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Polymer incarcerated Lewis acid metal catalyst

外国特許コード	F110003808
整理番号	E07607WO
掲載日	2011年7月5日
出願国	アメリカ合衆国
出願番号	59182905
公報番号	20070191624
公報番号	7470646
出願日	平成17年3月8日(2005.3.8)
公報発行日	平成19年8月16日(2007.8.16)
公報発行日	平成20年12月30日(2008.12.30)
国際出願番号	JP2005003949
国際公開番号	WO2005084802
国際出願日	平成17年3月8日(2005.3.8)
国際公開日	平成17年9月15日(2005.9.15)
優先権データ	特願2004-065250 (2004.3.9) JP 2005WO-JP03949 (2005.3.8) WO
発明の名称（英語）	Polymer incarcerated Lewis acid metal catalyst
発明の概要（英語）	(US7470646) The objective is to incarcerate a Lewis acid metal in a polymer and to make this catalyst recoverable while maintaining its function as a Lewis acid metal catalyst. The present invention is a polymer-incarcerated Lewis acid metal catalyst in which a Lewis acid metal is incarcerated in a crosslinked polymer and the crosslinked polymer is crosslinked using the crosslinking groups contained in a crosslinkable polymer. The polymer incarcerated Lewis acid metal catalyst is characterized by the crosslinkable polymer containing at least one type of monomer unit containing hydrophobic substituents and hydrophilic substituents containing crosslinking groups, and the hydrophobic substituents contain aromatic substituents. This crosslinkable polymer preferably comprises at least one type of monomer unit containing hydrophobic substituents and hydrophilic substituents containing crosslinking groups and a monomer unit containing hydrophobic substituents. This catalyst can be obtained by subjecting a polymer micelle incarcerated Lewis acid metal obtained by mixing an organic solution containing a crosslinkable polymer and a Lewis acid metal with a bad solvent to a crosslinking reaction. This catalyst is useful as a catalyst in aldol reactions, cyanolation reactions, allylation reactions, Michael reactions, Mannich reactions, Diels Alder reactions and Friedel Crafts reactions.
特許請求の範囲（英語）	[claim1] 1. A polymer incarcerated Lewis acid metal catalyst comprising a Lewis acid metal incarcerated in a crosslinked polymer, wherein the crosslinked polymer is obtained by crosslinking a crosslinkable polymer which has hydrophilic substituents containing crosslinking groups linked directly to the crosslinkable polymer main chain and hydrophobic substituents linked directly to the crosslinkable polymer main chain, wherein the hydrophobic substituents do not contain hydrophilic groups or crosslinking groups, and further wherein the crosslinkable polymer contains at least one type of monomer unit containing (a) an aromatic hydrophobic substituent which does not contain hydrophilic groups or crosslinking groups and (b) a hydrophilic substituent containing a crosslinking group. [claim2] 2. The catalyst of claim 1, wherein the crosslinkable polymer further contains at least one type of monomer unit containing a hydrophobic substituent but no hydrophilic substituent containing a crosslinking group. [claim3] 3. The catalyst of claim 2, wherein the crosslinkable polymer further contains at least one type of a monomer unit containing a hydrophobic substituent other than an aromatic substituent and a hydrophilic substituent containing a crosslinking group but no hydrophilic substituent containing a crosslinking group. [claim4] 4. The catalyst of claim 1, wherein the crosslinkable polymer contains a monomer unit containing a hydrophilic substituent containing an epoxy group and a monomer unit containing a hydrophilic substituent containing a group that reacts with the epoxy group. [claim5] 5. The catalyst of claim 4, wherein the crosslinkable polymer contains a monomer unit containing an aromatic substituent and a hydrophilic substituent containing an epoxy group, a monomer unit containing an aromatic substituent and a hydrophilic substituent containing a group that reacts with the epoxy group, and a monomer unit containing a hydrophobic substituent but no hydrophilic substituent containing a crosslinking group. [claim6] 6. The catalyst of claim 4, wherein the crosslinkable polymer contains a monomer unit containing an aromatic substituent and a hydrophilic substituent containing an epoxy group, a monomer unit containing a hydrophobic substituent other than an aromatic substituent and a hydrophilic substituent containing a group that reacts with the epoxy group and a monomer unit containing a hydrophobic substituent but no hydrophilic substituent containing a crosslinking group. [claim7] 7. The catalyst of claim 4, wherein the crosslinkable polymer contains a monomer unit containing an