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JP6004292B2 - Polymer-supported copper catalyst and method for producing the same - Google Patents

Polymer-supported copper catalyst and method for producing the same Download PDF

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JP6004292B2
JP6004292B2 JP2014500030A JP2014500030A JP6004292B2 JP 6004292 B2 JP6004292 B2 JP 6004292B2 JP 2014500030 A JP2014500030 A JP 2014500030A JP 2014500030 A JP2014500030 A JP 2014500030A JP 6004292 B2 JP6004292 B2 JP 6004292B2
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copper
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copper catalyst
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vinyl monomer
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山田　陽一
陽一 山田
シャヒーン シャルカール
シャヒーン シャルカール
泰広 魚住
泰広 魚住
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RIKEN Institute of Physical and Chemical Research
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Description

本発明は、従来のものよりも高い触媒活性を有し、かつ再利用性が高い、新規なポリマー担持銅触媒に関する。   The present invention relates to a novel polymer-supported copper catalyst having higher catalytic activity than conventional ones and having high reusability.

２００２年にMeldalとSharplessがそれぞれ独立に、水溶性の銅触媒を用いるアルキンと有機アジド化合物との１，３−双極子環化反応（ヒュスゲン環化）を報告している（非特許文献１および２）。この反応は医薬品合成や化成品合成に重要な反応である。しかし、均一系触媒を用いるため、触媒の回収および再利用が難しく、反応生成物に触媒由来の銅が残留する問題がある。   In 2002, Meldal and Sharpless independently reported a 1,3-dipolar cyclization reaction (Husgen cyclization) between an alkyne and an organic azide compound using a water-soluble copper catalyst (Non-Patent Document 1 and 2). This reaction is an important reaction for pharmaceutical synthesis and chemical synthesis. However, since a homogeneous catalyst is used, it is difficult to recover and reuse the catalyst, and there is a problem that copper derived from the catalyst remains in the reaction product.

そのような問題を解決するため、銅を高分子化合物などの担体で固定化した固定化銅触媒の調製が試みられている。しかし、調製された固定化銅触媒はいずれも触媒活性が低く、数モル％の触媒量を必要とするものしか得られていなかった。また、触媒の再利用性も低いのが現状であった。（非特許文献３〜１３）   In order to solve such a problem, preparation of an immobilized copper catalyst in which copper is immobilized by a carrier such as a polymer compound has been attempted. However, all of the prepared immobilized copper catalysts have low catalytic activity, and only those requiring a catalyst amount of several mol% have been obtained. In addition, the recyclability of the catalyst is low at present. (Non-patent documents 3 to 13)

C. W. Tornoe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67, pp.3057-3064C. W. Tornoe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67, pp. 3057-3064 V. V. Rostovtsev, L. G. Green, V. V. Fokin, Sharpless, K. B., Angew. Chem. Int. Ed. 2002, 41, pp.2596-2599V. V. Rostovtsev, L. G. Green, V. V. Fokin, Sharpless, K. B., Angew. Chem. Int. Ed. 2002, 41, pp. 2596-2599 A. Coelho, P. Diz, O. Caamano, E. Sotelo, Adv. Synth. Catal. 2010, 352, pp.1179-1192A. Coelho, P. Diz, O. Caamano, E. Sotelo, Adv. Synth. Catal. 2010, 352, pp.1179-1192 C. Girard, E. Oenen, M. Aufort, S. Beauviere, E. Samson, J. Herscovici, Org. Lett. 2006, 8, pp.1689-1692C. Girard, E. Oenen, M. Aufort, S. Beauviere, E. Samson, J. Herscovici, Org. Lett. 2006, 8, pp.1689-1692 I. S. Park, M. S. Kwon, Y. Kim, J. S. Lee, J. Park, Org. Lett. 2008, 10, pp.497-500I. S. Park, M. S. Kwon, Y. Kim, J. S. Lee, J. Park, Org. Lett. 2008, 10, pp.497-500 B. H. Lipshutz, B. R. Taft, Angew. Chem. Int. Ed. 2006, 45, pp.8235-8238B. H. Lipshutz, B. R. Taft, Angew. Chem. Int. Ed. 2006, 45, pp. 8235-8238 S. Chassaing, A. S. S. Sido, A. Alix, M. Kumarraja, P. Pale, J. Sommer, Chem. Eur. J. 2008, 14, pp.6713-6721S. Chassaing, A. S. S. Sido, A. Alix, M. Kumarraja, P. Pale, J. Sommer, Chem. Eur. J. 2008, 14, pp.6713-6721 S. Chassaing, M. Kumarraja, A. S. S. Sido, P. Pale, J. Sommer, Org. Lett. 2007, 9, pp.883-886S. Chassaing, M. Kumarraja, A. S. S. Sido, P. Pale, J. Sommer, Org. Lett. 2007, 9, pp.883-886 K. Namitharan, M. Kumarraja, K. Pitchumani, Chem. Eur. J. 2009, 15, pp.2755-2758K. Namitharan, M. Kumarraja, K. Pitchumani, Chem. Eur. J. 2009, 15, pp.2755-2758 A. Megia-Fernandez, M. Ortega-Munoz, J. Lopez-Jaramillo, F. Hernandez-Mateo, F. Santoyo-Gonzaleza, Adv. Synth. Catal. 2010, 352, pp.3306-3320A. Megia-Fernandez, M. Ortega-Munoz, J. Lopez-Jaramillo, F. Hernandez-Mateo, F. Santoyo-Gonzaleza, Adv. Synth. Catal. 2010, 352, pp.3306-3320 Y. Wang, J. Liu, C. Xia, Adv. Synth. Catal. 2011, 353, pp.1534-1542Y. Wang, J. Liu, C. Xia, Adv. Synth. Catal. 2011, 353, pp.1534-1542 M. Liu, O. Reiser, Org. Lett. 2011, 13, pp.1102-1105M. Liu, O. Reiser, Org. Lett. 2011, 13, pp.1102-1105 F. Alonso, Y. Moglie, G. Radivoy, M. Yus, Adv. Synth. Catal. 2010, 352, pp.3208-3214F. Alonso, Y. Moglie, G. Radivoy, M. Yus, Adv. Synth. Catal. 2010, 352, pp.3208-3214

本発明は、従来のものよりも触媒活性が高く、かつ容易に回収でき、繰り返し再利用することができる銅触媒を提供することを目的とする。   An object of the present invention is to provide a copper catalyst that has higher catalytic activity than conventional ones, can be easily recovered, and can be reused repeatedly.

