1989 年度実績報告書

ソルボリシスにおける置換機構仮説の実証

研究課題

研究課題/領域番号	62470024
研究機関	岡崎国立共同研究機構
研究代表者	都野雄甫岡崎国立共同研究機構, 分子科学研究所, 教授 (10029845)
キーワード	ソルボリシス機構 / イオン対機構 / ^<18>O同位体シフト / スクランブリング / 原系復帰
研究概要	ソルボリシス反応におけるイオン性中間体からの原系復帰の定量的追跡はソルボリシスの詳細機構の解明に不可欠である。アルコキシ炭素の^<13>CーNMRは^<16>Oと^<18>Oの直接置換により同位体シフトを示し、そのシグナル分裂より^<16>O/^<18>Oを定量する事ができる。目的の炭素の^<13>C標識は^<13>CーNMRによる直接反応の追跡を可能する。この新手法を^<13>C、^<18>O二重標識のネオフィル、2ーフィニルプロビル、2ーフェニルエチル、2ー(pーメトキシフェニル)エチル、およびベンジルトシラ-トのアセトリシス反応の原系復帰の研究に応用した。アセトリシス反応及びOー交換プロセス(原系復帰)が、少量のラベル化合物を使用し、直接NMR試料管中で^<13>CーNMRを測定する事により追跡できた。また2ーアダマンチルトシラ-トは^<13>C非濃縮体を用いて追跡に成功した。ネオフィル系では^<18>Oス寅クランブリングは見られず、従来の仮説の妥当性を初めて実証した。フェニルプロピル、フェネチル系でintimateイオン対からのリタ-ンは^<18>O不完全スクランブリングを与え、溶媒介在イオン対では完全スクランブリングを与え、イオン対の性質がスクランブリングにより区別でき定義できる。また、対称なフェノニウムイオン経由のフェネチル系で、リタ-ンの際、^<18>Oの攻撃が両メチレンに等価に起こる事実は、リタ-ンがカチオンーアニオンにイオン化後起こると言う決定的証拠を与えた。ベンジルトシラ-トでも、イオン対復帰が観測され、従来のS_N2型機構が否定された。また古典的Kc基質としてソルボリシス機構の解析の基準反応と考えられてきた2ーアダマンチル系に大きいリタ-ンが見られた。これは反応機構研究にきわめて重大な影響を与える。この^<13>CーNMRによる同位体シフト法はソルボリシスの^<18>O平衡法に一般的に用いることができ、マススペクトルを使った従来の破壊検査法に較べ優れている。

研究成果
(32件)

すべてその他

すべて文献書誌 (32件)

