JP2018192409A - Solid catalyst for reductive reaction - Google Patents
Solid catalyst for reductive reaction Download PDFInfo
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- JP2018192409A JP2018192409A JP2017097044A JP2017097044A JP2018192409A JP 2018192409 A JP2018192409 A JP 2018192409A JP 2017097044 A JP2017097044 A JP 2017097044A JP 2017097044 A JP2017097044 A JP 2017097044A JP 2018192409 A JP2018192409 A JP 2018192409A
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- transition metal
- solid catalyst
- reduction reaction
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Abstract
Description
本発明は、還元反応用固体触媒に関し、より詳しくは、タンパク質存在下での還元反応に使用する還元反応用固体触媒に関する。 The present invention relates to a solid catalyst for reduction reaction, and more particularly to a solid catalyst for reduction reaction used for a reduction reaction in the presence of protein.
酵素は、基質特異的かつ立体選択的な反応を進行させる機能を有するものであり、医薬品の製造過程において有用であることが知られている。しかしながら、これまで、酵素は高価であり、安定的な確保が困難であったため、化学反応における触媒として利用するには多くの課題があった。近年、遺伝子工学技術の進歩により、目的とする酵素を安価で大量に製造することが可能となり、医薬品、生理活性物質、農薬、機能性材料等の製造過程への適用等、酵素の工業的な利用が期待されている。 Enzymes have a function of advancing substrate-specific and stereoselective reactions, and are known to be useful in the manufacturing process of pharmaceuticals. However, until now, enzymes have been expensive, and it has been difficult to ensure their stability, so there have been many problems in using them as catalysts in chemical reactions. In recent years, advances in genetic engineering technology have made it possible to produce target enzymes at low cost and in large quantities, and industrial applications of enzymes such as application to the manufacturing process of pharmaceuticals, bioactive substances, agricultural chemicals, functional materials, etc. Use is expected.
例えば、特開２０１２−１０６２２５号公報（特許文献１）には、オキソバナジウム触媒及びリパーゼの存在下で、環状ラセミ体アリルアルコールとビニルエステルとを反応させて、医薬品等の合成中間体である光学活性アリルエステルを製造する方法が提案されている。この方法では、オキソバナジウム触媒によるアリルアルコールの１，３−転位反応及びラセミ化反応と、リパーゼによる光学分割反応とが同時に進行するため、これらの反応を１つの容器内で行うことによって製造工程の削減を図ることができる。 For example, JP 2012-106225 A (Patent Document 1) describes an optical compound that is a synthetic intermediate for pharmaceuticals and the like by reacting a cyclic racemic allyl alcohol with a vinyl ester in the presence of an oxovanadium catalyst and a lipase. Methods for producing active allyl esters have been proposed. In this method, the 1,3-rearrangement reaction and racemization reaction of allyl alcohol by an oxovanadium catalyst and the optical resolution reaction by lipase proceed simultaneously. Therefore, by performing these reactions in one container, Reduction can be achieved.
しかしながら、オキソバナジウム触媒等の遷移金属触媒を、リパーゼ等の酵素（タンパク質）の存在下で均一系触媒として使用すると、タンパク質の非特異的吸着により遷移金属触媒が失活するという問題があった。また、特許文献１に記載のように、遷移金属化合物をメソポーラスシリカの内部に固定化しても、タンパク質による遷移金属化合物の失活を十分に抑制することは困難であった。 However, when a transition metal catalyst such as an oxovanadium catalyst is used as a homogeneous catalyst in the presence of an enzyme (protein) such as lipase, there is a problem that the transition metal catalyst is deactivated due to nonspecific adsorption of the protein. Moreover, as described in Patent Document 1, even if the transition metal compound is immobilized in the mesoporous silica, it is difficult to sufficiently suppress the deactivation of the transition metal compound by the protein.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、タンパク質の存在下での還元反応において高い触媒活性を示す還元反応用固体触媒を提供することを目的とする。 This invention is made | formed in view of the subject which the said prior art has, and it aims at providing the solid catalyst for reduction reactions which shows high catalytic activity in the reduction reaction in presence of protein.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、ビピリジン基を備えるメソポーラス有機シリカと遷移金属化合物とを混合して、ビピリジン基が前記遷移金属化合物中の遷移金属原子に配位した遷移金属錯体を形成することによって、前記遷移金属化合物がメソポーラス有機シリカの細孔内表面に固定化されることを見出し、さらに、得られた遷移金属含有メソポーラス有機シリカがタンパク質の存在下での還元反応において優れた触媒活性を示すことを見出し、本発明を完成するに至った。 As a result of intensive research to achieve the above object, the present inventors have mixed mesoporous organic silica having a bipyridine group and a transition metal compound, and the bipyridine group is arranged on the transition metal atom in the transition metal compound. It was found that the transition metal compound was immobilized on the pore inner surface of the mesoporous organic silica by forming a transition metal complex, and the obtained transition metal-containing mesoporous organic silica was obtained in the presence of protein. The present inventors have found that the present invention has achieved excellent catalytic activity in the reduction reaction.
すなわち、本発明の還元反応用固体触媒は、下記式（１）： That is, the solid catalyst for reduction reaction of the present invention has the following formula (1):
〔前記式（１）中、Ｍは、配位子Ｌが結合していてもよい遷移金属原子を表し、Ｒ１〜Ｒ８のうちの少なくとも１つの基は、下記式（２）： [In the formula (1), M represents a transition metal atom to which a ligand L may be bonded, and at least one group of R 1 to R 8 is represented by the following formula (2):
（前記式（２）中、Ｙは、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、エーテル基、カルボニル基、アミノ基、アミド基及びイミド基からなる群から選択される２価又は３価の有機基或いは単結合であり、Ｒａは炭素数１〜８のアルキル基又は置換若しくは無置換のアリル基を表し、Ｒｂは水素原子又はシリル基を表し、ｋは１又は２であり、ｉは１〜３の整数であり、ｊは０〜２の整数であり、１≦ｉ＋ｊ≦３であり、ｉとｊとの組み合わせは、複数存在する前記式（２）で表される基においてそれぞれ独立であり、＊は隣接する構造との結合部位である。）
で表される基であり、Ｒ１〜Ｒ８のうちの残りの基はそれぞれ独立に水素原子、ハロゲン原子、或いはアルキル基、アリール基、ヒドロキシ基、アルコキシ基、フェノキシ基、カルボキシ基、カルボン酸エステル基、アセチル基、ベンゾイル基、アミノ基、アミド基、イミド基、ニトロ基及びシアノ基からなる群から選択される１価又は２価の有機基である。〕
で表される構造を備える遷移金属含有メソポーラス有機シリカからなり、タンパク質存在下での還元反応に使用することを特徴とするものである。
(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group, and an imide group. An organic group or a single bond, R a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group, R b represents a hydrogen atom or a silyl group, k is 1 or 2, and i Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a plurality of combinations of i and j are present in the group represented by the formula (2). Independent, * is a binding site with an adjacent structure.)
The remaining groups of R 1 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group, a phenoxy group, a carboxy group, or a carboxylic acid. It is a monovalent or divalent organic group selected from the group consisting of an ester group, acetyl group, benzoyl group, amino group, amide group, imide group, nitro group and cyano group. ]
It is characterized by using a transition metal-containing mesoporous organic silica having a structure represented by the following, and used for a reduction reaction in the presence of protein.
このような還元反応用固体触媒において、遷移金属含有メソポーラス有機シリカの中心細孔直径は２〜１０ｎｍであることが好ましい。また、前記タンパク質としては生理活性タンパク質が好ましく、血漿タンパク質、酵素、輸送タンパク質、貯蔵タンパク質、抗体からなる群から選択される少なくとも１種がより好ましい。 In such a solid catalyst for reduction reaction, the central pore diameter of the transition metal-containing mesoporous organic silica is preferably 2 to 10 nm. The protein is preferably a physiologically active protein, more preferably at least one selected from the group consisting of plasma protein, enzyme, transport protein, storage protein, and antibody.
また、本発明の還元反応用固体触媒においては、前記遷移金属原子がロジウム原子であることが好ましく、遷移金属原子にペンタメチルシクロペンタジエニルが配位していることが好ましい。さらに、前記還元反応は水素移動反応であることが好ましい。 In the solid catalyst for reduction reaction of the present invention, the transition metal atom is preferably a rhodium atom, and pentamethylcyclopentadienyl is preferably coordinated to the transition metal atom. Furthermore, the reduction reaction is preferably a hydrogen transfer reaction.
本発明によれば、タンパク質の存在下での還元反応において高い触媒活性を示す還元反応用固体触媒を得ることが可能となる。 According to the present invention, it is possible to obtain a solid catalyst for reduction reaction that exhibits high catalytic activity in a reduction reaction in the presence of protein.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
本発明の還元反応用固体触媒は、タンパク質存在下での還元反応に使用されるものであり、下記式（１）： The solid catalyst for reduction reaction of the present invention is used for a reduction reaction in the presence of protein, and has the following formula (1):
〔前記式（１）中、Ｍは、配位子Ｌが結合していてもよい遷移金属原子を表し、Ｒ１〜Ｒ８のうちの少なくとも１つの基は、下記式（２）： [In the formula (1), M represents a transition metal atom to which a ligand L may be bonded, and at least one group of R 1 to R 8 is represented by the following formula (2):
（前記式（２）中、Ｙは、アルキレン基、アルケニレン基、アルキニレン基、アリーレン基、エーテル基、カルボニル基、アミノ基、アミド基及びイミド基からなる群から選択される２価又は３価の有機基或いは単結合であり、Ｒａは炭素数１〜８のアルキル基又は置換若しくは無置換のアリル基を表し、Ｒｂは水素原子又はシリル基を表し、ｋは１又は２であり、ｉは１〜３の整数であり、ｊは０〜２の整数であり、１≦ｉ＋ｊ≦３であり、ｉとｊとの組み合わせは、複数存在する前記式（２）で表される基においてそれぞれ独立であり、＊は隣接する構造との結合部位である。）
で表される基であり、Ｒ１〜Ｒ８のうちの残りの基はそれぞれ独立に水素原子、ハロゲン原子、或いはアルキル基、アリール基、ヒドロキシ基、アルコキシ基、フェノキシ基、カルボキシ基、カルボン酸エステル基、アセチル基、ベンゾイル基、アミノ基、アミド基、イミド基、ニトロ基及びシアノ基からなる群から選択される１価又は２価の有機基である。〕
で表される構造を備える遷移金属含有メソポーラス有機シリカからなるものである。このような本発明の還元反応用固体触媒においては、タンパク質がメソポーラス有機シリカの細孔内に侵入しにくく、このような細孔内に触媒活性種である遷移金属原子が固定化されているため、タンパク質による触媒の失活が抑制され、タンパク質の存在下においても高い触媒活性を得ることが可能となる。
(In the formula (2), Y is a divalent or trivalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an ether group, a carbonyl group, an amino group, an amide group, and an imide group. An organic group or a single bond, R a represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted allyl group, R b represents a hydrogen atom or a silyl group, k is 1 or 2, and i Is an integer of 1 to 3, j is an integer of 0 to 2, 1 ≦ i + j ≦ 3, and a plurality of combinations of i and j are present in the group represented by the formula (2). Independent, * is a binding site with an adjacent structure.)
