1986 Fiscal Year Annual Research Report

有機化学における反応理論の体系化

Research Project

Project/Area Number	61303003
Research Institution	Kyushu University
Principal Investigator	都野雄甫九大, 理学部, 教授 (10029845)
Co-Investigator(Kenkyū-buntansha)	西本吉助大阪市立大学, 理学部, 教授 (20046949) 竹下斉九州大学, 生産研, 教授 (70004281) 速水醇一京都大学, 教養部, 教授 (30025283) 藤尾瑞枝九州大学, 理学部, 助手 (10029887) 三島正章九州大学, 理学部, 助手 (20037279)
Keywords	気相炭素陽イオン / イオンサイクロトロン共鳴(法) / 溶媒効果 / 置換基効果 / 基質-試薬会合錯体 / プロトン移動反応 / シグマトロピー / 芳香族求核置換反応
Research Abstract	1活性中間体とその反応挙動および構造-反応性相関関係:気相におけるベンジル陽イオン【C_6】【H_5】【CR2!〓】(R=【H_2】,MeH,【Me_2】,【CH_3】・【CF_3】)の本質的安定度を、イオンサイクロトロン共鳴法を用いてプロトン移動平衡およびクロライド移動平衡により決定し、各系の置換基効果の解析を行った。α-置換基によるカチオンの不安定化は、置換基効果の共鳴要求度の変化に明らかに現われ、その効果は溶液相におけるベンジル位ソルボリシスと全く同一の関係則(湯川-都野式)に従うことを見出した。これは200kcalにおよぶ溶媒和安定化が、遷移状態の相対座標位置にはほとんど変化を与えないことを意味し、従来の反応機構論からは想像できない重要な事実である。 2.分子間相互作用・溶媒効果:アミンを求核種とする芳香族求核置換反応において、非極性溶媒中では、基質-試薬間会合錯体が、反応座標に乗る真の中間体として介在し、イオン性中間体がイオン対として溶存する系では主反応が結果的に促進され、極性非プロトン性溶媒よりも加速されることを見出した。またプロトン移動が律速に関与するが、これは直接の律速関与ではなく、律速アニオン脱離の逆反応を抑えるF因子の制御と同じ意義を持つことを初めて示した。4.遷移状態構造・反応経路:トロポロンのベンジルエーテル及び複素環類似体は加熱によりラジカル転位を起すが、この反応の駆動力がトロポノイドの特異的共役構造による「1,9-シグマトロピー」という新概念で説明できることを証明した。プロトン移動反応に関して水素結合で相互作用が線形の場合、すなわち、それぞれの水素結合が独立にプロトン移動に関与する場合と、相互作用が非線形の場合、すなわち、それぞれの水素結合が協同的に働いてプロトン移動に関与する場合について研究を行ない、非線形相互作用の場合にはソリトン的プロトンが発生することを発見し、その方程式を導いた。

Research Products
(71 results)

All Other

All Publications (71 results)

