2002 Fiscal Year Annual Research Report

大環状化合物を反応場あるいは反応基貭とする新規ホスト分子の合成と応用

Research Project

Project/Area Number	11305063
Research Institution	Gunma University
Principal Investigator	西村淳群馬大学, 工学部, 教授 (10107352)
Co-Investigator(Kenkyū-buntansha)	中村洋介群馬大学, 工学部, 助手 (60261864) 岡田行弘群馬大学, 工学部, 助教授 (80211118)
Keywords	クラウンエーテル / シクロファン / カテナン / フラーレン / カリックスアレーン / レセプター / イオノファー / 高選択性
Research Abstract	1.クラウンエーテル部分とシクロファン部分を併せ持つ形の化合物であるクラウノファンをダブルアームド型に導いた。抽出実験を行った結果、Ag^+イオン抽出率(78%)を示し且つ独占的に抽出した。アミノ基を有するスチレン誘導体の[2+2]光環化付加反応によるクラウノファンン合成はこれまで困難であったが、塩酸塩として水中で、γ-シクロデキストリン存在下、光環化付加反応を試みた結果合成することに成功した。目的物はPb^<2+>イオンに高いイオン選択性を有している。カテナン合成は、二級ベンジルアンモニウム塩とジベンゾ-24-クラウン-8との錯形成に基づく擬ロタキサンの形成を応用して成功し、[3]カテナンと[2]カテナンが得られることがわかった。2.o-キノジメタン及びベンザインによる[60]フラーレン二付加反応を検討した。後者は付加物間の立体障害が小さいため、他の場合には得られなかったcis-1体も生成可能となった。さらに、光学活性な二付加体(trans-2,trans-3及びcis-3)については、キラルカラムを用いたHPLCにより光学分割にも成功した。二付加体の位置及び立体選択的合成にも成功した。架橋部位としてクラウンエーテルを有する二付加体については、その錯形成挙動において興味深い結果が見出され、アルカリ金属イオンとの錯形成能を検討したところ、錯形成挙動はクラウンエーテルの環サイズや付加位置に顕著に依存することが分かった。3.カリックスアレーンに1〜4個の酢酸エチル残基を導入しアルカリ金属イオンとの相互作用を検討した。配座変換がない剛直な分子では置換基が一つ減るにつれ約20%の抽出率の低下が認められた。本分子に水酸基を有するアミンを反応させると溶解度が増大し、水中においても利用可能なキラルなデンドリマーが合成できることがわかった。

Research Products
(36 results)

All Other

All Publications (36 results)