The remaining groups of R 1 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group, a phenoxy group, a carboxy group, or a carboxylic acid. It is a monovalent or divalent organic group selected from the group consisting of an ester group, acetyl group, benzoyl group, amino group, amide group, imide group, nitro group and cyano group. ]
It consists of transition metal containing mesoporous organic silica provided with the structure represented by these. In such a solid catalyst for reduction reaction according to the present invention, proteins are unlikely to enter the pores of mesoporous organic silica, and transition metal atoms that are catalytically active species are immobilized in such pores. Inactivation of the catalyst by the protein is suppressed, and high catalytic activity can be obtained even in the presence of the protein.
本発明の還元反応用固体触媒において、前記式（１）で表される構造は、前記遷移金属含有メソポーラス有機シリカの骨格中に含まれていることが好ましい。これにより、細孔内での反応基質の拡散性が阻害されにくくなり、高い触媒活性を得ることができる。 In the solid catalyst for reduction reaction of the present invention, the structure represented by the formula (1) is preferably contained in the skeleton of the transition metal-containing mesoporous organic silica. Thereby, the diffusibility of the reaction substrate in the pores is hardly inhibited, and high catalytic activity can be obtained.
本発明の還元反応用固体触媒は、前記式（１）で示されるように、ビピリジン基を含有しており、このビピリジン基が遷移金属原子に配位することによって遷移金属錯体が形成され、この遷移金属錯体が活性サイトとなって触媒作用を示す。なお、本発明の還元反応用固体触媒においては、全てのビピリジン基が前記遷移金属原子に配位している必要はない。また、前記遷移金属含有メソポーラス有機シリカにおいては、前記式（２）で表される基は架橋点を有する基（以下、「架橋基」ともいう）であり、この架橋基中のシロキサン結合（Ｓｉ−Ｏ結合）によってビピリジン基が三次元的に架橋されているため、本発明の還元反応用固体触媒は、機械的作用や化学的作用に対して高い耐久性を示すものとなる。 The solid catalyst for reduction reaction of the present invention contains a bipyridine group as represented by the formula (1), and a transition metal complex is formed by coordination of this bipyridine group to a transition metal atom. The transition metal complex becomes an active site and exhibits catalytic action. In the solid catalyst for reduction reaction of the present invention, it is not necessary that all bipyridine groups are coordinated to the transition metal atom. In the transition metal-containing mesoporous organic silica, the group represented by the formula (2) is a group having a crosslinking point (hereinafter, also referred to as “crosslinking group”), and a siloxane bond (Si Since the bipyridine group is three-dimensionally crosslinked by —O bond), the solid catalyst for reduction reaction of the present invention exhibits high durability against mechanical action and chemical action.
前記式（１）において、Ｍは遷移金属原子を表す。このような遷移金属原子としては、還元反応に触媒活性種として作用するものであれば特に制限はないが、還元反応において高い触媒活性を示す錯体触媒が得られるという観点から、周期表第９族の遷移金属原子が好ましく、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）がより好ましい。 In the formula (1), M represents a transition metal atom. Such a transition metal atom is not particularly limited as long as it acts as a catalytically active species in the reduction reaction, but from the viewpoint of obtaining a complex catalyst exhibiting high catalytic activity in the reduction reaction, it is Group 9 of the periodic table. Transition metal atoms are preferred, and rhodium (Rh) and iridium (Ir) are more preferred.
また、このような遷移金属原子Ｍには、配位子Ｌが結合していてもよい。Ｍに配位している配位子Ｌの数は１又は２以上であり、２以上の配位子Ｌが配位している場合、それらは同一のものであっても異なるものであってもよい。このような配位子Ｌとしては、前記遷移金属原子に配位するものであれば特に制限はないが、例えば、メトキシ基、エトキシ基、フェノキシ基、ヒドロキシル基、アセトキシ基等の酸素系配位子、カルボニル、１，５−シクロオクタジエン、ｃｉｓ−シクロオクテン、テトラメチルシクロペンタジエン、ペンタメチルシクロペンタジエン、シメン等の炭素系配位子、トリメチルホスフィン、トリブチルホスフィンといったトリアルキルホスフィン、トリフェニルホスフィンといったトリアリールホスフィン等のリン系配位子、アンモニア、シクロヘキシルジアミン、アルキルアミン等の窒素系配位子、クロロ、ブロモ、ヨード等のハロゲン系配位子、トリフラート、トシラート、メシラート等のスルホン酸系配位子が挙げられる。このような配位子のうち、触媒反応時に脱離しやすいという観点から、ハロゲン系配位子、スルホン酸系配位子が好ましく、スルホン酸系配位子がより好ましく、また、遷移金属原子上の電子密度を向上させるという観点から、炭素系配位子が好ましく、テトラメチルシクロペンタジエン、ペンタメチルシクロペンタジエンがより好ましい。また、テトラヒドロフラン（ＴＨＦ）やアセトニトリル（ＣＨ３ＣＮ）等の溶媒分子が配位していてもよい。 Further, the ligand L may be bonded to such a transition metal atom M. The number of ligands L coordinated to M is 1 or 2 or more, and when two or more ligands L are coordinated, they may be the same or different. Also good. Such a ligand L is not particularly limited as long as it coordinates to the transition metal atom. For example, oxygen-based coordination such as methoxy group, ethoxy group, phenoxy group, hydroxyl group, acetoxy group, etc. Carbonyl, 1,5-cyclooctadiene, cis-cyclooctene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, cymene and other carbon-based ligands, trialkylphosphine such as trimethylphosphine and tributylphosphine, and triphenylphosphine Phosphorus ligands such as triarylphosphine, nitrogen ligands such as ammonia, cyclohexyldiamine and alkylamine, halogen ligands such as chloro, bromo and iodo, and sulfonates such as triflate, tosylate and mesylate A rank is listed. Among these ligands, halogen-based ligands and sulfonic acid-based ligands are preferable, sulfonic acid-based ligands are more preferable, and transition metal atoms are more easily removed from the viewpoint of easy elimination during the catalytic reaction. From the standpoint of improving the electron density, a carbon-based ligand is preferable, and tetramethylcyclopentadiene and pentamethylcyclopentadiene are more preferable. Further, solvent molecules such as tetrahydrofuran (THF) and acetonitrile (CH 3 CN) may be coordinated.
また、前記式（１）において、Ｒ１〜Ｒ８のうちの少なくとも１つの基は、前記式（２）で表される架橋基であり、メソ細孔構造が形成されやすいという観点から、Ｒ１〜Ｒ４のうちの少なくとも１つの基及びＲ５〜Ｒ８のうちの少なくとも１つの基がそれぞれ独立に前記架橋基であることが好ましく、Ｒ２及びＲ６がそれぞれ独立に前記架橋基であることがより好ましい。 In the formula (1), at least one group of R 1 to R 8 is a cross-linking group represented by the formula (2), and from the viewpoint that a mesopore structure is easily formed, R Preferably, at least one group of 1 to R 4 and at least one group of R 5 to R 8 are each independently the bridging group, and R 2 and R 6 are each independently the bridging group. More preferably.
前記式（２）中のＹは、アルキレン基（好ましくは炭素数１〜１２、より好ましくは炭素数１〜６）、アルケニレン基（好ましくは炭素数２〜１２、より好ましくは炭素数２〜６）、アルキニレン基（好ましくは炭素数２〜１２、より好ましくは炭素数２〜６）、アリーレン基（好ましくは炭素数６〜１２）、エーテル基、カルボニル基、アミノ基、アミド基及びイミド基からなる群から選択される２価又は３価の有機基或いは単結合である。 Y in the formula (2) is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms) or an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). ), Alkynylene groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), arylene groups (preferably having 6 to 12 carbon atoms), ether groups, carbonyl groups, amino groups, amide groups and imide groups. A divalent or trivalent organic group or a single bond selected from the group consisting of
前記アルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられ、前記アルケニレン基としては、エテニレン基、プロペニレン基、ブテニレン基等が挙げられ、前記アルキニレン基としては、エチニレン基、プロピニレン基、ブチニレン基等が挙げられ、前記アリーレン基としては、例えば、フェニレン基等の単環の芳香族環、ナフチレン基、フルオレニレン基等の芳香族縮合環が挙げられる。 Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group include an ethenylene group, a propenylene group, and a butenylene group. Examples of the alkynylene group include an ethynylene group, Examples thereof include a propynylene group and a butynylene group. Examples of the arylene group include a monocyclic aromatic ring such as a phenylene group, and an aromatic condensed ring such as a naphthylene group and a fluorenylene group.
このような２価又は３価の有機基及び単結合のうち、固体触媒の機械的強度及び化学的安定性が向上するという観点から、アルキレン基及び単結合が好ましく、炭素数１〜６のアルキレン基及び単結合がより好ましい。 Among these divalent or trivalent organic groups and single bonds, an alkylene group and a single bond are preferable from the viewpoint of improving the mechanical strength and chemical stability of the solid catalyst, and alkylene having 1 to 6 carbon atoms. Groups and single bonds are more preferred.
前記式（２）中のＲａは、炭素数１〜８（好ましくは１〜４）のアルキル基又は置換若しくは無置換のアリル基を表し、前記アリル基はメチル基等の置換基を有していてもよい。また、前記式（２）中のＲｂは水素原子又はシリル基を表し、前記シリル基としては、トリメチルシリル基等のアルキルシリル基が挙げられ、Ｒｂとしては、化学的安定性が向上するという観点から、シリル基が好ましい。 Ra in the formula (2) represents an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4) or a substituted or unsubstituted allyl group, and the allyl group has a substituent such as a methyl group. It may be. In the formula (2), R b represents a hydrogen atom or a silyl group, and examples of the silyl group include alkylsilyl groups such as a trimethylsilyl group, and R b is said to improve chemical stability. From the viewpoint, a silyl group is preferable.
また、前記式（２）中の＊は、隣接する構造との結合部位である。前記隣接する構造としては、前記遷移金属含有メソポーラス有機シリカ中の前記式（１）で表される構造からなる繰り返し単位、後述する式（３）で表される構造からなる繰り返し単位、後述する式（４）で表される構造等が挙げられる。 Moreover, * in the said Formula (2) is a coupling | bond part with an adjacent structure. Examples of the adjacent structure include a repeating unit composed of the structure represented by the formula (1) in the transition metal-containing mesoporous organic silica, a repeating unit composed of a structure represented by the formula (3) described later, and a formula described below. Examples include the structure represented by (4).
前記式（２）中のｋは１又は２であり、ｉは１〜３の整数（好ましくは２〜３の整数）であり、ｊは０〜２の整数（好ましくは０〜１の整数）であり、１≦ｉ＋ｊ≦３（好ましくは２≦ｉ＋ｊ≦３）である。なお、ｉとｊとの組み合わせは、複数存在する前記架橋基においてそれぞれ独立であり、本発明の還元反応用固体触媒中の全ての前記架橋基において同じである必要はない。 In the formula (2), k is 1 or 2, i is an integer of 1 to 3 (preferably an integer of 2 to 3), and j is an integer of 0 to 2 (preferably an integer of 0 to 1). And 1 ≦ i + j ≦ 3 (preferably 2 ≦ i + j ≦ 3). The combination of i and j is independent for each of a plurality of the crosslinking groups, and need not be the same for all the crosslinking groups in the solid catalyst for reduction reaction of the present invention.
