1990 Fiscal Year Annual Research Report

分子の動的性質の設計

Research Project

Project/Area Number	02230108
Research Institution	Okayama University of Science
Principal Investigator	大木道則岡山理科大学, 理学部, 教授 (40011407)
Co-Investigator(Kenkyū-buntansha)	山本学東京大学, 理学部, 助手 (70011632) 深沢義正広島大学, 理学部, 教授 (50004502) 竹内敬人東京大学, 教養学部, 教授 (80012384) 兼松顯九州大学, 薬学部, 教授 (70023041) 石津和彦愛媛大学, 理学部, 教授 (60036184)
Keywords	溶媒効果 / 結合解離 / アレニルエ-テル / アレニルスルホン / 鉄TPP錯体 / 有機ゲルマニウム化合物 / シクロファン / 分子ギア
Research Abstract	溶媒分子の大きさが分子の解離速度に及ぼす影響を調べるため、ボラン・アミン錯体およびαークロロベンジル=エチル=エ-テルにつき、嵩高い分子の溶媒中での解離速度を求めた。前者は解離が速くなり、後者は遅くなった。このことは溶媒和に対する立体効果で説明が可能である。アレニルスルホンの分子内環状反応における構造・活性相関を調べた結果、基質のジエン部位がSーシス配座を取りやすい場合には[4+2]型付加体が、一方、基質の2位に置換基があってジエン部位の配座がSートランスを取りやすい場合には[2+2]付加体が優先することを明らかにした。ヘム酵素の酸素活性化機構を明らかにするため、モデル物質を作って過酸化物錯体生成の機構に関する情報を得、また膜輸送過程の研究の一環として銅(II)錯体の構造と輸送速度の相関について知見を得ることができた。ゲルマニウム原子を構成員とする種々の環状化合物を成合し、そのスペクトルおよび分子力学による計算の結果を元にして、その安定配座を求めた。ゲルマシクロペンタンは対称ねじれ構造が安定であった。これは、対応する炭素骨格とは全く異なる結果であり、炭素・ゲルマニウム結合が長いための効果と考えられる。架橋鎖にヘテロ原子を含む[m.m]シクロファンや芳香族部分にヘテロ原子を含むシクロファンを合成し、環電流効果を用いる配座決定法によってこれらの構造を求め、安定な配座を決定した。8ーハロー1,4ージメチルー9ー(2ーメチルベンジル)トリプチセンにおいて2種の安定な回転異性体を単離することに成功した。このうち一方の異性体は、加熱することにより、融解することなく、結晶中でもう一方の異性体に異性化することが分かった。結晶のなかで分子がこのような大きな運動をすることは、大変興味深いことである。

Research Products

(30 results)

All Other

All Publications (30 results)

