1996 Fiscal Year Annual Research Report

有機素反応理論の成立

Research Project

Project/Area Number	08354014
Research Institution	Kyoto University
Principal Investigator	大野惇吉京都大学, 化学研究所, 教授 (70027077)
Co-Investigator(Kenkyū-buntansha)	辻孝北海道大学, 理学部, 教授 (20029482) 山高博九州大学, 有機化学基礎研究センター, 助教授 (60029907) 奥山格大阪大学, 基礎工学部, 助教授 (40029484) 浅野努大分大学, 工学部, 教授 (40094057) 竹内賢一京都大学, 大学院工学研究科, 教授 (50026358)
Keywords	有機素反応 / ミクロ溶媒効果 / 溶液反応過程 / 溶媒効果理論
Research Abstract	表題に関する領域の研究を推進する方策を検討した。全体会議を2度開催し、主として関西存在の物理有機化学者を中心に溶液反応理論の専門家、有機合成や他の有機化学の関連分野の研究者と溶液素反応の問題点について集約的に検討した。さらに、これによって整理された問題点から、純粋の反応論のみならず、広い応用分野への実践的波及効果をも視野に入れた重点領域研究の申請を行うべく討議を重ねた。その結果、以上に述べるような共同研究計画の具体化及び、それを行うための組織造りに成功した。本計画は(i)ミクロ溶媒効果、(ii)溶液反応過程、(iii)溶媒効果理論の3つの研究項目からなり、以下の観点からそれぞれ研究を推進していく。 (i)ミクロ溶媒効果有機反応におけるミクロ機構を解析すると同時に有機合成での溶媒効果の問題を物理有機化学の実験的立場から検討する。 (ii)溶液反応過程反応経路を決定する因子、有機素反応の速度論的解析や活性中間体の構造と動的特性および、反応の遷移状態の構造とその基質依存性について検討する。 (iii)溶媒効果理論分子軌道法、モンテカルロ法等の種々の理論圭さんに基づき、溶液有機素反応過程における静的および動的溶媒効果を分子レベルで解明する。研究組織は組織全般の研究推進と円滑な運営を図るための統括班と各研究項目に分かれて実際に研究を押し進めていく研究班からなる。更に統括班は評価グループと実施グループに別れ、前者は本研究に対する評価及び、研究運営についての助言を行い、後者は研究実施における助言を行う。上記の研究計画は平成10年度に発足する科学研究費重点領域「有機溶液反応の実践的理論」として申請する運びとなった。

Research Products

(22 results)

All Other

All Publications (22 results)

