1993 Fiscal Year Annual Research Report

有機素反応過程の動的理解

Research Project

Project/Area Number	05353002
Research Institution	Kyushu University
Principal Investigator	都野雄甫九州大学, 有機化学基礎研究センター, 教授 (10029845)
Co-Investigator(Kenkyū-buntansha)	藤尾瑞枝九州大学, 有機化学基礎研究センター, 助教授 (10029887) 小林進二郎九州大学, 有機化学基礎研究センター, 助教授 (20037831) 西田進也北海道大学, 理学部, 教授 (40029400) 速水醇一京都大学大学院, 人間・環境学研究科, 教授 (30025283) 大木道則岡山理科大学, 理学部, 教授 (40011407)
Keywords	有機素反応 / 物理有機化学 / 反応触媒効果 / 活性化学種 / 構造反応性相関 / 反応経路解析 / 複合系反応解析 / 動的分子構造
Research Abstract	研究班の全体会議を京都において計2回開催し、新しい有機反応設計の指導原理の構築のための研究分野と研究態勢の現状の分析、推進すべき研究分野および共同研究に関して検討を加えた。特に第1回の会議においては、有機素反応研究会(日本化学会)のメンバーを加えて、微視的な立場から有機反応の動的理解および反応における選択性の発現機構の解明の方策について議論を深めた。研究班の専門委員会を計4回開催し、より具体的な研究分野について現状の分析と今後の研究推進の方向性および研究態勢の在り方について検討した。さらに、10月に福岡で開催された第5回物理有機化学九州国際会議に於いて、班員以外の全国の研究者および海外の指導的研究者から、有機反応設計の原理の構築のための方策について種々の観点からの意見の集約を計った。これらの議論から、分子クラスターの研究、ICRによる気相中のイオン性分子種の研究など気相からのアプローチが有機反応における溶媒効果の微細機構の理解に重要であること、また、短寿命中間体の特性に基づく有機素反応の遷移状態の動的理解の深化は、有機合成反応および生体反応における選択性の解明および新奇有機反応の開発など有機反応関連の応用分野の進展に不可欠であること、等が強く認識された。これらの研究分野の飛躍的進展には有機化学者だけでなく理論化学者および物理化学者から構成される高度に組織化された研究態勢が必要であるとの結論に達した。その具体化の方策として、基礎研究の推進を目的として設立された九州大学「有機化学基礎研究センター」を中核に据えた新機軸の研究推進ネットワークを組織し、(1)動的分子構造と機能、(2)反応媒質効果、(三)活性化学種の動的特性、(4)構造-反応性相関、(5)反応経路解析、(6)複合系反応解析の6研究課題を立案し、平成7年度発足科学研究費補助金「重点領域研究」の領域申請を行った。

Research Products
(42 results)

All Other

All Publications (42 results)

