JP4800902B2 - Pd-supported polymer catalyst having selective functional group reduction performance - Google Patents
Pd-supported polymer catalyst having selective functional group reduction performance Download PDFInfo
- Publication number
- JP4800902B2 JP4800902B2 JP2006300294A JP2006300294A JP4800902B2 JP 4800902 B2 JP4800902 B2 JP 4800902B2 JP 2006300294 A JP2006300294 A JP 2006300294A JP 2006300294 A JP2006300294 A JP 2006300294A JP 4800902 B2 JP4800902 B2 JP 4800902B2
- Authority
- JP
- Japan
- Prior art keywords
- nitro group
- catalyst
- group
- synthetic adsorbent
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は選択的官能基還元活性機能を備えたＰｄ等の金属担持ポリマー触媒に関するものである。本発明により提供される金属担持ポリマー触媒は、有機合成反応において選択的な官能基の還元触媒として有用である。 The present invention relates to a metal-supported polymer catalyst such as Pd having a selective functional group reduction activity function. The metal-supported polymer catalyst provided by the present invention is useful as a selective functional group reduction catalyst in an organic synthesis reaction.
Ｐｄ/Ｃ触媒は代表的な不均一系触媒として、各種化学反応に使用されている。近年では有機合成反応において、反応後の反応系からの触媒の分離容易性から、不均一系触媒が均一系触媒に代わり使用されつつある。
一般に液層系での有機合成反応において、Ｐｄ/Ｃ触媒の機能としては、各種官能基の水素化還元反応用が主である。しかしながら、通常のＰｄ/Ｃ触媒を用いた場合、複数の官能基を持つ化合物に対しては、その官能基に対する選択的還元性能に欠けるという問題があり、触媒設計の面から様々な改良・開発が行われている。
Pd / C catalysts are used in various chemical reactions as typical heterogeneous catalysts. In recent years, in organic synthesis reactions, heterogeneous catalysts are being used instead of homogeneous catalysts because of the ease of separation of the catalyst from the reaction system after the reaction.
In general, in the organic synthesis reaction in the liquid layer system, the function of the Pd / C catalyst is mainly for the hydroreduction reaction of various functional groups. However, when a normal Pd / C catalyst is used, there is a problem that a compound having a plurality of functional groups lacks the selective reduction performance with respect to the functional groups, and various improvements and developments from the aspect of catalyst design. Has been done.
本発明では、触媒の担体である物質の親水性・疎水性及び細孔構造の観点から、合成吸着剤に着眼し、鋭意研究を行った。その結果、ある種の特定の合成吸着剤（多孔性有機高分子ポリマー）にＰｄ等の貴金属を担持させることにより、選択的官能基還元特性を有する触媒を開発することに成功した。有機合成反応において、官能基の還元に対する選択性を有する触媒は、医薬品等の複雑な分子構造及び複数の官能基を持つ化合物の合成に極めて有用であり、有機合成反応の幅を著しく向上させることが期待される。 In the present invention, from the viewpoint of the hydrophilicity / hydrophobicity of the substance that is the catalyst carrier and the pore structure, the synthetic adsorbent was focused on and earnestly studied. As a result, we have succeeded in developing a catalyst having selective functional group reduction characteristics by supporting a noble metal such as Pd on a specific synthetic adsorbent (porous organic polymer). In organic synthesis reactions, catalysts with selectivity for functional group reduction are extremely useful for the synthesis of compounds with complex molecular structures and multiple functional groups, such as pharmaceuticals, and significantly improve the breadth of organic synthesis reactions. There is expected.
有機高分子ポリマーに貴金属を担持させた触媒例としては特許文献１〜３がある。
特許文献１には、参考例７にスチレン／４−ビニルベンジルグリシジルエーテル／メタクリル酸共重合体にＰｄを2.2wt％担持させた触媒、参考例８にスチレン／４−ビニルベンジルグリシジルエーテル／テトラエチレングリコールモノ−２−フェニル−２−プロペニルエーテル共重合体にＰｄを1.1wt％担持させた触媒、参考例９にスチレン／４−ビニルべンジルグリシジルエーテル／テトラエチレングリコールモノメタクリル酸エステル共重合体にＰｄを1.1wt％担持させた触媒の合成例が開示されている。特許文献１の発明は、該触媒を用いたアリールホウ酸化合物とハロゲン化アリール化合物とを反応させることによる炭素―炭素カップリング反応に関する発明である。
特許文献２には、触媒１として炭化ポリスルホン化ジビニルベンゼン−スチレン共重合体にＲｈを0.55wt％担持した触媒、触媒２として同様に該ポリマーにＩｒを1.02wt％担持した触媒、触媒３として該ポリマーにＰｔを0.95wt％担持した触媒が開示されている。特許文献２の発明は、これらの触媒を使用した低級アルコールのカルボニル化反応に関する発明である。
特許文献３には、特許文献２と同一の触媒がカルボニル化反応用触媒として開示されている。
Examples of catalysts in which a noble metal is supported on an organic polymer include Patent Documents 1 to 3.
