors of 12-substituted Dibenz〔c,f〕〔1,5〕azastibocine and Dibenz〔c,f〕〔1,5〕azabismocine Derivatives:Evidences of 10-pn-4 Type Hypervalent Interaction" Tetrahedron Letters. 30. 4841-4844 (1989)

[Publications] Katsuo Ohkata: "Restricted Rotation of Pyrimidine Ring in symmetrical 10-S-3 Sulfuranes:Evaluation of Hypervalent N-S-N Bond Energy" Tetrahedron Letters(accepted). 31. (1990)

[Publications] Kazuhisa Sakakibara: "Can Hydrogen Atoms in Alkyl Group Interact with π-electrons of Double Bond?Theoretical Study for the CH/π Interaction of Organic Molecules." Chemistry Letters. 1989. 921-924 (1989)

[Publications] Tamiki Komatsuzaki: "A New Method for Evaluating the Steric Hindrance by Substituent." Tetrahedron Letters. 30. 3309-3312 (1989)

[Publications] Yasunori Hase: "How to Determine the Force Constants of MM2 Force Field in a Consistent Way." Chemistry Letters. 1989. 1507-1510 (1989)

[Publications] Motohiro Nishio: "CH/π Interaction:Implications in Organic Chemistry." Tetrahedron. 45. 7201-7245 (1989)

[Publications] Masahiro Nakada: "Photoreactions of Polyhalobenzenes in Benzene.Formation of Terphenyls." Bulletin of the Chemical Society of Japan. 62. 3122-3126 (1989)

[Publications] Hiroko Suezawa: "Substituent Effects on the ^1H,^<18>C and ^<15>N NMR Spectra of Substituted Benzanilides." Bulletin of the Chemical society of Japan. 63. 328-333 (1990)

[Publications] H.Shizuka,: "Photolysis of Cyclotetrasilanes,Remarkable Dependence on Molecular Structure" J.Chem.Soc.,Faraday Trans.I. 85. 2369-2379 (1989)

[Publications] H.Shizuka,: "Fluorescene of Cyclotetrasilanes in Rigd Glass at 77 K,a Remarkably Large Stokes Shift" J.Chem.Soc.,Farasu Trans.I. 85. 2809-2817 (1989)

[Publications] M.Yoshifuji: "A Convenient New Route from Diphosphene to 1,3-diphospha-allene and Dynamic NMR Studies of the 2,4,6-Tri-t-butylphenyl Derivative" Tetrahedron Lett.30. 187-188 (1989)

[Publications] M.Yoshifuji: "A New Direct Method for Introducing 2-(2,4,6-Tri-t-butylphenyl)-2-phosphavinylidene Group.Formation of 1-phospha-and 1,3-diphospha-allenes" Terahedron Lett.30. 839-842 (1989)

[Publications] M.Yoshifuji: "A Versatile Preparation of 2,6-Di-t-butylbromobenzene.Application for Organophosphorus Compounds in Low Coordination" Tetrahedron Lett.30. 5433-5436 (1989)

[Publications] M.Yoshifuji: "The First Preparation of an Unsymmetrical 1,3-Diphospha-allene Carrying 2,4,6-Tri-t-butylphenyl and 2,4,6-tri-t-pentyl as Protecting Groups" J.Chem.Soc.,Chem.Commun.1732-1733 (1989)

[Publications] M.Yoshifuji: "Separation of an Optically Active Phosphaallene of Pseudo Axial Dissymmetry" Tetrahedron Lett.31. (1990)

[Publications] M.Yoshifuji: "Preparation of 2,4,6-Tri-t-pentylbromobenzene and Its Application as a New Protecting Group for Phosphorus Compounds.in Low Coordination State" Science Reports,Tohoku University,Ser.I. 72. (1989)

[Publications] H.Matsumoto: "Silicon-Branched Polysilances in New Aspects of Organic Chemistry" Kodansha,VCH, 303-326 (1989)

安藤亘筑波大学, 化学系, 教授 (30008429)