[文献書誌] M.Mishima,K.Arima,S.Usui,M.Fujio,and Y.Tsuno: "Substituent Effect on the Stability of Benzyl Cation in the Gas Phase" Chemistry Lett.1047-1050 (1987)
[文献書誌] R.Fujiyama,I.Kamimura,M.Yoshida,K.Suzuki,S.Kiyooka,A.Murata,M.Goto,M.Fujio,and Y.Tsuno: "Solvolysis of 1ーPhenylー1ーcyanoー2,2,2ーtrifluoroethyl Brosylate" Chemistry Lett.1043-1046 (1987)
[文献書誌] N.Shimizu,F.Shibata,and Y.Tsuno: "Synthesis of (1ーHaloー1ーalkenyl)trimethylsilanes via gemーTrimethylsilylation of Vinyl Halides" Bull.Chem.Soc.,Jpn.60. 777-778 (1987)
[文献書誌] N.Shimizu,F.Shibata,S.Imazu,and Y.Tsuno: "The Ene Reaction of Allylsilanes with Singlet Oxygen.Unusual Product Stereoselectivity" Chemistry Lett.1071-1074 (1987)
[文献書誌] M.Mishima,T.Terasaki,M.Fujio,and Y.Tsuno: "Substituent Effect on the Gas Phase Basicity of Pyridine NーOxide" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(1). 77-84 (1987)
[文献書誌] M.Fujio,M.Goto,T.Yoshino,K.Funatsu,Y.Tsuji,S.Ouchi,and Y.Tsuno: "WinsteinーGrunwald Solvent Parameters for Tosylate Reactivity" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(1). 85-100 (1987)
[文献書誌] M.Sawada,Y.Takai,S.Yamano,S.Misumi,T.Hanafusa,and Y.Tsuno: "Dual Resonance Functionality in Pyridine 1ーOxides.A Double Multinuclear NMR Approach" J.Org.Chem.53. 191-194 (1988)
[文献書誌] M.Fujio,F.Sanematsu,Y.Tsuno,M.Sawada,and Y.Takai: "Study of IonーPair Mechanism Using Oxygenー18 Scrambling" Tetrahedron Letters. 29. 93-96 (1988)
[文献書誌] S.Imazu,N.Shimizu,and Y.Tsuno: "Autooxidation of Aromatic Ketones via Trimethylsilyl Enol Ethers" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 189-192 (1988)
[文献書誌] M.Mishima,N.Shimizu,M.Fujio,and Y.Tsuno: "Gas Phase Substituent Effect on Basicity of N,NーDimetylbenzamide.Resonance in a Highly Stabilized Carbocation System" Mem.Fac.Sci.,Kyushu Uuiv.,Ser.C. 16(2). 207-216 (1988)
[文献書誌] M.Mishima,N.Shimizu,Y.Tsuno,S.Kobayashi,and H.Taniguchi: "Gas Phase Substituent Effect on Basicity of Phenylacetylene.Intrinsic Resonance Demand of a Vinylic Cation" Mem.Fac.Sci.,Kyushu Univ.,Ser.C,. 16(2). 217-224 (1988)
[文献書誌] A.Murata,M.Goto,R.Fujiyama,M.Fujio,and Y.Tsuno: "Substituent Effects on the solvolysis of 1ーArylー1ー(trifluoromethyl)ethyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 225-242 (1988)
[文献書誌] A.Murata,S.Sakaguchi,R.Fujiyama,M.Fujio,and Y.Tsuno: "Substituent Effects on the Highly Electronーdeficient Carbocation Solvolyses" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 243-256 (1988)
[文献書誌] M.Fujuo,M.Goto,A.Murata,Y.Tsuji,M.Mishima,and Y.Tsuno: "Varying Resonance Demands in Carbocationic Solvolyses" Mem.Fac.Sci.,Kyushu Univ.,Ser.C,. 16(2). 271-300 (1988)
[文献書誌] T.Tsuji,H.Koyama,M.Fujio,and Y.Tsuno: "Substituent Effect on the Solvolysis of αーtーButylbenzyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 257-270 (1988)
[文献書誌] S.ーD.Yoh,Y.Tsuno,M.Fujio,M.Sawada,and Y.Yukawa: "Multiple structureーReactivity Relationships for a Menschutkinーtype S_N2 Reaction" J.Chem.Soc.,Perkin II. 7-13 (1989)