[Publications] 大野惇吉: "Atropisomeric Flavoenzyme Models with a Modified Pyrimidine Ring : Syntheses,Physical Properties,and Stereochemistry in the Reactions with NAD(P)H Analogs" The Journal of Organic Chemistry. 61. 9344-9355 (1996)
[Publications] 稲垣都士: "Experimental and Theoretical Evidence for Oxirane Formation Reaction of Pentacoordinate 1,2 λ 6-Oxathictanes with Retension of Configuration" Journal of the American Chemical Society. 118. 12455-12456 (1996)
[Publications] 奥山格: "Buffer Catalysis of the Hydrolysis of Phenyl and Methyl Benzenesulfinates. Contrasting Bahavior between Acyclic and Cyclic Analogs" Bulletin of the Chemical Society of Japan. 69. 3281-3287 (1996)
[Publications] 岡崎廉治: "Synthesis,Structure,and Reactions of a Sulfenic Acid Bearing a Novel Bowl-type Substituent : The First Synthesis of a Stable Sulfenic Acid by Direct Oxidation of a Thiol" Journal of the American Society. 119. 1460-1461 (1997)
[Publications] 吉良満夫: "Synthesis and reactions of neutral hypercoordinate allylsilicon compounds having tropolonat ligand" Organometallics. 15. 5335-5341 (1996)
[Publications] 都野雄甫: "Varying Resonance Demands in Carbocationic Systems" Chemical Society Reviews.25. 129-139 (1996)
[Publications] 三島正章: "Gas-Phase Substituent Effects in Highly Electron-deficient Systems. I.Intrinsic Stabilities of 1-Aryl-1-(trifluoromethyl)ethyl Cations" Bulletin of the Chemical Society of Japan. 69. 3273-3280 (1996)
[Publications] 小倉克之: "Facile Optical Resolution of a Dibenzopyrazinoazepine Derivative and the Nature of Molecular Recognition of Amines by Chiral 2,3-Di-O-(arylcarbonyl)tartaric Acids." Bulletin of the Chemical Society of Japan. 69. 3581-3589 (1996)
[Publications] 小林進二郎: "SUBSTITUENT EFFECTS ON THE STABILITY OF 1-ARYL-3,3,3-TRIFLUOROPROPEN 1-YL CATIONS IN THE GAS PHASE" Gazzetta Chimica Italiana. 125. 611-613 (1995)
[Publications] 浅野努: "Effects of Solvent Fluctutations on the Rate of the Thermal Z/E Isomerization of N-Benzylideneanilines in a Highly Viscous Liquid Hydrocarbon" Bulletin of the Chemical Society of Japan. 70. 239-244 (1997)
[Publications] 沢木泰彦: "Mechnism of Sulfone Formation in the Reaction of Sulfides and Singlet Oxygen : Intermediacy of S-Hydroperoxysulfonium Ylide" Journal of the American Chemical Society. 118. 7265-7271 (1996)
[Publications] 竹内賢一: "Synthesis of Bifunctional Polycyclic Compounds and Their Application to Mechanistic Studies of Solvolysis Reactions" Bulletin of the Chemical Society of Japan. 69. 833-851 (1996)
[Publications] 中村栄一: "Unusually Stable Organomercury Hydrides and Radicals" Angewandte Chemie : International Edition.(印刷中).
[Publications] 辻孝: "Direct Synthesis of 2-Norbornanone Dithioacetals from 2-Cyclopentenone Dithioacetals and Dienophiles. Synthetic Application of Thermal Interconversion between Cyclic Dithioacetals and the Ring-Opened Vinyl Sulfide Forms" Tetrahedron. 52. 9979-9990 (1996)
[Publications] 藤森憲: "Thermal decomposition of diacyl peroxide.Part 11.^<18>O-scrambling in carbonyl-^<18>O-labelled phthaloyl peroxide. Extremely large return of unescapable acyloxyl radical pair" Journal of the Chemical Society. Perkin Transactions II. 413-417 (1996)
[Publications] 藤本博: "Transient Bonds and Chemical Reactivity of Molecules" International Journal of Quantum Chemistry. 60. 401-408 (1996)
[Publications] 富岡秀雄: "Anomalous Effects of Para Substituents on the Stability of Sterically Congested Triplet Diarylcarbenes. The First Triplet Carbene Surviving over Minutes under Normal Conditions" Journal of the American Chemical Society. 118. 8723-8734 (1996)
[Publications] 友田修司: "Nature of the Intramolecular Se-N Non-bonded Interaction of 2-Selenobenzylamine Derivatives. An Experimental Evaluation by ^1H,^<13>C,^<77>Se,and ^<15>N NMR Spectroscopy" Journal of the American Chemical Society. 118. 8077-8084 (1996)
[Publications] 脇坂昭弘: "Molecular self-assembly controlled by acid-base non-covalent interactions : A mass spectrometric study of some organic acids and bases" Journal of the Chemical Society : Faraday Transaction. 92. 3539-3544 (1996)
[Publications] 福住俊一: "Addition versus Oxygenation of Alkylbenzenes with 10-Methylacridinium Ion via Photoinduced Electron Transfer" Journal of the American Chemical Society. 118. 8566-8574 (1996)
[Publications] 山高博: "Stereoelectronic Effects in the Nucleophilic Addition to the sp-Hybridezed Carbon of a Ketene and Vinyl Cation : When is a Mesityl Effectively Smaller than a Phenyl Ring?" Journal of the American Chemical Society. 118. 12585-12587 (1996)
[Publications] 近藤泰彦: "Single-ion enthalpies of transfer-as a scale of nuclleophilic reactivity towards ethyl iodide in acetonitrile" Journal of the Chemical Society.Perkin Transactions II. 1699-1703 (1996)

1996 Fiscal Year Annual Research Report

有機素反応理論の成立

Principal Investigator

大野 惇吉 京都大学, 化学研究所, 教授 (70027077)

Research Products

[Publications] 大野惇吉: "Atropisomeric Flavoenzyme Models with a Modified Pyrimidine Ring : Syntheses,Physical Properties,and Stereochemistry in the Reactions with NAD(P)H Analogs" The Journal of Organic Chemistry. 61. 9344-9355 (1996)

[Publications] 稲垣都士: "Experimental and Theoretical Evidence for Oxirane Formation Reaction of Pentacoordinate 1,2 λ 6-Oxathictanes with Retension of Configuration" Journal of the American Chemical Society. 118. 12455-12456 (1996)

[Publications] 奥山格: "Buffer Catalysis of the Hydrolysis of Phenyl and Methyl Benzenesulfinates. Contrasting Bahavior between Acyclic and Cyclic Analogs" Bulletin of the Chemical Society of Japan. 69. 3281-3287 (1996)

[Publications] 岡崎廉治: "Synthesis,Structure,and Reactions of a Sulfenic Acid Bearing a Novel Bowl-type Substituent : The First Synthesis of a Stable Sulfenic Acid by Direct Oxidation of a Thiol" Journal of the American Society. 119. 1460-1461 (1997)

