1990 Fiscal Year Annual Research Report

低温光化学プロセスを用いる不安定有機化合物の合成とキャラクタリゼ-ション

Research Project

Project/Area Number	01303002
Research Institution	Mie University
Principal Investigator	富岡秀雄三重大学, 工学部, 教授 (20024599)
Co-Investigator(Kenkyū-buntansha)	小田雅司大阪大学, 理学部, 教授 (60004438) 稲垣都士岐阜大学, 工学部, 教授 (10108061) 宮仕勉東北大学, 理学部, 教授 (20004442) 西田進也北海道大学, 理学部, 教授 (40029400) 岩村秀東京大学, 理学部, 教授 (10011496)
Keywords	低温マトリックス分離分光法 / 不安定分子先駆体の合成 / 不安定分子の理論計算 / 不安定分子の反応解析 / 不安定分子の直接観測
Research Abstract	本総合研究は(1)不安定化合物先駆体の設計と合成、(2)不安定化合物からの反応生成物解析(3)不安定化合物の分光学的検出(4)不安定化合物の理論計算の4班から成立している。以下に各班毎の今年度の実績を述べる。 (1)オキソニウムイリド、スルホニウムイリド、ビニルカルボカチオン等を光化学的に発生しうる有効な先駆体を開発し、これらの中間体を含む反応解析を行ない、その有用性を示した。 (2)低温で発生可能なビラジカルの先駆体を合成し、これらビラジカルがDNA開裂等生物学的にも有用であることを示した。一方、インド-ル、ウラシル等は低温固相で特異な分子間的光化学反応を行なうことを明らかにした。 (3)ビニル置換シリレンや、ポリカルベンを低温マトリックス中観測し、その電子構造に関する知見を得ると共に、分子内及び分子間の磁気的相互作用の本質を解明した。一方、極低温での低分子化合物の回転異性体が赤外光でも相互変換することを明らかにし、その帰属と機構を解明した。さらに、極低温マトリックス中でNO_2を用いるとアルケンの立体特異的光エポキシ化が可能なことを示し、反応に含まれる中間体を明らかにした。ジシランの酸素酸化も行ない、酸化の中間体を含め種々の有用な不安定含酸素化合物を特性化した。種々の置換基を持つチオケテンを発生させ特性解析した。 (4)Si,Ge,Sn,Pbを含む三員環化合物及びそのラジカルカチオンの構造と安定性の関連を理論計算により評価し、特にPbの場合、二価中間体とアルケンの錯体が非常に安定となると予測した。以上の研究成果を全体会議で多方面的に議論し、本プロセスによって今後どのような不安定分子まで合成できるか総合的に検討を行なった。

Research Products

(32 results)

All Other

All Publications (32 results)