[文献書誌] M.Mishima,H.Inoue,M.Fujio,and Y.Tsuno: "Gas Phase Substituent Effects in a Highly Electron Deficient System.Intrinsic Resonance Demand of 1ーArylー1ー(trifluoromethyl)ethyl Cation" Tetrahedron Lett.30. 2101-2104 (1989)
[文献書誌] M.Mishima,S.Usui,H.Inoue,M.Fujio,and Y.Tsuno: "Stabilities of αーCumyl Cations in the Gas Phase" Nippon Kagaku Kaishi. 1262-1268 (1989)
[文献書誌] M.Misima,S.Usui,M.Fujio,and Y.Tsuno: "Substituent Effect on the Stability of 1ーPheynylethyl Cation in the Gas Phase" Nippon Kagaku Kaishi. 1269-1274 (1989)
[文献書誌] M.Fujio,F.Sanematsu,Y.Tsuno,Y.Takai,and M.Sawada: "Nonーdestructive Detection of Ionーpair Return in Acetolysis of ^<13>C and ^<18>O Doubly Labeled 2ーArylalkyl Tosylates.Quantitative ^<13>CーNMR Spectrometry by Using ^<18>O Isotope Effect" Nippon Kagaku Kaishi. 1371-1378 (1989)
[文献書誌] N.Shimizu,T.Miyahara,M.Mishima,and Y.Tsuno: "Photolysis of Alcohols and Alkanones in Acetone Solutions.Photochemical[2+2]Cycloaddition Reaction between Acetone and Aliphatic Enols" Bull.Chem.Soc.Jpn.62. 2032-2039 (1989)
[文献書誌] M.Mishima,T.Ariga,T.Terasaki,M.Fujio,and Y.Tsuno: "Gas Phase Basicities of Substituted Benzenes.Intrinsic Resonance Demand of Benzenium Ion" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 17(1). 159-170 (1989)
[文献書誌] M.Goto,K.Funatsu,N.Arita,M.Mishima,M.Fujio,and Y.Tsuno: "The Substituent Effect on Solvolyses of 2ーArylー1ーmethylethyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 17(1). 123-138 (1989)
[文献書誌] Y.Tsuji,M.Fujio,and Y.Tsuno: "Substituent Effect on the Solvolysis of αーtーButylbenzyl Tosylates.Solvent Modification of Substituent Effects" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 17(1). 139-158 (1989)
[文献書誌] M.Mishima,H.Inoue,M.Fujio,and Y.Tsuno: "Gas Phase Substituent Effects.Stabilities of 1ーArylー2,2,2ーtrifluoroethyl Cations" Tetrahedron Lett.31. 685-688 (1990)
[文献書誌] M.Fujio,M.Goto,A.Murata,Y.Tsuji,M.Mishima,and Y.Tsuno: "Varying Resonance Demands in Carbocationic Solvolyses" J.Phys.Org.Chem.
[文献書誌] M.Fujio,M.Goto.M.Mishima,and Y.Tsuno: "Substituent Effects.XVIII.The Resonance Demand in the Acetolysis of Neophyl Brosylates" Bull.Chem.Soc.Jpn.
[文献書誌] A.Murata,M.Goto,R.Fujiyama,M.Mishima,M.Fujio,and Y.Tsuno: "Substituent Effects.XIX.Solvolysis of 1ーArylー1ー(trifluoromethyl)ethyl Tosylates" Bull,Chem.Soc.Jpn.
[文献書誌] A.Murata,S.Sakaguchi,R.Fujiyama,M.Mishima,M.Fujio,and Y.Tsuno: "Substituent Effects.XX.Highly ElectronーDeficient Carbocation Solvolyses" Bull.Chem.Soc.Jpn.
[文献書誌] M.Fujio,M.Goto,T.Susuki,M.Mishima,and Y.Tsuno: "Substituent Effects.XXI.Solvolysis of Benzyl Tosylates" Bull.Chem.Soc.Jpn.
[文献書誌] Y.Tsuji,H.Koyama,M.Fujio,and Y.Tsuno: "Substituent Effects.XXII.Substituent Effect on the Solvolysis of αーtーButylbenzyl Tosylates" Bull.Chem.Soc.Jpn.
[文献書誌] M.Fujio,M.Goto,T.Susuki,M.Mishima,and Y.Tsuno: "Substituent Effects on Solvolysis of Benzyl Tosylates" J.Phys.Org.Chem.