[Publications] F.Hayakawa: "Silicon Effects. V.beta-Silicon Effect in the Solvolysis of 2-Phenylethyl Compounds" Bull.Chem.Soc.Jpn.66. 153-157 (1993)
[Publications] S.D.Yoh: "Alkaline Hydrolysis of Substituted Benzyl Substituted Benzoates" J.Phys.Org.Chem.6. 23-28 (1993)
[Publications] M.Mishima: "Effect of the Twisted Nitro Group on Gas Phase Acidities of Phenol,Toluene,Aniline,and Benzoic Acid. Steric Inhibition of Intrinsic ResonanceEffect" Chem. Lett.885-888 (1993)
[Publications] M.Mishima: "Substitutent Effect on Electron Affinity of 2,6-Dimethylnitrobenzene" Chem. Lett.889-892 (1993)
[Publications] M.Mishima: "Electron Affinities of Benzaldehyde. Substituent Effects on Stabilities of Aromatic Radical Anions" Tetrahedron Lett.34. 4223-4226 (1993)
[Publications] T.Asano: "Mechanism of Thermal Z/E Isomerization of Substituted N-Benzylideneanilines.Nature of the Activated Complex with a sp-Hybridized Nitrogen Atom" J.Org.Chem.58. 4418-4423 (1993)
[Publications] S.D.Yoh: "Nucleophilic Substitution Reaction and Elimimnation Reaction of 2-Phenylethyl Arensulfonates" Bull.Korean Chem.Soc.14. 531-533 (1993)
[Publications] M.Fujio: "The Importance of Resonance Stabilization in the Benzylic Solvolysis. Substituent Effects on the Solvolysis of alpha,alpha-Diisopropylbenzyl Chlorides" Tetrahedron Lett.34. 8309-8312 (1993)
[Publications] K.Yatsugi: "Kinetic Effects of Thiourea Addition on Benzylic Solvolyses" Tetrahedron Lett.34. 135-138 (1994)
[Publications] N.Shimizu: "Silicon Effects. IV.b-Silicon Effect of Various Silyl Groups in Solvolysis for alpha-Alkylbenzyl and alpha-Silylbenzyl Systems" Bull.Chem.Soc.Jpn.67. 500-504 (1994)
[Publications] H.Yamataka: "Distiction between Polar and Electron-transfer Routes.A Mechanistic Study on the Witting Reactions of Nonstabilized Ylides" J.Am.Chem.Soc.115. 8570-8572 (1993)
[Publications] H.Yamataka: "Reaction Pathway and Transition State of the Zn-Promated Barbier-Type Reactions of Benzaldehyde and Benzophenone with Allylic Iodines" Bull.Chem.Soc.Jpn.67. 242-245 (1993)
[Publications] F.Misaizu: "Formation of Protonated Ammonia Cluster Ions:Two-color Two-photon Ionization Study" J.Chem.Phys.98. 336-341 (1993)
[Publications] K.Ohashi: "Photodissociation Dynamics of (C_6H_6)_2^++" J.Chem.Phys.98. 390-398 (1993)
[Publications] P.Lablanquie: "Photodissociation Dynamics of C_6H_6^+ Created through multiphoton Ionization of para-Chlorotoluene" J.Chem.Phys.98. 399-408 (1993)
[Publications] H.Fukumura: "Mass Spectromtric Studies on Laser Ablation of Polystyrene Sensitizedwith Anthracene" J.Chem.Phys.98. 13761-13767 (1993)
[Publications] T.Okuyama: "Oxygen-18 Labeling of Cyclic and Acyclic Sulfinate Esters" Heteroatom Chem.4. 223-228 (1993)
[Publications] T.Okuyama: "Kinetic Studies of Hydrolysis of Some Alkyl Benzensulfinates" Heteroatom Chem.4. 459-462 (1993)
[Publications] Y.Tsuji: "The Study of 〓〓〓-Scrambling inthe Menschutkin Reaction of p-Methylbenyl Tosylate with N,N-Dimethylanilines in Acetonitrile" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 19(1). 47-62 (1993)
[Publications] G.A.Ahmed: "Solvent Effects on the Solvolysis of Simple Alkyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 19(1). 63-80 (1993)
[Publications] K.Yatsgi: "Solvolysis of 1-Adamantylmethyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 19(1). 81-96 (1993)
[Publications] S.Kobayashi: "Substituent Effect on Gas Phase Basicity of 1-Phenylpropyne. Thermo dynamic Stability and Resonance Demand of 1-Phenylpropenyl Cations" Tetrahedron Lett.34. 5903-5906 (1993)
