JP2008062215A - Magnetic particle-involved ruthenium catalyst - Google Patents
Magnetic particle-involved ruthenium catalyst Download PDFInfo
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- JP2008062215A JP2008062215A JP2006245578A JP2006245578A JP2008062215A JP 2008062215 A JP2008062215 A JP 2008062215A JP 2006245578 A JP2006245578 A JP 2006245578A JP 2006245578 A JP2006245578 A JP 2006245578A JP 2008062215 A JP2008062215 A JP 2008062215A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 43
- 230000005291 magnetic effect Effects 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000006249 magnetic particle Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 150000002576 ketones Chemical class 0.000 claims abstract description 11
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- -1 aldehyde compound Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 8
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 8
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052586 apatite Inorganic materials 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 10
- 150000001299 aldehydes Chemical class 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 27
- 229910001566 austenite Inorganic materials 0.000 description 25
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 235000019445 benzyl alcohol Nutrition 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- QYIXCDOBOSTCEI-QCYZZNICSA-N (5alpha)-cholestan-3beta-ol Chemical compound C([C@@H]1CC2)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCCC(C)C)[C@@]2(C)CC1 QYIXCDOBOSTCEI-QCYZZNICSA-N 0.000 description 1
- CHUAMRVJSRBRHT-UHFFFAOYSA-N 3,5-bis(phenylmethoxy)benzaldehyde Chemical compound C=1C(OCC=2C=CC=CC=2)=CC(C=O)=CC=1OCC1=CC=CC=C1 CHUAMRVJSRBRHT-UHFFFAOYSA-N 0.000 description 1
- PESKGJQREUXSRR-UXIWKSIVSA-N 5alpha-cholestan-3-one Chemical compound C([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCCC(C)C)[C@@]2(C)CC1 PESKGJQREUXSRR-UXIWKSIVSA-N 0.000 description 1
- PESKGJQREUXSRR-UHFFFAOYSA-N 5beta-cholestanone Natural products C1CC2CC(=O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 PESKGJQREUXSRR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- MHHXKZKHZMSINU-UHFFFAOYSA-N [3,5-bis(phenylmethoxy)phenyl]methanol Chemical compound C=1C(OCC=2C=CC=CC=2)=CC(CO)=CC=1OCC1=CC=CC=C1 MHHXKZKHZMSINU-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QYIXCDOBOSTCEI-UHFFFAOYSA-N alpha-cholestanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 QYIXCDOBOSTCEI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002902 ferrimagnetic material Substances 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- SBZZSNLTVKKWRQ-UHFFFAOYSA-K iron(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[Fe](Cl)Cl SBZZSNLTVKKWRQ-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N trifluorotoluene Substances FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 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
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、磁性粒子を内包し且つリン酸基を有する担体にルテニウムが担持されてなる、ルテニウム担持組成物、該組成物の製造方法、該組成物からなるルテニウム触媒、該触媒を用いたケトン又はアルデヒドの製造方法に関する。 The present invention relates to a ruthenium-carrying composition in which ruthenium is carried on a carrier encapsulating magnetic particles and having a phosphate group, a method for producing the composition, a ruthenium catalyst comprising the composition, and a ketone using the catalyst Alternatively, it relates to a method for producing an aldehyde.
ルテニウムは、水素化反応、酸化反応、脱水素反応等の触媒として、有用なものの一つとして知られている。現在、そのルテニウムを用いた触媒として、ハイドロキシアパタイト等のリン酸配位子にルテニウムを配位させた触媒が知られている（特開2001-246262号）。該触媒は、繰り返し使用することができ、選択的な酸化反応に用いることができるものであるが、その一方で、反応効率が良くないという問題点を有していた。
本発明は上記状況に鑑み、反応効率の高い、高選択性の酸化能を有するルテニウム触媒の提供を課題とする。また、本発明は、従来のルテニウム触媒よりもより簡便に回収でき、再利用しやすい触媒の提供も課題とする。 In view of the above circumstances, an object of the present invention is to provide a ruthenium catalyst having high reaction efficiency and high selectivity for oxidation. Another object of the present invention is to provide a catalyst that can be recovered more easily than a conventional ruthenium catalyst and is easy to reuse.
本発明は、磁性粒子を内包し且つリン酸基を有する担体にルテニウムが担持されてなるルテニウム担持組成物、磁性粒子を内包し且つリン酸基を有する担体に、ルテニウム化合物を接触させることを特徴とする前記組成物の製造方法、前記組成物を含んでなるルテニウム触媒、該触媒の存在下、酸素とアルコールとを接触させることを特徴とするケトン又はアルデヒドの製造方法に関する。 The present invention is a ruthenium-carrying composition in which ruthenium is supported on a carrier having phosphoric acid groups encapsulating magnetic particles, and a ruthenium compound in contact with a carrier enclosing magnetic particles and having phosphoric acid groups. The present invention relates to a method for producing the composition, a ruthenium catalyst comprising the composition, and a method for producing a ketone or aldehyde, wherein oxygen and alcohol are contacted in the presence of the catalyst.
すなわち、本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、磁性粒子を内包し且つリン酸基を有する担体にルテニウムが担持されたルテニウム担持組成物を触媒として例えばアルコール等に用いると、高効率に反応させることが可能となることを見出し、本発明を完成するに至った。 That is, as a result of intensive studies to solve the above problems, the present inventors have used a ruthenium-carrying composition in which ruthenium is carried on a carrier containing a magnetic particle and having a phosphate group as a catalyst, for example, alcohol or the like. As a result, it was found that the reaction can be carried out with high efficiency, and the present invention has been completed.
本発明のルテニウム担持組成物及びルテニウム触媒は、従来の触媒と比較して高効率な触媒作用、特に高効率な酸化反応性を有しており、これを用いれば、反応時間の短縮や少量の触媒で多量の生成物を得ることが可能となる。また、該組成物及び触媒は、それ自身が磁性体であるため、鉄等の磁化磁性体を用いることにより容易に回収することができるので、簡便な操作での回収を可能とする。更に、回収後の再利用に於いてもその触媒活性が低下しない有用なものでもある。そして、該組成物及び触媒を、アルコールの酸化反応に用いれば、そのアルコールに対応するケトン化合物、アルデヒド化合物を高効率に製造し得る。 The ruthenium-supporting composition and the ruthenium catalyst of the present invention have a high-efficiency catalytic action, particularly high-efficiency oxidation reactivity, compared to conventional catalysts. A large amount of product can be obtained with the catalyst. Moreover, since the composition and the catalyst are themselves magnetic materials, they can be easily recovered by using a magnetized magnetic material such as iron, so that they can be recovered by a simple operation. Further, it is useful in that its catalytic activity does not decrease even after reuse after recovery. And if this composition and a catalyst are used for the oxidation reaction of alcohol, the ketone compound and aldehyde compound corresponding to the alcohol can be manufactured with high efficiency.
本発明に係る磁性粒子としては、磁性を帯びることができる磁性体に由来するものであれば特に限定はされないが、具体的には鉄、ニッケル、コバルト、マンガン、クロム等の鉄族の遷移金属を含有する磁性体に由来するものが挙げられ、中でも鉄を含有する磁性体に由来するものが好ましい。鉄を含有する磁性体としては、マグネタイト（Fe3O4）、マグヘマイト（γ-Fe2O3）等のフェリ磁性体が挙げられるが、中でもマグヘマイトが好ましい。該磁性粒子の粒径としては、通常1nm〜10μm以下、好ましくは1〜100nm、より好ましくは1〜10nmである。 The magnetic particles according to the present invention are not particularly limited as long as they are derived from a magnetic substance capable of being magnetized, and specifically, iron group transition metals such as iron, nickel, cobalt, manganese, and chromium. The thing derived from the magnetic body containing this is mentioned, Especially the thing derived from the magnetic body containing iron is preferable. Examples of the iron-containing magnetic material include ferrimagnetic materials such as magnetite (Fe 3 O 4 ) and maghemite (γ-Fe 2 O 3 ). Among these, maghemite is preferable. The particle size of the magnetic particles is usually 1 nm to 10 μm or less, preferably 1 to 100 nm, more preferably 1 to 10 nm.
本発明に係るルテニウムとしては、この分野で用いられているものであれば全て含まれるが、Ru(III)、Ru(IV)、Ru(VIII)由来のものが好ましい。Ru(III)由来の化合物としては、塩化ルテニウム、硝酸ルテニウム等が挙げられ、Ru(IV)由来の化合物としては、酸化ルテニウム等が挙げられ、Ru(VIII)由来の化合物としては、テトラオキソルテニウム酸塩等が挙げられるが、これらの中でもRu(III)由来の化合物が好ましく、その中でも塩化ルテニウム由来のものが好ましい。 The ruthenium according to the present invention includes all those used in this field, but those derived from Ru (III), Ru (IV), and Ru (VIII) are preferred. Ru (III) -derived compounds include ruthenium chloride, ruthenium nitrate and the like, Ru (IV) -derived compounds include ruthenium oxide and the like, and Ru (VIII) -derived compounds include tetraoxoruthenium. Of these, compounds derived from Ru (III) are preferred, and those derived from ruthenium chloride are preferred.
本発明に係る、磁性粒子を内包し且つリン酸基を有する担体（以下、本発明に係る担体と略記する場合がある）としては、上記磁性粒子がその内部に存在し且つその表面にリン酸基を有するものであれば特に限定されないが、具体的にはアパタイト等のリン酸基を有する化合物の内部に磁性粒子を内包させたもの等が挙げられる。アパタイトの具体例としては、フッ素アパタイト、塩化アパタイト、ハイドロキシアパタイト、炭酸アパタイト、シリカアパタイト等が挙げられるが、中でもハイドロキシアパタイトが好ましい。ハイドロキシアパタイトの中でも、Ca10-Z(HPO4)Z(PO4)6-Z(OH)2-Z（但し、０＜Z≦１，1.50≦Ca/P＜1.67）で表されるものが特に好ましい。上記本発明に係る担体中の磁性粒子の量は、本発明に係る担体１g中通常１〜500mg、好ましくは10〜100mg、より好ましくは20〜100mgである。 The carrier encapsulating magnetic particles and having a phosphate group according to the present invention (hereinafter sometimes abbreviated as the carrier according to the present invention) includes the above-mentioned magnetic particles in the interior and phosphoric acid on the surface thereof. Although it will not specifically limit if it has a group, Specifically, what encapsulated the magnetic particle inside the compound which has phosphate groups, such as apatite, etc. are mentioned. Specific examples of apatite include fluorapatite, chlorinated apatite, hydroxyapatite, carbonate apatite, silica apatite, etc. Among them, hydroxyapatite is preferable. Among the hydroxyapatites, those represented by Ca 10-Z (HPO 4 ) Z (PO 4 ) 6-Z (OH) 2-Z (however, 0 <Z ≦ 1,1.50 ≦ Ca / P <1.67) Particularly preferred. The amount of the magnetic particles in the carrier according to the present invention is usually 1 to 500 mg, preferably 10 to 100 mg, more preferably 20 to 100 mg per 1 g of the carrier according to the present invention.
本発明に係る担体は、リン酸基を有する化合物の内部に磁性粒子を内包させる等の方法により製造されればよく、例えば、リン酸基を有する化合物を合成する際、その系内に磁性粒子を共存させ合成することにより磁性粒子を化合物中に内包させる方法が好ましい。 The carrier according to the present invention may be produced by a method such as encapsulating magnetic particles in a compound having a phosphate group. For example, when synthesizing a compound having a phosphate group, the magnetic particles are contained in the system. A method in which the magnetic particles are encapsulated in the compound by synthesizing them with each other is preferred.
本発明に係る担体を製造する際に用いられる磁性粒子の量は、得られる本発明に係る担体中の磁性粒子の量が、上記の範囲となるように適宜選択されるが、具体的には、本発明に係る担体１ｇ中に通常１〜500mg、好ましくは10〜100mg、より好ましくは20〜100mg添加すればよい。また、上記反応に用いられる反応溶媒としては、メタノール、エタノール、水等が挙げられるが、水が特に好ましい。反応温度は、80〜100℃、好ましくは90〜100℃であり、反応時間は、通常１〜５時間、好ましくは２〜３時間である。
具体的には例えば、ハイドロキシアパタイト中に磁性粒子を内包させる場合には、リン酸水素二アンモニウム、硝酸カルシウム及びマグネタイトを混合反応させ、乾燥、加熱することにより、本発明に係る担体を得ることができる。より詳細に説明すると、以下の如く製造される。
The amount of the magnetic particles used in producing the carrier according to the present invention is appropriately selected so that the amount of the magnetic particles in the obtained carrier according to the present invention falls within the above range. Specifically, In general, 1 to 500 mg, preferably 10 to 100 mg, more preferably 20 to 100 mg may be added to 1 g of the carrier according to the present invention. Moreover, as a reaction solvent used for the said reaction, methanol, ethanol, water, etc. are mentioned, However, Water is especially preferable. The reaction temperature is 80 to 100 ° C., preferably 90 to 100 ° C., and the reaction time is usually 1 to 5 hours, preferably 2 to 3 hours.
Specifically, for example, when magnetic particles are encapsulated in hydroxyapatite, the carrier according to the present invention can be obtained by mixing and reacting diammonium hydrogen phosphate, calcium nitrate and magnetite, drying and heating. it can. If it demonstrates in detail, it will manufacture as follows.
即ち、例えば硝酸カルシウム４水和物とリン酸水素ニアンモニウムとをモル比で５：３となるように混合する。一方で、硝酸カルシウム１molに対して三塩化鉄0.01〜0.5mol、好ましくは0.01〜0.1mol、より好ましくは0.05〜0.1mol、及び硝酸カルシウム１molに対してニ塩化鉄0.005〜0.25mol、好ましくは0.005〜0.05mol、より好ましくは0.025〜0.05molを用い、これら二塩化鉄及び三塩化鉄の混合液を塩基性にして反応させることによりマグネタイトを生成する。該マグネタイトに上記硝酸カルシウム４水和物とリン酸水素二アンモニウムの水溶液を、それぞれ添加し、80〜100℃、好ましくは90〜100℃で通常1〜5時間、好ましくは2〜3時間反応させ、必要であれば更に室温で一晩反応させる。尚、この際の溶媒としては水等が挙げられるが、塩基性であることが好ましく、pH11以上の溶媒がより好ましく、塩基性とする方法としては、例えば通常この分野でなされているような、アンモニア水等を添加する等によりなされればよい。このようにして得られた反応物を濾取、乾燥し、粉砕することにより、本発明に係る担体を得ることができる。尚、濾取、乾燥は通常この分野でなされている方法に基づいてなされればよいが、乾燥は真空乾燥により行うのが好ましく、乾燥時間は１〜20時間、好ましくは5〜10時間である。粉砕後、更に加熱（焼成）すると、マグネタイト（Fe3O4）として担持されている磁性粒子がマグヘマイト（γ-Fe2O3）となるので、より好ましい本発明に係る担体を得ることができる。尚、この際の温度は通常100〜300℃であり、好ましくは200〜300℃であり、加熱時間は通常１〜10時間、好ましくは１〜５時間である。 That is, for example, calcium nitrate tetrahydrate and diammonium hydrogen phosphate are mixed at a molar ratio of 5: 3. On the other hand, iron trichloride 0.01-0.5 mol, preferably 0.01-0.1 mol, more preferably 0.05-0.1 mol, and iron dichloride 0.005-0.25 mol, preferably 0.005, per 1 mol of calcium nitrate. Magnetite is produced by reacting a mixed solution of iron dichloride and iron trichloride with a basic amount of ˜0.05 mol, more preferably 0.025 to 0.05 mol. The magnetite is added with the aqueous solution of calcium nitrate tetrahydrate and diammonium hydrogen phosphate, respectively, and reacted at 80 to 100 ° C., preferably 90 to 100 ° C. for 1 to 5 hours, preferably 2 to 3 hours. If necessary, react overnight at room temperature. In addition, the solvent in this case includes water and the like, but is preferably basic, more preferably a solvent having a pH of 11 or more, and a basic method is, for example, usually performed in this field, What is necessary is just to make by adding ammonia water etc. The carrier according to the present invention can be obtained by collecting the reaction product thus obtained by filtration, drying and grinding. In addition, filtration and drying may be performed based on a method usually used in this field, but drying is preferably performed by vacuum drying, and the drying time is 1 to 20 hours, preferably 5 to 10 hours. . When the powder is further heated (baked) after pulverization, the magnetic particles supported as magnetite (Fe 3 O 4 ) become maghemite (γ-Fe 2 O 3 ), so that a more preferable carrier according to the present invention can be obtained. . In addition, the temperature in this case is 100-300 degreeC normally, Preferably it is 200-300 degreeC, and heating time is 1 to 10 hours normally, Preferably it is 1 to 5 hours.
本発明のルテニウム担持組成物は、上記本発明に係る担体にルテニウムが担持されているものであればよいが、本発明に係る担体上のリン酸基とルテニウムが化学結合により結合しているものが特に好ましい。該化学結合としては、配位結合、イオン結合、共有結合等が挙げられるが、中でもイオン結合が好ましい。本発明のルテニウム担持組成物中のルテニウムの量は、ルテニウムの効果を奏する量であればよいが、通常本発明のルテニウム担持組成物１ｇ中に0.01〜1mmol、好ましくは0.05〜0.5mmol、より好ましくは0.1〜0.5mmol担持されればよい。 The ruthenium-carrying composition of the present invention may be any composition as long as ruthenium is supported on the carrier according to the present invention, but the phosphate group on the carrier according to the present invention and ruthenium are bonded by a chemical bond. Is particularly preferred. Examples of the chemical bond include a coordination bond, an ionic bond, a covalent bond, and the like, and among them, an ionic bond is preferable. The amount of ruthenium in the ruthenium-carrying composition of the present invention may be an amount exhibiting the effect of ruthenium, but is usually 0.01 to 1 mmol, preferably 0.05 to 0.5 mmol, more preferably 1 g of the ruthenium-carrying composition of the present invention. May be carried by 0.1 to 0.5 mmol.
本発明のルテニウム担持組成物は、本発明に係る担体にルテニウムを担持させることにより製造されるが、具体的には例えば上記のように得た本発明に係る担体とルテニウム化合物とを接触させ、リン酸基にルテニウムを配位させることにより製造することができる。 The ruthenium-carrying composition of the present invention is produced by loading ruthenium on the carrier according to the present invention. Specifically, for example, the carrier according to the present invention obtained as described above and a ruthenium compound are contacted, It can be produced by coordinating ruthenium to a phosphate group.
本発明のルテニウム担持組成物を製造する際に用いられるルテニウム化合物の量は、本発明に係る担体1gに対して通常0.01〜1mmol、好ましくは0.05〜0.5mmol、より好ましくは0.1〜0.5mmolである。また、その際の反応溶媒は水が挙げられる。また、反応温度は、通常10〜30℃、好ましくは20〜30℃であり、反応時間は通常１〜10時間、好ましくは１〜５時間である。 The amount of the ruthenium compound used in producing the ruthenium-carrying composition of the present invention is usually 0.01 to 1 mmol, preferably 0.05 to 0.5 mmol, more preferably 0.1 to 0.5 mmol with respect to 1 g of the carrier according to the present invention. . Moreover, the reaction solvent in that case is water. Moreover, reaction temperature is 10-30 degreeC normally, Preferably it is 20-30 degreeC, and reaction time is 1 to 10 hours normally, Preferably it is 1 to 5 hours.
本発明のルテニウム担持組成物は、具体的には以下のようにして製造される。 Specifically, the ruthenium-supporting composition of the present invention is produced as follows.
即ち、上記の如くして得られた本発明に係る担体を水に添加し、本発明に係る担体１ｇに対して通常0.01〜1mmol、好ましくは0.05〜0.5mmol、より好ましくは0.1〜0.5mmolのルテニウム化合物又は該化合物含有水溶液を添加し、室温で通常１〜５時間、好ましくは２〜４時間反応させ、得られた反応物を濾取、乾燥し、粉砕することにより、本発明のルテニウム担持組成物を得ることができる。尚、濾取、乾燥は通常この分野でなされている方法に基づいてなされればよいが、乾燥は真空乾燥により行うのが好ましく、乾燥時間は１〜20時間、好ましくは５〜10時間である。
上記の如き本発明のルテニウム担持組成物は、磁性粒子を内包し且つリン酸基を有する担体にルテニウムを担持させることにより、従来知られているルテニウム触媒と比較して非常に高い効率で酸化反応を行うことができるものである。このような効果は本発明者らが初めて見出したものである。
That is, the carrier according to the present invention obtained as described above is added to water, and is usually 0.01 to 1 mmol, preferably 0.05 to 0.5 mmol, more preferably 0.1 to 0.5 mmol with respect to 1 g of the carrier according to the present invention. A ruthenium compound or an aqueous solution containing the compound is added and reacted at room temperature for usually 1 to 5 hours, preferably 2 to 4 hours. The obtained reaction product is collected by filtration, dried and pulverized, thereby supporting the ruthenium support of the present invention. A composition can be obtained. It should be noted that the filtration and drying may be performed based on a method usually used in this field, but the drying is preferably performed by vacuum drying, and the drying time is 1 to 20 hours, preferably 5 to 10 hours. .
The ruthenium-carrying composition of the present invention as described above has an oxidation reaction with a very high efficiency as compared with a conventionally known ruthenium catalyst by carrying ruthenium on a carrier encapsulating magnetic particles and having a phosphate group. Is something that can be done. Such an effect was first found by the present inventors.
本発明のルテニウム担持触媒は、前記本発明のルテニウム担持組成物を含有するものであれば特に限定されず、特に酸化反応に有用なものとして用いることができる触媒である。 The ruthenium-supported catalyst of the present invention is not particularly limited as long as it contains the ruthenium-supported composition of the present invention, and is a catalyst that can be particularly used as a useful catalyst for oxidation reactions.
本発明のルテニウム担持触媒を用いることで、その酸化反応により、アルコールから対応するケトン又はアルデヒド化合物を効率よく製造することができる。ここで用いられるアルコールは通常この分野で用いられるアルコール並びにヒドロキシル基を有する化合物であれば特に限定されず、本願発明のルテニウム担持触媒は、分子内の嵩高い置換基等の影響により反応性が低下したヒドロキシル基であっても酸化し、ケトン又はアルデヒドとすることができる。尚、以下このようなヒドロキシル基を「立体障害のあるヒドロキシル基」と略記する場合がある。 By using the ruthenium-supported catalyst of the present invention, the corresponding ketone or aldehyde compound can be efficiently produced from the alcohol by the oxidation reaction. The alcohol used here is not particularly limited as long as it is an alcohol usually used in this field and a compound having a hydroxyl group. The ruthenium-supported catalyst of the present invention has reduced reactivity due to the influence of bulky substituents in the molecule. Even hydroxyl groups that have been oxidized can be oxidized to ketones or aldehydes. Hereinafter, such a hydroxyl group may be abbreviated as “a hydroxyl group having steric hindrance”.
該ケトン又はアルデヒド化合物の製造方法としては、自体公知の方法に準じたものが挙げられ、例えば、本発明のルテニウム担持触媒存在下で、酸素とアルコールとを接触させる方法が好ましいものとして挙げられる。 Examples of the method for producing the ketone or aldehyde compound include those according to a method known per se. For example, a method in which oxygen and alcohol are brought into contact in the presence of the ruthenium-supported catalyst of the present invention is preferable.
ケトン又はアルデヒド化合物の製造方法における本発明のルテニウム担持触媒の使用量としては、アルコール1molに対してルテニウム担持触媒中のルテニウムの量として通常0.1〜100mmol、好ましくは0.1〜10mmol、より好ましくは1〜10mmol存在させるようにすればよい。また、この際、酸素は、通常1〜10気圧、好ましくは5〜10気圧で存在させればよいが、酸素気流下で反応させるのが好ましく、その場合には、10〜100ml/min、好ましくは50〜100ml/minで酸素を流すとよい。上記反応時の溶媒としては、例えばジクロロメタン、ベンゼン、アセトニトリル、酢酸エチル、トルエン等が挙げられるが、中でも、ジクロロメタン、ベンゼン、トルエン等が好ましい。その反応温度は、通常10〜100℃、好ましくは50〜100℃、より好ましくは90〜100℃であり、その反応時間は、通常１〜24時間、好ましくは1〜10時間、好ましくは1〜2時間である。本発明のケトン又はアルデヒド化合物の製造方法を用いれば、温度が低くても目的物を効率よく製造することができるが、温度を高くすることにより又は気圧を高くすることにより、更に高効率での製造が可能となる。
本発明のケトン又はアルデヒド化合物の製造方法は、具体的には、以下のようになされる。即ち、アルコールと、本発明のルテニウム担持触媒のトルエン懸濁液を、通常1〜10気圧、好ましくは5〜10気圧の酸素存在下、好ましくは通常10〜100ml/min、好ましくは50〜100ml/minの酸素気流下で、通常50〜100℃、より好ましくは90〜100℃で通常１〜3時間、好ましくは1〜2時間反応させることによりなされる。尚、ここで用いられる本発明のルテニウム担持触媒の量は、基質であるアルコールのmol数に基づいて上記本発明のルテニウム担持触媒の好ましい使用範囲から適宜選択して決定すればよい。これにより、アルコール中のヒドロキシル基は酸化され、ケトン又はアルデヒドとなる。
The amount of the ruthenium-supported catalyst of the present invention used in the method for producing a ketone or aldehyde compound is usually 0.1 to 100 mmol, preferably 0.1 to 10 mmol, more preferably 1 to 1 in terms of the amount of ruthenium in the ruthenium-supported catalyst with respect to 1 mol of alcohol. 10 mmol should be present. In this case, oxygen may be usually present at 1 to 10 atm, preferably 5 to 10 atm. However, the reaction is preferably carried out under an oxygen stream, and in that case, 10 to 100 ml / min, preferably Should flow oxygen at 50-100ml / min. Examples of the solvent for the above reaction include dichloromethane, benzene, acetonitrile, ethyl acetate, toluene and the like, among which dichloromethane, benzene, toluene and the like are preferable. The reaction temperature is usually 10 to 100 ° C., preferably 50 to 100 ° C., more preferably 90 to 100 ° C., and the reaction time is usually 1 to 24 hours, preferably 1 to 10 hours, preferably 1 to 2 hours. If the method for producing a ketone or aldehyde compound of the present invention is used, the target product can be produced efficiently even at a low temperature. However, by increasing the temperature or increasing the atmospheric pressure, the efficiency can be further increased. Manufacture is possible.
The production method of the ketone or aldehyde compound of the present invention is specifically performed as follows. That is, the toluene suspension of the alcohol and the ruthenium-supported catalyst of the present invention is usually 1 to 10 atmospheres, preferably 5 to 10 atmospheres of oxygen, preferably 10 to 100 ml / min, preferably 50 to 100 ml / min. The reaction is usually performed at 50 to 100 ° C., more preferably 90 to 100 ° C. for 1 to 3 hours, preferably 1 to 2 hours in a min oxygen stream. The amount of the ruthenium-supported catalyst of the present invention used here may be appropriately selected and determined from the preferred range of use of the ruthenium-supported catalyst of the present invention based on the number of moles of alcohol as a substrate. Thereby, the hydroxyl group in alcohol is oxidized and becomes a ketone or an aldehyde.
本発明の触媒は、反応後洗浄することにより繰り返し再利用することができる。具体的には、例えば、鉄、ニッケル、コバルト、マンガン、クロム等の磁化磁性体を用いて本発明の触媒がビーカー等の容器に残るようにして反応溶液を取り除き、その後反応で用いた反応溶媒で洗浄し、要すれば更にイオン交換水等で洗浄することにより、再利用できるようになる。このような処理を行うことにより、本発明の触媒は繰り返し使用することができ、その触媒効果は、繰り返し使用しても低下しない。 The catalyst of the present invention can be reused repeatedly by washing after the reaction. Specifically, for example, the reaction solution is removed by using a magnetized magnetic material such as iron, nickel, cobalt, manganese, and chromium so that the catalyst of the present invention remains in a container such as a beaker, and then the reaction solvent used in the reaction. It can be reused by washing with ion exchange water if necessary. By performing such treatment, the catalyst of the present invention can be used repeatedly, and the catalytic effect does not decrease even when used repeatedly.
以下に実験例、実施例を挙げて本発明をより具体的に説明するが、本発明はこれらにより何等限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to experimental examples and examples. However, the present invention is not limited to these examples.
実施例１ ルテニウム担持組成物の合成方法
（１）マグヘマイト内包ハイドロキシアパタイト（HAP-γ-Fe2O3）の合成方法
三塩化鉄４水和物368mg(1.85mmol、和光純薬（株）製)とニ塩化鉄６水和物1000mg(3.7mmol、和光純薬（株）製)をフラスコに取り、アルゴン置換を行った。次いで、これにイオン交換水50mlを添加撹拌し、更に25%水酸化アンモニウム溶液10mlを添加し、室温で15分間反応させた（溶液１）。一方、別のフラスコにリン酸水素ニアンモニウム［(NH4)2HPO4］4.40g(33.3mmol、和光純薬（株）製)を取り、これにイオン交換水75mlを添加し、更に25%水酸化アンモニウム溶液14mlを添加して、溶液２を得た。また、さらに別のフラスコに硝酸カルシウム４水和物13.11g(55.5mmol、和光純薬（株）製)を取り、これにイオン交換水60mlを添加し、更に25%水酸化アンモニウム溶液4mlを添加して、溶液３を得た。得られた溶液２及び３を溶液１に滴下した後、90℃で２3時間反応させ、更に、室温で一晩放置した。その後、目的物を濾取し、洗浄液が中性になるまでイオン交換水で洗浄した。次いで、一晩真空乾燥し、得られたものを粉砕し、更に、200℃で３時間焼成し、HAP-γ-Fe2O3 5.91gを得た。
（２）ルテニウムを担持したマグヘマイト内包ハイドロキシアパタイト（RuHAP-γ-Fe2O3）の合成方法
上記（１）で得られたHAP-γ-Fe2O3 5.91gおよびイオン交換水500mlをフラスコ内で撹拌した後、塩化ルテニウムn水和物141mg (Ruとして0.591mmol、NE. Chemcat 製)を添加し、室温で３時間反応させた。次いで、目的物を濾取し、洗浄液が中性になるまでイオン交換水で洗浄した。更に、一晩真空乾燥した後、粉砕してRuHAP-γ-Fe2O3 5.36ｇを得た。
Example 1 Method for Synthesizing Ruthenium-Supported Composition (1) Method for Synthesizing Maghemite Encapsulated Hydroxyapatite (HAP-γ-Fe 2 O 3 ) Iron trichloride tetrahydrate 368 mg (1.85 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) And 1000 mg of iron dichloride hexahydrate (3.7 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a flask and purged with argon. Next, 50 ml of ion-exchanged water was added thereto and stirred, and further 10 ml of 25% ammonium hydroxide solution was added and reacted at room temperature for 15 minutes (solution 1). On the other hand, 4.40 g (33.3 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) of diammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 ] was taken in another flask, and 75 ml of ion-exchanged water was added thereto, and further 25% Solution 2 was obtained by adding 14 ml of ammonium hydroxide solution. In another flask, take 13.11 g of calcium nitrate tetrahydrate (55.5 mmol, manufactured by Wako Pure Chemical Industries, Ltd.), add 60 ml of ion-exchanged water, and then add 4 ml of 25% ammonium hydroxide solution. Thus, a solution 3 was obtained. The obtained solutions 2 and 3 were added dropwise to the solution 1, then reacted at 90 ° C. for 23 hours, and further left overnight at room temperature. Thereafter, the target product was collected by filtration and washed with ion-exchanged water until the washing solution became neutral. Subsequently, it was vacuum-dried overnight, and the resulting product was pulverized and further calcined at 200 ° C. for 3 hours to obtain 5.91 g of HAP-γ-Fe 2 O 3 .
(2) maghemite containing hydroxyapatite (RuHAP-γ-Fe 2 O 3) synthetic methods (1) obtained in HAP-γ-Fe 2 O 3 5.91g of ion-exchanged water 500ml the flask carrying ruthenium Then, 141 mg of ruthenium chloride n-hydrate (0.591 mmol as Ru, manufactured by NE. Chemcat) was added and reacted at room temperature for 3 hours. Next, the target product was collected by filtration and washed with ion-exchanged water until the washing solution became neutral. Furthermore, after vacuum drying overnight, it was pulverized to obtain 5.36 g of RuHAP-γ-Fe 2 O 3 .
実施例２ RuHAP-γ-Fe2O3によるベンジルアルコールの酸化反応
RuHAP-γ-Fe2O3 （ルテニウム量として0.005mmol；基質であるベンジルアルコールに対して0.5mol%使用。以下、このような場合、0.5mol%のRuHAP-γ-Fe2O3と記載する）のトルエン懸濁液5mlに、酸素気流下（１気圧、50ml/min）、ベンジルアルコール1mmol (108mg、和光純薬（株）製)を加え90℃で1時間撹拌反応させた。反応液をガスクロマトグラフィーで分析した結果、生成物であるベンズアルデヒドを収率98%で得た。また、本反応の触媒回転効率(TOF)は196であった。尚、TOFは、以下の式より求めた。
TOF = 生成物のモル数(mol) / ［ (ルテニウムのモル数(mol) × 反応時間(hr) )
Example 2 Oxidation of benzyl alcohol with RuHAP-γ-Fe 2 O 3
RuHAP-γ-Fe 2 O 3 (0.005 mmol as the amount of ruthenium; 0.5 mol% used relative to the substrate benzyl alcohol. Hereinafter, in this case, 0.5 mol% RuHAP-γ-Fe 2 O 3 is described. ) Was added to 5 ml of a toluene suspension under an oxygen stream (1 atm, 50 ml / min), and 1 mmol of benzyl alcohol (108 mg, manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted with stirring at 90 ° C. for 1 hour. As a result of analyzing the reaction solution by gas chromatography, the product benzaldehyde was obtained in a yield of 98%. Further, the catalyst rotation efficiency (TOF) of this reaction was 196. The TOF was obtained from the following formula.
TOF = number of moles of product (mol) / [(number of moles of ruthenium (mol) x reaction time (hr))
実施例３ RuHAP-γ-Fe2O3の再利用によるベンジルアルコールの酸化反応
実施例２で用いたRuHAP-γ-Fe2O3を磁石を用いて回収した後、イオン交換水で洗浄し、再度実施例２と同様の方法によりベンジルアルコールの酸化反応を行った。その結果、収率は97％、TOFは194であり、１回目の酸化反応とほぼ同じ結果をもたらした。即ち、該結果より、本願発明のルテニウム担持触媒は、再利用によってもその効果が低下しないことが分かる。
After the RuHAP-γ-Fe 2 O 3 used in Example 3 RuHAP-γ-Fe 2 O oxidation reaction in Example 2 of benzyl alcohol by reuse of 3 is recovered by using a magnet, washed with deionized water, Again, the oxidation reaction of benzyl alcohol was carried out in the same manner as in Example 2. As a result, the yield was 97% and the TOF was 194, which was almost the same as the first oxidation reaction. That is, the results show that the effect of the ruthenium-supported catalyst of the present invention is not reduced even by reuse.
実施例４−１３ RuHAP-γ-Fe2O3による各種アルコールの酸化反応
実施例２のベンジルアルコールを表１記載の基質（1mmol）に変え、また、反応時間を表１記載の時間に変更して、各種アルコールの酸化反応を行った。但し、0.5mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.005mmol)のトルエン懸濁液の代わりに、実施例４，８，１２及び１３においては、1 mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.01mmol) のトルエン懸濁液を用い、実施例９及び１０においては、1 mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.01mmol) のα,α,α-トリフルオロトルエン（TFT）懸濁液を用いた。
得られた生成物の収率及びTOFを実施例２と同様に測定した結果を表１に併せて示す。
Example 4-13 Oxidation reaction of various alcohols with RuHAP-γ-Fe 2 O 3 The benzyl alcohol in Example 2 was changed to the substrate (1 mmol) shown in Table 1, and the reaction time was changed to the time shown in Table 1. Then, oxidation reactions of various alcohols were performed. However, instead of a toluene suspension of 0.5 mol% RuHAP-γ-Fe 2 O 3 (0.005 mmol as ruthenium amount), in Examples 4, 8, 12 and 13, 1 mol% RuHAP-γ- A toluene suspension of Fe 2 O 3 (0.01 mmol as ruthenium amount) was used, and in Examples 9 and 10, α, α of 1 mol% RuHAP-γ-Fe 2 O 3 (0.01 mmol as ruthenium amount) was used. α-trifluorotoluene (TFT) suspension was used.
The results of measuring the yield and TOF of the obtained product in the same manner as in Example 2 are also shown in Table 1.
比較例１ RuHAPによるベンジルアルコールの酸化反応
(1) RuHAPの調製
2.67×10-2M の塩化ルテニウム水溶液75ml およびハイドロキシアパタイト 1gをフラスコに入れ、25℃で24時間反応させた。次いで、目的物を濾取し、洗浄液が中性になるまでイオン交換水で洗浄した後、70℃で7時間、真空乾燥し、RuHAP 971mgを得た。
(2)TOFの測定
実施例２のRuHAP-γ-Fe2O3 の代わりにRuHAPを用いてベンジルアルコールの酸化反応を行った。即ち、16.9mol%のRuHAP（ルテニウム量として0.338mmol）のトルエン懸濁液に、酸素雰囲気下（１気圧）、ベンジルアルコール1mmol (108mg、和光純薬（株）製)を加え80℃で1時間撹拌反応させた。TOFを実施例２で記載した式により求めた。その結果TOFは２であった。
Comparative Example 1 Oxidation of benzyl alcohol with RuHAP
(1) Preparation of RuHAP
75 ml of a 2.67 × 10 −2 M ruthenium chloride solution and 1 g of hydroxyapatite were placed in a flask and reacted at 25 ° C. for 24 hours. Subsequently, the target product was collected by filtration, washed with ion-exchanged water until the washing solution became neutral, and then vacuum-dried at 70 ° C. for 7 hours to obtain 971 mg of RuHAP.
(2) Measurement of TOF An oxidation reaction of benzyl alcohol was carried out using RuHAP instead of RuHAP-γ-Fe 2 O 3 in Example 2. In other words, 1 mmol of benzyl alcohol (108 mg, manufactured by Wako Pure Chemical Industries, Ltd.) was added to a toluene suspension of 16.9 mol% RuHAP (0.338 mmol as the amount of ruthenium) in an oxygen atmosphere (1 atm) at 80 ° C. for 1 hour. The reaction was stirred. TOF was determined by the formula described in Example 2. As a result, the TOF was 2.
比較例２−７ RuHAPによる各種アルコールの酸化反応
実施例５、６、８、１１，１２，及び１３のRuHAP-γ-Fe2O3の代わりにRuHAPを用い、各種アルコールの酸化反応を行った。即ち、アルコールの種類を代えた以外は比較例１と同様の方法により、各種アルコール(1mmol)を酸化反応に付し、そのTOFを求めた。その結果を併せて表１に示す。
Comparative Example 2-7 Oxidation Reaction of Various Alcohols with RuHAP Various alcohols were oxidized using RuHAP instead of RuHAP-γ-Fe 2 O 3 in Examples 5, 6, 8, 11, 12, and 13. . That is, various alcohols (1 mmol) were subjected to an oxidation reaction in the same manner as in Comparative Example 1 except that the type of alcohol was changed, and the TOF was determined. The results are also shown in Table 1.
表１の結果から明らかなように、RuHAP-γ-Fe2O3を触媒として用いたアルコールの酸化反応は、多くが収率90％以上、悪くても80％以上であり、高収率で酸化反応が行えることが分かる。また、TOFも、RuHAPと比較して、5〜130倍も向上しており、RuHAP-γ-Fe2O3が非常に高い触媒活性を有していることが分かる。 As is clear from the results in Table 1, the oxidation reaction of alcohol using RuHAP-γ-Fe 2 O 3 as a catalyst is mostly yield of 90% or more and at most 80% or less, and high yield. It turns out that an oxidation reaction can be performed. Moreover, TOF is also improved 5 to 130 times compared to RuHAP, and it can be seen that RuHAP-γ-Fe 2 O 3 has a very high catalytic activity.
実施例１４ 立体障害のあるヒドロキシル基を有するアルコールの酸化反応
1mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.01mmol) のトルエン (5ml) 懸濁液に、酸素気流下（１気圧、50ml/min）、3,5-ジベンジルオキシベンジルアルコール 1mmol(320mg、和光純薬（株）製)を加え90℃で5時間撹拌し、反応させた。得られた反応液をガスクロマトグラフィーで分析した結果、生成物である3,5-ジベンジルオキシベンズアルデヒドの収率は99%以上であった。
Example 14 Oxidation reaction of alcohol having hydroxyl group having steric hindrance
To a suspension of 1 mol% RuHAP-γ-Fe 2 O 3 (0.01 mmol ruthenium) in toluene (5 ml) under an oxygen stream (1 atm, 50 ml / min), 3,5-dibenzyloxybenzyl alcohol 1 mmol (320 mg, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 90 ° C. for 5 hours to be reacted. As a result of analyzing the obtained reaction liquid by gas chromatography, the yield of 3,5-dibenzyloxybenzaldehyde as a product was 99% or more.
実施例１５ 立体障害のあるヒドロキシル基を有するアルコールの酸化反応２
2.5mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.025mmol)のトルエン (5ml) 懸濁液に、酸素気流下（１気圧、50ml/min）、コレスタノール1mmol (389mg、和光純薬（株）製)を加え90℃で24時間撹拌した。反応液をガスクロマトグラフィーで分析した結果、生成物であるコレスタノンの収率は99%以上であった。
A suspension of 2.5 mol% RuHAP-γ-Fe 2 O 3 (0.025 mmol as ruthenium) in toluene (5 ml) under oxygen flow (1 atm, 50 ml / min), 1 mmol of cholestanol (389 mg, Wako Pure Chemical) (Made by Co., Ltd.) was added and stirred at 90 ° C. for 24 hours. As a result of analyzing the reaction solution by gas chromatography, the yield of the product, cholestanone, was 99% or more.
上記実施例14及び15の結果より、本発明のルテニウム担持触媒は、立体障害のあるヒドロキシル基であっても、ほぼ100％の高い収率で酸化することができることが分かる。 From the results of Examples 14 and 15 above, it can be seen that the ruthenium-supported catalyst of the present invention can be oxidized with a high yield of almost 100% even if it is a sterically hindered hydroxyl group.
実施例１６−２０ 室温でのアルコールの酸化反応
1〜4mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.01~0.04mmol) のトルエン懸濁液5mlに、酸素気流下（１気圧、50ml/min）、表２記載の各種アルコール1mmolを加え室温で24時間撹拌し反応させた。得られた反応液をガスクロマトグラフィーで分析し、目的生成物の収率を求めた。
Examples 16-20 Oxidation reaction of alcohol at room temperature
To 5 ml of toluene suspension of 1 to 4 mol% RuHAP-γ-Fe 2 O 3 (0.01 to 0.04 mmol as ruthenium amount) under oxygen flow (1 atm, 50 ml / min), 1 mmol of various alcohols listed in Table 2 The mixture was stirred and reacted at room temperature for 24 hours. The obtained reaction solution was analyzed by gas chromatography to determine the yield of the desired product.
表２の結果より、本願発明のルテニウム担持触媒を用いれば、高温時の酸化反応に比較して、触媒濃度を上げて長時間反応させる必要があるものの、室温であっても高い収率でアルコールの酸化反応を行うことが出来ることが分かる。 From the results shown in Table 2, the use of the ruthenium-supported catalyst of the present invention requires that the catalyst concentration be increased and the reaction be performed for a long time as compared with the oxidation reaction at a high temperature. It can be seen that the oxidation reaction can be performed.
実施例２１−２７ 高気圧下でのアルコールの酸化反応
0.5mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.005mmol) のトルエン懸濁液5mlに、表３記載の各種アルコール基質(1mmol)を加え、酸素加圧下（５気圧）、90℃で0.5〜3時間撹拌し、反応させた。但し、0.5mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.005mmol) のトルエン懸濁液の代わりに、実施例22， 26及び27においては、1 mol%のRuHAP-γ-Fe2O3 (ルテニウム量として0.01mmol) を用い、反応液をガスクロマトグラフィーで分析して得た収率、及びTOFを表３に併せて示す。また、参考として、１気圧で酸素を流し、反応時間を代えた以外は同条件で反応を行っている実施例２，４〜８及び１３の収率及びTOFを参考として併せて示す。
Examples 21-27 Oxidation reaction of alcohol under high pressure
Various alcohol substrates (1 mmol) listed in Table 3 are added to 5 ml of a toluene suspension of 0.5 mol% RuHAP-γ-Fe 2 O 3 (0.005 mmol as the amount of ruthenium) at 90 ° C. under oxygen pressure (5 atm). And reacted for 0.5 to 3 hours. However, instead of the toluene suspension of 0.5 mol% RuHAP-γ-Fe 2 O 3 (0.005 mmol as ruthenium amount), in Examples 22, 26 and 27, 1 mol% RuHAP-γ-Fe 2 Table 3 shows the yield and TOF obtained by analyzing the reaction solution by gas chromatography using O 3 (0.01 mmol as the amount of ruthenium). For reference, the yield and TOF of Examples 2, 4 to 8 and 13 in which the reaction is carried out under the same conditions except that oxygen is passed at 1 atm and the reaction time is changed are also shown for reference.
この結果より、５気圧の酸素気流下での反応は、１気圧の酸素気流下での反応と比較して、約２倍程度高効率に反応が進行することが分かる。 From this result, it can be seen that the reaction proceeds under the efficiency of about twice as high as the reaction under an oxygen stream of 5 atm compared with the reaction under an oxygen stream of 1 atm.
Claims (9)
A method for producing a ketone or aldehyde compound, wherein oxygen and alcohol are contacted in the presence of the catalyst according to claim 7 or 8.
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| CN110963947A (en) * | 2019-12-23 | 2020-04-07 | 张家港格瑞特化学有限公司 | Preparation method of surfactant |
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| JPH04371233A (en) * | 1991-06-20 | 1992-12-24 | Kyodo Kumiai Syst Nau | Photocatalyst and device for decomposition treatment of organic halogen compound using the same |
| JP2001246262A (en) * | 2000-03-08 | 2001-09-11 | Sanyo Chem Ind Ltd | Highly selective catalyst for oxidation reaction |
| JP2005060319A (en) * | 2003-08-14 | 2005-03-10 | Nissei Kagaku Kogyosho:Kk | Method for producing (di)quinone derivative |
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| JPH04371233A (en) * | 1991-06-20 | 1992-12-24 | Kyodo Kumiai Syst Nau | Photocatalyst and device for decomposition treatment of organic halogen compound using the same |
| JP2001246262A (en) * | 2000-03-08 | 2001-09-11 | Sanyo Chem Ind Ltd | Highly selective catalyst for oxidation reaction |
| JP2005060319A (en) * | 2003-08-14 | 2005-03-10 | Nissei Kagaku Kogyosho:Kk | Method for producing (di)quinone derivative |
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| WO2012161091A1 (en) * | 2011-05-20 | 2012-11-29 | 国立大学法人秋田大学 | Exhaust gas purifying catalyst and carrier |
| JP2013006170A (en) * | 2011-05-20 | 2013-01-10 | Akita Univ | Exhaust gas purifying catalyst and carrier |
| CN103619471A (en) * | 2011-05-20 | 2014-03-05 | 三井金属矿业株式会社 | Exhaust gas purifying catalyst and carrier |
| US9162217B2 (en) | 2011-05-20 | 2015-10-20 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas purifying catalyst and carrier |
| CN110963947A (en) * | 2019-12-23 | 2020-04-07 | 张家港格瑞特化学有限公司 | Preparation method of surfactant |
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