[Publications] Y.Okada: "Synthesis and Characterization of Chiral Calixarene Analogs Locked in the Cone Conformation by the Photocycloaddition"Synlett. (in press).
[Publications] 岡田行弘: "キラルカリックス[4]アレーン"有機合成化学協会誌. (印刷中).
[Publications] 岡田行弘: "コーン型配座"有機合成化学協会誌. (印刷中).
[Publications] Seiichi Inokuma: "A Pseudo Thiacrown Compound Formed by Hydrophobic Interaction of Its Lipophilic Parts in Water : Ag^+-Selectivc Fluorophore in Water"Heterocycles. 60. 145-150 (2003)
[Publications] Y.Okada: "Behavior of [2.n]metacyclophane-fused cyclobutane rings in bromination"Tetrahedron Lett.. 43. 5821-5824 (2002)
[Publications] Y.Okada: "A Synthesis and Characterization of New Chiral Calix[4]arenes"Enantiomer. 7. 93-106 (2002)
[Publications] Y.Nakamura: "Synthesis and Properties of Triply-Bridged syn-Carbazolophanes"J. Org. Chem.. 67. 8706-8709 (2002)
[Publications] Y.Nakamura: "Regioselective Synthesis and Properties of Novel [60]Fullerene Bisadducts Containing a Dibenzocrown Ether Moiety"J. Am. Chem. Soc.. 124. 4329-4335 (2002)
[Publications] Y.Nakamura: "Photochemical Synthesis, Conformational Analysis, and Transformation of [60] Fullerene-o-quinodimethane Adducts Bearing a Hydroxy Group"J. Org. Chem.. 67. 1247-1252 (2002)
[Publications] S.Inokuma: "Synthesis and Complexing Properties of Thiacrownophanes"Heterocycles. 55. 1635-1639 (2001)
[Publications] S.Inokuma: "Synthesis of Crownophane possessing Pyridine Moieties on the Aromatic Nuclei (Pyridine-Lariat Crownophane) : A Crownophane Exhibiting Perfect Selectivity Toward Ag^+"Heterocycles. 55. 447-451 (2001)
[Publications] S.Inokuma: "Synthesis and Complexing Ability of Azacrownophanes : The Cyclodextrin Catalysis of the Photochemical Cyclization Reaction"J. Incl. Phenom.. 39. 35-40 (2001)
[Publications] Y.Nakamura: "Synthesis and Fluorescence Emission Behavior of anti-[2.3](3,10)Phenanthrenophane : Overlap between Phenanthrene Rings Reciuired for Excimer Formation"Chem. Lett.. 970-971 (2001)
[Publications] Y.Nakamura: "First Isolation and Characterization of Eight Regioisomers for [60]Fullerene-Benzyne Bisadducts"Org. Lett.. 3. 1193-1196 (2001)
[Publications] S.Inokuma: "Synthesis of Pyridinocrownophanes Exhibiting High Ag^+-Affinity"Heterocycles. 54. 123-130 (2001)
[Publications] Y.Okada: "The Formylation of syn-[2.n]Metacyclophanes and Application to Multi-bridged Cyclophane Synthesis"Tetrahedron Lett.. 42. 1919-1921 (2001)
[Publications] Y.Okada: "Synthesis and Characterization of Calixarene Analogs Locked in the Cone Conformation by the Dimerization of syn-Dihydroxymetacyclophanes as a Building Block"Tetrahedron. 57. 1219-1227 (2001)
[Publications] Y.Okada: "Chloromethylation of syn-[2.n]Metacyclophanes and Application toward Multi-bridged Cyclophane Synthesis"Tetrahedron Lett.. 42. 25-27 (2001)
[Publications] J.Nishimura: "Stereocontrol in Cyclophane Synthesis : Photochemical Method to Overlap Aromatic Rings"Acc. Chem. Res.. 33. 679-686 (2000)
[Publications] Y.Nakamura: "Separation and characterization of [60]fullerene bisadducts modified by 4,5-dimethoxy-o-quinodimethane"Tetrahedron. 56. 5429-5434 (2000)
[Publications] Y.Nakamura: "Langmuir and LB Films of Amphiphilic [60]Fullerene Derivatives"Bull. Chem. Soc. Jpn.. 73. 1615-1619 (2000)
[Publications] K.O-kawa: "Facile modification of [60]fullerene by photochemically generated hydroxy-o-quinodimethane derivatives"Tetrahedron Lett.. 41. 3103-3106 (2000)
[Publications] 林田喜任: "極性置換基を有する[2.n]ナフタレノファンの合成とその包接挙動"日本化学会誌. 247-255 (2000)
[Publications] Y.Nakamura: "Regioselective synthesis and complexation behavior of novel [60]fullerene bisadducts containing dibenzo-18-crown-6 moiety"Tetrahedron Lett.. 41. 2193-2197 (2000)
[Publications] Y.Nakamura: "Synthesis and fluorescence emission behavior of novel anti-[2.n](3,9)phenanthrenophanes"Tetrahedron Lett.. 41. 1419-1423 (2000)
[Publications] Y.Okada: "New Caixcrown-type Ionophores Derived from All Possible Regioisomers of Rigid Calix[4]arene"Synlett. 41-44 (2000)
[Publications] Y.Okada: "New Ionophores Derived from a Rigid Calixarenes Regioisomer"Tetrahedron Lett.. 40. 1353-1356 (1999)
[Publications] Y.Nakamura: "Excimer Fluorescence from anti-[2.3](2,7)Phenanthrenophane"Chem. Lett.. 1039-1040 (1999)
[Publications] Y.Hayashida: "Synthesis and Structure of Novel [2.n](4,4')Binaphthylophanes : A New Family in Cyclophane Chemistry"Tetrahedron Lett.. 40. 6435-6438 (1999)
[Publications] Y.Nakamura: "Synthesis and Photophysical Properties of syn-and anti-[2.n](3,9)Carbazolophanes"Tetrahedron Lett.. 40. 4693-4696 (1999)
[Publications] Y.Nakamura: "Synthesis of [2.n]Thiophenophanes by Intramolecular [2+2] Photocycloaddition"Heterocycles. 51. 1059-1065 (1999)
[Publications] Y.Nakamura: "Photophysical Properties of Various Regioisomers of [60]Fullerene-o-Quinodimethane Bisadducts"J. Chem. Soc., Perkin Trans. 2. 127-130 (1999)
[Publications] 猪熊精一: "分子内[2+2]光付加環化反応によるクラウノファン類の合成と錯形成能"日本化学会誌. 305-316 (1999)
[Publications] Seiichi Inokuma: "Crownophanes : Photochemical Preparation and Unique Comnlexing Ability"Cyclophane Chemistry for the 21^<th> Century, Research Signpost(in press).
[Publications] J.Nishimura: "Photochemical Synthesis of Cyclophane"Handbook of Organic Photochemistry(in press).
[Publications] Y.Nakamura: "Homocalixarenes"Calixarene 2001, ed. by Z. Asfari, J. Vicens, and V. Bohmer, Kluwer Academic Publishers. 219-234 (2001)