aromatic substituent and a hydrophilic substituent containing a group that reacts with an epoxy group, a monomer unit containing a hydrophobic substituent other than an aromatic substituent and a hydrophilic substituent containing an epoxy group and a monomer unit containing a hydrophobic substituent but no hydrophilic substituent containing a crosslinking group. [claim8] 8. The catalyst of claim 4, wherein the group that reacts with an epoxy group is at least one selected from a group comprising a hydroxyl group, an amino group, a thiol group and a carboxyl group. [claim9] 9. The polymer incarcerated Lewis acid metal catalyst of claim 1, wherein the crosslinkable polymer is obtained by polymerizing, as main monomers, a styrene monomer, a vinyl monomer represented by the general formula wherein R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group containing less than 14 carbon atoms, R3 represents an alkylene group having 1 to 6 carbon atoms, -- (CH2)n(OCH2CHR5)m -- , -- (CH2)n(OCH2CO.dbd.O)m -- or -- (CH2)n(COCH2)m -- , wherein R5 represents a hydrogen atom or a methyl group and n and m each independently represent integers 1 to 10, and R4 represents an epoxy group, and a vinyl monomer represented by the general formula wherein R1 to R3 and n and m independently represent the same as above, and R4 represents at least one reactive group selected from a group comprising a hydroxyl group, an amino group, a thiol group and a carboxyl group. [claim10] 10. The catalyst of claim 1 prepared by mixing an organic solution containing the crosslinkable polymer and the Lewis acid metal to prepare a polymer micelle incarcerating Lewis acid metal, and crosslinking the polymer micelle incarcerating Lewis acid metal. [claim11] 11. The catalyst of claim 1, wherein the Lewis acid metal is represented by MYn, wherein M represents Cu, Zn, Fe, Sc or a lanthanoid element, Y represents a halogen atom, OAc, OCOCF3, ClO4, SbF6, PF6 or OSO2CF3 and n is 2 or 3. [claim12] 12. An aldol, cyanolation, allylation, Michael, Mannich, Diels Alder or Friedel Craft reaction conducted in the presence of the catalyst of claim 1. [claim13] 13. The catalyst of claim 2, wherein the crosslinkable polymer contains a monomer unit containing a hydrophilic substituent containing an epoxy group and a monomer unit containing a hydrophilic substituent containing a group that reacts with the epoxy group. [claim14] 14. The catalyst of claim 3, wherein the crosslinkable polymer contains a monomer unit containing a hydrophilic substituent containing an epoxy group and a monomer unit containing a hydrophilic substituent containing a group that reacts with the epoxy group. [claim15] 15. The catalyst of claim 9 prepared by mixing an organic solution containing the crosslinkable polymer and the Lewis acid metal to prepare a polymer micelle incarcerating Lewis acid metal, and crosslinking the polymer micelle incarcerating Lewis acid metal. [claim16] 16. The catalyst of claim 9, wherein the Lewis acid metal is represented by MYn, wherein M represents Cu, Zn, Fe, Sc or a lanthanoid element, Y represents a halogen atom, OAc, OCOCF3, ClO4, SbF6, PF6 or OSO2CF3 and n is 2 or 3. [claim17] 17. The catalyst of claim 10, wherein the Lewis acid metal is represented by MYn, wherein M represents Cu, Zn, Fe, Sc or a lanthanoid element, Y represents a halogen atom, OAc, OCOCF3, ClO4, SbF6, PF6 or OSO2CF3 and n is 2 or 3. [claim18] 18. An aldol, cyanolation, allylation, Michael, Mannich, Diels Alder or Friedel Craft reaction conducted in the presence of the catalyst of claim 9. [claim19] 19. An aldol, cyanolation, allylation, Michael, Mannich, Diels Alder or Friedel Craft reaction conducted in the presence of the catalyst of claim 10.
発明者/出願人（英語）	KOBAYASHI SHU AKIYAMA RYO KAWAI NOBUYUKI TAKEUCHI MASAHIRO JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)	B01J 31/00 水素化物，配位錯体または有機化合物からなる触媒 B01J 31/26 グループＢ０１Ｊ３１／０２～Ｂ０１Ｊ３１／２４までに分類されない無機金属化合物をさらに含有するもの B01J 31/28 白金族金属，鉄族金属または銅に関するもの C07C 45/46 フリーデル―クラフツ反応によるもの C07C 45/51 熱分解，転位または分解によるもの C07C 45/72 ＞Ｃ＝Ｏ基を含有する化合物と＞Ｃ＝Ｏ基を含有する同一または他の化合物との反応によるもの C07C 45/73 水素化と組み合せたもの C07C 49/245 ６員芳香環を含有するもの C07C 49/255 エーテル基，「図」基，「図」基，または「図」基を含有するもの C07C 49/507 多環式のもの C07C 49/573 水酸基を含有するもの C07C 49/76 ６員芳香環に結合しているケト基を含有するケトン C07C 49/83 多環式のもの C07C 67/00 カルボン酸エステルの製造 C07C 67/347 炭素―炭素不飽和結合への付加によるもの C07C 227/12 アミノ基とカルボキシル基の形成 C07C 229/34 炭素骨格が６員芳香環を含有するもの C07C 327/22 エステル化されたチオカルボキシル基の炭素原子が水素原子または非環式炭素原子に結合しているもの
参考情報（研究プロジェクト等）	ERATO KOBAYASHI Highly Functionalized Reaction Environments AREA