[Publications] T.Harada: "Generation and Alkylation Reaction of Lithium 1ーHalocyclopropylzincate" Tetrahedron Lett.30. 6035-6038 (1989)
[Publications] T.Harada: "Stereoselective Synthesis of gemーDisubstituted Cyclopropanes from gemーDibromocyclopropanes" Tetrahedron Lett.30. 6039-6040 (1989)
[Publications] K.Okada: "Photochemical Chlorodecarboxylation via an Electron Transfer Mechanism" J.Chem.Soc.,Chem.Commun.1636-1637 (1989)
[Publications] K.Okada: "Photodecarboxylation of Unmodified Carboxylic Acids with Use of Aza Aromatic Compounds" Tetrahedron Lett.30. 6733-6736 (1989)
[Publications] T.Kitamura: "Ipso Substitution by Alkoxide Ions in Photolysis of Triarylvinyl Halides.Firm Evidence for Intervention of Vinyl Cations" Chem.Lett.1867-1870 (1990)
[Publications] T.Kitamura: "Photolysis of Vinyl Halides.Reaction of Photogenerated Vinyl Cations with Cyanate and Thiocyanate Ions" J.Org.Chem.55. 1801-1805 (1990)
[Publications] I.Saito: "A Multistep Photochemical Reaction of 5ーFormylー1,3ーdimethyluracils with Inodole in the Solid State" Tetrahedron. 46. 2367-2370 (1990)
[Publications] J.ーB.Meng: "Selectivity in the SolidーState Photoreaction of 6ーCyanouracils with Aromatic Hydrocarbons" Chem.Lett.1247-1248 (1990)
[Publications] H.Sugiyama: "Specific Detection of Cー4' Hydroxylated Abasic Sites Generated by Bleomycin and Neocarzinostatin in DNA" J.Am.Chem.Soc.112. 5252-5257 (1990)
[Publications] R.Nagata: "DNA Cleavage by Acylic EneyneーAllen Systems Related to Neocarziostatin and EsperamicinーCalicheamicin" Tetrahedron Lett.31. 2907-2910 (1990)
[Publications] T.Miyashi: "Photoinduced ElectronーTransfer Reactions of the Cope and Related Systems" Pure Appl.Chem.62. 1531-1538 (1990)
[Publications] T.Miyashi: "ElectronーTransfer Photoreactions of Smallーring Compounds:Nature and Role of Cationーradical Intermediates" Pure Appl.Chem.63. 223-230 (1991)
[Publications] T.Tsumuraya: "Photolysis of an Azidogermane:Observation of a Germanimine(Ge=N) in Hydrocarbon Matrices" Chem.Lett.1043-1046 (1989)
[Publications] A.Sakakibara: "Photoreactions of Cyclotetrasilane and Cyclotetragermane in the Presence of Azobenzene" Nippon Kagaku Kaishi. 536-540 (1990)
[Publications] H.Iwamura: "Magnetic Coupling of Two Triplet Phenylnitrene Units Joined through an Acetylenic or Diacetylenic Linkage" Mol.Cryst.Liq.Cryst.176. 33-48 (1989)
[Publications] I.Fujita: "Design,Preparation,and ESR Detection of a GroundーState Undecet (S=5) Hydrocarbon" J.Am.Chem.Soc.112. 4074-4075 (1990)
[Publications] T.Tsuji: "Photochemical Generation of Bicyclo[4.2.2]decapentaene.Preference of [4]Paracyclophaー1,3ーdiene Structure over Bicyclo[4.2.2]decaー1,3,5,7,9ーpentaene Structure" J.Am.Chem.Soc.111. 368-369 (1989)
[Publications] M.Ohkita: "3,4ーBenzotropone:Generation,Spectroscopic Characterization,and Reactions" J.Chem.Soc.,Chem.Commun.924-926 (1989)
[Publications] M.Kira: "Photochemical 1,3ーSilyl Migration in Allylsilanes Occurring with Inversion of Silyl Configuration" J.Org.Chem.54. 5647-5648 (1989)
[Publications] M.Kira: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allysilicates in Hydroxylic Media.Discrimination between Linear and αーBranched Alkanals" J.Am.Chem.Soc.112. 257-260 (1990)
[Publications] S.Murata: "Matrix Studies of the Photolysis of oーCarbomethoxyーphenyldiazomethane.Direct Observation of Carbonyl Ylide and Its Photoinduced Valence Tautomerization" Chem.Lett.853-856 (1989)
[Publications] S.Murata: "Reaction of Bicyclo[6.3.0]undecaー2,4,6,8ーpentaenー10ーylidene in OxygenーDoped Matrices:Characterization of the First Carbonyl Oxide with a πーDonating Ring System" J.Org.Chem.55. 4502-4504 (1990)
[Publications] 石橋孝章: "アルゴンマトリックス中単離したイソプレンの準安定異性体の赤外分光法による研究" 日本化学会誌. 1418-1422 (1989)
[Publications] M.Tasumi: "Reーinvestigation of Infraredーinduced Conformational Isomerizations of 1,2ーEthanediol in Lowーtemperature Ar Matrices and Reverse Reaction in the Dark" J.Phys.Chem.
[Publications] M.Nakata: "Stereoselective Photooxidation of transー2ーButene to Epoxide by Nitrogen Dioxide Excited with Red Light in a Cryogenic Matrix" J.Am.Chem.Soc.111. 5240-5247 (1989)
[Publications] M.Nakata: "Vibronic Excitation of OxygenーAtom Transfer from NO_2 to Ethylene by LongーWavelength Visible Light in a Cryogenic Matrix" J.Phys.Chem.94. 8168-8175 (1990)
[Publications] E.Suzuki: "Thermal Decomposition of 1,3ーDithiethane 1,3ーDioxide and Infrared Spectrum of MatrixーIsolated Sulfine" J.Mol.Struct.238. 71-77 (1990)
[Publications] E.Suzuki: "Infrared Spectra of MatrixーIsolated Propadienethione,H_2C=C=C=S" Chem.Phys.Lett.168. 1-4 (1990)
[Publications] S.Inagaki: "Preference of [6e/4p],[6e/5p],[6e/6p] Conjugations in Determining Relative Stabilities of Fused FiveーMembered Heteroaromatic Isomers" Bull.Chem.Soc.Jpn.63. 3117-3121 (1990)
[Publications] M.Ishida: "Application of the Orbital Mixing Rule to HeteroatomーDependent πーFacial Selectivity in the DielsーAlder Reaction of 5ーSubstituted 1,3ーCyclopentadiene" J.Am.Chem.Soc.112. 8980-8982 (1990)
[Publications] T.Kudo: "JahnーTeller Distortions in SnH_4^+ and PbH_4^+" Chem.Phys.Lett.156. 289-295 (1989)
[Publications] T.Kudo: "The Cyclotrisilane Radical Cation and its RingーOpened Isomers.A Theoretical Study of Si_3H_6^+" Chem.Phys.Lett.164. 217-224 (1989)

