1989 Fiscal Year Annual Research Report

分子の動的性質の設計

Research Project

Project/Area Number	01648007
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	ボラン・アミン錯体 / 有機ゲルマニウム化合物 / ビタミンE / アレニルエ-テル / 分子ギア / DNMR / ESR / 分子力学
Research Abstract	分子内アミン・ボラン錯体の解離速度をDNMR法によって求めるため、ボランとしてボロン酸エステルを含む化合物の合成を行った。解離速度は、一般に溶媒の極性が高くなるにつれて遅くなったが、ホウ素に配位できる原子をもつ溶媒は、解離速度を速めることが明らかになった。ヘムが関与する活性化機構の解析を行なうため、生体内で生じた過酸化物を除去すると考えられているビタミンE誘導体の分子設計をし、その合成を行った。さらにいくつかの化合物については、ESRの測定を行って、還元の機構について考察した。分子内環状反応における構造ー反応性相関を種々の基質を用いて検討し、基質の立体配座によって〔4+2〕型付加体を生成する場合と〔2+2〕付加体を生成する場合があることを明らかにした。tーブチルゲルマシクロヘキサンのエクアトリアルとアキシアルの配座エネルギ-差が約1.2kcal/molであることを明らかにした。また、ゲルマシクロペンタンの安定構造が対称ねじれ構造であることを、NMR及び分子力学計算で示し、対応する炭素骨格の化合物とは大きく異なることを明らかにした。14員環状構造をもつ〔4.4〕メタシクロファンのX線構造解析・NMRにおける環電流効果・分子力学計算によって、溶液中で存在する数種の立体配座の寄与を見積もることに成功した。環電流効果に基ずく配座解析は、一般の場合にも応用可能なものと考えられる。2枚歯と3枚歯からなる分子ギアである9ーベンジルトリプチセン及び9ーフェノキシトリプチセンの分子内運動を検討し、その結果を用いて、1.4ージメチルー8ーブロモー9ー(2ーメチルベンジン)トリプチセンにおいてギア回転系のアトロブ異性体を現出することができた。

Research Products

(23 results)

All Other

All Publications (23 results)