Patent Document 1 discloses a catalyst in which Pd is supported on a styrene / 4-vinylbenzylglycidyl ether / methacrylic acid copolymer in Reference Example 7 and styrene / 4-vinylbenzylglycidyl ether / tetraethylene in Reference Example 8. A catalyst in which 1.1 wt% of Pd was supported on a glycol mono-2-phenyl-2-propenyl ether copolymer, and Reference Example 9 was a styrene / 4-vinylbenzylglycidyl ether / tetraethylene glycol monomethacrylate copolymer. Discloses a synthesis example of a catalyst in which 1.1 wt% of Pd is supported. The invention of Patent Document 1 is an invention relating to a carbon-carbon coupling reaction by reacting an arylboric acid compound and a halogenated aryl compound using the catalyst.
Patent Document 2 discloses a catalyst in which 0.55 wt% of Rh is supported on a carbonized polysulfonated divinylbenzene-styrene copolymer as catalyst 1, a catalyst in which 1.02 wt% of Ir is similarly supported on the polymer as catalyst 2, and A catalyst having 0.95 wt% Pt supported on a polymer is disclosed. The invention of Patent Document 2 is an invention relating to a carbonylation reaction of a lower alcohol using these catalysts.
Patent Document 3 discloses the same catalyst as Patent Document 2 as a carbonylation reaction catalyst.
これらの特許文献には、有機高分子ポリマーに貴金属を担持した触媒の製造例は開示されてはいるものの、その触媒を使用して、反応物の官能基を選択的に還元した例も、それらを示唆した記述もない。
近年、有機合成反応において、ある特定の官能基を選択的に還元するための不均一触媒が、反応後の触媒除去の容易性から切に望まれている。これらの現状を鑑み、Ｐｄ/Ｃ触媒に代わる官能基選択還元性能を備えた担持触媒を目的にして、触媒担体及び触媒調製方法の検討を行う中で、合成吸着剤が、酸、アルカリ、又は溶媒中においても劣化せず、活性炭ほどの大きな比表面積を有する等の、触媒担体としての要求性能を満足するものであることが判明し、本発明を完成するに至った。
Although these patent documents disclose examples of producing a catalyst in which a noble metal is supported on an organic polymer polymer, examples of selectively reducing functional groups of reactants using the catalyst are also disclosed. There is no description that suggests.
In recent years, a heterogeneous catalyst for selectively reducing a specific functional group in an organic synthesis reaction has been eagerly desired because of the ease of catalyst removal after the reaction. In view of these current conditions, in the study of a catalyst carrier and a catalyst preparation method for the purpose of a supported catalyst having a functional group selective reduction performance instead of a Pd / C catalyst, a synthetic adsorbent is an acid, an alkali, or It has been found that it does not deteriorate even in a solvent and satisfies the required performance as a catalyst carrier, such as having a specific surface area as large as that of activated carbon, and the present invention has been completed.