2002 Fiscal Year Annual Research Report

大環状化合物を反応場あるいは反応基貭とする新規ホスト分子の合成と応用

Principal Investigator

西村 淳 群馬大学, 工学部, 教授 (10107352)

Research Products

[Publications] Y.Okada: "Synthesis and Characterization of Chiral Calixarene Analogs Locked in the Cone Conformation by the Photocycloaddition"Synlett. (in press).

[Publications] 岡田行弘: "キラルカリックス[4]アレーン"有機合成化学協会誌. (印刷中).

[Publications] 岡田行弘: "コーン型配座"有機合成化学協会誌. (印刷中).

[Publications] Seiichi Inokuma: "A Pseudo Thiacrown Compound Formed by Hydrophobic Interaction of Its Lipophilic Parts in Water : Ag^+-Selectivc Fluorophore in Water"Heterocycles. 60. 145-150 (2003)

[Publications] Y.Okada: "Behavior of [2.n]metacyclophane-fused cyclobutane rings in bromination"Tetrahedron Lett.. 43. 5821-5824 (2002)

[Publications] Y.Okada: "A Synthesis and Characterization of New Chiral Calix[4]arenes"Enantiomer. 7. 93-106 (2002)

[Publications] Y.Nakamura: "Synthesis and Properties of Triply-Bridged syn-Carbazolophanes"J. Org. Chem.. 67. 8706-8709 (2002)

[Publications] Y.Nakamura: "Regioselective Synthesis and Properties of Novel [60]Fullerene Bisadducts Containing a Dibenzocrown Ether Moiety"J. Am. Chem. Soc.. 124. 4329-4335 (2002)

[Publications] Y.Nakamura: "Photochemical Synthesis, Conformational Analysis, and Transformation of [60] Fullerene-o-quinodimethane Adducts Bearing a Hydroxy Group"J. Org. Chem.. 67. 1247-1252 (2002)

[Publications] S.Inokuma: "Synthesis and Complexing Properties of Thiacrownophanes"Heterocycles. 55. 1635-1639 (2001)

[Publications] S.Inokuma: "Synthesis of Crownophane possessing Pyridine Moieties on the Aromatic Nuclei (Pyridine-Lariat Crownophane) : A Crownophane Exhibiting Perfect Selectivity Toward Ag^+"Heterocycles. 55. 447-451 (2001)

[Publications] S.Inokuma: "Synthesis and Complexing Ability of Azacrownophanes : The Cyclodextrin Catalysis of the Photochemical Cyclization Reaction"J. Incl. Phenom.. 39. 35-40 (2001)

[Publications] Y.Nakamura: "Synthesis and Fluorescence Emission Behavior of anti-[2.3](3,10)Phenanthrenophane : Overlap between Phenanthrene Rings Reciuired for Excimer Formation"Chem. Lett.. 970-971 (2001)

[Publications] Y.Nakamura: "First Isolation and Characterization of Eight Regioisomers for [60]Fullerene-Benzyne Bisadducts"Org. Lett.. 3. 1193-1196 (2001)

[Publications] S.Inokuma: "Synthesis of Pyridinocrownophanes Exhibiting High Ag^+-Affinity"Heterocycles. 54. 123-130 (2001)