前記式（１）において、Ｒ１〜Ｒ８のうちの残りの基はそれぞれ独立に水素原子、ハロゲン原子、或いはアルキル基（好ましくは炭素数１〜１２）、アリール基（好ましくは炭素数６〜１２）、ヒドロキシ基、アルコキシ基（好ましくは炭素数１〜１２）、フェノキシ基、カルボキシ基、カルボン酸エステル基（好ましくは炭素数１〜４）、アセチル基、ベンゾイル基、アミノ基、アミド基、イミド基、ニトロ基及びシアノ基からなる群から選択される１価又は２価の有機基である。 In the formula (1), the remaining groups of R 1 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), an aryl group (preferably having 6 to 6 carbon atoms). 12), a hydroxy group, an alkoxy group (preferably having 1 to 12 carbon atoms), a phenoxy group, a carboxy group, a carboxylic acid ester group (preferably having 1 to 4 carbon atoms), an acetyl group, a benzoyl group, an amino group, an amide group, It is a monovalent or divalent organic group selected from the group consisting of an imide group, a nitro group and a cyano group.
前記アルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられ、前記アリール基としては、例えば、フェニル基等の単環の芳香族環、ナフチル基、フルオレニル基等の芳香族縮合環が挙げられ、前記アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられ、前記カルボン酸エステル基としては、カルボン酸メチル基、カルボン酸エチル基、カルボン酸プロピル基、カルボン酸ブチル基等が挙げられる。 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a monocyclic aromatic ring such as a phenyl group, and an aromatic group such as a naphthyl group and a fluorenyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the carboxylic acid ester group include a carboxylic acid methyl group, a carboxylic acid ethyl group, and a carboxylic acid propyl group. And carboxylic acid butyl group.
このような１価又は２価の有機基のうち、固体触媒の機械的強度及び化学的安定性が向上するという観点から、水素原子、メチル基、エチル基、メトキシ基、フェニル基、フェノキシ基が好ましく、水素原子がより好ましい。 Among such monovalent or divalent organic groups, from the viewpoint of improving the mechanical strength and chemical stability of the solid catalyst, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, and a phenoxy group Preferably, a hydrogen atom is more preferable.
前記式（１）で表される構造を備える遷移金属含有メソポーラス有機シリカにおいて、遷移金属含有メソポーラス有機シリカ１ｇあたりの遷移金属原子の固定化量としては、０．０１ｍｍｏｌ／ｇ以上であれば特に制限はないが、触媒活性の向上と遷移金属原子の有効利用という観点から、０．０１〜３．０ｍｍｏｌ／ｇが好ましく、０．０２〜２．５ｍｍｏｌ／ｇがより好ましく、０．０５〜２．０ｍｍｏｌ／ｇがさらに好ましく、０．０７５〜１．５ｍｍｏｌ／ｇが特に好ましく、０．１０〜１．０ｍｍｏｌ／ｇが最も好ましい。 In the transition metal-containing mesoporous organic silica having the structure represented by the formula (1), the amount of transition metal atoms immobilized per 1 g of the transition metal-containing mesoporous organic silica is particularly limited as long as it is 0.01 mmol / g or more. However, 0.01 to 3.0 mmol / g is preferred, 0.02 to 2.5 mmol / g is more preferred, and 0.05 to 2. 0 mmol / g is more preferable, 0.075 to 1.5 mmol / g is particularly preferable, and 0.10 to 1.0 mmol / g is most preferable.
このような遷移金属原子の固定化量は、ビピリジン基含有メソポーラス有機シリカ中のビピリジン基の含有量に応じて任意に調整することができ、また、前記ビピリジン基の含有量も任意に調整することができる。特に、本発明の還元反応用固体触媒においては、細孔直径が比較的大きいメソポーラス有機シリカを担体として用いているため、細孔が閉塞したり、細孔直径が小さくなったりしにくいため、触媒性能を低下させることなく、遷移金属原子の固定化量を増加させることができる。 The amount of the transition metal atom immobilized can be arbitrarily adjusted according to the content of the bipyridine group in the bipyridine group-containing mesoporous organic silica, and the content of the bipyridine group can also be arbitrarily adjusted. Can do. In particular, in the solid catalyst for reduction reaction of the present invention, since mesoporous organic silica having a relatively large pore diameter is used as a carrier, the pores are not easily blocked or the pore diameter is not easily reduced. The amount of transition metal atoms immobilized can be increased without degrading the performance.
また、前記式（１）で表される構造を備える遷移金属含有メソポーラス有機シリカにおいては、前記式（１）で表される構造以外の構造（以下、「その他の構造」という）を含んでいてもよい。このようなその他の構造としては、下記式（３）及び（４）： Further, the transition metal-containing mesoporous organic silica having the structure represented by the formula (1) includes a structure other than the structure represented by the formula (1) (hereinafter referred to as “other structure”). Also good. Such other structures include the following formulas (3) and (4):
で表される構造が好ましく、これらの構造はいずれか一方が含まれていても両方が含まれていてもよい。 The structure represented by these is preferable and these structures may contain either one or both.
前記式（３）において、Ｒ９は、２〜４価の有機基であり、アルキレン基（好ましくは炭素数１〜１２、より好ましくは炭素数１〜６）、アリーレン基（好ましくは炭素数６〜１２）等が挙げられる。前記式（３）及び（４）において、Ｒｃはそれぞれ独立に炭素数１〜８（好ましくは１〜４）のアルキル基又は置換若しくは無置換のアリル基を表し、前記アリル基はメチル基等の置換基を有していてもよい。また、前記式（３）及び（４）において、Ｒｄはそれぞれ独立に水素原子又はシリル基を表し、前記シリル基としては、トリメチルシリル基等のアルキルシリルが挙げられ、Ｒｄとしては、化学的安定性が向上するという観点から、シリル基が好ましい。 In the formula (3), R 9 is a divalent to tetravalent organic group, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an arylene group (preferably having 6 carbon atoms). ~ 12) and the like. In the formulas (3) and (4), each R c independently represents an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4) or a substituted or unsubstituted allyl group, and the allyl group is a methyl group or the like. You may have the substituent of. Further, in the formula (3) and (4), R d each independently represent a hydrogen atom or a silyl group, examples of the silyl groups include alkylsilyl such as trimethylsilyl group, as R d is chemically From the viewpoint of improving stability, a silyl group is preferred.
また、前記式（３）及び（４）中の＊は、隣接する構造との結合部位である。前記隣接する構造としては、前記遷移金属含有メソポーラス有機シリカ中の前記式（１）で表される構造からなる繰り返し単位、前記式（３）で表される構造からなる繰り返し単位、前記式（４）で表される構造等が挙げられる。 Moreover, * in said Formula (3) and (4) is a coupling | bond part with an adjacent structure. Examples of the adjacent structure include a repeating unit composed of the structure represented by the formula (1) in the transition metal-containing mesoporous organic silica, a repeating unit composed of the structure represented by the formula (3), and the formula (4) ) And the like.
前記式（３）及び（４）中のｒはそれぞれ独立に１又は２であり、ｐはそれぞれ独立に１〜３の整数（好ましくは２〜３の整数）であり、ｑはそれぞれ独立に０〜２の整数（好ましくは０〜１の整数）であり、１≦ｐ＋ｑ≦３（好ましくは２≦ｐ＋ｑ≦３）である。なお、ｐとｑとの組み合わせは、複数存在する前記式（３）又は（４）で表される構造においてそれぞれ独立であり、本発明の還元反応用固体触媒中の全ての前記式（３）又は（４）で表される構造において同じである必要はない。 In the formulas (3) and (4), r is independently 1 or 2, p is independently an integer of 1 to 3 (preferably an integer of 2 to 3), and q is independently 0. An integer of ˜2 (preferably an integer of 0 to 1), and 1 ≦ p + q ≦ 3 (preferably 2 ≦ p + q ≦ 3). In addition, the combination of p and q is independent in each of the structures represented by the formula (3) or (4), and all the formulas (3) in the solid catalyst for reduction reaction of the present invention are used. Or it is not necessary to be the same in the structure represented by (4).
前記式（１）で表される構造を備える遷移金属含有メソポーラス有機シリカにおいて、このようなその他の構造の割合としては、前記式（１）で表される構造とその他の構造との合計量に対して、９９．５ｍｏｌ％以下であれば特に制限はないが、触媒活性が向上するという観点から、０〜９０ｍｏｌ％が好ましく、０〜７０ｍｏｌ％がより好ましく、０〜５０ｍｏｌ％がさらに好ましく、０〜３０ｍｏｌ％が特に好ましい。 In the transition metal-containing mesoporous organic silica having the structure represented by the formula (1), the ratio of the other structure is the total amount of the structure represented by the formula (1) and the other structure. On the other hand, there is no particular limitation as long as it is 99.5 mol% or less, but from the viewpoint of improving catalytic activity, 0 to 90 mol% is preferable, 0 to 70 mol% is more preferable, 0 to 50 mol% is further preferable, and 0 ˜30 mol% is particularly preferred.
本発明にかかる遷移金属含有メソポーラス有機シリカはメソ細孔を有する構造（メソ細孔構造）を有する。このようなメソ細孔構造における細孔径（中心細孔直径）としては、タンパク質が細孔内に侵入することを防ぐという観点から、タンパク質分子の大きさより小さいことが好ましく、具体的には、１〜２０ｎｍが好ましく、２〜１０ｎｍがより好ましい。中心細孔直径が前記下限未満になると、触媒反応における反応基質がメソ細孔内に十分に拡散せず、触媒反応が十分に進行しない傾向にあり、他方、前記上限を超えると、タンパク質が細孔内に侵入し、触媒活性種である遷移金属原子が失活する傾向にある。 The transition metal-containing mesoporous organic silica according to the present invention has a structure having mesopores (mesopore structure). The pore diameter (center pore diameter) in such a mesopore structure is preferably smaller than the size of the protein molecule from the viewpoint of preventing the protein from entering the pore. -20 nm is preferable and 2-10 nm is more preferable. When the central pore diameter is less than the lower limit, the reaction substrate in the catalytic reaction does not sufficiently diffuse into the mesopores and the catalytic reaction tends not to proceed sufficiently. It tends to enter the pores and deactivate the transition metal atom that is a catalytically active species.
また、前記メソ細孔構造における全細孔容量としては、０．１ｃｍ３／ｇ以上が好ましく、０．２ｃｍ３／ｇ以上がより好ましい。全細孔容量が前記下限未満になると、触媒反応における反応基質がメソ細孔内に十分に拡散せず、触媒反応が十分に進行しない傾向にある。さらに、前記遷移金属含有メソポーラス有機シリカにおいて、ＢＥＴ比表面積としては、１００ｃｍ２／ｇ以上が好ましく、３００ｃｍ２／ｇ以上がより好ましい。ＢＥＴ比表面積が前記下限未満になると、十分な触媒活性が得られない傾向にある。 The total pore volume in the mesopore structure is preferably 0.1 cm 3 / g or more, more preferably 0.2 cm 3 / g or more. When the total pore volume is less than the lower limit, the reaction substrate in the catalytic reaction does not sufficiently diffuse into the mesopores, and the catalytic reaction tends not to proceed sufficiently. Further, in the transition metal-containing mesoporous organic silica, the BET specific surface area is preferably 100 cm 2 / g or more, and more preferably 300 cm 2 / g or more. When the BET specific surface area is less than the lower limit, sufficient catalytic activity tends not to be obtained.