[Publications] Masaaki Mishima;Mizue Fujio;Yuho Tsuno: Tetrahedron Lett.27. 939-942 (1986)
[Publications] Masaaki Mishima;Mizue Fujio;Yuho Tsuno: Tetrahedron Lett.27. 951-954 (1986)
[Publications] Masami Sawada;Yoshio Takai;Satoshi Kimura;Soichi Misumi;Yuho Tsuno: Tetrahedron Lett.27. 3013-3016 (1986)
[Publications] TsunoMasami Sawada;Yoshio Takai;Satoshi Kimura;Satoshi Yamano;Soichi Misumi;Terukiyo Hanafusa;Yuho: Tetrahedron Lett.27. 5649-5650 (1986)
[Publications] Mizue Fujio;Kimito Funatsu;Mutsuo Goto;Masaaki Mishima;Yuho Tsuno: Bull.Chem.Soc.Jpn.60. 1091-1095 (1987)
[Publications] Mizue Fujio;Mutsuo Goto;Yoji Seki;Masaaki Mishima;Yuho Tsuno;Masami Sawada;Yoshio Takai: Bull.Chem.Soc.Jpn.60. 1097-1101 (1987)
[Publications] Takahiro Tezuka;Setsuo Ando;Toshinori Wada: Chemistry Letters. 1667-1670 (1986)
[Publications] Takahiro Tezuka;Setsuo Ando: Chemistry Letters. 1671-1674 (1986)
[Publications] Takahiro Tezuka;Takashi Otsuka;Pi-Chao Wang;Mie Murata: Tetrahedron Letters. 27. 3627-3630 (1986)
[Publications] Takahiro Tezuka;Takashi Otsuka: Tetrahedron Letters,submitted. (1987)
[Publications] J.Hayami;S.Otani;F.Yamaguchi;Y.Nishikawa: Chemistry Letters. 4 (1987)
[Publications] J.Hayami;K.Kinoshita: Chemistry Letters,to be submitted. 4 (1987)
[Publications] Kichisuke NISHIMOTO;H.FUKUNAGA;K.YAGI: J.Biochem.100. 1647-1653 (1986)
[Publications] Yoshiki KASHIMORI;F.CHIEN;K.NISHIMOTO: Chem.Phys.107. 389-396 (1986)
[Publications] Katsunori SAKURAI;K.KITAMURA;K.NISHIMOTO: Theor.Chim.Acta. 69. 23-34 (1986)
[Publications] Yoshihisa OHTA;H.TANAKA;Y.BABA;A.KAGEMOTO;N.NISHIMOTO: J.Phys.Chem.90. 4438-4442 (1986)
[Publications] Takae TAKEUCHI;M.YAMAMOTO;K.NISHIMOTO: Mass Spectrometry. 34. 267-298 (1986)
[Publications] M.Fujio;K.Funatsu;M.Goto;M.Mishima;Y.Tsuno: Tetrahedron. (1987)
[Publications] Kazuhiro Maruyama;Hiroyuki Furuta;Atsuhiro Osuka: Chemistry Letters. 475-478 (1986)
[Publications] Atsuhiro Osuka;Hiroyuki Furuta;Kazuhiro Maruyama: Chemistry Letters. 479-482 (1986)
[Publications] Kazuhiro Maruyama;Hiroyuki Furuta;Atsuhiro Osuka: Tetrahedron. 42. 6149-6155 (1986)
[Publications] Atsuhiro Osuka;Kazuhiro Maruyama: Chemistry Letters. 1853-1856 (1986)
[Publications] Atsuhiro Osuka;Soichi Morikawa;Kazuhiro Maruyama: J.Chemical Society,Chemical Communication. (1987)
[Publications] Tomomi KINOSHITA;Keizo IKAI;Tsugunori KASHIMURA;Masataka FUJIWARA;Kunio OKAMOTO: Bull.Chem.Soc.Jpn.59. 2843-2849 (1986)
[Publications] T.Fueno;T.Okuyama;H.Nagamatsu;M.Kitano: J.Org.Chem.51. 1516-1521 (1986)
[Publications] T.Fueno;T.Okuyama;M.Toyoda: Can.J.Chem.64. 1116-1123 (1986)
[Publications] T.Fueno: Applied Quantum Chemistry. 33-41 (1986)
[Publications] T.Fueno;H.Yamaguchi;Y.Takahara: Applied Quantum Chemistry. 155-184 (1986)
[Publications] T.Tsuji;S.Nishida: Chem.Lett.1389 (1986)
[Publications] R.Gleiter;G.Krennrich;P.Bischof;T.Tsuji;S.Nishida: Helv.Chim.Acta.69. 962 (1986)
[Publications] M.Murakami;T.Tsuji;M.Oda;S.Nishida: Chem.Lett.(1987)
[Publications] T.Tsuji;S.Nishida: J.Chem.Soc.,Chem.Commun.(1987)
[Publications] K.Ohta;G.L.Closs;K.Morokuma;N.J.Green: J.Am.Chem.Soc.108. 1319 (1986)
[Publications] Z.Latajka;W.B.Person;K.Morokuma: J.Mol.Str.135. 253 (1986)
[Publications] S.Sakai;K.Morokuma: J.Phys.Chem.(1987)
[Publications] N.Koga;T.Ozawa;K.Morokuma: J.Am.Chem.Soc.,submitted. 109. (1987)
[Publications] Masao OKUBO;Shunsei Yoshida;Yoshiji EGAMI;Koji MATSUO;Shigeru NAGASE: Bull.Chem.Soc.Jpn.,Vol.60,in press.
[Publications] Masao OKUBO;Toshiki TSUTSUMI;Koji MATSUO: Bull.Chem.Soc.Jpn.,Vol.60,in press.