[Publications] S.Toyota: "Dissociation of the NーB Bond in the Coordinated Form of 2ー〔2ー(Dimethylaminomethy1)pheny1〕ー4,4ーdipheny1ー1,3,2ーdioxaborolane and Related compounds" Bull.Chem.Soc.Jpn.63. (1990)
[Publications] K.Tajima: "Generation of Fe(III)OEPーHydrogen Peroxide Complex by Reduction of Fe(II)OEPーO_2 Complex with Ascorbic Acid Sodium Salt" J.Chem.Soc.,Chem.Commun.(1990)
[Publications] K.Tajima: "An Important Role of Fe(III)TPPーOxygenーSkatole Ternary Complex in Tryptophan Dioxygenase Model Reaction System" Inorganica Chimica Acta. (1990)
[Publications] K.Tajima: "A Possible Model of HemoproteinーFatty Acid Peroxide Complex Demonstrated by Electron Spin Resonance" Biochem.Biophys.Res.Commun.(1990)
[Publications] K.Mukai: "Kinetic Study of Vitamin C with Vitamin E Radicals(Tocopherocyl)in Solution" Biochem.Biophys.Acta.991. 276-279 (1989)
[Publications] K.Tajima: "ENDOR Studies of the Complexation Reaction between SpinーLabeled Crown Ether and Alkali Metal Salts" Bull.Chem.Soc.Jpn.62. 2061-2063 (1989)
[Publications] K.Tajima: "Autoreduction of Six Coordinate Fe(III)TPPーnーButyl Peroxide Complex to the Ferrous LowーSpin Complex" Inorganica Chimica Acta.
[Publications] K.Hayakawa: "Competitive Intramolecular〔4+2〕Cycloaddition and Tandem〔2+2〕Cycloaddition/〔3.3〕ーSigmatropic Rearrangement Sequence of Alleny1 3ーViny1ー2ーcyclohexeny1 Ethers" J.Am.Chem.Soc.111. 5312-5320 (1989)
[Publications] Y.Yamaguchi: "Chirality Transfer from the Furan Ring Transfer Reaction" J.Chem.Soc.,Chem.Commun.470-472 (1989)
[Publications] T.Yasukouchi: "An Efficient Approach to the Basic Skeleton fo the cisーTrikentrins" J.Chem.Soc.,Chem.Commun.953-954 (1989)
[Publications] K.Kanematsu: "An Efficient Synthesis of a Key Intermediate fo Forskolin" J.Chem.Soc.,Chem.Commun.1028-1029 (1989)
[Publications] Y.Takeuchi: "NMR Spectra of Organogermanium Compounds.IX.NMR Spectra and Molecular Mechanics Calculation of 1ーtーButylgermacyclohexanes" Bull.Chem.Soc.Jpn.63. (1990)
[Publications] K.Tanaka: "Mass Spectrometry of Organogermanium Compounds.Mechnism of Fragmentation Process of 1ーGermacycloーhexane and Their Methyl Derivatives" Heterocycles. (1990)
[Publications] Y.Takeuchi: "Sterochemical Studies of Germacyclohexanes" Main Group Metal Chemistry. 12. (1990)
[Publications] T.Harazono: "Relaxation Mechanism of Germaniumー73 in Tetrabromoーgermanes and Tetraiodogermane at High Temperature" Inorg.Chem.28. 1813-1815 (1990)
[Publications] S.Tomoda: "Molecular Structure of 2,2,5,5ーTetramethy1ー1,3ーdiselenaー2ーgermacyclohexane.Evidence for Symmetrical Twistーboat Conformation" J.Chem.Soc.,Chem.Commun.1304-1306 (1989)
[Publications] T.Okajima: "Structure of 2,11ーDithia〔3.3〕orthocyclophane and Its Diselena Analogue" Tetrahedron Lett.30. 1551-1554 (1989)
[Publications] Y.Fukazawa: "Nucleophilic Reaction of Azulene Derivatives with Some Ketone Enolates" J.Org.Chem.54. 2982-2985 (1989)
[Publications] Y.Fukazawa: "1,11ーoーBenzeno〔2〕orthocyclo〔1〕(6,8)heptafulvenophane" Tetrahedron Lett.30. 3163-3166 (1989)
[Publications] Y.Fukazawa: "Synthesis and Structure of 1,11ーoーBenzeno[z](4,5)ーtropolophane" Tetrahedron Lett. 31. (1990)
[Publications] G.Yamamoto: "Detailed Dynamic NMR Study of a Molecular Gear,1ーMethoxyー9ー(3,5ーdimethylbenzyl)triptycene" Bull.Chem.Soc.Jpn.62. 4058-4060 (1989)
[Publications] G.Yamamoto: "Dynamic Stereochemistry of Molecular Gears,9ーBenzy1ーtriptycene and 9ーPhenoxytriptycene Studied by ^<13>C Dynamic NMR Spectroscopy and Molecular Mechanics" Tetrahedron.
[Publications] G.Yamamoto: "Use of Benzene Rings as Parts of Rigid Rotars: Dynamic Sterochemistry of 9ー(Ary1ーX)triptycene Derivatives" Pure & Appl.Chem.62. (1990)

1989 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] S.Toyota: "Dissociation of the NーB Bond in the Coordinated Form of 2ー〔2ー(Dimethylaminomethy1)pheny1〕ー4,4ーdipheny1ー1,3,2ーdioxaborolane and Related compounds" Bull.Chem.Soc.Jpn.63. (1990)

[Publications] K.Tajima: "Generation of Fe(III)OEPーHydrogen Peroxide Complex by Reduction of Fe(II)OEPーO_2 Complex with Ascorbic Acid Sodium Salt" J.Chem.Soc.,Chem.Commun.(1990)

[Publications] K.Tajima: "An Important Role of Fe(III)TPPーOxygenーSkatole Ternary Complex in Tryptophan Dioxygenase Model Reaction System" Inorganica Chimica Acta. (1990)

[Publications] K.Tajima: "A Possible Model of HemoproteinーFatty Acid Peroxide Complex Demonstrated by Electron Spin Resonance" Biochem.Biophys.Res.Commun.(1990)