1990 Fiscal Year Annual Research Report

低温光化学プロセスを用いる不安定有機化合物の合成とキャラクタリゼ-ション

Principal Investigator

富岡 秀雄 三重大学, 工学部, 教授 (20024599)

Research Products

[Publications] T.Harada: "Generation and Alkylation Reaction of Lithium 1ーHalocyclopropylzincate" Tetrahedron Lett.30. 6035-6038 (1989)

[Publications] T.Harada: "Stereoselective Synthesis of gemーDisubstituted Cyclopropanes from gemーDibromocyclopropanes" Tetrahedron Lett.30. 6039-6040 (1989)

[Publications] K.Okada: "Photochemical Chlorodecarboxylation via an Electron Transfer Mechanism" J.Chem.Soc.,Chem.Commun.1636-1637 (1989)

[Publications] K.Okada: "Photodecarboxylation of Unmodified Carboxylic Acids with Use of Aza Aromatic Compounds" Tetrahedron Lett.30. 6733-6736 (1989)

[Publications] T.Kitamura: "Ipso Substitution by Alkoxide Ions in Photolysis of Triarylvinyl Halides.Firm Evidence for Intervention of Vinyl Cations" Chem.Lett.1867-1870 (1990)

[Publications] T.Kitamura: "Photolysis of Vinyl Halides.Reaction of Photogenerated Vinyl Cations with Cyanate and Thiocyanate Ions" J.Org.Chem.55. 1801-1805 (1990)

[Publications] I.Saito: "A Multistep Photochemical Reaction of 5ーFormylー1,3ーdimethyluracils with Inodole in the Solid State" Tetrahedron. 46. 2367-2370 (1990)

[Publications] J.ーB.Meng: "Selectivity in the SolidーState Photoreaction of 6ーCyanouracils with Aromatic Hydrocarbons" Chem.Lett.1247-1248 (1990)

[Publications] H.Sugiyama: "Specific Detection of Cー4' Hydroxylated Abasic Sites Generated by Bleomycin and Neocarzinostatin in DNA" J.Am.Chem.Soc.112. 5252-5257 (1990)

[Publications] R.Nagata: "DNA Cleavage by Acylic EneyneーAllen Systems Related to Neocarziostatin and EsperamicinーCalicheamicin" Tetrahedron Lett.31. 2907-2910 (1990)

[Publications] T.Miyashi: "Photoinduced ElectronーTransfer Reactions of the Cope and Related Systems" Pure Appl.Chem.62. 1531-1538 (1990)

[Publications] T.Miyashi: "ElectronーTransfer Photoreactions of Smallーring Compounds:Nature and Role of Cationーradical Intermediates" Pure Appl.Chem.63. 223-230 (1991)

[Publications] T.Tsumuraya: "Photolysis of an Azidogermane:Observation of a Germanimine(Ge=N) in Hydrocarbon Matrices" Chem.Lett.1043-1046 (1989)

[Publications] A.Sakakibara: "Photoreactions of Cyclotetrasilane and Cyclotetragermane in the Presence of Azobenzene" Nippon Kagaku Kaishi. 536-540 (1990)