[Publications] S.Toyota: "Dynamic NMR as a Nondestructive Method for the Determination of Rates of Dissociation.XVII.Dissociation of the NーB Bond in the Coordinated Form of 2ー[2ー(Dimethylaminomethyl)phenyl]ー4,4ーdiphenyl]ー1,3,2ーdioxaborolane and Related Compounds" Bull.Chem.Soc.Jpn.63. 1168-1173 (1990)
[Publications] Y.Tamura: "Molecular Structure of 9ーChloromethylー1,4ーdimethoxytriptycene and Its Implications for the Presence of 0...CH_2Cl Interactions" Bull.Chem.Soc.Jpn.63. 2555-2563 (1990)
[Publications] G.Yamamoto: "Restricted Rotation Involving the Tetra edral Carbon.LX.periーSubstituent Effect on the Rotational Barrier of the ^h9ーMethyl Group in Several Triptycene Derivatives" Bull.Chem.Soc.Jpn.63. 3550-3559 (1990)
[Publications] M.O^^ーki: "Methyl Group Can Stabilize Carbocations" Chem.Lett.2209-2212 (1990)
[Publications] S.Toyota: "Dynamic NMR as a Nondestructive Method for the Determination of Rates of Dissociation.XVIII.Factors Affecting the Rates of Dissociation of NーB Bond in the Coordinated Form of 9ー[2ー(Dialkylaminomethyl)phenyl]ー9ーborabicyclo[3.3.1]nonane" Bull.Chem.Soc.Jpn.
[Publications] S.toyota: "Dynamic NMRoas a Nondestructive Method for the Determination of Rates of Dissociation.XIX.Sulfur Inversion in 9ー[2ー(Ethylthiomethyl)phenyl]ー9ーborabicycloー[3.3.1]nonane Proceeds via Dissociative Mechanism" Bill.Chem.Soc.Jpn.
[Publications] K.Ishizu: "Important Role of Fe(III)TPPーOxygenーSkatole Ternary Complex in Triptophan Dioxygenase Model Reaction System" Inorganica Chim.Acta. 172. 83-91 (1990)
[Publications] K.Ishizu: "Generation of Fe(III)OEPーHydrogen Peroxide Complex by Reduction of Fe(II)OEPーOxygen Complex with Ascorbic Acid Sodium Salt" J.Chem.Soc.,Chem.Commun.144-145 (1990)
[Publications] K.Ishizu: "Coordination Structure and ChemicalReactivity of HemoproteinーButyl Peroxide Complex Studied by ESR and Optical Spectroscopy" Biochem.Biophys.Chem.Res.
[Publications] 石津和彦: "界面活性アザクラウンエ-テルで修飾されたポソ-ムの銅(II)イオン取り込みの動的過程" 日本化学会誌.
[Publications] K.Hayakawa: "Competitive Intramolecular [4+2] Cycloaddition and Tandem [2+2] Cycloaddition/[3,3]ーSigmatropic Rearrangement Sequence of allenylー3ーvinylー2ーcyclohexenyl Ethers: Evidence for Switching of the Reaction pathway by the Substituent Ethrs" J.Am.Chem.Soc.111. 5312-5320 (1989)
[Publications] M.Aso: "Furannulation Strategy,An Efficient Synthesis of Fused 3ーMethylfurans" Heterocycles. 31. 1003-1006 (1990)
[Publications] Y.Yamaguchi: "4,5,6,7ーTetrahydroisobenzofuranー5ーone as a Versatile Building Block Leading to the Basic Skeleton of Naturally Occurring Fused Furans" Heterocycles. 30. 223-226 (1990)
[Publications] S.Nagashima: "A Synthesis of an Optically Active Forskolin Intermediate via Allenyl Ether Intramolecular Cycloaddition Strategy" Tetrahedron:Asymmetry. 1. 743-749 (1990)
[Publications] K.Kanematsu: "Competitive Intramolecular [4+2] Cycloaddition and [2+2] Cycloaddition of Sulfonylallene" Tetrahedron Lett.(1991)
[Publications] K.Kanematsu: "Tatal Syntheses of Euryfuran and Xestoquinone Demonstrating an Efficient Furan Ring Transfer Reaction Strategy for the Preparation of Functionallized Polycyclic Furan Ring Systems" J.Am.Chem.Soc.
[Publications] Y.Takeuchi: "NMR Spectra of Organogermanium Compounds.IX.NMR Spectra and Molecular Mechanics Calculations of 1ーtーButylgermacyclohexanes" Bull.Chem.Soc.Jpn.63. 708-715 (1990)
[Publications] Y.Takeuchi: "Stereochemical Studies of Germacyclohexanes" Main Group Metal Chemistry. 13. 323-354 (1990)
[Publications] K.Tanaka: "Mass Spectroscopy of Organogermanium Compounds.Fragmentation Process of 1ーGermacyclohexane and Their Methyl Derivatives" Heterocycles. 30. 949-956 (1990)
[Publications] Y.Takeuchi: "NMR Spectra of Organogermanium Compounds.X.Cー13 and Geー73 NMR Spectra and Molecular Mechanics Calculations of Germacyclopentanes and Germacyclopentenes" Bull.Chem.Soc.Jpn.64. 91-98 (1991)
[Publications] Y.Fukazawa: "Synthesis and Structure of 1,11ーoーBenzeno[2]orthocyclo[2](4,5)troponophane" Tetrahedron Lett.31. 1309-1312 (1990)
[Publications] Y.Fukazawa: "Solid State Structure of a Large Ring Compound in Solution.Structure of Tetramethyl[4.4]paracyclophanedione" Tetrahedron Lett.31. 1309-1312 (1990)
[Publications] Y.Fukazawa: "Novel AcidーCatalysed Rearrangement of 4ーSubstituted Pentacycylo[5.3.0^<2.5>.O^<3.1>.0^<4.8>]decanー6ーones" J.Chem.Soc.Perkin 2. 1735-1738 (1990)
[Publications] Y.Fukazawa: "Structure of 2,11ーDioxa[3.3]orthocyclophane" Chem.Lett.37-40 (1991)
[Publications] Y.Fukazawa: "Asymmetric Synthesis of 5ー and 6ーMembered Lactones from Cyclic Substrate Bearing a C_2ーChiral Auxiliary" J.Org.Chem.56. (1991)
[Publications] T.Mitsuhashi: "Analysis of Solvent Effects on the Rates of the Cope Rearrangement: Evidence for Its HydrogenーBondーInsusceptible Nature" Bull.Chem.Soc.Jpn.63. 643-645 (1990)
[Publications] G.Yamamoto: "Use of Benzene Rings as Parts of Rigid Rotors: Dynamic Stereochemistry of 9ー(ArylーX)triptycene Derivatives" Pure Appl.Chem.62. 569-574 (1990)
[Publications] M.A.Cremonini: "Conformation and Stereodynamics of a Highly Hindered Ethane,1,2ーBis(2,4,6ーtriーtertーbutylphenyl)ethane,and of the Corresponding Ethyl Radical" J.Am.Chem.Soc.112. 2915-2921 (1990)
[Publications] G.Yamamoto: "Dynamic Stereochemistry of Molecular Gears,9ーBenzyltriptycene and 9ーPhenoxytriptycene,Studied by 13ーC Dynamic NMR Spectroscopy and Molecular Mechanics Calculations" Tetrahedron. 46. 2761-2772 (1990)
[Publications] G.Yamamoto: "Atropisomerism in a Molecular Gear,8ーBromoー1,4ーdimethylー9ー(2ーmethylbenzyl)ーtriptycene" Chem.Lett.1373-1376 (1990)