1989 年度 実績報告書

ソルボリシスにおける置換機構仮説の実証

研究代表者

都野 雄甫 岡崎国立共同研究機構, 分子科学研究所, 教授 (10029845)

研究成果

[文献書誌] M.Mishima,K.Arima,S.Usui,M.Fujio,and Y.Tsuno: "Substituent Effect on the Stability of Benzyl Cation in the Gas Phase" Chemistry Lett.1047-1050 (1987)

[文献書誌] R.Fujiyama,I.Kamimura,M.Yoshida,K.Suzuki,S.Kiyooka,A.Murata,M.Goto,M.Fujio,and Y.Tsuno: "Solvolysis of 1ーPhenylー1ーcyanoー2,2,2ーtrifluoroethyl Brosylate" Chemistry Lett.1043-1046 (1987)

[文献書誌] N.Shimizu,F.Shibata,and Y.Tsuno: "Synthesis of (1ーHaloー1ーalkenyl)trimethylsilanes via gemーTrimethylsilylation of Vinyl Halides" Bull.Chem.Soc.,Jpn.60. 777-778 (1987)

[文献書誌] N.Shimizu,F.Shibata,S.Imazu,and Y.Tsuno: "The Ene Reaction of Allylsilanes with Singlet Oxygen.Unusual Product Stereoselectivity" Chemistry Lett.1071-1074 (1987)

[文献書誌] M.Mishima,T.Terasaki,M.Fujio,and Y.Tsuno: "Substituent Effect on the Gas Phase Basicity of Pyridine NーOxide" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(1). 77-84 (1987)

[文献書誌] M.Fujio,M.Goto,T.Yoshino,K.Funatsu,Y.Tsuji,S.Ouchi,and Y.Tsuno: "WinsteinーGrunwald Solvent Parameters for Tosylate Reactivity" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(1). 85-100 (1987)

[文献書誌] M.Sawada,Y.Takai,S.Yamano,S.Misumi,T.Hanafusa,and Y.Tsuno: "Dual Resonance Functionality in Pyridine 1ーOxides.A Double Multinuclear NMR Approach" J.Org.Chem.53. 191-194 (1988)

[文献書誌] M.Fujio,F.Sanematsu,Y.Tsuno,M.Sawada,and Y.Takai: "Study of IonーPair Mechanism Using Oxygenー18 Scrambling" Tetrahedron Letters. 29. 93-96 (1988)

[文献書誌] S.Imazu,N.Shimizu,and Y.Tsuno: "Autooxidation of Aromatic Ketones via Trimethylsilyl Enol Ethers" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 189-192 (1988)

[文献書誌] M.Mishima,N.Shimizu,M.Fujio,and Y.Tsuno: "Gas Phase Substituent Effect on Basicity of N,NーDimetylbenzamide.Resonance in a Highly Stabilized Carbocation System" Mem.Fac.Sci.,Kyushu Uuiv.,Ser.C. 16(2). 207-216 (1988)

[文献書誌] M.Mishima,N.Shimizu,Y.Tsuno,S.Kobayashi,and H.Taniguchi: "Gas Phase Substituent Effect on Basicity of Phenylacetylene.Intrinsic Resonance Demand of a Vinylic Cation" Mem.Fac.Sci.,Kyushu Univ.,Ser.C,. 16(2). 217-224 (1988)

[文献書誌] A.Murata,M.Goto,R.Fujiyama,M.Fujio,and Y.Tsuno: "Substituent Effects on the solvolysis of 1ーArylー1ー(trifluoromethyl)ethyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 225-242 (1988)

[文献書誌] A.Murata,S.Sakaguchi,R.Fujiyama,M.Fujio,and Y.Tsuno: "Substituent Effects on the Highly Electronーdeficient Carbocation Solvolyses" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 243-256 (1988)

[文献書誌] M.Fujuo,M.Goto,A.Murata,Y.Tsuji,M.Mishima,and Y.Tsuno: "Varying Resonance Demands in Carbocationic Solvolyses" Mem.Fac.Sci.,Kyushu Univ.,Ser.C,. 16(2). 271-300 (1988)

[文献書誌] T.Tsuji,H.Koyama,M.Fujio,and Y.Tsuno: "Substituent Effect on the Solvolysis of αーtーButylbenzyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 16(2). 257-270 (1988)

[文献書誌] S.ーD.Yoh,Y.Tsuno,M.Fujio,M.Sawada,and Y.Yukawa: "Multiple structureーReactivity Relationships for a Menschutkinーtype S_N2 Reaction" J.Chem.Soc.,Perkin II. 7-13 (1989)

[文献書誌] M.Mishima,H.Inoue,M.Fujio,and Y.Tsuno: "Gas Phase Substituent Effects in a Highly Electron Deficient System.Intrinsic Resonance Demand of 1ーArylー1ー(trifluoromethyl)ethyl Cation" Tetrahedron Lett.30. 2101-2104 (1989)

[文献書誌] M.Mishima,S.Usui,H.Inoue,M.Fujio,and Y.Tsuno: "Stabilities of αーCumyl Cations in the Gas Phase" Nippon Kagaku Kaishi. 1262-1268 (1989)