[Publications] H.Iwamura: "Magnetic Coupling of Two Triplet Phenylnitrene Units Joined through an Acetylenic or Diacetylenic Linkage" Mol.Cryst.Liq.Cryst.176. 33-48 (1989)

[Publications] I.Fujita: "Design,Preparation,and ESR Detection of a GroundーState Undecet (S=5) Hydrocarbon" J.Am.Chem.Soc.112. 4074-4075 (1990)

[Publications] T.Tsuji: "Photochemical Generation of Bicyclo[4.2.2]decapentaene.Preference of [4]Paracyclophaー1,3ーdiene Structure over Bicyclo[4.2.2]decaー1,3,5,7,9ーpentaene Structure" J.Am.Chem.Soc.111. 368-369 (1989)

[Publications] M.Ohkita: "3,4ーBenzotropone:Generation,Spectroscopic Characterization,and Reactions" J.Chem.Soc.,Chem.Commun.924-926 (1989)

[Publications] M.Kira: "Photochemical 1,3ーSilyl Migration in Allylsilanes Occurring with Inversion of Silyl Configuration" J.Org.Chem.54. 5647-5648 (1989)

[Publications] M.Kira: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allysilicates in Hydroxylic Media.Discrimination between Linear and αーBranched Alkanals" J.Am.Chem.Soc.112. 257-260 (1990)

[Publications] S.Murata: "Matrix Studies of the Photolysis of oーCarbomethoxyーphenyldiazomethane.Direct Observation of Carbonyl Ylide and Its Photoinduced Valence Tautomerization" Chem.Lett.853-856 (1989)

[Publications] S.Murata: "Reaction of Bicyclo[6.3.0]undecaー2,4,6,8ーpentaenー10ーylidene in OxygenーDoped Matrices:Characterization of the First Carbonyl Oxide with a πーDonating Ring System" J.Org.Chem.55. 4502-4504 (1990)

[Publications] 石橋 孝章: "アルゴンマトリックス中単離したイソプレンの準安定異性体の赤外分光法による研究" 日本化学会誌. 1418-1422 (1989)

[Publications] M.Tasumi: "Reーinvestigation of Infraredーinduced Conformational Isomerizations of 1,2ーEthanediol in Lowーtemperature Ar Matrices and Reverse Reaction in the Dark" J.Phys.Chem.

[Publications] M.Nakata: "Stereoselective Photooxidation of transー2ーButene to Epoxide by Nitrogen Dioxide Excited with Red Light in a Cryogenic Matrix" J.Am.Chem.Soc.111. 5240-5247 (1989)

[Publications] M.Nakata: "Vibronic Excitation of OxygenーAtom Transfer from NO_2 to Ethylene by LongーWavelength Visible Light in a Cryogenic Matrix" J.Phys.Chem.94. 8168-8175 (1990)

[Publications] E.Suzuki: "Thermal Decomposition of 1,3ーDithiethane 1,3ーDioxide and Infrared Spectrum of MatrixーIsolated Sulfine" J.Mol.Struct.238. 71-77 (1990)

[Publications] E.Suzuki: "Infrared Spectra of MatrixーIsolated Propadienethione,H_2C=C=C=S" Chem.Phys.Lett.168. 1-4 (1990)

[Publications] S.Inagaki: "Preference of [6e/4p],[6e/5p],[6e/6p] Conjugations in Determining Relative Stabilities of Fused FiveーMembered Heteroaromatic Isomers" Bull.Chem.Soc.Jpn.63. 3117-3121 (1990)

[Publications] M.Ishida: "Application of the Orbital Mixing Rule to HeteroatomーDependent πーFacial Selectivity in the DielsーAlder Reaction of 5ーSubstituted 1,3ーCyclopentadiene" J.Am.Chem.Soc.112. 8980-8982 (1990)

[Publications] T.Kudo: "JahnーTeller Distortions in SnH_4^+ and PbH_4^+" Chem.Phys.Lett.156. 289-295 (1989)

[Publications] T.Kudo: "The Cyclotrisilane Radical Cation and its RingーOpened Isomers.A Theoretical Study of Si_3H_6^+" Chem.Phys.Lett.164. 217-224 (1989)

富岡秀雄三重大学, 工学部, 教授 (20024599)

[Publications] 石橋孝章: "アルゴンマトリックス中単離したイソプレンの準安定異性体の赤外分光法による研究" 日本化学会誌. 1418-1422 (1989)