なお、前記中心細孔直径とは、細孔容積（Ｖ）を細孔直径（Ｄ）で微分した値（ｄＶ／ｄＤ）を細孔直径（Ｄ）に対してプロットした曲線（細孔径分布曲線）の最大ピークにおける細孔直径であり、次に述べる方法により求めることができる。すなわち、試料を液体窒素温度（−１９６℃）に冷却して窒素ガスを導入し、定容量法或いは重量法によりその吸着量を求め、次いで、導入する窒素ガスの圧力を徐々に増加させ、各平衡圧に対する窒素ガスの吸着量をプロットし、吸着等温線を得る。この吸着等温線を用い、ＤＦＴ（Ｄｅｎｓｉｔｙ−Ｆｕｎｃｔｉｏｎａｌ−Ｔｈｅｏｒｙ）法、Ｃｒａｎｓｔｏｎ−Ｉｎｋｌａｙ法、Ｐｏｌｌｉｍｏｒｅ−Ｈｅａｌ法、ＢＪＨ法等の計算法により細孔径分布曲線を求めることができる。 The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). ) At the maximum peak, and can be determined by the method described below. That is, the sample is cooled to liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a constant volume method or a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased, Plot the adsorption amount of nitrogen gas against the equilibrium pressure to obtain the adsorption isotherm. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as DFT (Density-Functional-Theory) method, Cranston-Inklay method, Pollimore-Heal method, BJH method.
また、本発明にかかる遷移金属含有メソポーラス有機シリカのＸ線回折パターンには、１〜５０ｎｍのｄ値に相当する回折角度に１本以上の回折ピークが存在していることが好ましい。Ｘ線回折ピークは、そのピーク角度に相当するｄ値の周期構造が試料中に存在することを意味する。従って、１〜５０ｎｍのｄ値に相当する回折角度に１本以上の回折ピークがあることは、細孔が１〜５０ｎｍの間隔で規則的に配列している、規則的なメソ細孔構造を備えていることを意味する。このような規則的なメソ細孔構造を備える遷移金属含有メソポーラス有機シリカは、前記遷移金属錯体が安定に固定化されており、触媒活性に優れている。 In the X-ray diffraction pattern of the transition metal-containing mesoporous organic silica according to the present invention, it is preferable that one or more diffraction peaks exist at a diffraction angle corresponding to a d value of 1 to 50 nm. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle exists in the sample. Therefore, the presence of one or more diffraction peaks at a diffraction angle corresponding to a d value of 1 to 50 nm indicates that a regular mesopore structure in which pores are regularly arranged at intervals of 1 to 50 nm. It means to have. The transition metal-containing mesoporous organic silica having such a regular mesoporous structure has excellent catalytic activity because the transition metal complex is stably immobilized.
このような本発明の還元反応用固体触媒は、例えば、下記式（１ａ）： Such a solid catalyst for reduction reaction of the present invention includes, for example, the following formula (1a):
〔前記式（１ａ）中、Ｒ１〜Ｒ８は前記式（１）中のＲ１〜Ｒ８と同一の基である。〕
で表される構造を備えるビピリジン基含有メソポーラス有機シリカと遷移金属化合物とを混合することによって製造することができる。これにより、前記式（１ａ）中の窒素原子が前記遷移金属化合物中の遷移金属原子に配位し、前記式（１）で表される構造を備える遷移金属含有メソポーラス有機シリカが得られる。このような混合は、触媒反応を行う前に、触媒反応系とは異なる系で行なってもよいし、触媒反応系において行なってもよい。
[In the formula (1a), R 1 to R 8 are the same groups as R 1 to R 8 in the formula (1). ]
It can manufacture by mixing a bipyridine group containing mesoporous organic silica provided with the structure represented by these, and a transition metal compound. Thereby, the nitrogen atom in the said formula (1a) coordinates to the transition metal atom in the said transition metal compound, and the transition metal containing mesoporous organic silica provided with the structure represented by the said Formula (1) is obtained. Such mixing may be performed in a system different from the catalytic reaction system before the catalytic reaction, or may be performed in the catalytic reaction system.
前記遷移金属化合物としては特に制限はないが、遷移金属原子Ｍに１又は２以上の前記配位子Ｌが配位している遷移金属錯体が好ましい。このような遷移金属錯体としては、（ペンタメチルシクロペンタジエニル）ロジウム（III）ジクロリドダイマー（［ＲｈＣｐ＊Ｃｌ２］２）、（ペンタメチルシクロペンタジエニル）イリジウム（III）ジクロリドダイマー（［ＩｒＣｐ＊Ｃｌ２］２）等が挙げられる。 The transition metal compound is not particularly limited, but a transition metal complex in which one or two or more of the ligands L are coordinated to the transition metal atom M is preferable. Such transition metal complexes include (pentamethylcyclopentadienyl) rhodium (III) dichloride dimer ([RhCp * Cl 2 ] 2 ), (pentamethylcyclopentadienyl) iridium (III) dichloride dimer ([IrCp * Cl 2 ] 2 ) and the like.
前記式（１ａ）で表される構造を備えるメソポーラス有機シリカにおいて、前記式（１ａ）で表される構造は、前記メソポーラス有機シリカの骨格中に含まれていることが好ましい。これにより、細孔内での反応基質の拡散性が阻害されにくく、高い触媒活性を有する還元反応用固体触媒を得ることができる。 In the mesoporous organic silica having the structure represented by the formula (1a), the structure represented by the formula (1a) is preferably included in the skeleton of the mesoporous organic silica. Thereby, the diffusibility of the reaction substrate in the pores is hardly inhibited, and a solid catalyst for reduction reaction having high catalytic activity can be obtained.
また、上述したように、前記式（１ａ）中のＲ１〜Ｒ８は前記式（１）中のＲ１〜Ｒ８と同一の基である。前記式（１ａ）における前記式（２）中のＲｂとしては、化学的安定性が向上するという観点から、シリル基が好ましい。また、前記式（１ａ）における前記式（２）中の結合部位＊に結合する隣接する構造としては、前記メソポーラス有機シリカ中の前記式（１ａ）で表される構造からなる繰り返し単位、前記式（３）で表される構造、前記式（４）で表される構造等が挙げられる。 In addition, as described above, R 1 to R 8 in the formula (1a) are the same groups as R 1 to R 8 in the formula (1). Rb in the formula (2) in the formula (1a) is preferably a silyl group from the viewpoint of improving chemical stability. Further, as the adjacent structure bonded to the binding site * in the formula (2) in the formula (1a), the repeating unit consisting of the structure represented by the formula (1a) in the mesoporous organic silica, the formula Examples include the structure represented by (3) and the structure represented by the formula (4).
前記式（１ａ）で表される構造を備えるメソポーラス有機シリカにおいて、メソポーラス有機シリカ１ｇあたりの前記式（１ａ）で表される構造の導入量としては、０．０１ｍｍｏｌ／ｇ以上であれば特に制限はないが、遷移金属錯体の形成のしやすさという観点から、０．０５ｍｍｏｌ／ｇ以上が好ましく、０．１０ｍｍｏｌ／ｇ以上がより好ましく、０．１５ｍｍｏｌ／ｇ以上がさらに好ましく、０．２０ｍｍｏｌ／ｇ以上が特に好ましい。なお、前記式（１ａ）で表される構造の導入量の上限としては特に制限はないが、４ｍｍｏｌ／ｇ以下が好ましい。本発明の還元反応用固体触媒においては、このような前記式（１ａ）で表される構造の導入量（すなわち、ビピリジン基の導入量）を適宜調整することができ、その結果、遷移金属原子の固定化量を容易に制御することが可能となる。 In the mesoporous organic silica having the structure represented by the formula (1a), the amount of the structure represented by the formula (1a) per 1 g of the mesoporous organic silica is particularly limited as long as it is 0.01 mmol / g or more. However, from the viewpoint of easy formation of a transition metal complex, 0.05 mmol / g or more is preferable, 0.10 mmol / g or more is more preferable, 0.15 mmol / g or more is more preferable, and 0.20 mmol / g g or more is particularly preferable. The upper limit of the introduction amount of the structure represented by the formula (1a) is not particularly limited, but is preferably 4 mmol / g or less. In the solid catalyst for reduction reaction of the present invention, the introduction amount of the structure represented by the formula (1a) (that is, the introduction amount of the bipyridine group) can be appropriately adjusted, and as a result, the transition metal atom It is possible to easily control the amount of immobilization.
また、前記式（１ａ）で表される構造を備えるメソポーラス有機シリカにおいては、前記式（１ａ）で表される構造以外の構造（以下、「その他の構造」という）を含んでいてもよい。このようなその他の構造としては、前記式（３）及び（４）で表される構造が好ましく、これらの構造はいずれか一方が含まれていても両方が含まれていてもよい。 Further, the mesoporous organic silica having the structure represented by the formula (1a) may include a structure other than the structure represented by the formula (1a) (hereinafter referred to as “other structure”). As such other structures, the structures represented by the formulas (3) and (4) are preferable, and either one or both of these structures may be included.
前記式（１ａ）で表される構造を備えるメソポーラス有機シリカにおいて、このようなその他の構造の割合としては、前記式（１ａ）で表される構造との合計量に対して、９９．５ｍｏｌ％以下であれば特に制限はないが、触媒活性が向上するという観点から、０〜９０ｍｏｌ％が好ましく、０〜７０ｍｏｌ％がより好ましく、０〜５０ｍｏｌ％がさらに好ましく、０〜３０ｍｏｌ％が特に好ましい。 In the mesoporous organic silica having the structure represented by the formula (1a), the ratio of such other structures is 99.5 mol% with respect to the total amount with the structure represented by the formula (1a). Although it will not be restrict | limited especially if it is below, from a viewpoint that catalyst activity improves, 0-90 mol% is preferable, 0-70 mol% is more preferable, 0-50 mol% is further more preferable, 0-30 mol% is especially preferable.
なお、このような前記式（１ａ）で表される構造を備えるメソポーラス有機シリカは、例えば、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．、２０１４年、第１３６巻、第１０号、４００３〜４０１１頁、特開２０１４−１９３４５７号公報、特開２０１７−０２９９２６号公報等に記載の方法により製造することができる。 In addition, the mesoporous organic silica provided with such a structure represented by the formula (1a) is, for example, J.P. Am. Chem. Soc. 2014, Vol. 136, No. 10, pages 4003 to 4011, JP-A-2014-193457, JP-A-2017-029926 and the like.
＜還元反応＞
本発明の還元反応用固体触媒は、タンパク質の存在下での還元反応に使用される。前記タンパク質としては、本発明の還元反応用固体触媒による効果（すなわち、タンパク質による遷移金属原子の触媒活性の失活を抑制するという効果）が十分に発揮されるという観点から、生理活性タンパク質が好ましく、血漿タンパク質（例えば、アルブミン、グロブリン、フィブリノゲン）、酵素（例えば、エステラーゼ、グリコシダーゼ、ペプチダーゼ、リパーゼ等の加水分解酵素、アルコールデヒドロゲナーゼ、アルデヒドデヒドロゲナーゼ、グルタミン酸デヒドロゲナーゼ等の脱水素酵素）がより好ましい。これらのタンパク質は、１種が単独で存在していても２種以上が存在していてもよい。
<Reduction reaction>
The solid catalyst for reduction reaction of the present invention is used for a reduction reaction in the presence of protein. As the protein, a physiologically active protein is preferable from the viewpoint that the effect of the solid catalyst for reduction reaction of the present invention (that is, the effect of suppressing the deactivation of the catalytic activity of the transition metal atom by the protein) is sufficiently exerted. More preferred are plasma proteins (eg, albumin, globulin, fibrinogen) and enzymes (eg, hydrolases such as esterase, glycosidase, peptidase, lipase, dehydrogenases such as alcohol dehydrogenase, aldehyde dehydrogenase, glutamate dehydrogenase). These proteins may exist alone or in combination of two or more.
前記還元反応としては特に制限はないが、水素転移反応、水素移動反応、炭素−炭素不飽和結合の水素化反応、カルボニルの水素化反応、イミンの水素化反応等が挙げられる。 The reduction reaction is not particularly limited, and examples thereof include a hydrogen transfer reaction, a hydrogen transfer reaction, a carbon-carbon unsaturated bond hydrogenation reaction, a carbonyl hydrogenation reaction, and an imine hydrogenation reaction.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
（調製例１）
＜ビピリジン基含有メソポーラス有機シリカの調製＞
オクタデシルトリメチルアンモニウムクロリド（Ｃ１８ＴＭＡＣｌ、３．７８ｇ（１０．８ｍｍｏｌ））、蒸留水（２０２ｍｌ）及び６Ｎ水酸化ナトリウム水溶液（０．５９ｍｌ（３．５４ｍｍｏｌ））を混合して５０℃に加熱し、得られた混合物に、激しく撹拌しながら、５，５’−ビス（トリイソプロポキシシリル）−２，２’−ビピリジン（Ｓｉ−ＢＰｙ−Ｓｉ、４．５９ｇ（８．１２ｍｍｏｌ））のエタノール溶液（９．１７ｍｌ）を９０分間かけて滴下した。得られた溶液を５０℃で加熱しながら３日間激しく撹拌し、さらに５０℃で加熱しながら３日間静置して、下記反応式（Ｐ１）：
(Preparation Example 1)
<Preparation of bipyridine group-containing mesoporous organic silica>
Octadecyltrimethylammonium chloride (C 18 TMACl, 3.78 g (10.8 mmol)), distilled water (202 ml) and 6N aqueous sodium hydroxide solution (0.59 ml (3.54 mmol)) were mixed and heated to 50 ° C., An ethanol solution of 5,5′-bis (triisopropoxysilyl) -2,2′-bipyridine (Si-BPy-Si, 4.59 g (8.12 mmol)) was added to the resulting mixture with vigorous stirring. 9.17 ml) was added dropwise over 90 minutes. The resulting solution was stirred vigorously for 3 days while being heated at 50 ° C., and was further allowed to stand for 3 days while being heated at 50 ° C., and the following reaction formula (P1):
で表される反応を行なった。生成した沈殿物を加圧ろ過により回収し、鋳型界面活性剤（Ｃ１８ＴＭＡＣｌ）を含むビピリジン基含有有機シリカメソ構造体を得た。この有機シリカメソ構造体を酸性エタノール（エタノール３４６ｍｌと２Ｍ塩酸１０．２ｍｌの混合溶液）に添加し、一晩懸濁させて前記鋳型界面活性剤を除去し、薄黄色〜灰色の固体であるビピリジン基含有メソポーラス有機シリカ（ＢＰｙ−ＰＭＯ）を得た。このＢＰｙ−ＰＭＯのビピリジン基含有量は３．１８ｍｍｏｌ−ＢＰｙ／ｇであった。 The reaction represented by The generated precipitate was recovered by pressure filtration to obtain a bipyridine group-containing organic silica mesostructure containing a template surfactant (C 18 TMACl). The organosilica mesostructure is added to acidic ethanol (mixed solution of ethanol 346 ml and 2M hydrochloric acid 10.2 ml) and suspended overnight to remove the template surfactant, and the bipyridine group which is a light yellow to gray solid Containing mesoporous organic silica (BPy-PMO) was obtained. The bipyridine group content of this BPy-PMO was 3.18 mmol-BPy / g.
（比較調製例１）
＜ビピリジン基担持ノンポーラスシリカの調製＞
アルゴン雰囲気下、非晶質シリカゲル（ｓｉｌｉｃａ、関東化学株式会社製「球状シリカゲル６０Ｎ」、比表面積６８０ｍ２／ｇ、細孔径５．４ｎｍ）（１．００ｇ）をトルエン（３０ｍｌ）中に分散させ、この分散液に５−（４−トリエトキシシリルブチル）−５’−メチル−２，２’−ビピリジン（２５０ｍｇ（６４３μｍｏｌ））を添加した。得られた懸濁液にトリフルオロ酢酸（２０μｌ）を滴下した後、還流しながら１日間撹拌して、下記反応式（Ｐ２）：
(Comparative Preparation Example 1)
<Preparation of bipyridine group-supported nonporous silica>
Under an argon atmosphere, amorphous silica gel (silica, “spherical silica gel 60N” manufactured by Kanto Chemical Co., Inc., specific surface area 680 m 2 / g, pore diameter 5.4 nm) (1.00 g) was dispersed in toluene (30 ml), To this dispersion was added 5- (4-triethoxysilylbutyl) -5′-methyl-2,2′-bipyridine (250 mg (643 μmol)). Trifluoroacetic acid (20 μl) was added dropwise to the resulting suspension, followed by stirring for 1 day while refluxing, and the following reaction formula (P2):
で表される反応を行なった。得られた懸濁液を、メンブレンフィルター（孔径０．５μｍ）を用いて減圧ろ過し、ろ滓をトルエンおよびメタノールで洗浄した後、減圧乾燥して、ピリジン基担持ノンポーラスシリカ（ＢＰｙ−ｓｉｌｉｃａ）を得た。このＢＰｙ−ｓｉｌｉｃａのビピリジン基含有量は０．５１４ｍｍｏｌ−ＢＰｙ／ｇであった。 The reaction represented by The obtained suspension was filtered under reduced pressure using a membrane filter (pore size: 0.5 μm), and the filter cake was washed with toluene and methanol, and then dried under reduced pressure to give a pyridine group-supported nonporous silica (BPy-silica). Got. The bipyridine group content of this BPy-silica was 0.514 mmol-BPy / g.
（比較調製例２）
＜ビピリジン基担持メソポーラスシリカの調製＞
アルゴン雰囲気下、メソポーラスシリカ（ＦＳＭ−１６、太陽化学株式会社製「ＴＭＰＳ−４Ｒ」、比表面積８９７ｍ２／ｇ、細孔径３．９ｎｍ）（２００ｍｇ）をトルエン（１０ｍｌ）中に分散させ、この分散液に５−（４−トリエトキシシリルブチル）−５’−メチル−２，２’−ビピリジン（ＢＰｙ−Ｃ４−Ｓｉ、５０ｍｇ（１２９μｍｏｌ））を添加した。得られた懸濁液にトリフルオロ酢酸（２０μｌ）を滴下した後、還流しながら１日間撹拌して、下記反応式（Ｐ３）：
(Comparative Preparation Example 2)
<Preparation of bipyridine group-supported mesoporous silica>
Under an argon atmosphere, mesoporous silica (FSM-16, “TMPS-4R” manufactured by Taiyo Kagaku Co., Ltd., specific surface area 897 m 2 / g, pore diameter 3.9 nm) (200 mg) was dispersed in toluene (10 ml). To the solution, 5- (4-triethoxysilylbutyl) -5′-methyl-2,2′-bipyridine (BPy-C4-Si, 50 mg (129 μmol)) was added. Trifluoroacetic acid (20 μl) was added dropwise to the resulting suspension, followed by stirring for 1 day while refluxing, and the following reaction formula (P3):
で表される反応を行なった。得られた懸濁液を、メンブレンフィルター（孔径０．５μｍ）を用いて減圧ろ過し、ろ滓をトルエンおよびメタノールで洗浄した後、減圧乾燥して、ビピリジン基担持メソポーラスシリカ（ＢＰｙ−ＦＳＭ）を得た。このＢＰｙ−ＦＳＭのビピリジン基含有量は０．５１５ｍｍｏｌ−ＢＰｙ／ｇであった。 The reaction represented by The resulting suspension was filtered under reduced pressure using a membrane filter (pore size: 0.5 μm), and the filter cake was washed with toluene and methanol and then dried under reduced pressure to obtain bipyridine group-supported mesoporous silica (BPy-FSM). Obtained. The bipyridine group content of this BPy-FSM was 0.515 mmol-BPy / g.
（合成例１）
＜Ｒｈ含有メソポーラス有機シリカの合成＞
アルゴン雰囲気下、調製例１で得られたＢＰｙ−ＰＭＯ（５０ｍｇ、０．１５９ｍｍｏｌ−ＢＰｙ）及び（ペンタメチルシクロペンタジエニル）ロジウム（III）ジクロリドダイマー（［ＲｈＣｐ＊Ｃｌ２］２、２ｍｇ（３．２μｍｏｌ））を量り取り、さらに、Ｎ，Ｎ’−ジメチルホルムアミド（５０ｍｌ）を添加し、６０℃で加熱しながら１６時間撹拌して、下記反応式（Ｓ１）：
(Synthesis Example 1)
<Synthesis of Rh-containing mesoporous organic silica>
Under an argon atmosphere, BPy-PMO (50 mg, 0.159 mmol-BPy) and (pentamethylcyclopentadienyl) rhodium (III) dichloride dimer ([RhCp * Cl 2 ] 2 , 2 mg (3 2 μmol)), N, N′-dimethylformamide (50 ml) was added, and the mixture was stirred for 16 hours while heating at 60 ° C. The following reaction formula (S1):
で表される反応を行なった。得られた分散液をメンブレンフィルター（孔径０．４５μｍ）に通して固体成分を回収した。得られた固体成分をＮ，Ｎ’−ジメチルホルムアミド及びエタノールで洗浄した後、真空乾燥して、Ｒｈ原子に配位したビピリジン基を含有するメソポーラス有機シリカ（Ｒｈ−ＢＰｙ−ＰＭＯ、Ｒｈ／ＢＰｙ−ＰＭＯ＝２／５０）を得た。 The reaction represented by The obtained dispersion was passed through a membrane filter (pore size 0.45 μm) to recover the solid component. The obtained solid component was washed with N, N′-dimethylformamide and ethanol, and then vacuum-dried, and mesoporous organic silica containing a bipyridine group coordinated to Rh atoms (Rh-BPy-PMO, Rh / BPy— PMO = 2/50) was obtained.
（合成例２）
＜Ｒｈ含有メソポーラス有機シリカの合成＞
ＢＰｙ−ＰＭＯの量を１００ｍｇ（０．３１８ｍｍｏｌ−ＢＰｙ）に、［ＲｈＣｐ＊Ｃｌ２］２の量を５ｍｇ（８．１μｍｏｌ）に変更した以外は合成例１と同様にして、Ｒｈ原子に配位したビピリジン基を含有するメソポーラス有機シリカ（Ｒｈ−ＢＰｙ−ＰＭＯ、Ｒｈ／ＢＰｙ−ＰＭＯ＝５／１００）を得た。
(Synthesis Example 2)
<Synthesis of Rh-containing mesoporous organic silica>
Coordinated to Rh atoms in the same manner as in Synthesis Example 1 except that the amount of BPy-PMO was changed to 100 mg (0.318 mmol-BPy) and the amount of [RhCp * Cl 2 ] 2 was changed to 5 mg (8.1 μmol). The mesoporous organic silica (Rh-BPy-PMO, Rh / BPy-PMO = 5/100) containing a bipyridine group was obtained.