[Publications] M.Fujio: "The Substituent Effect Studiesof Aryl-assisted Solvolyses.I. The Acetolysis of 2,2-Bis(substituted phenyl) ethyl Tosylates" Bull.Chem.Soc.Jpn.66. 3015-3020 (1993)
[Publications] M.Fujio: "The Substituent Effect Studiesof Aryl-assisted Solvolyses.II. The Acetolysis of 2-Phenyl-2-Bis(substituted phenyl) ethyl Tosylates" Bull.Chem.Soc.Jpn.66. 3021-3029 (1993)
[Publications] T.Okuyama: "Ring Opening and Closure and Oxygen Isotope Excahange of Cyclic Sulfinate Esters" J.Org.Chem.59. 472-476 (1993)
[Publications] T.Okuyama: "On the Mechanism of Acid-catalyzedHydrolysis of Sulfinate Esters.Oxygen Isotopoe Exchange anf Theoretical Studies" J.Chem.Soc.,Perkin Trans.2. (in press). (1994)
[Publications] Y.Kondo: "Nucleophilic Reactivity and Solvation of Succinimide and Phthalimide Anions in Acetonitrile-Methanol Mixtures" J.Chem.Soc.,Perkin Trans.2. 1141-1145 (1993)
[Publications] Y.Kondo: "Single-ion Enthalpies of Transfer for Conjugate-base Anions of Imides in Acetonitrile-Methanole Mixtures21GC28:J.Chem.Soc.,Faraday Trans." 121-125 (1994)
[Publications] Y.Kondo: "Charactorization of Solute-Solvent Interaction at the Transition State by Thermodynamic and Quantum-mechanical Approaches,Reactions of Imides Ions with EthylIodide in Acetonitrile-Methanol" J.Chem.Soc.,Perkin Trans.2. (in press). (1994)
[Publications] M.Okamura: "NAD(P)+-NAD(P)H Models.81.Temperature-Dependent Stereospecificity in the Interconversion between Central and Axial Chiralities" Bull.Chem.Soc./Jpn.66. 1191-1196 (1993)
[Publications] M.Okamura: "NAD(P)+-NAD(P)H Models.82.Effect of Magnesium on the Stereospecificity and Conformations at the Ground nad Transition Statesof the Reaction" Bull.Chem.Soc.Jpn.66. 1197-1203 (1993)
[Publications] K.Nakamura: "Stereochemical Control in Microbial Reduction. 21.Effect of Organic Solvents on Reduction of alpha-Keto Esters Mediated by Bakers'Yeast" Bull.Chem.Soc.Jpn.2783-2743 (1993)
[Publications] K.Nakamura: "Asymmetric Reduction of Ketopantolactone by Bakers'Yeast" Tetrahedron; Asymmetry. 4. 1253-1254 (1993)
[Publications] S.Yasui: "The Arbuzov Reaction of Alkyl Diphenylphosphinites with 10-Methylacridinium Ion Kinetic Study on the Formation and the Decomposition of Phosphonium Intermediates" Bull.Chem.Soc.Jpn.66. 2077-2083 (1993)
[Publications] S.Yasui: "The Catalytic Role of Iodide Ion/Iodine Couple in the Photo-Reduction of 10-Methylacridinium Ion with Diphenylphosphine Oxide" Chem. Lett.1393-1396 (1993)
[Publications] K.Nakamura: "Diastereoselective Reduction of Ethyl a-Methyl-b-oxobutanoate by Immobilized Geotrichum candidum in an Organic Solvent" Tetrahedron Lett.34. 6087-6090 (1993)
[Publications] M.S.Tang: "A MO Study of the Electronic Spectra and Molecular Conformation of Thiophene oligomers" Chem.Express. 8. 257-260 (1993)
[Publications] M.Iyoda: "Synthesis of the Tris(9-fluorenylidene)cyclopropane Dianion and Related Dianions:[3]-Radialenes with Novel Electronic Properties" Angew. Chemie. 32. 89-90 (1993)
[Publications] K.Nishimoto: "A MO Theoretical Study of Organic Dynes 1.Effect of Chemical Softness on the Electronic Spectra" Bull.Chem.Soc.Jpn.66. 1876-1880 (1993)
[Publications] T.Asada: "Theoretical Study on Binding Enthalpies and Populations of Isomers of Cl^-(H_2O)_n Clusters at Room Temperature" J.Phy.Chem.97. 7724-7729 (1993)
[Publications] K.Hiruta: "Evaluation of two Center Electron Repulsion Integral New-gamma for the PPPMolecular Orbital Calculation of p-band of cata-Condensed Polycyclic Aromatic Hydrocarbons" J.Chem.Software. 1. 157-164 (1993)
[Publications] I.Maki: "VB Structures Contained in LCAO MO Results I.The Ground State of Conjugated Systems" Theor.Chim. Acta. in press. (1994)