1990 Fiscal Year Annual Research Report

分子の動的性質の設計

Principal Investigator

大木 道則 岡山理科大学, 理学部, 教授 (40011407)

Research Products

[Publications] Y.Tamura: "Molecular Structure of 9ーChloromethylー1,4ーdimethoxytriptycene and Its Implications for the Presence of 0...CH_2Cl Interactions" Bull.Chem.Soc.Jpn.63. 2555-2563 (1990)

[Publications] G.Yamamoto: "Restricted Rotation Involving the Tetra edral Carbon.LX.periーSubstituent Effect on the Rotational Barrier of the ^h9ーMethyl Group in Several Triptycene Derivatives" Bull.Chem.Soc.Jpn.63. 3550-3559 (1990)

[Publications] M.O^^ーki: "Methyl Group Can Stabilize Carbocations" Chem.Lett.2209-2212 (1990)

[Publications] S.Toyota: "Dynamic NMR as a Nondestructive Method for the Determination of Rates of Dissociation.XVIII.Factors Affecting the Rates of Dissociation of NーB Bond in the Coordinated Form of 9ー[2ー(Dialkylaminomethyl)phenyl]ー9ーborabicyclo[3.3.1]nonane" Bull.Chem.Soc.Jpn.

[Publications] S.toyota: "Dynamic NMRoas a Nondestructive Method for the Determination of Rates of Dissociation.XIX.Sulfur Inversion in 9ー[2ー(Ethylthiomethyl)phenyl]ー9ーborabicycloー[3.3.1]nonane Proceeds via Dissociative Mechanism" Bill.Chem.Soc.Jpn.

[Publications] K.Ishizu: "Important Role of Fe(III)TPPーOxygenーSkatole Ternary Complex in Triptophan Dioxygenase Model Reaction System" Inorganica Chim.Acta. 172. 83-91 (1990)

[Publications] K.Ishizu: "Generation of Fe(III)OEPーHydrogen Peroxide Complex by Reduction of Fe(II)OEPーOxygen Complex with Ascorbic Acid Sodium Salt" J.Chem.Soc.,Chem.Commun.144-145 (1990)

[Publications] K.Ishizu: "Coordination Structure and ChemicalReactivity of HemoproteinーButyl Peroxide Complex Studied by ESR and Optical Spectroscopy" Biochem.Biophys.Chem.Res.

[Publications] 石津 和彦: "界面活性アザクラウンエ-テルで修飾されたポソ-ムの銅(II)イオン取り込みの動的過程" 日本化学会誌.