本発明者等は、合成吸着剤の特異な多孔体構造による特性（合成吸着剤の細孔内への拡散特性）及び親水性・疎水性特性（被吸着物質と合成吸着剤との吸着反応力）に着眼し、Ｐｄ等の金属の担持方法につき様々な試行錯誤の検討を繰り返した結果、ある種の合成吸着剤と特定の金属とを組合せた触媒により、反応物質の官能基への水素化活性の制御が可能であることを見出した。
即ち、本発明は、合成吸着剤にＰｔ、Ｐｄ、Ｒｈ、Ｒｕ、及びＡｇから成る群から選ばれる少なくとも１種の金属元素を担持したことを特徴とする官能基選択還元用触媒を提供するものである。
また、本発明は、芳香族基に結合したニトロ基（−ＮＯ２基）と脂肪族基に結合したシアノ基（−ＣＮ基）とが存在する反応系において、上記官能基選択還元用触媒を使用して、水又はメタノール中で該ニトロ基を選択的に還元することを特徴とする、ニトロ基の選択的還元方法を提供するものである。
The inventors of the present invention describe the characteristics of the synthetic adsorbent due to the unique porous structure (diffusion characteristics of the synthetic adsorbent into the pores) and hydrophilic / hydrophobic characteristics (adsorption reaction force between the adsorbed substance and the synthetic adsorbent). As a result of repeated trial and error studies on the loading method of metals such as Pd, hydrogenation of reactants to functional groups is achieved using a catalyst that combines a certain kind of synthetic adsorbent and a specific metal. It was found that the activity can be controlled.
That is, the present invention provides a functional group selective reduction catalyst characterized in that a synthetic adsorbent carries at least one metal element selected from the group consisting of Pt, Pd, Rh, Ru, and Ag. It is.
The present invention also provides a catalyst for selective reduction of the functional group in a reaction system in which a nitro group (—NO 2 group) bonded to an aromatic group and a cyano group (—CN group) bonded to an aliphatic group are present. The present invention provides a method for selectively reducing a nitro group, characterized in that the nitro group is selectively reduced in water or methanol.
本発明の触媒は、選択的にある種の官能基のみを選択的に還元することができる。即ち、本発明の触媒は脂肪族シアノ基に対し還元不活性であり、芳香族ニトロ基に還元活性を有する。従って、分子内または反応系内に脂肪族シアノ基及び芳香族ニトロ基を有する化合物の芳香族ニトロ基のみを選択的に還元することが可能である。さらに、本発明の触媒は不均一系触媒であり、均一系触媒と比較して、反応系からの触媒の分離及び触媒の調製が容易である。 The catalyst of the present invention can selectively reduce only certain functional groups. That is, the catalyst of the present invention is reduction-inactive with respect to the aliphatic cyano group and has a reduction activity with respect to the aromatic nitro group. Therefore, it is possible to selectively reduce only the aromatic nitro group of a compound having an aliphatic cyano group and an aromatic nitro group in the molecule or reaction system. Furthermore, the catalyst of the present invention is a heterogeneous catalyst, and the catalyst can be easily separated from the reaction system and the catalyst can be prepared as compared with the homogeneous catalyst.
本願で合成吸着剤とは、化学的に安定でかつ温和な条件で再生可能で、活性炭に匹敵する高比表面積を有する、化学合成により製造された有機高分子の多孔体である。本発明で用いられる合成吸着剤としては、化学構造的には芳香族系、置換芳香族系、アクリル系の重合体若しくは共重合体〔以下、「重合体若しくは共重合体」を「（共）重合体」とも云う〕が用いられる。芳香族系（共）重合体としては、スチレン／ジビニルベンゼン共重合体、ジビニルベンゼン重合体が挙げられる。置換芳香族系（共）重合体としては、ブロモスチレン／ジビニルベンゼン共重合体が挙げられる。アクリル系（共）重合体としては、メタクリル酸メチル／ビス（メタクリル酸）エチレングリコール共重合体のようなメタアクリル酸エステル系（共）重合体が挙げられる。合成吸着剤の細孔容積は0.1〜2.0ml/ｇ、特に0.5〜2.0ml/ｇであるのが好ましい。合成吸着剤の比表面積は、目的とする官能基の種類及び反応条件（温度、圧力）により変化し、従って特段限定されるものではないが、反応性の面から通常400〜2000m2／gr、好ましくは500〜1500m2/grである。さらに、合成吸着剤の細孔半径も、目的とする反応物質の分子の大きさ等により、適宜選択されるが、通常10〜500Å（オングストローム）であるのが好ましく、30〜300Åであるのが更に好ましい。また、合成吸着剤の表面の親水性・疎水性を調整する為に、合成吸着剤に各種官能基を導入することができる。導入される官能基としては、カルボキシル基、スルホン酸基、ハロゲン（フッ素、塩素、臭素、ヨウ素）原子、フェニル基、水酸基、アルキル基、ビニル基、アルコキシ基、シリル基、またこれらの組合せが挙げられる。合成吸着剤の形状は特に限定されるものではないが、球状、ペレット、円柱状等が使用可能である。
合成吸着剤の例を挙げると、三菱化学により以下のものが開発されている。