1993 Fiscal Year Annual Research Report

有機素反応過程の動的理解

Principal Investigator

都野 雄甫 九州大学, 有機化学基礎研究センター, 教授 (10029845)

Research Products

[Publications] F.Hayakawa: "Silicon Effects. V.beta-Silicon Effect in the Solvolysis of 2-Phenylethyl Compounds" Bull.Chem.Soc.Jpn.66. 153-157 (1993)

[Publications] S.D.Yoh: "Alkaline Hydrolysis of Substituted Benzyl Substituted Benzoates" J.Phys.Org.Chem.6. 23-28 (1993)

[Publications] M.Mishima: "Effect of the Twisted Nitro Group on Gas Phase Acidities of Phenol,Toluene,Aniline,and Benzoic Acid. Steric Inhibition of Intrinsic ResonanceEffect" Chem. Lett.885-888 (1993)

[Publications] M.Mishima: "Substitutent Effect on Electron Affinity of 2,6-Dimethylnitrobenzene" Chem. Lett.889-892 (1993)

[Publications] M.Mishima: "Electron Affinities of Benzaldehyde. Substituent Effects on Stabilities of Aromatic Radical Anions" Tetrahedron Lett.34. 4223-4226 (1993)

[Publications] T.Asano: "Mechanism of Thermal Z/E Isomerization of Substituted N-Benzylideneanilines.Nature of the Activated Complex with a sp-Hybridized Nitrogen Atom" J.Org.Chem.58. 4418-4423 (1993)

[Publications] S.D.Yoh: "Nucleophilic Substitution Reaction and Elimimnation Reaction of 2-Phenylethyl Arensulfonates" Bull.Korean Chem.Soc.14. 531-533 (1993)

[Publications] M.Fujio: "The Importance of Resonance Stabilization in the Benzylic Solvolysis. Substituent Effects on the Solvolysis of alpha,alpha-Diisopropylbenzyl Chlorides" Tetrahedron Lett.34. 8309-8312 (1993)

[Publications] K.Yatsugi: "Kinetic Effects of Thiourea Addition on Benzylic Solvolyses" Tetrahedron Lett.34. 135-138 (1994)

[Publications] N.Shimizu: "Silicon Effects. IV.b-Silicon Effect of Various Silyl Groups in Solvolysis for alpha-Alkylbenzyl and alpha-Silylbenzyl Systems" Bull.Chem.Soc.Jpn.67. 500-504 (1994)

[Publications] H.Yamataka: "Distiction between Polar and Electron-transfer Routes.A Mechanistic Study on the Witting Reactions of Nonstabilized Ylides" J.Am.Chem.Soc.115. 8570-8572 (1993)

[Publications] H.Yamataka: "Reaction Pathway and Transition State of the Zn-Promated Barbier-Type Reactions of Benzaldehyde and Benzophenone with Allylic Iodines" Bull.Chem.Soc.Jpn.67. 242-245 (1993)

[Publications] F.Misaizu: "Formation of Protonated Ammonia Cluster Ions:Two-color Two-photon Ionization Study" J.Chem.Phys.98. 336-341 (1993)

[Publications] K.Ohashi: "Photodissociation Dynamics of (C_6H_6)_2^++" J.Chem.Phys.98. 390-398 (1993)

[Publications] P.Lablanquie: "Photodissociation Dynamics of C_6H_6^+ Created through multiphoton Ionization of para-Chlorotoluene" J.Chem.Phys.98. 399-408 (1993)

[Publications] H.Fukumura: "Mass Spectromtric Studies on Laser Ablation of Polystyrene Sensitizedwith Anthracene" J.Chem.Phys.98. 13761-13767 (1993)

[Publications] T.Okuyama: "Oxygen-18 Labeling of Cyclic and Acyclic Sulfinate Esters" Heteroatom Chem.4. 223-228 (1993)

[Publications] T.Okuyama: "Kinetic Studies of Hydrolysis of Some Alkyl Benzensulfinates" Heteroatom Chem.4. 459-462 (1993)

[Publications] Y.Tsuji: "The Study of 〓〓〓-Scrambling inthe Menschutkin Reaction of p-Methylbenyl Tosylate with N,N-Dimethylanilines in Acetonitrile" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 19(1). 47-62 (1993)

[Publications] G.A.Ahmed: "Solvent Effects on the Solvolysis of Simple Alkyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 19(1). 63-80 (1993)

[Publications] K.Yatsgi: "Solvolysis of 1-Adamantylmethyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 19(1). 81-96 (1993)

[Publications] S.Kobayashi: "Substituent Effect on Gas Phase Basicity of 1-Phenylpropyne. Thermo dynamic Stability and Resonance Demand of 1-Phenylpropenyl Cations" Tetrahedron Lett.34. 5903-5906 (1993)

[Publications] M.Fujio: "The Substituent Effect Studiesof Aryl-assisted Solvolyses.I. The Acetolysis of 2,2-Bis(substituted phenyl) ethyl Tosylates" Bull.Chem.Soc.Jpn.66. 3015-3020 (1993)

[Publications] M.Fujio: "The Substituent Effect Studiesof Aryl-assisted Solvolyses.II. The Acetolysis of 2-Phenyl-2-Bis(substituted phenyl) ethyl Tosylates" Bull.Chem.Soc.Jpn.66. 3021-3029 (1993)