（合成例３）
＜Ｒｈ含有メソポーラス有機シリカの合成＞
ＢＰｙ−ＰＭＯの量を１００ｍｇ（０．３１８ｍｍｏｌ−ＢＰｙ）に、［ＲｈＣｐ＊Ｃｌ２］２の量を１０ｍｇ（１６μｍ）に変更した以外は合成例１と同様にして、Ｒｈ原子に配位したビピリジン基を含有するメソポーラス有機シリカ（Ｒｈ−ＢＰｙ−ＰＭＯ、Ｒｈ／ＢＰｙ−ＰＭＯ＝１０／１００）を得た。
(Synthesis Example 3)
<Synthesis of Rh-containing mesoporous organic silica>
Bipyridine coordinated to Rh atoms in the same manner as in Synthesis Example 1 except that the amount of BPy-PMO was changed to 100 mg (0.318 mmol-BPy) and the amount of [RhCp * Cl 2 ] 2 was changed to 10 mg (16 μm). A mesoporous organic silica containing a group (Rh-BPy-PMO, Rh / BPy-PMO = 10/100) was obtained.
（比較合成例１）
＜Ｒｈ含有ビピリジンの合成＞
［ＲｈＣｐ＊Ｃｌ２］２（５０ｍｇ（８０．９μｍｏｌ））をＮ，Ｎ’−ジメチルホルムアミド（２．０ｍｌ）に溶解した。得られた溶液に２，２’−ビピリジン（３１ｍｇ（１９８μｍｏｌ））を添加し、室温で２時間撹拌して、下記反応式（Ｓ２）：
(Comparative Synthesis Example 1)
<Synthesis of Rh-containing bipyridine>
[RhCp * Cl 2] 2 a (50mg (80.9μmol)) was dissolved in N, N'- dimethylformamide (2.0 ml). 2,2′-Bipyridine (31 mg (198 μmol)) was added to the resulting solution, and the mixture was stirred at room temperature for 2 hours. The following reaction formula (S2):
で表される反応を行なった。得られた反応液にジエチルエーテル（５ｍｌ）を添加し、生成した沈殿物を、メンブレンフィルター（孔径０．２０μｍ）を用いて吸引ろ過により回収し、ジエチルエーテルで洗浄した後、真空乾燥して、ＲｈＣｐ＊ＣｌのＲｈ原子にビピリジン基が配位した均一系Ｒｈ錯体（Ｒｈ−ＢＰｙ、Ｒｈ／ＢＰｙ＝１／１）を得た。このＲｈ−ＢＰｙにおけるＲｈ含有量は２．１５ｍｍｏｌ−Ｒｈ／ｇであった。 The reaction represented by Diethyl ether (5 ml) was added to the resulting reaction solution, and the resulting precipitate was collected by suction filtration using a membrane filter (pore size 0.20 μm), washed with diethyl ether, and then vacuum dried. A homogeneous Rh complex (Rh-BPy, Rh / BPy = 1/1) in which a bipyridine group was coordinated to the Rh atom of RhCp * Cl was obtained. The Rh content in this Rh-BPy was 2.15 mmol-Rh / g.
（比較合成例２）
＜Ｒｈ含有ノンポーラスシリカの合成＞
アルゴン雰囲気下、比較調製例１で得られたＢＰｙ−ｓｉｌｉｃａ（２００ｍｇ、０．１０３ｍｍｏｌ−ＢＰｙ）及び（ペンタメチルシクロペンタジエニル）ロジウム（III）ジクロリドダイマー（［ＲｈＣｐ＊Ｃｌ２］２、２０ｍｇ（３２．４μｍｏｌ））を量り取り、さらに、脱水メタノール（５０ｍｌ）を添加し、６５℃で加熱しながら１６時間撹拌して、下記反応式（Ｓ３）：
(Comparative Synthesis Example 2)
<Synthesis of Rh-containing nonporous silica>
Under an argon atmosphere, BPy-silica (200 mg, 0.103 mmol-BPy) and (pentamethylcyclopentadienyl) rhodium (III) dichloride dimer ([RhCp * Cl 2 ] 2 , 20 mg obtained in Comparative Preparation Example 1 32.4 μmol)) was further weighed, dehydrated methanol (50 ml) was further added, and the mixture was stirred for 16 hours while being heated at 65 ° C. The following reaction formula (S3):
で表される反応を行なった。得られた分散液をメンブレンフィルター（孔径０．４５μｍ）に通して固体成分を回収した。得られた固体成分をメタノールで洗浄した後、真空乾燥して、Ｒｈ原子に配位したビピリジン基を含有するノンポーラスシリカ（Ｒｈ−ＢＰｙ−ｓｉｌｉｃａ、Ｒｈ／ＢＰｙ−ｓｉｌｉｃａ＝１０／１００）を得た。このＲｈ−ＢＰｙ−ｓｉｌｉｃａにおけるＲｈ含有量は０．１３６ｍｍｏｌ−Ｒｈ／ｇであった。 The reaction represented by The obtained dispersion was passed through a membrane filter (pore size 0.45 μm) to recover the solid component. The obtained solid component was washed with methanol and then vacuum-dried to obtain nonporous silica (Rh-BPy-silica, Rh / BPy-silica = 10/100) containing a bipyridine group coordinated to Rh atoms. It was. The Rh content in this Rh-BPy-silica was 0.136 mmol-Rh / g.
（比較合成例３）
＜Ｒｈ含有メソポーラスシリカの合成＞
比較調製例１で得られたＢＰｙ−ｓｉｌｉｃａの代わりに比較調製例２で得られたＢＰｙ−ＦＳＭ（２００ｍｇ、０．１０３ｍｍｏｌ−ＢＰｙ）を用いた以外は、比較合成例２と同様にして、下記反応式（Ｓ４）：
(Comparative Synthesis Example 3)
<Synthesis of Rh-containing mesoporous silica>
In the same manner as in Comparative Synthesis Example 2, except that BPy-FSM (200 mg, 0.103 mmol-BPy) obtained in Comparative Preparation Example 2 was used instead of BPy-silica obtained in Comparative Preparation Example 1, Reaction formula (S4):
で表される反応を行い、Ｒｈ原子に配位したビピリジン基を含有するメソポーラスシリカ（Ｒｈ−ＢＰｙ−ＦＳＭ、Ｒｈ／ＢＰｙ−ＦＳＭ＝１０／１００）を得た。このＲｈ−ＢＰｙ−ＦＳＭにおけるＲｈ含有量は０．２９２ｍｍｏｌ−Ｒｈ／ｇであった。 The mesoporous silica (Rh-BPy-FSM, Rh / BPy-FSM = 10/100) containing the bipyridine group coordinated to the Rh atom was obtained. The Rh content in this Rh-BPy-FSM was 0.292 mmol-Rh / g.
〔Ｘ線回折パターン及び窒素吸着等温線〕
調製例１で得られたＢＰｙ−ＰＭＯ及び合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯのＸ線回折パターンを、粉末Ｘ線回折装置（株式会社リガク製「ＲＩＮＴ−ＴＴＲ」）を用いて測定したところ、２θ＝１．８２°（ｄ＝４．８５ｎｍ）に規則的なメソ構造に由来する回折ピークが観察された。また、２θ＝７．６０°（ｄ＝１．１６ｎｍ）、２θ＝１５．６°（ｄ＝０．５６８ｎｍ）及び２θ＝２３．０°（ｄ＝０．３８７ｎｍ）にビピリジン基の層状配列構造に由来する回折ピークが観察された。なお、図１には、一例として、調製例１で得られたＢＰｙ−ＰＭＯ及び合成例１で得られたＲｈ−ＢＰｙ−ＰＭＯのＸ線回折パターンを示す。
[X-ray diffraction pattern and nitrogen adsorption isotherm]
Using the X-ray diffraction pattern of BPy-PMO obtained in Preparation Example 1 and Rh-BPy-PMO obtained in Synthesis Examples 1 to 3, using a powder X-ray diffractometer (“RINT-TTR” manufactured by Rigaku Corporation) As a result, a diffraction peak derived from a regular mesostructure was observed at 2θ = 1.82 ° (d = 4.85 nm). In addition, a layered arrangement structure of bipyridine groups at 2θ = 7.60 ° (d = 1.16 nm), 2θ = 15.6 ° (d = 0.568 nm) and 2θ = 23.0 ° (d = 0.387 nm) A diffraction peak derived from was observed. In addition, in FIG. 1, the X-ray-diffraction pattern of BPy-PMO obtained by the preparation example 1 and Rh-BPy-PMO obtained by the synthesis example 1 is shown as an example.
また、調製例１で得られたＢＰｙ−ＰＭＯ及び合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯの窒素吸着等温線を、自動比表面積／細孔分布測定装置（カンタクローム社製「Ａｕｔｏｓｏｒｂ−１ ｓｙｓｔｅｍ」）を用い、液体窒素温度（−１９６℃）条件で定容量式ガス吸着法により求めたところ、いずれもIV型であった。なお、図２には、合成例１で得られたＲｈ−ＢＰｙ−ＰＭＯの窒素吸脱着等温線を示す。 In addition, the nitrogen adsorption isotherm of BPy-PMO obtained in Preparation Example 1 and Rh-BPy-PMO obtained in Synthesis Examples 1 to 3 was measured using an automatic specific surface area / pore distribution measuring device (“Autosorb, manufactured by Cantachrome). −1 system ”) and liquid nitrogen temperature (−196 ° C.) by a constant capacity gas adsorption method, all were IV type. FIG. 2 shows the nitrogen adsorption / desorption isotherm of Rh-BPy-PMO obtained in Synthesis Example 1.
したがって、Ｘ線回折パターン及び窒素吸脱着等温線から、調製例１で得られたＢＰｙ−ＰＭＯ及び合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯはいずれも規則的なメソ細孔を有するものであり、調製例１で得られたＢＰｙ−ＰＭＯにＲｈを固定化しても、規則的なメソ細孔構造が維持されていることが確認された。 Therefore, from the X-ray diffraction pattern and the nitrogen adsorption / desorption isotherm, both BPy-PMO obtained in Preparation Example 1 and Rh-BPy-PMO obtained in Synthesis Examples 1 to 3 have regular mesopores. It was confirmed that even when Rh was immobilized on BPy-PMO obtained in Preparation Example 1, a regular mesopore structure was maintained.
また、窒素吸着等温線に基づいて、調製例１で得られたＢＰｙ−ＰＭＯ及び合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯの中心細孔直径をＤＦＴ法により算出し、比表面積をＢＥＴ法により算出した。それらの結果を表１に示す。 Further, based on the nitrogen adsorption isotherm, the central pore diameters of BPy-PMO obtained in Preparation Example 1 and Rh-BPy-PMO obtained in Synthesis Examples 1 to 3 were calculated by the DFT method, and the specific surface area was calculated. It was calculated by the BET method. The results are shown in Table 1.
〔紫外可視拡散反射スペクトル〕
合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯの紫外可視拡散反射スペクトルを、紫外可視分光光度計（日本分光株式会社製「Ｖ−６７０」）を用いて測定したところ、いずれのＲｈ−ＢＰｙ−ＰＭＯにおいても、ビピリジン基のπ−π＊遷移に由来する３００ｎｍを極大波長とする吸収ピークに加えて、Ｒｈ原子にビピリジン基が錯配位していることを示す３８０ｎｍ付近の吸収ピークが観測された。また、この３８０ｎｍ付近の吸収ピークの強度は、［ＲｈＣｐ＊Ｃｌ２］２の添加量が増加するにつれて大きくなった。これは、Ｒｈの固定化量が増加したことによるものと考えられる。
(UV-visible diffuse reflection spectrum)
When the ultraviolet visible diffuse reflection spectrum of Rh-BPy-PMO obtained in Synthesis Examples 1 to 3 was measured using an ultraviolet visible spectrophotometer ("V-670" manufactured by JASCO Corporation), any Rh- In BPy-PMO, in addition to the absorption peak having a maximum wavelength of 300 nm derived from the π-π * transition of the bipyridine group, an absorption peak near 380 nm indicating that the bipyridine group is complex-coordinated to the Rh atom is also present. Observed. Further, the intensity of the absorption peak around 380 nm increased as the amount of [RhCp * Cl 2 ] 2 increased. This is considered to be due to an increase in the amount of immobilized Rh.
〔エネルギー分散型Ｘ線分光分析（ＥＤＸ分析）〕
合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯについて、エネルギー分散型Ｘ線分光分析装置を備えた走査型電子顕微鏡（株式会社日立ハイテクノロジーズ製「３６００−Ｎ」）を用いてＥＤＸ分析を行なったところ、いずれのＲｈ−ＢＰｙ−ＰＭＯにおいても、ＥＤＸマッピング像から、ケイ素原子（ＳｉＫ線）とロジウム原子（ＲｈＬ線）は均一に分布していることが確認された。また、ＥＤＸ分析結果に基づいて、合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯにおけるケイ素、ロジウム及び塩素の原子組成含有率を算出し、ビピリジン基に対するロジウムのモル比を求めた。さらに、このモル比から、Ｒｈ−ＢＰｙ−ＰＭＯ（１ｇ）に対するロジウム含有量を算出した。それらの結果を表１に示す。
[Energy dispersive X-ray spectroscopy (EDX analysis)]
For Rh-BPy-PMO obtained in Synthesis Examples 1 to 3, EDX analysis was performed using a scanning electron microscope (“3600-N” manufactured by Hitachi High-Technologies Corporation) equipped with an energy dispersive X-ray spectrometer. As a result, in any Rh-BPy-PMO, it was confirmed from the EDX mapping image that silicon atoms (SiK lines) and rhodium atoms (RhL lines) were uniformly distributed. Moreover, based on the EDX analysis result, the atomic composition content rate of silicon, rhodium and chlorine in Rh-BPy-PMO obtained in Synthesis Examples 1 to 3 was calculated, and the molar ratio of rhodium to the bipyridine group was obtained. Furthermore, the rhodium content with respect to Rh-BPy-PMO (1 g) was calculated from this molar ratio. The results are shown in Table 1.
表１に示した結果から明らかなように、［ＲｈＣｐ＊Ｃｌ２］２の添加量が増加するにつれて、Ｒｈの固定化量が増加することが確認された。 As is clear from the results shown in Table 1, it was confirmed that the amount of Rh immobilized increased as the amount of [RhCp * Cl 2 ] 2 increased.
〔Ｘ線吸収微細構造（ＸＡＦＳ）解析〕
合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯ及び比較合成例１で得られたＲｈ−ＢＰｙのＸ線吸収微細構造（ＸＡＦＳ）解析を、ＳＰｒｉｎｇ−８（ＢＬ１４Ｂ２）を利用して透過法により行なった。すなわち、Ｓｉ（３１１）二結晶分光器により単色化されたＸ線を用いて、室温でＲｈのＫ吸収端付近のＸＡＦＳスペクトルを測定した。得られたＸ線広域微細構造（ＥＸＡＦＳ）スペクトルについて、Ａｔｈｅｎａを用いてデータ処理を行なった。すなわち、ＥＸＡＦＳ振動χ（ｋ）にｋ３の重みをかけて２Å−１＜ｋ＜１２Å−１の領域においてフーリエ変換を行い、動径分布関数を得た。その結果、合成例１〜３で得られたＲｈ−ＢＰｙ−ＰＭＯは、ＸＡＮＥＳスペクトル及び動径分布関数が均一系Ｒｈ錯体（ＲｈＣｐ＊（ＢＰｙ）Ｃｌ２）と同様の形状を有しており、比較合成例１で得られた均一系Ｒｈ錯体（Ｒｈ−ＢＰｙ）と同様の配位構造を有していることが確認された。
[X-ray absorption fine structure (XAFS) analysis]
The X-ray absorption fine structure (XAFS) analysis of Rh-BPy-PMO obtained in Synthesis Examples 1 to 3 and Rh-BPy obtained in Comparative Synthesis Example 1 was conducted using SPring-8 (BL14B2). Performed. That is, the XAFS spectrum near the K absorption edge of Rh was measured at room temperature using X-rays monochromatized by a Si (311) double crystal spectrometer. The obtained X-ray broad-area fine structure (EXAFS) spectrum was subjected to data processing using Athens. That is, the EXAFS vibration χ (k) was weighted by k 3 and Fourier-transformed in the region of 2Å −1 <k <12Å −1 to obtain a radial distribution function. As a result, the Rh-BPy-PMO obtained in Synthesis Examples 1 to 3 has the same shape as the homogeneous Rh complex (RhCp * (BPy) Cl 2 ) in XANES spectrum and radial distribution function, It was confirmed to have the same coordination structure as the homogeneous Rh complex (Rh-BPy) obtained in Comparative Synthesis Example 1.
（参考例１）
固体触媒として合成例２で得られたＲｈ−ＢＰｙ−ＰＭＯ（Ｒｈ／ＢＰｙ−ＰＭＯ＝５／１００、３．２３ｍｇ、０．４μｍｏｌ−Ｒｈ）と、反応基質として２−シクロヘキセ−１−オン（４０μｍｏｌ）とを量り取り、これに０．１Ｍリン酸ナトリウム緩衝液（２ｍｌ、ｐＨ７）、０．５Ｍギ酸ナトリウム（６８ｍｇ）、及び内部標準物質としてフェノール（１μｌ／ｍｌ）を添加して４０℃で加熱しながら６時間攪拌して、下記反応式（Ｅ１）：
(Reference Example 1)
Rh-BPy-PMO (Rh / BPy-PMO = 5/100, 3.23 mg, 0.4 μmol-Rh) obtained in Synthesis Example 2 as a solid catalyst, and 2-cyclohex-1-one (40 μmol) as a reaction substrate. ), 0.1M sodium phosphate buffer (2 ml, pH 7), 0.5 M sodium formate (68 mg), and phenol (1 μl / ml) as an internal standard substance were added and heated at 40 ° C. While stirring for 6 hours, the following reaction formula (E1):
で表される反応を行なった。反応終了後、得られた反応液を０．１ｍｌ採取し、酢酸エチル（０．５ｍｌ）で抽出操作を３回行い、得られた有機層を無水硫酸ナトリウムで乾燥した後、ガスクロマトグラフィで分析し、基質転化率を求めた。その結果を図３及び図４に示す。 The reaction represented by After completion of the reaction, 0.1 ml of the resulting reaction solution was collected, extracted three times with ethyl acetate (0.5 ml), and the resulting organic layer was dried over anhydrous sodium sulfate and analyzed by gas chromatography. The substrate conversion rate was determined. The results are shown in FIGS.
（実施例１）
ウシ血清アルブミン（ＢＳＡ）を、濃度が２ｍｇ／ｍｌ、５ｍｇ／ｍｌ、１０ｍｇ／ｍｌ、又は２０ｍｇ／ｍｌとなるように更に添加した以外は参考例１と同様にして、前記反応式（Ｅ１）で表される反応を行い、基質転化率を求めた。その結果を図３に示す。
Example 1
In the same manner as in Reference Example 1, except that bovine serum albumin (BSA) was further added to a concentration of 2 mg / ml, 5 mg / ml, 10 mg / ml, or 20 mg / ml, the reaction formula (E1) The reaction indicated was performed to determine the substrate conversion. The result is shown in FIG.
（参考例２）
固体触媒として合成例３で得られたＲｈ−ＢＰｙ−ＰＭＯ（Ｒｈ／ＢＰｙ−ＰＭＯ＝１０／１００、１．７９ｍｇ、０．４μｍｏｌ−Ｒｈ）を用いた以外は参考例１と同様にして、前記反応式（Ｅ１）で表される反応を行い、基質転化率を求めた。その結果を図３に示す。
(Reference Example 2)
In the same manner as in Reference Example 1, except that Rh-BPy-PMO (Rh / BPy-PMO = 10/100, 1.79 mg, 0.4 μmol-Rh) obtained in Synthesis Example 3 was used as the solid catalyst, The reaction represented by the reaction formula (E1) was performed to determine the substrate conversion rate. The result is shown in FIG.
（実施例２）
ウシ血清アルブミン（ＢＳＡ）を、濃度が２ｍｇ／ｍｌ、５ｍｇ／ｍｌ、１０ｍｇ／ｍｌ、又は２０ｍｇ／ｍｌとなるように更に添加した以外は参考例２と同様にして、前記反応式（Ｅ１）で表される反応を行い、基質転化率を求めた。その結果を図３に示す。
(Example 2)
In the same manner as in Reference Example 2, except that bovine serum albumin (BSA) was further added to a concentration of 2 mg / ml, 5 mg / ml, 10 mg / ml, or 20 mg / ml, the reaction formula (E1) The reaction indicated was performed to determine the substrate conversion. The result is shown in FIG.
（比較参考例１）
触媒として比較合成例１で得られた均一系Ｒｈ錯体（Ｒｈ−ＢＰｙ、Ｒｈ／ＢＰｙ＝１／１、０．１８６ｍｇ、０．４μｍｏｌ−Ｒｈ）を用いた以外は参考例１と同様にして、下記反応式（Ｃ１）：
(Comparative Reference Example 1)
As in Reference Example 1, except that the homogeneous Rh complex (Rh-BPy, Rh / BPy = 1/1, 0.186 mg, 0.4 μmol-Rh) obtained in Comparative Synthesis Example 1 was used as a catalyst. The following reaction formula (C1):
で表される反応を行い、基質転化率を求めた。その結果を図３に示す。 The substrate conversion rate was determined. The result is shown in FIG.
（比較例１）
ウシ血清アルブミン（ＢＳＡ）を、濃度が２ｍｇ／ｍｌ、５ｍｇ／ｍｌ、１０ｍｇ／ｍｌ、又は２０ｍｇ／ｍｌとなるように更に添加した以外は比較参考例１と同様にして、前記反応式（Ｃ１）で表される反応を行い、基質転化率を求めた。その結果を図３に示す。
(Comparative Example 1)
Bovine serum albumin (BSA) was added in the same manner as in Comparative Reference Example 1 except that bovine serum albumin (BSA) was further added to a concentration of 2 mg / ml, 5 mg / ml, 10 mg / ml, or 20 mg / ml. The substrate conversion rate was determined. The result is shown in FIG.
（比較参考例２）
固体触媒として比較合成例２で得られたＲｈ−ＢＰｙ−ｓｉｌｉｃａ（Ｒｈ／ＢＰｙ−ｓｉｌｉｃａ＝１０／１００、２．９４ｍｇ、０．４μｍｏｌ−Ｒｈ）を用いた以外は参考例１と同様にして、下記反応式（Ｃ２）：
(Comparative Reference Example 2)
As in Reference Example 1, except that Rh-BPy-silica (Rh / BPy-silica = 10/100, 2.94 mg, 0.4 μmol-Rh) obtained in Comparative Synthesis Example 2 was used as the solid catalyst. The following reaction formula (C2):
で表される反応を行い、基質転化率を求めた。その結果を図４に示す。 The substrate conversion rate was determined. The result is shown in FIG.
（比較参考例３）
固体触媒として比較合成例３で得られたＲｈ−ＢＰｙ−ＦＳＭ（Ｒｈ／ＢＰｙ−ＦＳＭ＝１０／１００、１．３４ｍｇ、０．４μｍｏｌ−Ｒｈ）を用いた以外は参考例１と同様にして、下記反応式（Ｃ３）：
(Comparative Reference Example 3)
As in Reference Example 1, except that Rh-BPy-FSM obtained in Comparative Synthesis Example 3 (Rh / BPy-FSM = 10/100, 1.34 mg, 0.4 μmol-Rh) was used as the solid catalyst, The following reaction formula (C3):
で表される反応を行い、基質転化率を求めた。その結果を図４に示す。 The substrate conversion rate was determined. The result is shown in FIG.
図３に示した結果から明らかなように、触媒としてＲｈ原子に配位したビピリジン基を含有するメソポーラス有機シリカ（Ｒｈ−ＢＰｙ−ＰＭＯ）を用いた場合（実施例１、２）には、タンパク質であるウシ血清アルブミン（ＢＳＡ）の存在下においても、高い触媒活性（基質転化率７０％以上）が維持されることがわかった。一方、触媒として均一系Ｒｈ錯体（Ｒｈ−ＢＰｙ）を用いた場合（比較例１）には、ＢＳＡ濃度が増加するにつれて、触媒活性が大幅に低下することがわかった（ＢＳＡ：２０ｍｇ／ｍｌの場合、基質転化率：１７％）。 As is apparent from the results shown in FIG. 3, when mesoporous organic silica (Rh-BPy-PMO) containing a bipyridine group coordinated to an Rh atom was used as a catalyst (Examples 1 and 2), protein It was found that even in the presence of bovine serum albumin (BSA), high catalytic activity (substrate conversion rate of 70% or more) was maintained. On the other hand, when the homogeneous Rh complex (Rh-BPy) was used as the catalyst (Comparative Example 1), it was found that the catalytic activity decreased significantly as the BSA concentration increased (BSA: 20 mg / ml). In case of substrate conversion: 17%).
また、図４に示した結果から明らかなように、固体触媒として、Ｒｈ原子に配位したビピリジン基を含有するノンポーラスシリカ（Ｒｈ−ＢＰｙ−ｓｉｌｉｃａ、比較参考例２）及びＲｈ原子に配位したビピリジン基を含有するメソポーラスシリカ（Ｒｈ−ＢＰｙ−ＦＳＭ、比較参考例３）を用いた場合には、Ｒｈ原子に配位したビピリジン基を含有するメソポーラス有機シリカ（Ｒｈ−ＢＰｙ−ＰＭＯ、参考例１）を用いた場合に比べて、触媒活性が低くなった。これは、Ｒｈ−ＢＰｙ−ｓｉｌｉｃａやＲｈ−ＢＰｙ−ＦＳＭにおいては、非晶質シリカゲルやメソポーラスシリカの表面にビピリジン基が担持されているため、このビピリジン基によって細孔内での反応基質の拡散性が阻害されたこと、また、非晶質シリカゲルやメソポーラスシリカの表面が不均質であることが原因であると推察される。一方、Ｒｈ−ＢＰｙ−ＰＭＯにおいては、ビピリジン基がメソポーラス有機シリカの骨格中に含まれているため、反応基質の拡散性が阻害されず、高い触媒活性が得られたと考えられる。 Further, as is apparent from the results shown in FIG. 4, as the solid catalyst, the non-porous silica containing a bipyridine group coordinated to the Rh atom (Rh-BPy-silica, Comparative Reference Example 2) and the Rh atom are coordinated. When mesoporous silica containing a bipyridine group (Rh-BPy-FSM, Comparative Reference Example 3) is used, a mesoporous organic silica containing a bipyridine group coordinated to an Rh atom (Rh-BPy-PMO, Reference Example) Compared with the case of using 1), the catalytic activity was low. In Rh-BPy-silica and Rh-BPy-FSM, the bipyridine group is supported on the surface of amorphous silica gel or mesoporous silica. This is presumed to be caused by the fact that the surface of amorphous silica gel and mesoporous silica was inhomogeneous. On the other hand, in Rh-BPy-PMO, since the bipyridine group is contained in the skeleton of the mesoporous organic silica, it is considered that the diffusibility of the reaction substrate is not inhibited and high catalytic activity is obtained.
（参考例３）
固体触媒として合成例１で得られたＲｈ−ＢＰｙ−ＰＭＯ（Ｒｈ／ＢＰｙ−ＰＭＯ＝２／５０、１１．６ｍｇ、１．０μｍｏｌ−Ｒｈ）と、反応基質として酸化型ニコチンアミドアデニンジヌクレオチド（ＮＡＤ＋、１．０ｍＭ）とを量り取り、これに０．１Ｍリン酸ナトリウム緩衝液（１０ｍｌ、ｐＨ７）及び１０Ｍギ酸ナトリウム水溶液（１００μｌ）を添加して２５℃で１８０分間攪拌して、下記反応式（Ｅ２）：
(Reference Example 3)
Rh-BPy-PMO (Rh / BPy-PMO = 2/50, 11.6 mg, 1.0 μmol-Rh) obtained in Synthesis Example 1 as a solid catalyst, and oxidized nicotinamide adenine dinucleotide (NAD) as a reaction substrate + , 1.0 mM) and 0.1 M sodium phosphate buffer (10 ml, pH 7) and 10 M sodium formate aqueous solution (100 μl) were added thereto and stirred at 25 ° C. for 180 minutes. (E2):
〔前記式（Ｅ２）中、Ｒはアデニンジヌクレオチドを示す。〕
で表される反応を行なった。反応終了後、得られた反応液中の還元型ニコチンアミドアデニンジヌクレオチド（ＮＡＤＨ）の生成量を測定し、反応収率を求めた。その結果を表２に示す。
[In the formula (E2), R represents an adenine dinucleotide. ]
The reaction represented by After completion of the reaction, the amount of reduced nicotinamide adenine dinucleotide (NADH) produced in the resulting reaction solution was measured to determine the reaction yield. The results are shown in Table 2.
（実施例３）
ウシ血清アルブミン（ＢＳＡ）を、濃度が１０ｍｇ／ｍｌとなるように更に添加した以外は参考例３と同様にして、前記反応式（Ｅ２）で表される反応を行い、反応収率を求めた。その結果を表２に示す。
Example 3
The reaction represented by the reaction formula (E2) was performed in the same manner as in Reference Example 3 except that bovine serum albumin (BSA) was further added so that the concentration was 10 mg / ml, and the reaction yield was determined. . The results are shown in Table 2.
（比較参考例４）
触媒として比較合成例１で得られた均一系Ｒｈ錯体（Ｒｈ−ＢＰｙ、Ｒｈ／ＢＰｙ＝１／１、０．４６５ｍｇ（１．０μｍｏｌ）、１．０μｍｏｌ−Ｒｈ）を用いた以外は参考例３と同様にして、下記反応式（Ｃ４）：
(Comparative Reference Example 4)
Reference Example 3 except that the homogeneous Rh complex (Rh-BPy, Rh / BPy = 1/1, 0.465 mg (1.0 μmol), 1.0 μmol-Rh) obtained in Comparative Synthesis Example 1 was used as the catalyst. In the same manner as in the following reaction formula (C4):
〔前記式（Ｃ４）中、Ｒはアデニンジヌクレオチドを示す。〕
で表される反応を行い、反応収率を求めた。その結果を表２に示す。
[In the formula (C4), R represents adenine dinucleotide. ]
The reaction yield was determined. The results are shown in Table 2.
（比較例２）
ウシ血清アルブミン（ＢＳＡ）を、濃度が１０ｍｇ／ｍｌとなるように更に添加した以外は比較参考例４と同様にして、前記反応式（Ｃ４）で表される反応を行い、反応収率を求めた。その結果を表２に示す。
(Comparative Example 2)
The reaction represented by the above reaction formula (C4) was carried out in the same manner as in Comparative Reference Example 4 except that bovine serum albumin (BSA) was further added to a concentration of 10 mg / ml to obtain the reaction yield. It was. The results are shown in Table 2.
表２に示した結果から明らかなように、触媒として、Ｒｈ原子に配位したビピリジン基を含有するメソポーラス有機シリカ（Ｒｈ−ＢＰｙ−ＰＭＯ）を用いた場合（実施例３）には、均一系Ｒｈ錯体（Ｒｈ−ＢＰｙ）を用いた場合（比較例２）に比べて、タンパク質であるウシ血清アルブミン（ＢＳＡ）の存在下における触媒活性の維持率が高くなることがわかった。 As is clear from the results shown in Table 2, when mesoporous organic silica (Rh-BPy-PMO) containing a bipyridine group coordinated to Rh atoms was used as the catalyst (Example 3), a homogeneous system was used. It was found that the maintenance rate of catalytic activity in the presence of bovine serum albumin (BSA), which is a protein, was higher than when Rh complex (Rh-BPy) was used (Comparative Example 2).
以上説明したように、本発明によれば、タンパク質の存在下での還元反応において高い触媒活性を示す還元反応用固体触媒を得ることが可能となる。したがって、本発明の還元反応用固体触媒は、医薬品、生理活性物質、農薬、機能性材料等の製造過程における還元反応（特に、水素転移反応、水素移動反応、炭素−炭素不飽和結合の水素化反応、カルボニルの水素化反応、イミンの水素化反応）に使用される固体触媒などとして有用である。 As described above, according to the present invention, it is possible to obtain a solid catalyst for reduction reaction that exhibits high catalytic activity in a reduction reaction in the presence of protein. Therefore, the solid catalyst for reduction reaction of the present invention is a reduction reaction (especially hydrogen transfer reaction, hydrogen transfer reaction, hydrogenation of carbon-carbon unsaturated bond) in the production process of pharmaceuticals, bioactive substances, agricultural chemicals, functional materials and the like. It is useful as a solid catalyst used in the reaction, hydrogenation reaction of carbonyl, hydrogenation reaction of imine).
Claims (7)
で表される基であり、Ｒ１〜Ｒ８のうちの残りの基はそれぞれ独立に水素原子、ハロゲン原子、或いはアルキル基、アリール基、ヒドロキシ基、アルコキシ基、フェノキシ基、カルボキシ基、カルボン酸エステル基、アセチル基、ベンゾイル基、アミノ基、アミド基、イミド基、ニトロ基及びシアノ基からなる群から選択される１価又は２価の有機基である。〕
で表される構造を備える遷移金属含有メソポーラス有機シリカからなり、タンパク質存在下での還元反応に使用することを特徴とする還元反応用固体触媒。 Following formula (1):
The remaining groups of R 1 to R 8 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group, a phenoxy group, a carboxy group, or a carboxylic acid. It is a monovalent or divalent organic group selected from the group consisting of an ester group, acetyl group, benzoyl group, amino group, amide group, imide group, nitro group and cyano group. ]
A solid catalyst for reduction reaction, which comprises a transition metal-containing mesoporous organic silica having a structure represented by the formula (1) and is used for a reduction reaction in the presence of protein.
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