[Publications] Masao OKUBO;Toshiki TSUTSUMI;Noritake YASUOKA;Yukiteru KATSUBE: Bull.Chem.Soc.Jpn.,in preparation.
[Publications] Masao OKUBO;Keiko ASAO;Hiroyuki HYAKUTAKE;Koji MATSUO.: Bull.Chem.Soc.Jpn.,in preparation.
[Publications] Y.Suezawa;Minoru Hirota;Y.Shibata;I.Takeuchi;Y.Hamada: Bull.Chem.Soc.Jpn.59. 2362-2364 (1986)
[Publications] K.Abe;K.Ito;Y.Suezawa;M.Hirota;M.Nishita: Bull.Chem.Soc.Jpn.59. 3125-3130 (1986)
[Publications] M.Karatsu;Y.Suezawa;K.Abe;M.Hirota;M.Nishio: Bull.Chem.Soc.Jpn.59. 3529-3534 (1986)
[Publications] K.Murofushi;K.Abe;M.Hirota: J.Chem.Soc.Perkin 【II】. (1987)
[Publications] H.Satonaka,K.Abe,M.Hirota: Bull.Chem.Soc.Jpn.60. (1987)
[Publications] K.Akiba;K.Takee;Y.Shimizu;K.Ohkata: J.Am.Chem.Soc.108. 6320-6327 (1986)
[Publications] K.Akiba;K.Okada;K.Ohkata: Tetrahedron Lett.27. 5221-5224 (1986)
[Publications] K.Akiba;H.Fujikawa;Y.Sunaguchi;Y.Yamamoto: J.Am.Chem.Soc.109. (1987)
[Publications] Hiroshi Yamataka;Terukiyo Hanafusa: J.Am.Chem.Soc.108. 6643-6646 (1986)
[Publications] Hiroshi Yamataka;Toyoki Matsuyama;Terukiyo Hanafusa: Chem.Lett.
[Publications] Terukiyo Hanafusa;Junko Ichihara;Tetsuya Ashida: Chem.Lett.
[Publications] T.Kawashima;Y.Miki;T.Tomita;N.Inamoto: Chem.Lett.501-504 (1986)
[Publications] N.Inamoto;S.Masuda: Chem.Lett.1287-1290 (1986)
[Publications] T.Kawashima;Y.Miki;N.Inamoto: Chem.Lett.1883-1884 (1986)
[Publications] Y.Nakadaira;T.Kobayashi;H.Sakurai: Bull.Chem.Soc.Jpn.59. 1509-1513 (1986)
[Publications] Y.Nakadaira;K.Oharu;H.Sakurai: J.Organomet.Chem.309. 247-256 (1986)
[Publications] A.Hosomi;M.Ando;H.Sakurai: Chem.Lett.365-368 (1986)
[Publications] H.Sakurai;M.Ando;N.Kawada;K.Sato;A.Hosomi: Tetrahedron Lett.27. 75-76 (1986)
[Publications] M.Kira;H.Nakazawa;H.Sakurai: Chem.Lett.497-450 (1986)
[Publications] H.Sakurai: l'actualite chim.26-32 (1986)
[Publications] Shigeru SUGIYAMA;Hitoshi TAKESHITA: Chemistry Letters. 1203-1204 (1986)
[Publications] Hitoshi Takeshita;Akira Mori;Tomoyuki Kusaba: Synthesis. 578-579 (1986)
[Publications] Hitoshi Takeshita;Hiroaki Mametsuka;Hideshi Motomura: Journal of Heterocyclic Chemistry. 23. 1211-1214 (1986)
[Publications] Shigeru Sugiyama;Tohru Tsuda;Akira Mori;Hitoshi Takeshita;Mitsuaki Kodama: Chemistry Letters. 1315-1318 (1986)
[Publications] Hitoshi Takeshita;Shigeru Sugiyama;Toshihide Hatsui: Journal of Chemical Society,Perkin Transaction,【II】. 1491-1493 (1986)
[Publications] Nobuo Kato;Shinya Tanaka;Hitoshi Takeshita: Chemistry Letters. 1989-1992 (1986)
[Publications] Yoho Tsuno;Akihisa Murata;Mutsuo Goto;Mizue Fujio: "Proceedings of the 8th IUPAC Conference on Physical Organic Chemistry,Tokyo 1986 Substituent Effect on the Solvolysis of 1-Aryl-1-(trifluoromethyl)ethyl Tosylates" Elsvier Publishers, 8 (1987)
[Publications] Yuho Tsuno: "Proceedings of the 1st International Symposium on Physical Organic Chemistry,Korea 1986 Varying Resonance Demands in Carbocationic Solvolyses" Korean Chemical Society, 14 (1987)
[Publications] Takahiro Tezuka;Setsuo Ando;Toshinori Wada: "8th IUPAC Conference on Physical Organic Chemistry(Tokyo),1986(Reaction of diazonium ions generated from α-azohydroperoxide)" Elsevier Science Publshers B.V., (1987)
[Publications] J.Hayami;S.Otani;S.Hashimoto: "Solute-Solvent Interactions in the Finkelstein Reaction System-Characterization of Chloride and Perchlorate Anion-" Elsevier Publishers, 6 (1987)
[Publications] T.Ando;T.Kimura;T.Yamataka: ""Variation in the Transistion-State Structure of Aliphatic Nucleophilic Substitution"in"Nucleophilicity"ed by J.M.Harris and S.P.McManus,Chapter7." American Chemical Society,