In the present application, the synthetic adsorbent is a porous body of organic polymer produced by chemical synthesis, which is chemically stable and can be regenerated under mild conditions, and has a high specific surface area comparable to activated carbon. The synthetic adsorbent used in the present invention is an aromatic, substituted aromatic, or acrylic polymer or copolymer in terms of chemical structure [hereinafter referred to as “polymer or copolymer” as “(co)]. Also referred to as "polymer". Examples of the aromatic (co) polymer include styrene / divinylbenzene copolymer and divinylbenzene polymer. Examples of substituted aromatic (co) polymers include bromostyrene / divinylbenzene copolymers. Examples of the acrylic (co) polymer include methacrylic acid ester (co) polymers such as methyl methacrylate / bis (methacrylic acid) ethylene glycol copolymer. The pore volume of the synthetic adsorbent is preferably 0.1 to 2.0 ml / g, particularly preferably 0.5 to 2.0 ml / g. The specific surface area of the synthetic adsorbent varies depending on the type of target functional group and the reaction conditions (temperature, pressure), and is not particularly limited, but is usually 400 to 2000 m 2 / gr from the viewpoint of reactivity. Preferably it is 500-1500m < 2 > / gr. Furthermore, the pore radius of the synthetic adsorbent is also appropriately selected depending on the molecular size of the target reactant, etc., but it is usually preferably 10 to 500 cm (angstrom), and preferably 30 to 300 mm. Further preferred. Moreover, in order to adjust the hydrophilicity / hydrophobicity of the surface of the synthetic adsorbent, various functional groups can be introduced into the synthetic adsorbent. Examples of functional groups to be introduced include carboxyl groups, sulfonic acid groups, halogen (fluorine, chlorine, bromine, iodine) atoms, phenyl groups, hydroxyl groups, alkyl groups, vinyl groups, alkoxy groups, silyl groups, and combinations thereof. It is done. The shape of the synthetic adsorbent is not particularly limited, but a spherical shape, a pellet, a cylindrical shape, or the like can be used.
As examples of synthetic adsorbents, Mitsubishi Chemical has developed the following.
各種合成吸着剤 Various synthetic adsorbents
本発明の触媒に使用可能な金属元素としては、パラジウム（Ｐｄ）、白金（Ｐｔ）、ロジウム（Ｒｈ）、ルテニウム（Ｒｕ）、銀（Ａｇ）、及びこれらの２種以上の混合物が挙げられる。これらの金属元素の中で、Ｐｄ単独、又はＰｄとＰｔ、Ｒｈ、Ｒｕ及びＡｇから選ばれる少なくとも１種との混合物が好ましい。金属元素の担持量は、触媒全体の0.1〜20wt％、更に１〜13wt％、特に１〜10wt％であるのが好ましい。Ｐｄを１〜10wt％含む触媒が特に好ましい。 Examples of the metal element that can be used in the catalyst of the present invention include palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), silver (Ag), and a mixture of two or more thereof. Among these metal elements, Pd alone or a mixture of Pd and at least one selected from Pt, Rh, Ru and Ag is preferable. The amount of the metal element supported is preferably 0.1 to 20 wt%, more preferably 1 to 13 wt%, particularly 1 to 10 wt% of the entire catalyst. A catalyst containing 1 to 10 wt% of Pd is particularly preferable.
本発明の触媒がＰｄを含む場合、触媒調製に用いられるパラジウム塩は、水溶性又は有機溶剤に溶解するものであれば特に制限されるものではない。例えば、酢酸パラジウム、塩化パラジウム、硫酸パラジウム、プロピオン酸パラジウム、各種パラジウムの複塩、テトラクロロパラジウム酸カリウム、テトラクロロパラジウム酸ナトリウム、テトラキス（トリフェニルホスフィン）パラジウム、及びビス（ジベンジリデンアセトン）パラジウムが使用し得る。 When the catalyst of the present invention contains Pd, the palladium salt used for catalyst preparation is not particularly limited as long as it is water-soluble or soluble in an organic solvent. For example, palladium acetate, palladium chloride, palladium sulfate, palladium propionate, various double salts of palladium, potassium tetrachloropalladate, sodium tetrachloropalladate, tetrakis (triphenylphosphine) palladium, and bis (dibenzylideneacetone) palladium Can be used.