[Publications] Y.Okada: "The Formylation of syn-[2.n]Metacyclophanes and Application to Multi-bridged Cyclophane Synthesis"Tetrahedron Lett.. 42. 1919-1921 (2001)

[Publications] Y.Okada: "Synthesis and Characterization of Calixarene Analogs Locked in the Cone Conformation by the Dimerization of syn-Dihydroxymetacyclophanes as a Building Block"Tetrahedron. 57. 1219-1227 (2001)

[Publications] Y.Okada: "Chloromethylation of syn-[2.n]Metacyclophanes and Application toward Multi-bridged Cyclophane Synthesis"Tetrahedron Lett.. 42. 25-27 (2001)

[Publications] J.Nishimura: "Stereocontrol in Cyclophane Synthesis : Photochemical Method to Overlap Aromatic Rings"Acc. Chem. Res.. 33. 679-686 (2000)

[Publications] Y.Nakamura: "Separation and characterization of [60]fullerene bisadducts modified by 4,5-dimethoxy-o-quinodimethane"Tetrahedron. 56. 5429-5434 (2000)

[Publications] Y.Nakamura: "Langmuir and LB Films of Amphiphilic [60]Fullerene Derivatives"Bull. Chem. Soc. Jpn.. 73. 1615-1619 (2000)

[Publications] K.O-kawa: "Facile modification of [60]fullerene by photochemically generated hydroxy-o-quinodimethane derivatives"Tetrahedron Lett.. 41. 3103-3106 (2000)

[Publications] 林田喜任: "極性置換基を有する[2.n]ナフタレノファンの合成とその包接挙動"日本化学会誌. 247-255 (2000)

[Publications] Y.Nakamura: "Regioselective synthesis and complexation behavior of novel [60]fullerene bisadducts containing dibenzo-18-crown-6 moiety"Tetrahedron Lett.. 41. 2193-2197 (2000)

[Publications] Y.Nakamura: "Synthesis and fluorescence emission behavior of novel anti-[2.n](3,9)phenanthrenophanes"Tetrahedron Lett.. 41. 1419-1423 (2000)

[Publications] Y.Okada: "New Caixcrown-type Ionophores Derived from All Possible Regioisomers of Rigid Calix[4]arene"Synlett. 41-44 (2000)

[Publications] Y.Okada: "New Ionophores Derived from a Rigid Calixarenes Regioisomer"Tetrahedron Lett.. 40. 1353-1356 (1999)

[Publications] Y.Nakamura: "Excimer Fluorescence from anti-[2.3](2,7)Phenanthrenophane"Chem. Lett.. 1039-1040 (1999)

[Publications] Y.Hayashida: "Synthesis and Structure of Novel [2.n](4,4')Binaphthylophanes : A New Family in Cyclophane Chemistry"Tetrahedron Lett.. 40. 6435-6438 (1999)

[Publications] Y.Nakamura: "Synthesis and Photophysical Properties of syn-and anti-[2.n](3,9)Carbazolophanes"Tetrahedron Lett.. 40. 4693-4696 (1999)

[Publications] Y.Nakamura: "Synthesis of [2.n]Thiophenophanes by Intramolecular [2+2] Photocycloaddition"Heterocycles. 51. 1059-1065 (1999)

[Publications] Y.Nakamura: "Photophysical Properties of Various Regioisomers of [60]Fullerene-o-Quinodimethane Bisadducts"J. Chem. Soc., Perkin Trans. 2. 127-130 (1999)

[Publications] 猪熊精一: "分子内[2+2]光付加環化反応によるクラウノファン類の合成と錯形成能"日本化学会誌. 305-316 (1999)

[Publications] Seiichi Inokuma: "Crownophanes : Photochemical Preparation and Unique Comnlexing Ability"Cyclophane Chemistry for the 21^<th> Century, Research Signpost(in press).

[Publications] J.Nishimura: "Photochemical Synthesis of Cyclophane"Handbook of Organic Photochemistry(in press).

[Publications] Y.Nakamura: "Homocalixarenes"Calixarene 2001, ed. by Z. Asfari, J. Vicens, and V. Bohmer, Kluwer Academic Publishers. 219-234 (2001)

西村淳群馬大学, 工学部, 教授 (10107352)