[Publications] 吉良満夫: "Synthesis and reactions of neutral hypercoordinate allylsilicon compounds having tropolonat ligand" Organometallics. 15. 5335-5341 (1996)

[Publications] 都野雄甫: "Varying Resonance Demands in Carbocationic Systems" Chemical Society Reviews.25. 129-139 (1996)

[Publications] 三島正章: "Gas-Phase Substituent Effects in Highly Electron-deficient Systems. I.Intrinsic Stabilities of 1-Aryl-1-(trifluoromethyl)ethyl Cations" Bulletin of the Chemical Society of Japan. 69. 3273-3280 (1996)

[Publications] 小倉克之: "Facile Optical Resolution of a Dibenzopyrazinoazepine Derivative and the Nature of Molecular Recognition of Amines by Chiral 2,3-Di-O-(arylcarbonyl)tartaric Acids." Bulletin of the Chemical Society of Japan. 69. 3581-3589 (1996)

[Publications] 小林進二郎: "SUBSTITUENT EFFECTS ON THE STABILITY OF 1-ARYL-3,3,3-TRIFLUOROPROPEN 1-YL CATIONS IN THE GAS PHASE" Gazzetta Chimica Italiana. 125. 611-613 (1995)

[Publications] 浅野努: "Effects of Solvent Fluctutations on the Rate of the Thermal Z/E Isomerization of N-Benzylideneanilines in a Highly Viscous Liquid Hydrocarbon" Bulletin of the Chemical Society of Japan. 70. 239-244 (1997)

[Publications] 沢木泰彦: "Mechnism of Sulfone Formation in the Reaction of Sulfides and Singlet Oxygen : Intermediacy of S-Hydroperoxysulfonium Ylide" Journal of the American Chemical Society. 118. 7265-7271 (1996)

[Publications] 竹内賢一: "Synthesis of Bifunctional Polycyclic Compounds and Their Application to Mechanistic Studies of Solvolysis Reactions" Bulletin of the Chemical Society of Japan. 69. 833-851 (1996)

[Publications] 中村栄一: "Unusually Stable Organomercury Hydrides and Radicals" Angewandte Chemie : International Edition.(印刷中).

[Publications] 辻孝: "Direct Synthesis of 2-Norbornanone Dithioacetals from 2-Cyclopentenone Dithioacetals and Dienophiles. Synthetic Application of Thermal Interconversion between Cyclic Dithioacetals and the Ring-Opened Vinyl Sulfide Forms" Tetrahedron. 52. 9979-9990 (1996)

[Publications] 藤森憲: "Thermal decomposition of diacyl peroxide.Part 11.^<18>O-scrambling in carbonyl-^<18>O-labelled phthaloyl peroxide. Extremely large return of unescapable acyloxyl radical pair" Journal of the Chemical Society. Perkin Transactions II. 413-417 (1996)

[Publications] 藤本博: "Transient Bonds and Chemical Reactivity of Molecules" International Journal of Quantum Chemistry. 60. 401-408 (1996)

[Publications] 富岡秀雄: "Anomalous Effects of Para Substituents on the Stability of Sterically Congested Triplet Diarylcarbenes. The First Triplet Carbene Surviving over Minutes under Normal Conditions" Journal of the American Chemical Society. 118. 8723-8734 (1996)

[Publications] 友田修司: "Nature of the Intramolecular Se-N Non-bonded Interaction of 2-Selenobenzylamine Derivatives. An Experimental Evaluation by ^1H,^<13>C,^<77>Se,and ^<15>N NMR Spectroscopy" Journal of the American Chemical Society. 118. 8077-8084 (1996)

[Publications] 脇坂昭弘: "Molecular self-assembly controlled by acid-base non-covalent interactions : A mass spectrometric study of some organic acids and bases" Journal of the Chemical Society : Faraday Transaction. 92. 3539-3544 (1996)

[Publications] 福住俊一: "Addition versus Oxygenation of Alkylbenzenes with 10-Methylacridinium Ion via Photoinduced Electron Transfer" Journal of the American Chemical Society. 118. 8566-8574 (1996)

[Publications] 山高博: "Stereoelectronic Effects in the Nucleophilic Addition to the sp-Hybridezed Carbon of a Ketene and Vinyl Cation : When is a Mesityl Effectively Smaller than a Phenyl Ring?" Journal of the American Chemical Society. 118. 12585-12587 (1996)

[Publications] 近藤泰彦: "Single-ion enthalpies of transfer-as a scale of nuclleophilic reactivity towards ethyl iodide in acetonitrile" Journal of the Chemical Society.Perkin Transactions II. 1699-1703 (1996)

大野惇吉京都大学, 化学研究所, 教授 (70027077)