パラジウム塩の代わりに白金塩を担持させることにより、白金担持合成吸着剤の触媒調製も可能である。白金は、パラジウムと同様に、水素化活性を有することは一般に良く知られている。本発明の触媒に使用可能な白金塩は、パラジウム塩同様に、水溶性又は有機溶剤に溶解するものであれば特に制限されるものではない。例えば、塩化白金、ヘキサクロロ白金酸カリウム、テトラアンミン白金酢酸塩、テトラアンミン白金硝酸塩、ビス（アセチルアセトナト）白金、及びテトラアンミン白金炭酸塩が使用可能である。 A catalyst for a platinum-supported synthetic adsorbent can be prepared by supporting a platinum salt instead of a palladium salt. It is generally well known that platinum, like palladium, has hydrogenation activity. The platinum salt that can be used in the catalyst of the present invention is not particularly limited as long as it is water-soluble or soluble in an organic solvent, like the palladium salt. For example, platinum chloride, potassium hexachloroplatinate, tetraammineplatinum acetate, tetraammineplatinum nitrate, bis (acetylacetonato) platinum, and tetraammineplatinum carbonate can be used.
ロジウム、ルテニウム又は銀を担持させる場合に使用可能な塩は、パラジウム塩及び白金塩と同様に、水溶性又は有機溶剤に溶解するものであれば特に制限されるものではない。例えば、ロジウム塩としては塩化ロジウム、ヘキサクロロロジウム酸アンモニウム、酢酸ロジウム、及び硝酸ロジウム；ルテニウム塩としては塩化ルテニウム、硝酸ルテニウムニトロシル、及びトリス（アセチルアセトナト）ルテニウム；銀塩としては硝酸銀、及び酢酸銀が使用可能である。 The salt that can be used when rhodium, ruthenium, or silver is supported is not particularly limited as long as it is soluble in a water-soluble or organic solvent like the palladium salt and the platinum salt. For example, rhodium chloride as rhodium chloride, ammonium hexachlororhodate, rhodium acetate, and rhodium nitrate; ruthenium salt as ruthenium chloride, ruthenium nitrosyl nitrate, and tris (acetylacetonato) ruthenium; silver salt as silver nitrate, and silver acetate Can be used.
触媒調製時に使用される溶媒としては、触媒被毒とならないものであり、使用する貴金属塩を溶解するものであれば特に制限されるものではない。例えば、水、メタノール及びその他の低級アルコール（Ｃ２〜Ｃ４）、アセトン、エーテル、ペンタン、ヘキサン、塩化メチル、クロロホルム、ベンゼン等が挙げられる。これらの中でも、水、メタノール及びこれらの混合物が好ましい。溶媒の使用量については、合成吸着剤１グラムに対して３〜30ｍｌ、特に１０ｍｌ程度が好ましいが、担持する塩を十分溶解する量であれば別段制限されるものではない。 The solvent used in preparing the catalyst is not particularly limited as long as it does not cause catalyst poisoning and can dissolve the noble metal salt to be used. For example, water, methanol and other lower alcohols (C2 to C4), acetone, ether, pentane, hexane, methyl chloride, chloroform, benzene and the like can be mentioned. Among these, water, methanol, and a mixture thereof are preferable. The amount of the solvent used is preferably 3 to 30 ml, particularly about 10 ml, with respect to 1 gram of the synthetic adsorbent, but is not particularly limited as long as the amount of the salt to be supported is sufficiently dissolved.
本発明の触媒は、合成吸着剤及び金属塩を溶媒に溶解し、攪拌し、生成した金属／合成吸着剤を濾取し、水及び／又はメタノールで洗浄し、乾燥することにより調製することができる。 The catalyst of the present invention can be prepared by dissolving a synthetic adsorbent and a metal salt in a solvent, stirring, collecting the produced metal / synthetic adsorbent by filtration, washing with water and / or methanol, and drying. it can.