1986 Fiscal Year Annual Research Report

有機化学における反応理論の体系化

Principal Investigator

都野 雄甫 九大, 理学部, 教授 (10029845)

Research Products

[Publications] Masaaki Mishima;Mizue Fujio;Yuho Tsuno: Tetrahedron Lett.27. 939-942 (1986)

[Publications] Masaaki Mishima;Mizue Fujio;Yuho Tsuno: Tetrahedron Lett.27. 951-954 (1986)

[Publications] Masami Sawada;Yoshio Takai;Satoshi Kimura;Soichi Misumi;Yuho Tsuno: Tetrahedron Lett.27. 3013-3016 (1986)

[Publications] TsunoMasami Sawada;Yoshio Takai;Satoshi Kimura;Satoshi Yamano;Soichi Misumi;Terukiyo Hanafusa;Yuho: Tetrahedron Lett.27. 5649-5650 (1986)

[Publications] Mizue Fujio;Kimito Funatsu;Mutsuo Goto;Masaaki Mishima;Yuho Tsuno: Bull.Chem.Soc.Jpn.60. 1091-1095 (1987)

[Publications] Mizue Fujio;Mutsuo Goto;Yoji Seki;Masaaki Mishima;Yuho Tsuno;Masami Sawada;Yoshio Takai: Bull.Chem.Soc.Jpn.60. 1097-1101 (1987)

[Publications] Takahiro Tezuka;Setsuo Ando;Toshinori Wada: Chemistry Letters. 1667-1670 (1986)

[Publications] Takahiro Tezuka;Setsuo Ando: Chemistry Letters. 1671-1674 (1986)

[Publications] Takahiro Tezuka;Takashi Otsuka;Pi-Chao Wang;Mie Murata: Tetrahedron Letters. 27. 3627-3630 (1986)

[Publications] Takahiro Tezuka;Takashi Otsuka: Tetrahedron Letters,submitted. (1987)

[Publications] J.Hayami;S.Otani;F.Yamaguchi;Y.Nishikawa: Chemistry Letters. 4 (1987)

[Publications] J.Hayami;K.Kinoshita: Chemistry Letters,to be submitted. 4 (1987)

[Publications] Kichisuke NISHIMOTO;H.FUKUNAGA;K.YAGI: J.Biochem.100. 1647-1653 (1986)

[Publications] Yoshiki KASHIMORI;F.CHIEN;K.NISHIMOTO: Chem.Phys.107. 389-396 (1986)

[Publications] Katsunori SAKURAI;K.KITAMURA;K.NISHIMOTO: Theor.Chim.Acta. 69. 23-34 (1986)

[Publications] Yoshihisa OHTA;H.TANAKA;Y.BABA;A.KAGEMOTO;N.NISHIMOTO: J.Phys.Chem.90. 4438-4442 (1986)

[Publications] Takae TAKEUCHI;M.YAMAMOTO;K.NISHIMOTO: Mass Spectrometry. 34. 267-298 (1986)