[Publications] M.Aso: "Furannulation Strategy,An Efficient Synthesis of Fused 3ーMethylfurans" Heterocycles. 31. 1003-1006 (1990)

[Publications] Y.Yamaguchi: "4,5,6,7ーTetrahydroisobenzofuranー5ーone as a Versatile Building Block Leading to the Basic Skeleton of Naturally Occurring Fused Furans" Heterocycles. 30. 223-226 (1990)

[Publications] S.Nagashima: "A Synthesis of an Optically Active Forskolin Intermediate via Allenyl Ether Intramolecular Cycloaddition Strategy" Tetrahedron:Asymmetry. 1. 743-749 (1990)

[Publications] K.Kanematsu: "Competitive Intramolecular [4+2] Cycloaddition and [2+2] Cycloaddition of Sulfonylallene" Tetrahedron Lett.(1991)

[Publications] K.Kanematsu: "Tatal Syntheses of Euryfuran and Xestoquinone Demonstrating an Efficient Furan Ring Transfer Reaction Strategy for the Preparation of Functionallized Polycyclic Furan Ring Systems" J.Am.Chem.Soc.

[Publications] Y.Takeuchi: "NMR Spectra of Organogermanium Compounds.IX.NMR Spectra and Molecular Mechanics Calculations of 1ーtーButylgermacyclohexanes" Bull.Chem.Soc.Jpn.63. 708-715 (1990)

[Publications] Y.Takeuchi: "Stereochemical Studies of Germacyclohexanes" Main Group Metal Chemistry. 13. 323-354 (1990)

[Publications] K.Tanaka: "Mass Spectroscopy of Organogermanium Compounds.Fragmentation Process of 1ーGermacyclohexane and Their Methyl Derivatives" Heterocycles. 30. 949-956 (1990)

[Publications] Y.Takeuchi: "NMR Spectra of Organogermanium Compounds.X.Cー13 and Geー73 NMR Spectra and Molecular Mechanics Calculations of Germacyclopentanes and Germacyclopentenes" Bull.Chem.Soc.Jpn.64. 91-98 (1991)

[Publications] Y.Fukazawa: "Synthesis and Structure of 1,11ーoーBenzeno[2]orthocyclo[2](4,5)troponophane" Tetrahedron Lett.31. 1309-1312 (1990)

[Publications] Y.Fukazawa: "Solid State Structure of a Large Ring Compound in Solution.Structure of Tetramethyl[4.4]paracyclophanedione" Tetrahedron Lett.31. 1309-1312 (1990)

[Publications] Y.Fukazawa: "Novel AcidーCatalysed Rearrangement of 4ーSubstituted Pentacycylo[5.3.0^<2.5>.O^<3.1>.0^<4.8>]decanー6ーones" J.Chem.Soc.Perkin 2. 1735-1738 (1990)

[Publications] Y.Fukazawa: "Structure of 2,11ーDioxa[3.3]orthocyclophane" Chem.Lett.37-40 (1991)

[Publications] Y.Fukazawa: "Asymmetric Synthesis of 5ー and 6ーMembered Lactones from Cyclic Substrate Bearing a C_2ーChiral Auxiliary" J.Org.Chem.56. (1991)

[Publications] T.Mitsuhashi: "Analysis of Solvent Effects on the Rates of the Cope Rearrangement: Evidence for Its HydrogenーBondーInsusceptible Nature" Bull.Chem.Soc.Jpn.63. 643-645 (1990)

[Publications] G.Yamamoto: "Use of Benzene Rings as Parts of Rigid Rotors: Dynamic Stereochemistry of 9ー(ArylーX)triptycene Derivatives" Pure Appl.Chem.62. 569-574 (1990)

[Publications] M.A.Cremonini: "Conformation and Stereodynamics of a Highly Hindered Ethane,1,2ーBis(2,4,6ーtriーtertーbutylphenyl)ethane,and of the Corresponding Ethyl Radical" J.Am.Chem.Soc.112. 2915-2921 (1990)

[Publications] G.Yamamoto: "Dynamic Stereochemistry of Molecular Gears,9ーBenzyltriptycene and 9ーPhenoxytriptycene,Studied by 13ーC Dynamic NMR Spectroscopy and Molecular Mechanics Calculations" Tetrahedron. 46. 2761-2772 (1990)

[Publications] G.Yamamoto: "Atropisomerism in a Molecular Gear,8ーBromoー1,4ーdimethylー9ー(2ーmethylbenzyl)ーtriptycene" Chem.Lett.1373-1376 (1990)

大木道則岡山理科大学, 理学部, 教授 (40011407)

[Publications] 石津和彦: "界面活性アザクラウンエ-テルで修飾されたポソ-ムの銅(II)イオン取り込みの動的過程" 日本化学会誌.