本発明の触媒は、芳香族基に結合したニトロ基（芳香族ニトロ基）と脂肪族基に結合したシアノ基（脂肪族シアノ基）が存在する反応系における該ニトロ基の選択的還元に有用である。該芳香族ニトロ基における芳香族基としては、Ｃ１−Ｃ４アルコキシ基、ハロゲン原子若しくはＣ１−Ｃ４アルキル基で置換されたフェニル基又は非置換のフェニル基が好ましい。該脂肪族シアノ基における脂肪族基としては、炭素数１〜６の脂肪族基、特に炭素数１〜３のアルキル基が好ましい。該脂肪族基はＣ１−Ｃ４アルコキシ基、ハロゲン原子若しくはＣ１−Ｃ４アルキル基で置換されたフェニル基又は非置換のフェニル基のような芳香族基に結合されていてもよい。該芳香族ニトロ基及び該脂肪族シアノ基は、反応系の一分子中に存在しても、或いは別個の分子中に存在してもよい。 The catalyst of the present invention is useful for selective reduction of a nitro group in a reaction system in which a nitro group bonded to an aromatic group (aromatic nitro group) and a cyano group bonded to an aliphatic group (aliphatic cyano group) are present. It is. The aromatic group in the aromatic nitro group is preferably a C1-C4 alkoxy group, a phenyl group substituted with a halogen atom or a C1-C4 alkyl group, or an unsubstituted phenyl group. The aliphatic group in the aliphatic cyano group is preferably an aliphatic group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 3 carbon atoms. The aliphatic group may be bonded to an aromatic group such as a C1-C4 alkoxy group, a phenyl group substituted with a halogen atom or a C1-C4 alkyl group, or an unsubstituted phenyl group. The aromatic nitro group and the aliphatic cyano group may be present in one molecule of the reaction system or in separate molecules.
本発明の選択的還元における溶媒としては、水、又は低級アルコール、例えばメタノール、エタノール等、が好ましく、更に水又はメタノールが好ましく、合成吸着剤の種類によっては特に水が好ましい。溶媒の使用量は、還元すべき化合物（芳香族ニトロ基を有する化合物）を溶解する量であれば特に限定されないが、反応系中の還元すべき化合物１モルに対して10〜10,000ｍｌ、特に1,000ｍｌ程度が好ましい。 As the solvent in the selective reduction of the present invention, water or lower alcohols such as methanol, ethanol, etc. are preferable, water or methanol is more preferable, and water is particularly preferable depending on the kind of the synthetic adsorbent. The amount of the solvent used is not particularly limited as long as it is an amount capable of dissolving the compound to be reduced (a compound having an aromatic nitro group), but it is 10 to 10,000 ml with respect to 1 mol of the compound to be reduced in the reaction system. About 1,000 ml is preferable.
触媒調製法
参考例１
合成吸着剤ダイヤイオンＨＰ20（商品名、スチレン／ジビニルベンゼン共重合体、三菱化学社製、含水品）5ｇ、酢酸パラジウム527mg（パラジウム金属としてＨＰ20乾燥重量に対して10wt％になる様に秤量した）をメタノール50mlに溶解し、室温下、４日間溶液の色が透明になるまで攪拌した。生成したPd担持ＨＰ20（Pd/ＨＰ20）を吸引ろ取し、メタノール、水の順で洗浄し、減圧下乾燥して所定の10wt％Ｐｄ/ＨＰ20触媒を得た。
Catalyst preparation method
Reference example 1
Synthetic adsorbent Diaion HP20 (trade name, styrene / divinylbenzene copolymer, manufactured by Mitsubishi Chemical Co., Ltd., water-containing product) 5 g, palladium acetate 527 mg (weighed as palladium metal to 10 wt% with respect to the dry weight of HP20) Was dissolved in 50 ml of methanol and stirred at room temperature for 4 days until the color of the solution became clear. The produced Pd-supported HP20 (Pd / HP20) was collected by suction filtration, washed with methanol and water in that order, and dried under reduced pressure to obtain a predetermined 10 wt% Pd / HP20 catalyst.