本発明者らは上述したような問題を検討した結果、両親媒性であるビニルモノマーと含窒素複素環式基を有するビニルモノマーを少なくとも含むモノマーが重合してなるポリマーの溶液に銅塩を加えることにより、従来にみられなかったような高い触媒活性を有し、かつ使用後の回収および再利用が容易な形状を有するポリマー固定化銅触媒が得られることを見出した。本発明の要旨は以下のとおりである。   As a result of examining the above-mentioned problems, the present inventors have added a copper salt to a polymer solution obtained by polymerizing at least a monomer containing an amphiphilic vinyl monomer and a vinyl monomer having a nitrogen-containing heterocyclic group. As a result, it has been found that a polymer-immobilized copper catalyst having a high catalytic activity not seen in the past and having a shape that can be easily recovered and reused after use can be obtained. The gist of the present invention is as follows.

（１）両親媒性であるビニルモノマーＡと含窒素複素環式基を有するビニルモノマーＢを少なくとも含むモノマーが重合してなるポリマー中に１価または２価の銅が担持されていることを特徴とするポリマー担持銅触媒。 (1) A monovalent or divalent copper is supported in a polymer obtained by polymerizing a monomer containing at least an amphiphilic vinyl monomer A and a vinyl monomer B having a nitrogen-containing heterocyclic group. A polymer-supported copper catalyst.

（２）ビニルモノマーＡが、式（Ｉ）

Figure 0006004292
(2) The vinyl monomer A has the formula (I)
Figure 0006004292

［式中、Ｒ１とＲ２はそれぞれ独立して、Ｈ、ならびに置換または非置換のＣ１−１０アルキル、Ｃ３−１０シクロアルキル、Ｃ３−１０シクロアルキル−Ｃ１−６アルキル、Ｃ６−１０アリールおよびＣ６−１０アリール−Ｃ１−６アルキルから選択され、ただしＲ１とＲ２が同時にＨとなることはない］
で表される化合物から選択される、（１）に記載の銅触媒。[Wherein, R 1 and R 2 each independently represent H, and substituted or unsubstituted C 1-10 alkyl, C 3-10 cycloalkyl, C 3-10 cycloalkyl-C 1-6 alkyl, C Selected from 6-10 aryl and C 6-10 aryl-C 1-6 alkyl, provided that R 1 and R 2 are not H at the same time]
The copper catalyst as described in (1) selected from the compound represented by these.

（３）ビニルモノマーＢが、式（ＩＩ）

Figure 0006004292
(3) The vinyl monomer B has the formula (II)
Figure 0006004292

［式中、Ｒ３はピロリル、ピロリジニル、イミダゾリル、ピラゾリル、トリアゾリル、テトラゾリル、ピリジニル、ピラジニル、ピリミジニル、ピリダジニルおよびトリアジニルから選択され、ｎは０〜３の整数である］
で表される化合物から選択される、（１）または（２）に記載の銅触媒。[Wherein R 3 is selected from pyrrolyl, pyrrolidinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl and triazinyl, and n is an integer of 0-3]
The copper catalyst as described in (1) or (2) selected from the compound represented by these.

（４）ヒュスゲン環化反応に用いる、（１）〜（３）のいずれかに記載の銅触媒。 (4) The copper catalyst according to any one of (1) to (3), which is used for the Huisgen cyclization reaction.

（５）両親媒性であるビニルモノマーＡと含窒素複素環式基を有するビニルモノマーＢを少なくとも含むモノマーが重合してなるポリマーの溶液に１価または２価の銅塩を加えることを含む、（１）〜（４）のいずれかに記載の銅触媒の製造方法。 (5) adding a monovalent or divalent copper salt to a polymer solution obtained by polymerizing a monomer containing at least a vinyl monomer A that is amphiphilic and a vinyl monomer B having a nitrogen-containing heterocyclic group; (1) The manufacturing method of the copper catalyst in any one of (4).

（６）（１）〜（４）のいずれかに記載の銅触媒を用いるヒュスゲン環化反応。 (6) Huesgen cyclization reaction using the copper catalyst according to any one of (1) to (4).

本発明によれば、従来知られた固定化銅触媒よりも触媒活性が高い銅触媒を提供することができる。本発明の銅触媒は不溶性の固体であるため、使用後の回収が容易であり、該触媒を使用して得られる生成物に銅が混入することもない。さらに、本発明の銅触媒はくり返し使用しても高い触媒活性を維持することができる。本発明の銅触媒は有機合成化学などの分野において、汚染物質を排出することなく目的生成物を製造するグリーンケミストリーに非常に有用である。   According to the present invention, a copper catalyst having higher catalytic activity than a conventionally known immobilized copper catalyst can be provided. Since the copper catalyst of the present invention is an insoluble solid, it can be easily recovered after use, and copper is not mixed into the product obtained by using the catalyst. Furthermore, the copper catalyst of the present invention can maintain high catalytic activity even when used repeatedly. The copper catalyst of the present invention is very useful for green chemistry for producing a target product without emitting pollutants in fields such as organic synthetic chemistry.

本明細書は、本願の優先権の基礎である特願２０１２−０２９７３２号の明細書、特許請求の範囲および図面に記載された内容を包含する。   This specification includes the contents described in the specification, claims and drawings of Japanese Patent Application No. 2012-029732 which is the basis of the priority of the present application.

実施例で得られた銅触媒のエネルギー分散Ｘ線分光スペクトルである。It is an energy dispersive X-ray-spectroscopy spectrum of the copper catalyst obtained in the Example. 実施例で得られた銅触媒のＸ線光電子分光スペクトルである。It is a X-ray photoelectron spectroscopy spectrum of the copper catalyst obtained in the examples.

本発明のポリマー担持銅触媒は、両親媒性であるビニルモノマーＡと含窒素複素環式基を有するビニルモノマーＢを少なくとも含むモノマーが重合してなるポリマー中に１価または２価の銅が担持されていることを特徴とする。   The polymer-supported copper catalyst of the present invention is supported by monovalent or divalent copper in a polymer obtained by polymerizing at least a monomer containing an amphiphilic vinyl monomer A and a vinyl monomer B having a nitrogen-containing heterocyclic group. It is characterized by being.

ビニルモノマーＡは両親媒性であり、極性溶媒と非極性溶媒のいずれにも可溶である。ビニルモノマーＡの具体例としては、例えば下記の式（Ｉ）で表される構造を有する化合物が挙げられる。

Figure 0006004292
Vinyl monomer A is amphiphilic and is soluble in both polar and nonpolar solvents. Specific examples of the vinyl monomer A include compounds having a structure represented by the following formula (I).
Figure 0006004292

式（Ｉ）において、Ｒ１とＲ２はそれぞれ独立して、Ｈ、ならびに置換または非置換のＣ１−１０アルキル、Ｃ３−１０シクロアルキル、Ｃ３−１０シクロアルキル−Ｃ１−６アルキル、Ｃ６−１０アリールおよびＣ６−１０アリール−Ｃ１−６アルキルから選択される。ただしＲ１とＲ２が同時にＨとなることはない。また、その他のビニルモノマーＡの具体例としては、親水性基を有するスチレン（例えばベンゼン環上にヒドロキシル基、カルボキシル基、アミノ基、スルホン基などの親水性基を有するスチレン、あるいはそれらの親水性基を有するＣ１−６アルキル基などを少なくとも１個ベンゼン環上に有するスチレン）、アクリロニトリル、Ｃ１−６アルキルビニルエーテルなどが挙げられる。ビニルモノマーＡとしては、上記の式（Ｉ）で表される化合物が特に好ましい。また、式（Ｉ）において、Ｒ１とＲ２の一方がＨであり、他方がＣ１−１０アルキル、特にＣ１−６アルキルであることが好ましい。両親媒性であるビニルモノマーＡは１種のみを用いても、２種以上を混合して用いてもよい。In formula (I), R 1 and R 2 are each independently H, and substituted or unsubstituted C 1-10 alkyl, C 3-10 cycloalkyl, C 3-10 cycloalkyl-C 1-6 alkyl , C 6-10 aryl and C 6-10 aryl-C 1-6 alkyl. However, R 1 and R 2 are not H at the same time. Other specific examples of the vinyl monomer A include styrene having a hydrophilic group (for example, styrene having a hydrophilic group such as hydroxyl group, carboxyl group, amino group, and sulfone group on the benzene ring, or hydrophilicity thereof. Styrene having at least one C 1-6 alkyl group having a group on the benzene ring), acrylonitrile, C 1-6 alkyl vinyl ether, and the like. As the vinyl monomer A, a compound represented by the above formula (I) is particularly preferable. In the formula (I), it is preferable that one of R 1 and R 2 is H and the other is C 1-10 alkyl, particularly C 1-6 alkyl. The vinyl monomer A that is amphiphilic may be used alone or in combination of two or more.

ここで、本明細書において各用語は以下に示す意味を有する。   Here, in this specification, each term has the meaning shown below.

Ｃ１−１０アルキル：１〜１０個の炭素原子を有する飽和炭化水素基、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペンチル、イソペンチル、ヘキシル、２−エチルヘキシル、ヘプチル、オクチル、ノニルおよびデシルなど。Ｃ１−６アルキルは、同様に１〜６個の炭素原子を有する飽和炭化水素基を意味する。C 1-10 alkyl: a saturated hydrocarbon group having 10 to 10 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , Hexyl, 2-ethylhexyl, heptyl, octyl, nonyl and decyl. C 1-6 alkyl likewise denotes a saturated hydrocarbon group having 1 to 6 carbon atoms.

Ｃ３−１０シクロアルキル：３〜１０個の炭素原子を有する脂肪族環式飽和炭化水素基、例えばシクロプロピル、シクロブチル、シクロペンチル、シクロへキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシルおよびアダマンチル。C 3-10 cycloalkyl: an aliphatic cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and adamantyl.

Ｃ６−１０アリール：６〜１０個の炭素原子を有する芳香族炭化水素基、例えばフェニル、トリルおよびナフチル。C 6-10 aryl: an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as phenyl, tolyl and naphthyl.

Ｃ３−１０シクロアルキル−Ｃ１−６アルキル：Ｃ３−１０シクロアルキルを有するＣ１−６アルキル。例えばシクロペンチルメチル、シクロペンチルエチル、シクロペンチルプロピル、シクロヘキシルメチル、シクロヘキシルエチルおよびシクロヘキシルプロピル。C 3-10 cycloalkyl -C 1-6 alkyl: C 1-6 alkyl having C 3-10 cycloalkyl. For example, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl.

Ｃ６−１０アリール−Ｃ１−６アルキル：Ｃ６−１０アリールを有するＣ１−６アルキル。例えばベンジル、フェニルエチル、フェニルプロピル、ナフタレニルメチル、ナフタレニルエチルおよびナフタレニルプロピル。C 6-10 aryl -C 1-6 alkyl: C 1-6 alkyl having C 6-10 aryl. For example benzyl, phenylethyl, phenylpropyl, naphthalenylmethyl, naphthalenylethyl and naphthalenylpropyl.

置換または非置換の：対象とする基が、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、ヒドロキシル基、１〜４個の炭素原子を有する飽和炭化水素基（Ｃ１−４アルキル）、１〜４個の炭素原子を有するアルコキシ基（Ｃ１−４アルコキシ）、１〜５個の炭素原子を有するアシルオキシ基（Ｃ１−５アシルオキシ）、カルボキシル基、２〜５個の炭素原子を有するアルコキシカルボニル基（Ｃ２−５アルコキシカルボニル）、シアノ基、ニトロ基などの置換基により置換されている、あるいは非置換であることを意味する。Substituted or unsubstituted: the target group is a halogen atom (F, Cl, Br, I), a hydroxyl group, a saturated hydrocarbon group having 1 to 4 carbon atoms ( C1-4 alkyl), 1 to Alkoxy group having 4 carbon atoms ( C1-4 alkoxy), acyloxy group having 1 to 5 carbon atoms ( C1-5 acyloxy), carboxyl group, alkoxycarbonyl having 2 to 5 carbon atoms It means substituted or unsubstituted with a substituent such as a group (C 2-5 alkoxycarbonyl), cyano group, nitro group and the like.