[Publications] K.Mukai: "Kinetic Study of Vitamin C with Vitamin E Radicals(Tocopherocyl)in Solution" Biochem.Biophys.Acta.991. 276-279 (1989)

[Publications] K.Tajima: "ENDOR Studies of the Complexation Reaction between SpinーLabeled Crown Ether and Alkali Metal Salts" Bull.Chem.Soc.Jpn.62. 2061-2063 (1989)

[Publications] K.Tajima: "Autoreduction of Six Coordinate Fe(III)TPPーnーButyl Peroxide Complex to the Ferrous LowーSpin Complex" Inorganica Chimica Acta.

[Publications] K.Hayakawa: "Competitive Intramolecular〔4+2〕Cycloaddition and Tandem〔2+2〕Cycloaddition/〔3.3〕ーSigmatropic Rearrangement Sequence of Alleny1 3ーViny1ー2ーcyclohexeny1 Ethers" J.Am.Chem.Soc.111. 5312-5320 (1989)

[Publications] Y.Yamaguchi: "Chirality Transfer from the Furan Ring Transfer Reaction" J.Chem.Soc.,Chem.Commun.470-472 (1989)

[Publications] T.Yasukouchi: "An Efficient Approach to the Basic Skeleton fo the cisーTrikentrins" J.Chem.Soc.,Chem.Commun.953-954 (1989)

[Publications] K.Kanematsu: "An Efficient Synthesis of a Key Intermediate fo Forskolin" J.Chem.Soc.,Chem.Commun.1028-1029 (1989)

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

[Publications] K.Tanaka: "Mass Spectrometry of Organogermanium Compounds.Mechnism of Fragmentation Process of 1ーGermacycloーhexane and Their Methyl Derivatives" Heterocycles. (1990)

[Publications] Y.Takeuchi: "Sterochemical Studies of Germacyclohexanes" Main Group Metal Chemistry. 12. (1990)

[Publications] T.Harazono: "Relaxation Mechanism of Germaniumー73 in Tetrabromoーgermanes and Tetraiodogermane at High Temperature" Inorg.Chem.28. 1813-1815 (1990)

[Publications] S.Tomoda: "Molecular Structure of 2,2,5,5ーTetramethy1ー1,3ーdiselenaー2ーgermacyclohexane.Evidence for Symmetrical Twistーboat Conformation" J.Chem.Soc.,Chem.Commun.1304-1306 (1989)

[Publications] T.Okajima: "Structure of 2,11ーDithia〔3.3〕orthocyclophane and Its Diselena Analogue" Tetrahedron Lett.30. 1551-1554 (1989)

[Publications] Y.Fukazawa: "Nucleophilic Reaction of Azulene Derivatives with Some Ketone Enolates" J.Org.Chem.54. 2982-2985 (1989)

[Publications] Y.Fukazawa: "1,11ーoーBenzeno〔2〕orthocyclo〔1〕(6,8)heptafulvenophane" Tetrahedron Lett.30. 3163-3166 (1989)

[Publications] Y.Fukazawa: "Synthesis and Structure of 1,11ーoーBenzeno[z](4,5)ーtropolophane" Tetrahedron Lett. 31. (1990)

[Publications] G.Yamamoto: "Detailed Dynamic NMR Study of a Molecular Gear,1ーMethoxyー9ー(3,5ーdimethylbenzyl)triptycene" Bull.Chem.Soc.Jpn.62. 4058-4060 (1989)

[Publications] G.Yamamoto: "Dynamic Stereochemistry of Molecular Gears,9ーBenzy1ーtriptycene and 9ーPhenoxytriptycene Studied by ^<13>C Dynamic NMR Spectroscopy and Molecular Mechanics" Tetrahedron.

[Publications] G.Yamamoto: "Use of Benzene Rings as Parts of Rigid Rotars: Dynamic Sterochemistry of 9ー(Ary1ーX)triptycene Derivatives" Pure & Appl.Chem.62. (1990)

大木道則岡山理科大学, 理学部, 教授 (40011407)