参考例２、実施例１〜２
合成吸着剤ダイヤイオンＨＰ20の代わりに合成吸着剤ダイヤイオンＨＰ2MG（商品名、アクリル酸エステル系共重合体、三菱化学社製）（参考例２）、セパビ−ズSP700（商品名、ジビニルベンゼン重合体、三菱化学社製）（実施例１）、又はセパビ−ズSP850（商品名、スチレン／ジビニルベンゼン共重合体、三菱化学社製）（実施例２）を用いた以外は参考例１と同様にして、各10wt％Ｐｄ触媒を得た。
Reference Example 2, Examples 1-2
Synthetic adsorbent Diaion HP2MG (trade name, acrylate copolymer, manufactured by Mitsubishi Chemical Corporation) ( Reference Example 2) instead of synthetic adsorbent Diaion HP20, Sepaviz SP700 (trade name, divinylbenzene polymer) , manufactured by Mitsubishi Chemical Corporation) (example 1), or Sepabi -'s SP850 (trade name, styrene / divinylbenzene copolymer, except for using the product of Mitsubishi Chemical) (example 2) in the same manner as in reference example 1 Thus, each 10 wt% Pd catalyst was obtained.
比較例１
Ｐｄの担体として、合成吸着剤の代わりに活性炭粉末（和光純薬、中性品）を用いた以外は参考例１と同様にして、10wt％Ｐｄ/Ｃ触媒を得た。
Comparative Example 1
A 10 wt% Pd / C catalyst was obtained in the same manner as in Reference Example 1 except that activated carbon powder (Wako Pure Chemical, Neutral) was used as the Pd carrier instead of the synthetic adsorbent.
芳香族ニトロ基還元活性評価１：
CH3０−C6H4−NO２ → CH3０−C6H4−NH2
触媒15ｍg（0.014mmol）をマグネチックスターラー付きの三口なす形フラスコに入れ、溶媒としてメタノールまたは水1ｍｌを添加し、次に、４−ニトロアニソール0.12ｍｌ（1mmol）を添加し、攪拌しながら窒素ガスによりフラスコ内を20分程度パージした。三口フラスコの一方から水素ガスを導入して、ガラス管を用いて溶液中にバブリングを所定時間行った。所定時間の後にＮＭＲにより反応液の一部を採取し、分析を行った。実施結果を表２に示す。
Aromatic nitro group reducing activity evaluation 1:
CH 3 0-C 6 H 4 -NO 2 → CH 3 0-C 6 H 4 -NH 2
Place 15 mg (0.014 mmol) of catalyst in a three-necked flask equipped with a magnetic stirrer, add 1 ml of methanol or water as a solvent, then add 0.12 ml (1 mmol) of 4-nitroanisole and nitrogen gas with stirring. To purge the flask for about 20 minutes. Hydrogen gas was introduced from one side of the three-necked flask, and bubbling was performed in the solution for a predetermined time using a glass tube. After a predetermined time, a part of the reaction solution was collected by NMR and analyzed. The results are shown in Table 2.
脂肪族シアノ基還元活性評価２：
CH3０−C6H4−CH2-CN → CH3０−C6H4−CH2-CH2−NH2
４−ニトロアニソールの代わりに４−メトキシフェニルアセトニトリルを用いた以外は水素還元活性評価１と同様に評価を実施した。触媒及び反応物質の反応混合比は、モル比で水素還元活性評価１と同一となるようにした。実施結果を表３に示す。
Aliphatic cyano group reduction activity evaluation 2:
CH 3 0-C 6 H 4 -CH 2 -CN → CH 3 0-C 6 H 4 -CH 2 -CH 2 -NH 2
Evaluation was carried out in the same manner as in hydrogen reduction activity evaluation 1 except that 4-methoxyphenylacetonitrile was used instead of 4-nitroanisole. The reaction mixture ratio of the catalyst and the reactants was made to be the same as the hydrogen reduction activity evaluation 1 in terms of molar ratio. The results are shown in Table 3.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006300294A JP4800902B2 (en) | 2006-11-06 | 2006-11-06 | Pd-supported polymer catalyst having selective functional group reduction performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006300294A JP4800902B2 (en) | 2006-11-06 | 2006-11-06 | Pd-supported polymer catalyst having selective functional group reduction performance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008114164A JP2008114164A (en) | 2008-05-22 |
| JP4800902B2 true JP4800902B2 (en) | 2011-10-26 |
Family
ID=39500582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006300294A Expired - Fee Related JP4800902B2 (en) | 2006-11-06 | 2006-11-06 | Pd-supported polymer catalyst having selective functional group reduction performance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4800902B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012128515A2 (en) * | 2011-03-18 | 2012-09-27 | Lg Chem, Ltd. | Polymer supported reagents and methods of reducing aromatic nitro compounds by using the same |
| JP7715542B2 (en) | 2021-06-17 | 2025-07-30 | オルガノ株式会社 | Catalytic hydrogenation reduction method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4313018A (en) * | 1977-04-14 | 1982-01-26 | Western Kentucky University | Heterogeneous catalytic hydrogenation |
| US6235673B1 (en) * | 2000-04-05 | 2001-05-22 | Eastman Chemical Company | Carbonylation catalyst supported on a carbonized polysulfonated divinylbenzene-styrene copolymer |
| US6452043B1 (en) * | 2000-04-05 | 2002-09-17 | Eastman Chemical Company | Carbonylation of lower alkyl alcohols and their derivatives using metals supported on carbonized polysulfonated divinylbenzene-styrene copolymers |