ビニルモノマーＢは、少なくとも１個の含窒素複素環式基を有する。ビニルモノマーＢが有する含窒素複素環式基としては、環員数が４〜１２であり、少なくとも１個の窒素原子を有する、単環式または多環式の、脂肪族または芳香族複素環式基が挙げられる。そのような含窒素複素環式基の具体例としては、例えば、ピロリル、ピロリジニル、イミダゾリル、ピラゾリル、トリアゾリル、テトラゾリル、ピリジニル、ピラジニル、ピリミジニル、ピリダジニル、トリアジニル、インドリジニル、イソインドリニル、インドリニル、インダゾリル、プリニル、キノリジニル、イソキノリニル、キノリニル、フタラジニル、ナフチリジニル、キノキサリニル、キナゾリル、オキサゾリル、イソオキサゾリル、チアゾリル、イソチアゾリル、モルホリニルなどが挙げられる。好ましくは、含窒素複素環式基は、環員数が４〜６であり、複素原子として窒素のみを有する基、例えばピロリル、ピロリジニル、イミダゾリル、ピラゾリル、トリアゾリル、テトラゾリル、ピリジニル、ピラジニル、ピリミジニル、ピリダジニル、トリアジニルから選択される。   The vinyl monomer B has at least one nitrogen-containing heterocyclic group. The nitrogen-containing heterocyclic group that the vinyl monomer B has is a monocyclic or polycyclic aliphatic or aromatic heterocyclic group having 4 to 12 ring members and having at least one nitrogen atom. Is mentioned. Specific examples of such nitrogen-containing heterocyclic groups include, for example, pyrrolyl, pyrrolidinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, isoindolinyl, indolinyl, indazolyl, purinyl, quinolidinyl , Isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, morpholinyl and the like. Preferably, the nitrogen-containing heterocyclic group has 4 to 6 ring members and has only nitrogen as a hetero atom, such as pyrrolyl, pyrrolidinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, Selected from triazinyl.

ビニルモノマーＢは、好ましくは下記の式（ＩＩ）で表される構造を有する。

Figure 0006004292
The vinyl monomer B preferably has a structure represented by the following formula (II).
Figure 0006004292

式（ＩＩ）において、Ｒ３は上述したような含窒素複素環式基を表す。ｎは０〜３の整数であり、好ましくは０、１または２、より好ましくは０または１、最も好ましくは０である。含窒素複素環式基を有するビニルモノマーＢは１種のみを用いても、２種以上を混合して用いてもよい。In the formula (II), R 3 represents a nitrogen-containing heterocyclic group as described above. n is an integer of 0 to 3, preferably 0, 1 or 2, more preferably 0 or 1, and most preferably 0. The vinyl monomer B having a nitrogen-containing heterocyclic group may be used alone or in combination of two or more.

ビニルモノマーＡとビニルモノマーＢの重合は、従来知られた方法、例えば両モノマーをトルエンなどの適切な溶媒に溶解させた後、溶液にアゾビスイソブチロニトリルなどの重合開始剤を加えることにより行うことができる。ビニルモノマーＡとビニルモノマーＢの混合比は、モル比で１：２０〜２０：１の範囲、特に１：１０〜１０：１の範囲、とりわけ１：５〜５：１の範囲とすることが好ましい。   The polymerization of vinyl monomer A and vinyl monomer B is performed by a conventionally known method, for example, by dissolving both monomers in a suitable solvent such as toluene and then adding a polymerization initiator such as azobisisobutyronitrile to the solution. It can be carried out. The mixing ratio of vinyl monomer A and vinyl monomer B should be in the range of 1:20 to 20: 1, in particular in the range of 1:10 to 10: 1, in particular in the range of 1: 5 to 5: 1. preferable.

本発明のポリマー担持銅触媒に用いるポリマーは、ビニルモノマーＡおよびビニルモノマーＢに加えて、それらとは異なる種のモノマー（モノマーＣ）を用いて調製されていてもよい。そのようなモノマーとしては、例えば少なくとも一つの二重結合を有し、かつ２〜６個の炭素原子を有するオレフィン系炭化水素（Ｃ２−６アルケン：例えばエチレン、プロピレン、ブテン、ペンテン、ヘキセンなど）、および２〜６個の炭素原子を有するオレフィン系炭化水素基により置換されたＣ６−１０アリール基（Ｃ２−６アルケニル−Ｃ６−１０アリール：例えばスチレン、メチルスチレン、エチルスチレン、ジメチルスチレン、アリルベンゼン、アリルメチルベンゼン、アリルエチルベンゼン、アリルジメチルベンゼンなど）が挙げられる。ポリマー調製時におけるビニルモノマーＡとビニルモノマーＢの和に対するモノマーＣの混合比（Ａ＋Ｂ：Ｃ）は、５０：５０〜１００：０の範囲、特に７０：３０〜１００：０の範囲、とりわけ９０：１０〜１００：０の範囲であることが好ましい。In addition to vinyl monomer A and vinyl monomer B, the polymer used for the polymer-supported copper catalyst of the present invention may be prepared using a different type of monomer (monomer C). Examples of such a monomer include an olefinic hydrocarbon having at least one double bond and having 2 to 6 carbon atoms (C 2-6 alkene: for example, ethylene, propylene, butene, pentene, hexene, etc. And a C 6-10 aryl group substituted by an olefinic hydrocarbon group having 2 to 6 carbon atoms (C 2-6 alkenyl-C 6-10 aryl: for example, styrene, methyl styrene, ethyl styrene, dimethyl Styrene, allylbenzene, allylmethylbenzene, allylethylbenzene, allyldimethylbenzene, etc.). The mixing ratio of monomer C to the sum of vinyl monomer A and vinyl monomer B (A + B: C) during the preparation of the polymer is in the range of 50:50 to 100: 0, in particular in the range of 70:30 to 100: 0, in particular 90: A range of 10 to 100: 0 is preferable.

ビニルモノマーＡとビニルモノマーＢ、および場合によりモノマーＣとを重合させて得られるポリマーは、水または極性有機溶媒に可溶性であり、各モノマーが実質的に架橋することなく直鎖状に重合した構造を有することが好ましい。従って、ビニルモノマーＡおよびＢ、ならびにモノマーＣは、いずれもビニル基以外に重合して架橋構造を構成し得る基を有しないことが好ましい。ポリマーの重合度は、５０００〜５０００００の範囲、特に５０００〜５００００の範囲であることが好ましい。   A polymer obtained by polymerizing vinyl monomer A and vinyl monomer B, and optionally monomer C, is soluble in water or a polar organic solvent, and has a structure in which each monomer is linearly polymerized without being substantially crosslinked. It is preferable to have. Therefore, it is preferable that both vinyl monomers A and B and monomer C do not have a group capable of forming a crosslinked structure by polymerization other than the vinyl group. The degree of polymerization of the polymer is preferably in the range of 5000 to 500000, particularly in the range of 5000 to 50000.

本発明のポリマー担持銅触媒は、上述のようにして得られるポリマー中に１価または２価の銅が分散して担持された構造を有する。本発明のポリマー担持銅触媒は、該ポリマーの溶液中に１価または２価の銅塩を加えることにより得ることができる。従って、本発明は別の側面において、両親媒性であるビニルモノマーＡと含窒素複素環式基を有するビニルモノマーＢを少なくとも含むモノマーが（好ましくは直鎖状に）重合したポリマーの溶液に１価または２価の銅塩を加えることを含む、ポリマー担持銅触媒の製造方法に関する。   The polymer-supported copper catalyst of the present invention has a structure in which monovalent or divalent copper is dispersed and supported in the polymer obtained as described above. The polymer-supported copper catalyst of the present invention can be obtained by adding a monovalent or divalent copper salt to a solution of the polymer. Therefore, in another aspect, the present invention provides a polymer solution in which a monomer containing at least a vinyl monomer A that is amphiphilic and a vinyl monomer B having a nitrogen-containing heterocyclic group is polymerized (preferably linearly). The present invention relates to a method for producing a polymer-supported copper catalyst, comprising adding a divalent or divalent copper salt.

１価または２価の銅塩としては、例えば硫酸銅、塩化銅、ヨウ化銅、臭化銅、フッ化銅、酢酸銅、硝酸銅、酸化銅、トリフルオロメタンスルホン酸銅、などが挙げられる。また、銅塩を加える際にポリマーを溶解させておく溶媒は、１価または２価の銅を還元させることがない不活性な溶媒、例えばクロロホルム、水、テトラヒドロフラン、アセトン、酢酸エチル、ｔ−ブチルアルコールおよびそれらの混合溶媒を使用することが望ましい。   Examples of the monovalent or divalent copper salt include copper sulfate, copper chloride, copper iodide, copper bromide, copper fluoride, copper acetate, copper nitrate, copper oxide, and copper trifluoromethanesulfonate. The solvent for dissolving the polymer when adding the copper salt is an inert solvent that does not reduce monovalent or divalent copper, such as chloroform, water, tetrahydrofuran, acetone, ethyl acetate, t-butyl. It is desirable to use alcohol and mixed solvents thereof.

ポリマーの溶液中に銅塩を加えると、溶解していたポリマーの凝集が起こり、ポリマー担持銅触媒が不溶性の沈殿物として得られる。これは、銅塩を加えたことにより、ポリマー中の含窒素複素環式基部分が１価または２価の銅（Ｃｕ＋またはＣｕ２＋）に配位することによるものと考えられる。そうして得られるポリマー担持銅触媒は、ポリマーからなるスポンジ状の塊中に、１価または２価の銅が均一に分散して担持された構造を有する。ここで、１価または２価の銅は、一定数の原子が固まってナノ粒子を形成しているのではなく、原子レベルで均一にポリマー中に分散している。そのように配位され固定化された１価または２価の銅は、ポリマーから容易に脱落することがない。When a copper salt is added to the polymer solution, aggregation of the dissolved polymer occurs, and the polymer-supported copper catalyst is obtained as an insoluble precipitate. This is considered to be due to the fact that the nitrogen-containing heterocyclic group portion in the polymer is coordinated to monovalent or divalent copper (Cu + or Cu 2+ ) by adding a copper salt. The polymer-supported copper catalyst thus obtained has a structure in which monovalent or divalent copper is uniformly dispersed and supported in a sponge-like lump made of a polymer. Here, monovalent or divalent copper does not form a nanoparticle by solidifying a certain number of atoms, but is uniformly dispersed in the polymer at the atomic level. The monovalent or divalent copper so coordinated and immobilized does not easily fall off from the polymer.

本発明のポリマー担持銅触媒は、銅触媒を利用する様々な反応に用いることができる。そのような反応としては、例えばアルドール反応、ウルマン反応、グレーサー反応、ヒュスゲン環化反応、アルコールまたはアルケンの酸化、芳香族アミノ化が挙げられる。中でも、本発明のポリマー担持銅触媒は、ヒュスゲン環化反応において顕著に高い触媒活性を示す。ヒュスゲン環化反応は、別名クリック反応とも呼ばれる［３＋２］双極子付加環化反応の一種であり、アルキンとアジドから極めて高い官能基選択性でトリアゾールを生成する反応である。本発明は、別の側面において、上述したポリマー担持銅触媒を用いるヒュスゲン環化反応に関する。   The polymer-supported copper catalyst of the present invention can be used in various reactions using a copper catalyst. Examples of such reaction include aldol reaction, Ullmann reaction, Gracer reaction, Huesgen cyclization reaction, oxidation of alcohol or alkene, and aromatic amination. Among these, the polymer-supported copper catalyst of the present invention exhibits a remarkably high catalytic activity in the Hüsgen cyclization reaction. The Hüsgen cyclization reaction is a kind of [3 + 2] dipole cycloaddition reaction, which is also called “click reaction”, and produces triazole from alkyne and azide with very high functional group selectivity. In another aspect, the present invention relates to a Hüsgen cyclization reaction using the polymer-supported copper catalyst described above.

本発明のポリマー担持銅触媒を用いたヒュスゲン環化反応は、例えば任意のアルキンと有機アジド化合物を適切な溶媒（例えばｔ−ブタノール、水など）に加え、そこにポリマー担持銅触媒を、２価の銅を１価の銅に還元する作用を有するアスコルビン酸ナトリウムと共に加え、必要に応じて加熱することにより行うことができる。あるいは、アルキン、有機ハロゲン化合物およびナトリウムアジドを用いても同様の反応を行うことができる。なお、反応に使用した後も触媒は塊状の形状を維持しており、大掛かりな濾過装置などを使用しなくても触媒は容易に回収することができる。また、回収した触媒は再利用が可能であり、繰り返し使用しても（例えば１０回程度）その触媒活性は殆ど低下することがない。   In the Huesgen cyclization reaction using the polymer-supported copper catalyst of the present invention, for example, an arbitrary alkyne and an organic azide compound are added to a suitable solvent (for example, t-butanol, water, etc.), and the polymer-supported copper catalyst is added to the divalent The copper can be added together with sodium ascorbate having the effect of reducing the copper to monovalent copper and heated as necessary. Alternatively, the same reaction can be performed using alkyne, an organic halogen compound and sodium azide. In addition, the catalyst maintains a lump shape after being used for the reaction, and the catalyst can be easily recovered without using a large-scale filtration device or the like. Further, the recovered catalyst can be reused, and even if it is repeatedly used (for example, about 10 times), its catalytic activity hardly decreases.

本発明のポリマー担持銅触媒を用いたヒュスゲン環化反応において、銅触媒の濃度は、アルキンに対する１価または２価の銅の濃度として、例えば０．２５ｍｏｌ％以下、０．１ｍｏｌ％以下、０．０５ｍｏｌ％以下、０．０１ｍｏｌ％以下、０．００５ｍｏｌ％以下としても、さらに場合によっては銅触媒の濃度を０．０００５ｍｏｌ％以下としても、目的生成物を高い収率で得ることができる。   In the Hüsgen cyclization reaction using the polymer-supported copper catalyst of the present invention, the concentration of the copper catalyst is, for example, 0.25 mol% or less, 0.1 mol% or less, 0.0 or less as the concentration of monovalent or divalent copper with respect to alkyne. The target product can be obtained in high yield even when the concentration is not more than 05 mol%, not more than 0.01 mol%, not more than 0.005 mol%, and in some cases even if the concentration of the copper catalyst is not more than 0.0005 mol%.

以下、実施例を用いて本発明をより詳細に説明するが、本発明はこれら実施例に限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples.

（１）ポリマーの調製
トルエン（４０ｍＬ）中のＮ−ビニルイミダゾール（１ｇ、１０．６２ｍｍｏｌ）とＮ−イソプロピルアクリルアミド（６．０１ｇ、５３．１３ｍｍｏｌ）をアルゴン雰囲気下で３０分間脱ガスした。アゾビスイソブチロニトリル（１６．４ｍｇ、０．１ｍｍｏｌ）を反応混合物に加え、アルゴン雰囲気下でさらに３０分間脱ガスした。次いで溶液を７０℃で１２時間加熱したところ、その間に無色の粉末が析出した。ガラスフィルターを用いて析出物を濾過し、トルエンで洗浄した。得られた固体を減圧下で乾燥させ、目的のポリマーを収率８３％で得た。(1) Preparation of polymer N-vinylimidazole (1 g, 10.62 mmol) and N-isopropylacrylamide (6.01 g, 53.13 mmol) in toluene (40 mL) were degassed under an argon atmosphere for 30 minutes. Azobisisobutyronitrile (16.4 mg, 0.1 mmol) was added to the reaction mixture and degassed for an additional 30 minutes under an argon atmosphere. The solution was then heated at 70 ° C. for 12 hours, during which time a colorless powder precipitated. The precipitate was filtered using a glass filter and washed with toluene. The obtained solid was dried under reduced pressure to obtain the target polymer in a yield of 83%.

1H NMR (CDCl3, 500 MHz):δ= 7.18-6.93 (m, 3 H), 4.12-3.81 (m, 5 H), 2.92 (m, 5 H), 2.09 (m, 5H), 1.85-1.30 (m, 13 H), 1.12 (m, 30 H); 13C NMR (CDCl3, 125 MHz) δ = 174.2, 129.7, 129.0, 128.2, 42.5, 41.3, 27.5, 22.6; IR (KBr) 3294, 2971, 2932, 2878, 1650, 1543, 1458, 1386, 1367, 1228, 1173, 1131, 1079, 915, 816, 667 cm-1; Anal. Calcd for C35H61N7O5・2H2O: C, 60.40; H, 9.41; N, 14.09. Found: C, 60.73, H, 9.38, N, 13.55.
（２）銅触媒の調製

Figure 0006004292
1 H NMR (CDCl 3 , 500 MHz): δ = 7.18-6.93 (m, 3 H), 4.12-3.81 (m, 5 H), 2.92 (m, 5 H), 2.09 (m, 5H), 1.85- 1.30 (m, 13 H), 1.12 (m, 30 H); 13 C NMR (CDCl 3 , 125 MHz) δ = 174.2, 129.7, 129.0, 128.2, 42.5, 41.3, 27.5, 22.6; IR (KBr) 3294, 2971, 2932, 2878, 1650, 1543, 1458, 1386, 1367, 1228, 1173, 1131, 1079, 915, 816, 667 cm -1 ; Anal.Calcd for C 35 H 61 N 7 O 5・ 2H 2 O: C, 60.40; H, 9.41; N, 14.09.Found: C, 60.73, H, 9.38, N, 13.55.
(2) Preparation of copper catalyst
Figure 0006004292

上記（１）で得られたポリマー１（１ｇ、１．５１ｍｍｏｌのイミダゾールを含有）のクロロホルム溶液（１０ｍＬ）に、硫酸銅五水和物の水溶液（１８９ｍｇ、０．７５７ｍｍｏｌ；１０ｍＬ）を２５℃でゆっくり加えたところ、青い沈殿物が生成した。その懸濁液を７０℃で１２時間加熱した。室温に冷却後、ガラスフィルターを用いて沈殿物を濾過した。得られた生成物をクロロホルムと水で洗浄し、減圧下で乾燥させ、目的の銅触媒３を収率８０％（９５０ｍｇ）で得た。   To a chloroform solution (10 mL) of polymer 1 (1 g, containing 1.51 mmol of imidazole) obtained in (1) above, an aqueous solution of copper sulfate pentahydrate (189 mg, 0.757 mmol; 10 mL) was added at 25 ° C. When slowly added, a blue precipitate formed. The suspension was heated at 70 ° C. for 12 hours. After cooling to room temperature, the precipitate was filtered using a glass filter. The obtained product was washed with chloroform and water and dried under reduced pressure to obtain the target copper catalyst 3 in a yield of 80% (950 mg).

Anal. Calcd for C105H183N21O19CuS・2H2O: C, 57.97; H, 8.66; N, 13.52; Cu, 2.92; S, 1.47. Found: C, 57.75; H, 8.59; N, 13.92; Cu, 2.66; S, 1.32. IR (KBr): 3303, 2971, 2940, 2873, 1645, 1537, 1457, 1387, 1367, 1234, 1172, 1131, 1037, 835, 667 cm-1 Anal.Calcd for C 105 H 183 N 21 O 19 CuS ・ 2H 2 O: C, 57.97; H, 8.66; N, 13.52; Cu, 2.92; S, 1.47. Found: C, 57.75; H, 8.59; N, 13.92; Cu, 2.66; S, 1.32. IR (KBr): 3303, 2971, 2940, 2873, 1645, 1537, 1457, 1387, 1367, 1234, 1172, 1131, 1037, 835, 667 cm -1

図１は、得られた銅触媒３のエネルギー分散Ｘ線分光スペクトルである。このスペクトルから、硫酸銅に由来する銅と硫黄が存在することがわかる。図２は、得られた銅触媒３のＸ線光電子分光スペクトルである。Ｃｕ ２ｐ３／２とＳ ２ｐ３／２がそれぞれ９３４．８ｅＶと１６７．９ｅＶにピークを示しており、それらは硫酸銅に由来するＣｕ（ＩＩ）とＳ（ＩＶ）に相当するものであると同定された。FIG. 1 is an energy dispersive X-ray spectrum of the obtained copper catalyst 3. From this spectrum, it can be seen that copper and sulfur derived from copper sulfate are present. FIG. 2 is an X-ray photoelectron spectrum of the obtained copper catalyst 3. Cu 2p 3/2 and S 2p 3/2 have peaks at 934.8 eV and 167.9 eV, respectively, and they correspond to Cu (II) and S (IV) derived from copper sulfate. Identified.

ポリマー１と銅触媒３のそれぞれについて赤外線吸収スペクトルを測定したところ、ポリマー１では１５４３ｃｍ−１に、銅触媒３では１５３７ｃｍ−１にそれぞれＣ−Ｎ伸縮振動に帰属されるピークがみられた。このことは、銅触媒３ではポリマー１におけるイミダゾールユニットが硫酸銅に配位した構造が形成されていることを示唆していると考えられる。Measurement of the infrared absorption spectrum for each of the polymer 1 and the copper catalyst 3, the polymer 1, 1543cm -1, a peak of each of 1537cm -1 in a copper catalyst 3 is attributed to the C-N stretching vibration was observed. This is considered to suggest that the copper catalyst 3 has a structure in which the imidazole unit in the polymer 1 is coordinated to copper sulfate.

（３）アルキンと有機アジドとの環化反応例

Figure 0006004292
(3) Example of cyclization reaction between alkyne and organic azide
Figure 0006004292

上記（２）で調製した銅触媒３（３ｍｇ、０．２５ｍｏｌ％）、アルキン４（０．５０ｍｍｏｌ）、有機アジド５（０．５０ｍｍｏｌ）、アスコルビン酸ナトリウム（１０ｍｏｌ％）、ｔ−ブチルアルコール（０．５ｍＬ）、水（１．５ｍＬ）をガラス容器に入れ、５０℃で１．５時間振盪した。この間に無色の沈殿物が生じた。反応液を酢酸エチルと水により希釈し、銅触媒３をピンセットでつまみ上げて回収した。反応液から有機相を分離した後、水相を酢酸エチルで抽出した（２ｍＬで３回）。有機相を合わせ、硫酸マグネシウムで乾燥させた後、濃縮および乾燥させることにより、目的のトリアゾール６を得た。得られた生成物は、酢酸エチル／ヘキサンで再結晶させて精製した。   Copper catalyst 3 prepared in the above (2) (3 mg, 0.25 mol%), alkyne 4 (0.50 mmol), organic azide 5 (0.50 mmol), sodium ascorbate (10 mol%), t-butyl alcohol (0 0.5 mL) and water (1.5 mL) were placed in a glass container and shaken at 50 ° C. for 1.5 hours. During this time, a colorless precipitate formed. The reaction solution was diluted with ethyl acetate and water, and the copper catalyst 3 was picked up with tweezers and collected. After separating the organic phase from the reaction solution, the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were combined, dried over magnesium sulfate, concentrated and dried to obtain the desired triazole 6. The resulting product was purified by recrystallization from ethyl acetate / hexane.

表１に種々のアルキン４と有機アジド５を用いて反応を行った結果をまとめた。いずれの反応においても、０．２５ｍｏｌ％という低い触媒濃度にもかかわらず、高い収率で目的生成物を得ることができた。エントリー１〜５の実験は銅触媒３を順次再利用して（すなわちエントリー２ではエントリー１の反応後に回収した触媒を使用、エントリー３ではエントリー２の反応後に回収した触媒を使用、以下同様）反応を行ったが、４回の触媒再利用を繰り返したエントリー５の反応においても触媒活性は低下せず、高い収率を維持することができた。   Table 1 summarizes the results of reactions using various alkynes 4 and organic azides 5. In any reaction, the target product could be obtained in high yield despite the catalyst concentration as low as 0.25 mol%. In the experiments of entries 1 to 5, the copper catalyst 3 is sequentially reused (that is, the catalyst recovered after the reaction of entry 1 is used in entry 2, the catalyst recovered after the reaction of entry 2 is used in entry 3, and so on). However, even in the reaction of entry 5 in which the catalyst was reused four times, the catalytic activity did not decrease and a high yield could be maintained.

なお、エントリー１と同様の反応を、銅触媒３の濃度を４５ｍｏｌ ｐｐｍ（０．００４５ｍｏｌ％）とし、振盪時間を１８時間にして行ったところ、目的生成物の収率は９５％であった。また、銅触媒３の濃度を４．５ｍｏｌ ｐｐｍ（０．０００４５ｍｏｌ％）とし、振盪時間を３１時間にして行ったところ、目的生成物の収率は９４％であった。

Figure 0006004292
When the same reaction as in Entry 1 was carried out with the concentration of the copper catalyst 3 being 45 mol ppm (0.0045 mol%) and the shaking time being 18 hours, the yield of the desired product was 95%. Further, when the concentration of the copper catalyst 3 was 4.5 mol ppm (0.00045 mol%) and the shaking time was 31 hours, the yield of the target product was 94%.
Figure 0006004292

（４）アルキン、有機ハライドおよびナトリウムアジドの三成分環化反応例

Figure 0006004292
(4) Example of ternary cyclization reaction of alkyne, organic halide and sodium azide
Figure 0006004292

上記（２）で調製した銅触媒３（３ｍｇ、０．２５ｍｏｌ％）、アルキン４（０．５０ｍｍｏｌ）、有機ハライド７（０．５０ｍｍｏｌ）、ナトリウムアジド（０．５ｍｍｏｌ）、アスコルビン酸ナトリウム（１０ｍｏｌ％）、ｔ−ブチルアルコール（０．５ｍＬ）、水（１．５ｍＬ）をガラス容器に入れ、５０℃で２．５時間振盪した。この間に無色の沈殿物が生じた。反応液を酢酸エチルと水により希釈し、銅触媒３をピンセットでつまみ上げて回収した。反応液から有機相を分離した後、水相を酢酸エチルで抽出した（２ｍＬで３回）。有機相を合わせ、硫酸マグネシウムで乾燥させた後、濃縮および乾燥させることにより、目的のトリアゾール６を得た。得られた生成物は、酢酸エチル／ヘキサンで再結晶させて精製した。   Copper catalyst 3 (3 mg, 0.25 mol%) prepared in (2) above, alkyne 4 (0.50 mmol), organic halide 7 (0.50 mmol), sodium azide (0.5 mmol), sodium ascorbate (10 mol%) ), T-butyl alcohol (0.5 mL) and water (1.5 mL) were placed in a glass container and shaken at 50 ° C. for 2.5 hours. During this time, a colorless precipitate formed. The reaction solution was diluted with ethyl acetate and water, and the copper catalyst 3 was picked up with tweezers and collected. After separating the organic phase from the reaction solution, the aqueous phase was extracted with ethyl acetate (3 × 2 mL). The organic phases were combined, dried over magnesium sulfate, concentrated and dried to obtain the desired triazole 6. The resulting product was purified by recrystallization from ethyl acetate / hexane.

表２に種々のアルキン４と有機ハライド７を用いて反応を行った結果をまとめた。いずれの反応においても、０．２５ｍｏｌ％という低い触媒濃度にもかかわらず、高い収率で目的生成物を得ることができた。エントリー１〜５の実験は銅触媒３を順次再利用して反応を行ったが、４回の触媒再利用を繰り返したエントリー５の反応においても触媒活性は低下せず、高い収率を維持することができた。   Table 2 summarizes the results of reactions using various alkynes 4 and organic halides 7. In any reaction, the target product could be obtained in high yield despite the catalyst concentration as low as 0.25 mol%. In the experiments of entries 1 to 5, the reaction was carried out by sequentially reusing the copper catalyst 3, but in the reaction of entry 5 in which the catalyst was reused four times, the catalytic activity was not lowered and a high yield was maintained. I was able to.

なお、エントリー１と同様の反応を、銅触媒３の濃度を４５ｍｏｌ ｐｐｍ（０．００４５ｍｏｌ％）とし、振盪時間を１８時間にして行ったところ、目的生成物の収率は９６％であった。

Figure 0006004292
Note that the same reaction as in Entry 1 was carried out at a copper catalyst 3 concentration of 45 mol ppm (0.0045 mol%) and a shaking time of 18 hours. The yield of the desired product was 96%.
Figure 0006004292

（５）環化反応の応用例
上記（３）および（４）と同様に下記式の反応をそれぞれ行った。いずれの反応においても、目的生成物を非常に高い収率で得ることができた。

Figure 0006004292
(5) Application example of cyclization reaction The reactions of the following formulas were carried out in the same manner as in the above (3) and (4). In any reaction, the target product could be obtained in a very high yield.
Figure 0006004292

本明細書中で引用した全ての刊行物、特許および特許出願をそのまま参考として本明細書中にとり入れるものとする。   All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety.

Claims (3)

両親媒性であるビニルモノマーＡと含窒素複素環式基を有するビニルモノマーＢを少なくとも含むモノマーが重合してなるポリマー中に１価または２価の銅が担持されている、ヒュスゲン環化反応に用いるためのポリマー担持銅触媒であって、
前記ビニルモノマーＡがＮ−イソプロピルアクリルアミドであり、かつ前記ビニルモノマーＢがＮ−ビニルイミダゾールである、前記触媒。 For the Hüsgen cyclization reaction in which monovalent or divalent copper is supported in a polymer obtained by polymerizing a monomer comprising at least an amphiphilic vinyl monomer A and a vinyl monomer B having a nitrogen-containing heterocyclic group. A polymer-supported copper catalyst for use , comprising:
The catalyst, wherein the vinyl monomer A is N-isopropylacrylamide and the vinyl monomer B is N-vinylimidazole . Ｎ−イソプロピルアクリルアミドとＮ−ビニルイミダゾールを少なくとも含むモノマーが重合してなるポリマーの溶液に１価または２価の銅塩を加えることを含む、請求項１に記載の銅触媒の製造方法。 The method for producing a copper catalyst according to claim 1 , comprising adding a monovalent or divalent copper salt to a polymer solution obtained by polymerizing a monomer containing at least N -isopropylacrylamide and N-vinylimidazole . 請求項１に記載の銅触媒を用いるヒュスゲン環化反応。 Hyusugen cyclization reaction using the copper catalyst according to claim 1.
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