[Publications] T.Okuyama: "Ring Opening and Closure and Oxygen Isotope Excahange of Cyclic Sulfinate Esters" J.Org.Chem.59. 472-476 (1993)

[Publications] T.Okuyama: "On the Mechanism of Acid-catalyzedHydrolysis of Sulfinate Esters.Oxygen Isotopoe Exchange anf Theoretical Studies" J.Chem.Soc.,Perkin Trans.2. (in press). (1994)

[Publications] Y.Kondo: "Nucleophilic Reactivity and Solvation of Succinimide and Phthalimide Anions in Acetonitrile-Methanol Mixtures" J.Chem.Soc.,Perkin Trans.2. 1141-1145 (1993)

[Publications] Y.Kondo: "Single-ion Enthalpies of Transfer for Conjugate-base Anions of Imides in Acetonitrile-Methanole Mixtures21GC28:J.Chem.Soc.,Faraday Trans." 121-125 (1994)

[Publications] Y.Kondo: "Charactorization of Solute-Solvent Interaction at the Transition State by Thermodynamic and Quantum-mechanical Approaches,Reactions of Imides Ions with EthylIodide in Acetonitrile-Methanol" J.Chem.Soc.,Perkin Trans.2. (in press). (1994)

[Publications] M.Okamura: "NAD(P)+-NAD(P)H Models.81.Temperature-Dependent Stereospecificity in the Interconversion between Central and Axial Chiralities" Bull.Chem.Soc./Jpn.66. 1191-1196 (1993)

[Publications] M.Okamura: "NAD(P)+-NAD(P)H Models.82.Effect of Magnesium on the Stereospecificity and Conformations at the Ground nad Transition Statesof the Reaction" Bull.Chem.Soc.Jpn.66. 1197-1203 (1993)

[Publications] K.Nakamura: "Stereochemical Control in Microbial Reduction. 21.Effect of Organic Solvents on Reduction of alpha-Keto Esters Mediated by Bakers'Yeast" Bull.Chem.Soc.Jpn.2783-2743 (1993)

[Publications] K.Nakamura: "Asymmetric Reduction of Ketopantolactone by Bakers'Yeast" Tetrahedron; Asymmetry. 4. 1253-1254 (1993)

[Publications] S.Yasui: "The Arbuzov Reaction of Alkyl Diphenylphosphinites with 10-Methylacridinium Ion Kinetic Study on the Formation and the Decomposition of Phosphonium Intermediates" Bull.Chem.Soc.Jpn.66. 2077-2083 (1993)

[Publications] S.Yasui: "The Catalytic Role of Iodide Ion/Iodine Couple in the Photo-Reduction of 10-Methylacridinium Ion with Diphenylphosphine Oxide" Chem. Lett.1393-1396 (1993)

[Publications] K.Nakamura: "Diastereoselective Reduction of Ethyl a-Methyl-b-oxobutanoate by Immobilized Geotrichum candidum in an Organic Solvent" Tetrahedron Lett.34. 6087-6090 (1993)

[Publications] M.S.Tang: "A MO Study of the Electronic Spectra and Molecular Conformation of Thiophene oligomers" Chem.Express. 8. 257-260 (1993)

[Publications] M.Iyoda: "Synthesis of the Tris(9-fluorenylidene)cyclopropane Dianion and Related Dianions:[3]-Radialenes with Novel Electronic Properties" Angew. Chemie. 32. 89-90 (1993)

[Publications] K.Nishimoto: "A MO Theoretical Study of Organic Dynes 1.Effect of Chemical Softness on the Electronic Spectra" Bull.Chem.Soc.Jpn.66. 1876-1880 (1993)

[Publications] T.Asada: "Theoretical Study on Binding Enthalpies and Populations of Isomers of Cl^-(H_2O)_n Clusters at Room Temperature" J.Phy.Chem.97. 7724-7729 (1993)

[Publications] K.Hiruta: "Evaluation of two Center Electron Repulsion Integral New-gamma for the PPPMolecular Orbital Calculation of p-band of cata-Condensed Polycyclic Aromatic Hydrocarbons" J.Chem.Software. 1. 157-164 (1993)

[Publications] I.Maki: "VB Structures Contained in LCAO MO Results I.The Ground State of Conjugated Systems" Theor.Chim. Acta. in press. (1994)

都野雄甫九州大学, 有機化学基礎研究センター, 教授 (10029845)