[文献書誌] M.Misima,S.Usui,M.Fujio,and Y.Tsuno: "Substituent Effect on the Stability of 1ーPheynylethyl Cation in the Gas Phase" Nippon Kagaku Kaishi. 1269-1274 (1989)

[文献書誌] M.Fujio,F.Sanematsu,Y.Tsuno,Y.Takai,and M.Sawada: "Nonーdestructive Detection of Ionーpair Return in Acetolysis of ^<13>C and ^<18>O Doubly Labeled 2ーArylalkyl Tosylates.Quantitative ^<13>CーNMR Spectrometry by Using ^<18>O Isotope Effect" Nippon Kagaku Kaishi. 1371-1378 (1989)

[文献書誌] N.Shimizu,T.Miyahara,M.Mishima,and Y.Tsuno: "Photolysis of Alcohols and Alkanones in Acetone Solutions.Photochemical[2+2]Cycloaddition Reaction between Acetone and Aliphatic Enols" Bull.Chem.Soc.Jpn.62. 2032-2039 (1989)

[文献書誌] M.Mishima,T.Ariga,T.Terasaki,M.Fujio,and Y.Tsuno: "Gas Phase Basicities of Substituted Benzenes.Intrinsic Resonance Demand of Benzenium Ion" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 17(1). 159-170 (1989)

[文献書誌] M.Goto,K.Funatsu,N.Arita,M.Mishima,M.Fujio,and Y.Tsuno: "The Substituent Effect on Solvolyses of 2ーArylー1ーmethylethyl Tosylates" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 17(1). 123-138 (1989)

[文献書誌] Y.Tsuji,M.Fujio,and Y.Tsuno: "Substituent Effect on the Solvolysis of αーtーButylbenzyl Tosylates.Solvent Modification of Substituent Effects" Mem.Fac.Sci.,Kyushu Univ.,Ser.C. 17(1). 139-158 (1989)

[文献書誌] M.Mishima,H.Inoue,M.Fujio,and Y.Tsuno: "Gas Phase Substituent Effects.Stabilities of 1ーArylー2,2,2ーtrifluoroethyl Cations" Tetrahedron Lett.31. 685-688 (1990)

[文献書誌] M.Fujio,M.Goto,A.Murata,Y.Tsuji,M.Mishima,and Y.Tsuno: "Varying Resonance Demands in Carbocationic Solvolyses" J.Phys.Org.Chem.

[文献書誌] M.Fujio,M.Goto.M.Mishima,and Y.Tsuno: "Substituent Effects.XVIII.The Resonance Demand in the Acetolysis of Neophyl Brosylates" Bull.Chem.Soc.Jpn.

[文献書誌] A.Murata,M.Goto,R.Fujiyama,M.Mishima,M.Fujio,and Y.Tsuno: "Substituent Effects.XIX.Solvolysis of 1ーArylー1ー(trifluoromethyl)ethyl Tosylates" Bull,Chem.Soc.Jpn.

[文献書誌] A.Murata,S.Sakaguchi,R.Fujiyama,M.Mishima,M.Fujio,and Y.Tsuno: "Substituent Effects.XX.Highly ElectronーDeficient Carbocation Solvolyses" Bull.Chem.Soc.Jpn.

[文献書誌] M.Fujio,M.Goto,T.Susuki,M.Mishima,and Y.Tsuno: "Substituent Effects.XXI.Solvolysis of Benzyl Tosylates" Bull.Chem.Soc.Jpn.

[文献書誌] Y.Tsuji,H.Koyama,M.Fujio,and Y.Tsuno: "Substituent Effects.XXII.Substituent Effect on the Solvolysis of αーtーButylbenzyl Tosylates" Bull.Chem.Soc.Jpn.

[文献書誌] M.Fujio,M.Goto,T.Susuki,M.Mishima,and Y.Tsuno: "Substituent Effects on Solvolysis of Benzyl Tosylates" J.Phys.Org.Chem.

1989 年度実績報告書

都野雄甫岡崎国立共同研究機構, 分子科学研究所, 教授 (10029845)