[Publications] M.Fujio;K.Funatsu;M.Goto;M.Mishima;Y.Tsuno: Tetrahedron. (1987)

[Publications] Kazuhiro Maruyama;Hiroyuki Furuta;Atsuhiro Osuka: Chemistry Letters. 475-478 (1986)

[Publications] Atsuhiro Osuka;Hiroyuki Furuta;Kazuhiro Maruyama: Chemistry Letters. 479-482 (1986)

[Publications] Kazuhiro Maruyama;Hiroyuki Furuta;Atsuhiro Osuka: Tetrahedron. 42. 6149-6155 (1986)

[Publications] Atsuhiro Osuka;Kazuhiro Maruyama: Chemistry Letters. 1853-1856 (1986)

[Publications] Atsuhiro Osuka;Soichi Morikawa;Kazuhiro Maruyama: J.Chemical Society,Chemical Communication. (1987)

[Publications] Tomomi KINOSHITA;Keizo IKAI;Tsugunori KASHIMURA;Masataka FUJIWARA;Kunio OKAMOTO: Bull.Chem.Soc.Jpn.59. 2843-2849 (1986)

[Publications] T.Fueno;T.Okuyama;H.Nagamatsu;M.Kitano: J.Org.Chem.51. 1516-1521 (1986)

[Publications] T.Fueno;T.Okuyama;M.Toyoda: Can.J.Chem.64. 1116-1123 (1986)

[Publications] T.Fueno: Applied Quantum Chemistry. 33-41 (1986)

[Publications] T.Fueno;H.Yamaguchi;Y.Takahara: Applied Quantum Chemistry. 155-184 (1986)

[Publications] T.Tsuji;S.Nishida: Chem.Lett.1389 (1986)

[Publications] R.Gleiter;G.Krennrich;P.Bischof;T.Tsuji;S.Nishida: Helv.Chim.Acta.69. 962 (1986)

[Publications] M.Murakami;T.Tsuji;M.Oda;S.Nishida: Chem.Lett.(1987)

[Publications] T.Tsuji;S.Nishida: J.Chem.Soc.,Chem.Commun.(1987)

[Publications] K.Ohta;G.L.Closs;K.Morokuma;N.J.Green: J.Am.Chem.Soc.108. 1319 (1986)

[Publications] Z.Latajka;W.B.Person;K.Morokuma: J.Mol.Str.135. 253 (1986)

[Publications] S.Sakai;K.Morokuma: J.Phys.Chem.(1987)

[Publications] N.Koga;T.Ozawa;K.Morokuma: J.Am.Chem.Soc.,submitted. 109. (1987)

[Publications] Masao OKUBO;Shunsei Yoshida;Yoshiji EGAMI;Koji MATSUO;Shigeru NAGASE: Bull.Chem.Soc.Jpn.,Vol.60,in press.

[Publications] Masao OKUBO;Toshiki TSUTSUMI;Koji MATSUO: Bull.Chem.Soc.Jpn.,Vol.60,in press.

[Publications] Masao OKUBO;Toshiki TSUTSUMI;Noritake YASUOKA;Yukiteru KATSUBE: Bull.Chem.Soc.Jpn.,in preparation.

[Publications] Masao OKUBO;Keiko ASAO;Hiroyuki HYAKUTAKE;Koji MATSUO.: Bull.Chem.Soc.Jpn.,in preparation.

[Publications] Y.Suezawa;Minoru Hirota;Y.Shibata;I.Takeuchi;Y.Hamada: Bull.Chem.Soc.Jpn.59. 2362-2364 (1986)

[Publications] K.Abe;K.Ito;Y.Suezawa;M.Hirota;M.Nishita: Bull.Chem.Soc.Jpn.59. 3125-3130 (1986)

[Publications] M.Karatsu;Y.Suezawa;K.Abe;M.Hirota;M.Nishio: Bull.Chem.Soc.Jpn.59. 3529-3534 (1986)

[Publications] K.Murofushi;K.Abe;M.Hirota: J.Chem.Soc.Perkin 【II】. (1987)

[Publications] H.Satonaka,K.Abe,M.Hirota: Bull.Chem.Soc.Jpn.60. (1987)

[Publications] K.Akiba;K.Takee;Y.Shimizu;K.Ohkata: J.Am.Chem.Soc.108. 6320-6327 (1986)

[Publications] K.Akiba;K.Okada;K.Ohkata: Tetrahedron Lett.27. 5221-5224 (1986)

[Publications] K.Akiba;H.Fujikawa;Y.Sunaguchi;Y.Yamamoto: J.Am.Chem.Soc.109. (1987)

[Publications] Hiroshi Yamataka;Terukiyo Hanafusa: J.Am.Chem.Soc.108. 6643-6646 (1986)

[Publications] Hiroshi Yamataka;Toyoki Matsuyama;Terukiyo Hanafusa: Chem.Lett.

[Publications] Terukiyo Hanafusa;Junko Ichihara;Tetsuya Ashida: Chem.Lett.

[Publications] T.Kawashima;Y.Miki;T.Tomita;N.Inamoto: Chem.Lett.501-504 (1986)

[Publications] N.Inamoto;S.Masuda: Chem.Lett.1287-1290 (1986)

[Publications] T.Kawashima;Y.Miki;N.Inamoto: Chem.Lett.1883-1884 (1986)

[Publications] Y.Nakadaira;T.Kobayashi;H.Sakurai: Bull.Chem.Soc.Jpn.59. 1509-1513 (1986)

[Publications] Y.Nakadaira;K.Oharu;H.Sakurai: J.Organomet.Chem.309. 247-256 (1986)

[Publications] A.Hosomi;M.Ando;H.Sakurai: Chem.Lett.365-368 (1986)

[Publications] H.Sakurai;M.Ando;N.Kawada;K.Sato;A.Hosomi: Tetrahedron Lett.27. 75-76 (1986)

[Publications] M.Kira;H.Nakazawa;H.Sakurai: Chem.Lett.497-450 (1986)

[Publications] H.Sakurai: l'actualite chim.26-32 (1986)

[Publications] Shigeru SUGIYAMA;Hitoshi TAKESHITA: Chemistry Letters. 1203-1204 (1986)

[Publications] Hitoshi Takeshita;Akira Mori;Tomoyuki Kusaba: Synthesis. 578-579 (1986)

[Publications] Hitoshi Takeshita;Hiroaki Mametsuka;Hideshi Motomura: Journal of Heterocyclic Chemistry. 23. 1211-1214 (1986)

[Publications] Shigeru Sugiyama;Tohru Tsuda;Akira Mori;Hitoshi Takeshita;Mitsuaki Kodama: Chemistry Letters. 1315-1318 (1986)

[Publications] Hitoshi Takeshita;Shigeru Sugiyama;Toshihide Hatsui: Journal of Chemical Society,Perkin Transaction,【II】. 1491-1493 (1986)

[Publications] Nobuo Kato;Shinya Tanaka;Hitoshi Takeshita: Chemistry Letters. 1989-1992 (1986)

[Publications] Yoho Tsuno;Akihisa Murata;Mutsuo Goto;Mizue Fujio: "Proceedings of the 8th IUPAC Conference on Physical Organic Chemistry,Tokyo 1986 Substituent Effect on the Solvolysis of 1-Aryl-1-(trifluoromethyl)ethyl Tosylates" Elsvier Publishers, 8 (1987)

[Publications] Yuho Tsuno: "Proceedings of the 1st International Symposium on Physical Organic Chemistry,Korea 1986 Varying Resonance Demands in Carbocationic Solvolyses" Korean Chemical Society, 14 (1987)

[Publications] Takahiro Tezuka;Setsuo Ando;Toshinori Wada: "8th IUPAC Conference on Physical Organic Chemistry(Tokyo),1986(Reaction of diazonium ions generated from α-azohydroperoxide)" Elsevier Science Publshers B.V., (1987)

[Publications] J.Hayami;S.Otani;S.Hashimoto: "Solute-Solvent Interactions in the Finkelstein Reaction System-Characterization of Chloride and Perchlorate Anion-" Elsevier Publishers, 6 (1987)

[Publications] T.Ando;T.Kimura;T.Yamataka: ""Variation in the Transistion-State Structure of Aliphatic Nucleophilic Substitution"in"Nucleophilicity"ed by J.M.Harris and S.P.McManus,Chapter7." American Chemical Society,

都野雄甫九大, 理学部, 教授 (10029845)