| JP5028707B2 (en) * | 2000-09-22 | 2012-09-19 | 三菱瓦斯化学株式会社 | Method for producing aromatic carboxylic acid |
| JP4497864B2 (en) * | 2003-08-19 | 2010-07-07 | 和光純薬工業株式会社 | Carbon-carbon coupling method using palladium catalyst composition |
| JPWO2006028146A1 (en) * | 2004-09-07 | 2008-05-08 | 和光純薬工業株式会社 | Palladium-immobilized ion exchange resin and reduction method using the same |
-
2006
- 2006-11-06 JP JP2006300294A patent/JP4800902B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008114164A (en) | 2008-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1219733C (en) | Method and catalyst for preparing oxide containing two carbon atoms from synthetic gas | |
| Wan et al. | Asymmetric synthesis of naproxen by a new heterogeneous catalyst | |
| CN103894208B (en) | For the low noble metal catalyst without mercury of acetylene hydrochlorination reaction, its preparation method and application | |
| EP1268061B1 (en) | Carbonylation catalyst supported on a carbonized polysulfonated divinylbenzene-styrene copolymer | |
| Liu et al. | Chelating Bis (N‐Heterocyclic Carbene) Palladium‐Catalyzed Reactions | |
| CN101733162A (en) | Organic metal framework supported palladium, preparation method and application thereof | |
| JP2020511307A (en) | Catalyst for the preparation of 1,5-pentanediol by hydrogenolysis of tetrahydrofurfuryl alcohol, its preparation method and its use | |
| CN106854220B (en) | Preparation and Application of Two Chiral Ligands, Chiral Porous Organic Polymers | |
| WO2006000733A1 (en) | A catalyst and process for the synthesis of c2-oxygenates by the hydrogenation of carbon monoxide | |
| US7601668B2 (en) | Methods for manufacturing bi-metallic catalysts having a controlled crystal face exposure | |
| CN114515604A (en) | Quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst, preparation method and application | |
| JP4519498B2 (en) | Novel polymer-supported transition metal complex having phosphorus-containing α-methylstyrene copolymer as ligand and catalyst comprising the complex | |
| JPH09124543A5 (en) | ||
| JP4800902B2 (en) | Pd-supported polymer catalyst having selective functional group reduction performance | |
| Ganina et al. | Cu-MOF-catalyzed carboxylation of alkynes and epoxides | |
| JP2019141838A (en) | Noble metal catalyst, reduction method and method for producing compound | |
| CA2651369A1 (en) | Process for producing hydrogen peroxide | |
| JP5664030B2 (en) | Defluorination method for fluorine-containing compounds | |
| JP5013173B2 (en) | Organometallic complex, occlusion material and catalyst using the same | |
| CA2740074C (en) | Polymer bound solid metal complex catalyst for hydrogen reforming from formic acid | |
| Marshall et al. | Asymmetric Rh diene catalysis under confinement: isoxazole ring‐contraction in mesoporous solids | |
| CN114524719A (en) | Method for preparing acetaldehyde, ethanol and ethyl acetate by methanol reduction carbonylation | |
| CN114797974B (en) | Eggshell catalyst, preparation method thereof and propylene hydroformylation reaction application | |
| Hamdi et al. | Ambient Pressure Ir@ Hal-Catalyzed Hydrogenation of Aryl Aldehydes, Ketones, and Phenol | |
| KR100834963B1 (en) | Metal-doped sulfonated cation exchange resin catalyst and preparation method of methyl isobutyl ketone using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090701 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20090701 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110126 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110201 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20110322 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20110325 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110422 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20110422 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110705 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110708 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110726 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110804 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140812 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4800902 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |