JP4998889B2 - ニトロ基還元用触媒 - Google Patents
ニトロ基還元用触媒 Download PDFInfo
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- JP4998889B2 JP4998889B2 JP2008028303A JP2008028303A JP4998889B2 JP 4998889 B2 JP4998889 B2 JP 4998889B2 JP 2008028303 A JP2008028303 A JP 2008028303A JP 2008028303 A JP2008028303 A JP 2008028303A JP 4998889 B2 JP4998889 B2 JP 4998889B2
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- Prior art keywords
- rhodium
- complex
- iron
- dendrimer
- amidoamine
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- 239000003054 catalyst Substances 0.000 title claims description 53
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 title claims description 25
- 239000010948 rhodium Substances 0.000 claims description 161
- 229910052703 rhodium Inorganic materials 0.000 claims description 136
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 133
- 239000000412 dendrimer Substances 0.000 claims description 93
- 229920000736 dendritic polymer Polymers 0.000 claims description 90
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 85
- 239000002105 nanoparticle Substances 0.000 claims description 65
- 229910052742 iron Inorganic materials 0.000 claims description 37
- 238000006722 reduction reaction Methods 0.000 claims description 37
- 150000004698 iron complex Chemical class 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 18
- 150000003512 tertiary amines Chemical class 0.000 claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 150000002828 nitro derivatives Chemical class 0.000 claims description 12
- 125000000962 organic group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000000536 complexating effect Effects 0.000 claims description 7
- 150000003283 rhodium Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229920000962 poly(amidoamine) Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 150000004696 coordination complex Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- -1 hydroxyethyl group Chemical group 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000009918 complex formation Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- LZXXNPOYQCLXRS-UHFFFAOYSA-N methyl 4-aminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1 LZXXNPOYQCLXRS-UHFFFAOYSA-N 0.000 description 1
- YOJAHJGBFDPSDI-UHFFFAOYSA-N methyl 4-nitrobenzoate Chemical compound COC(=O)C1=CC=C([N+]([O-])=O)C=C1 YOJAHJGBFDPSDI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
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
また、アミドアミンデンドリマー・ロジウム/鉄錯体から調製されるロジウム/鉄ナノ微粒子は水素化反応においても極めて高い触媒活性を有しており、安定かつ安価な水素化反応用触媒として有用である。
例1
反応は全て窒素雰囲気下で遮光して行った。式(II)で表されるPAMAM G4-OH(0.500 g、3.50 mmol、10%メタノール溶液)の溶媒を留去し, 残留物を蒸留水(4 mL)に溶解した。この水溶液に2 mLの蒸留水に溶解した塩化ロジウム(III)三水和物(0.0550 g、210 mmol, デンドリマーに対して60当量、これはデンドリマー中の全3級アミンのモル当量に相当する)を加えて真空ポンプにより溶液の脱気を行った。30分撹拌した後、この溶液に水素化ホウ素ナトリウム(0.0397 g、1050 mmol、ロジウムに対して5当量)のメタノール溶液(2 mL)を滴下した。この溶液を終夜よく撹拌してデンドリマー内部にナノサイズの金属ロジウムを保持したロジウムナノ微粒子(PAMAM G4-OH-Rh)の分散液を得た。
反応は全て窒素雰囲気下で遮光して行った。PAMAM G4-OH(0.500 g、3.50 mmol、10%メタノール溶液)の溶媒を留去し、残留物を蒸留水(4 mL)に溶解した。この水溶液に1 mLの蒸留水に溶解した塩化鉄(III)の六水和物(0.0265 g、98.0 mmol、デンドリマーに対して28当量)を加え、真空ポンプにより溶液の脱気を行った。30分撹拌した後、1 mLの蒸留水に溶解した塩化ロジウム(III)三水和物(0.0295 g、112 mmol、デンドリマーに対して32当量)を加えた。溶液をさらに30分撹拌し、水素化ホウ素ナトリウム(0.0397 g、1050 mmol、鉄とロジウムの合計に対して5当量)のメタノール溶液(2 mL)を滴下した。この溶液を終夜よく撹拌してデンドリマー内部にナノサイズの金属ロジウム/鉄を保持したロジウム/鉄ナノ微粒子(PAMAM G4-OH-Rh/Fe)の分散液を得た。このデンドリマー内部に保持された金属ロジウム/鉄粒子を透過型電子顕微鏡(TEM)により観察したところ粒径1.2±0.2 nmの均一な粒子であった。
例1で得た本発明のロジウムナノ微粒子(PAMAM G4-OH-Rh)を用いてニトロ基の還元反応を以下の方法に従って行った。全ての反応を遮光及び室温下に1気圧の水素雰囲気下で行った。よく乾燥させた磁気撹拌子を入れたシュレンクを窒素ガスにより置換した。ニトロ化合物(0.7 mmol)のメタノール溶液(5 mL)をこのシュレンクに導入し、本発明のロジウムナノ微粒子又はロジウム/鉄ナノ微粒子(ニトロ化合物に対して0.3 mol%の金属を含む)の分散液を加えた。水素ガスを風船から供給し、溶液をよく撹拌して還元反応を進行させた。反応の追跡は反応液を一部採取してGC-MSを測定することにより行った。比較のためフェニルアゾメチンデンドリマーロジウム錯体を還元して得られるロジウムナノ微粒子(TPP-DPA G4-Rh)を触媒として用いて同様の反応を行った。結果を図1〜5に示す。いずれの反応においても本発明の触媒はTPP-DPA G4-Rhに比べて顕著に高い触媒活性を有しており、ニトロ基の還元において極めて高活性な触媒として使用できることが示された。
例2で得た本発明のロジウム/鉄ナノ微粒子(PAMAM G4-OH-Rh/Fe)を用いてオレフィンの還元及びニトロ基の還元を行った。ニトロ基の還元反応は上記例3と同様に行い、オレフィンの還元では基質の物質量を1.75 mmolとしてニトロ基の還元の場合と同様に反応を行った。結果を図6及び7に示す。本発明のロジウム/鉄ナノ微粒子(PAMAM G4-OH-Rh/Fe)はオレフィンの水素化反応及びニトロ基の還元反応のいずれにおいても極めて高活性であり、オレフィンの水素化反応においてフェニルアゾメチンデンドリマーロジウム錯体を還元して得られるロジウムナノ微粒子(TPP-DPA G4-Rh)を触媒として用いる場合と同等の触媒活性を有することが示された。
Claims (10)
- ニトロ基の還元用触媒であって、下記の一般式(I):
- nが4であり、x、y、及びzが2であり、mが4であり、R2及びR3がそれぞれ独立に水酸基を有する1価の有機基である請求項1に記載の触媒。
- アミドアミンデンドリマーが下記の式(II):
- アミドアミンデンドリマー・ロジウム錯体がアミドアミンデンドリマーに含まれる3級アミンのうち実質的に全ての3級アミンにおいてロジウム錯体と錯形成したアミドアミンデンドリマー・ロジウム錯体である請求項1ないし3のいずれか1項に記載の触媒。
- アミドアミンデンドリマー・ロジウム/鉄錯体がアミドアミンデンドリマーに含まれる3級アミンのうち実質的に全ての3級アミンにおいてロジウム錯体又は鉄錯体と錯形成したアミドアミンデンドリマー・ロジウム/鉄錯体である請求項1ないし3のいずれか1項に記載の触媒。
- ニトロ基の還元方法であって、請求項1ないし5のいずれか1項に記載の触媒の存在下でニトロ化合物と水素ガスとを接触させる工程を含む方法。
- 請求項1に記載のアミドアミンデンドリマーとロジウム錯体及び鉄錯体とが錯形成したアミドアミンデンドリマー・ロジウム/鉄錯体。
- 請求項7に記載のアミドアミンデンドリマー・ロジウム/鉄錯体を還元することにより得ることができるロジウム/鉄ナノ微粒子。
- 請求項8に記載のロジウム/鉄ナノ微粒子を含む還元用触媒。
- 還元反応が水素化反応又はニトロ基の還元反応である請求項9に記載の触媒。
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JP4998889B2 true JP4998889B2 (ja) | 2012-08-15 |
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