JP2013043132A - Oxidation catalyst using mononuclear metal complex as effective component and use thereof - Google Patents
Oxidation catalyst using mononuclear metal complex as effective component and use thereof Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 17
- 239000004480 active ingredient Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- -1 propylsulfo group Chemical group 0.000 claims description 6
- 239000003586 protic polar solvent Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000004699 copper complex Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 229910020366 ClO 4 Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229940005561 1,4-benzoquinone Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 238000000967 suction filtration Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- HXAZBSDTBQIPMS-UHFFFAOYSA-N 1-ethyl-2-[(1-ethylbenzimidazol-2-yl)methyl]benzimidazole Chemical compound C1=CC=C2N(CC)C(CC=3N(C4=CC=CC=C4N=3)CC)=NC2=C1 HXAZBSDTBQIPMS-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 238000001196 time-of-flight mass spectrum Methods 0.000 description 1
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite 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
Abstract
Description
本発明は、単核系金属錯体を有効成分とする酸化触媒に関するものである。 The present invention relates to an oxidation catalyst containing a mononuclear metal complex as an active ingredient.
本出願人は、新規の単核系金属錯体を有効成分とする酸化触媒について出願している（特願２０１０−１４１１７５号）。この酸化触媒は、ベンゼンのような難度の高い酸化反応を触媒的に水酸化する触媒である。 The present applicant has applied for an oxidation catalyst containing a novel mononuclear metal complex as an active ingredient (Japanese Patent Application No. 2010-141175). This oxidation catalyst is a catalyst that catalytically hydroxylates a highly difficult oxidation reaction such as benzene.
この特許出願に記載の新規単核銅錯体[Cu(Pr3bbim)Cl2]および[Cu(Pr3bbim)Br2]を用いたベンゼンの酸化反応による生成物（フェノール、１，４−ベンゾキノン）のＴＯＮ（Turn Over Number）は、次の通りであった。なお、次のＴＯＮは、単核銅錯体一分子当たりの値として算出したものである。 Products (phenol, 1,4-benzoquinone) produced by the oxidation reaction of benzene using the novel mononuclear copper complexes [Cu (Pr 3 bbim) Cl 2 ] and [Cu (Pr 3 bbim) Br 2 ] described in this patent application ) (Turn Over Number) was as follows. The following TON is calculated as a value per molecule of the mononuclear copper complex.
Cu(Pr3bbim)Cl2を用いた場合であって、溶媒としてアセトニトリル溶媒（MeCN）を用いた場合、フェノールは２．４、ベンゾキノンは１９であり、溶媒としてアセトニトリル：水＝1 : 1の混合溶媒（MeCN/H2O）を用いた場合、フェノールは１７、ベンゾキノンは４５であった。 When Cu (Pr 3 bbim) Cl 2 is used and acetonitrile solvent (MeCN) is used as a solvent, phenol is 2.4, benzoquinone is 19, and acetonitrile: water = 1: 1 as a solvent. When a mixed solvent (MeCN / H 2 O) was used, the phenol was 17 and the benzoquinone was 45.
Cu(Pr3bbim)Br2を用いた場合であって、溶媒としてMeCNを用いた場合、フェノールは４．０、ベンゾキノンは１５であり、溶媒としてMeCN/H2Oを用いた場合、フェノールは１３、ベンゾキノンは３２であった。 When Cu (Pr 3 bbim) Br 2 is used, when MeCN is used as a solvent, phenol is 4.0, benzoquinone is 15, and when MeCN / H 2 O is used as a solvent, phenol is 13 and benzoquinone were 32.
しかし、上述の特願２０１０−１４１１７５号に記載の酸化触媒を、ベンゼンからフェノールが生成する酸化反応に用いた場合、生成したフェノールがさらに酸化されてベンゾキノンへと反応が進むことにより、ベンゾキノンのＴＯＮがフェノールのものより大きかった。すなわち、ベンゾキノンの生成量がフェノールの生成量よりも多く、フェノールの生成量が少なかった。 However, when the oxidation catalyst described in the above-mentioned Japanese Patent Application No. 2010-141175 is used for an oxidation reaction in which phenol is produced from benzene, the produced phenol is further oxidized and the reaction proceeds to benzoquinone. Was larger than that of phenol. That is, the amount of benzoquinone produced was larger than the amount of phenol produced, and the amount of phenol produced was small.
本発明は上記点に鑑みて、少なくともベンゼンからフェノールが生成する酸化反応における触媒機能を有し、ベンゾキノンの生成量をフェノールの生成量よりも少なくできる単核系金属錯体を有効成分とする新規酸化触媒を提供することを目的とする。 In view of the above points, the present invention has a catalytic function in at least an oxidation reaction in which phenol is produced from benzene, and a novel oxidation comprising a mononuclear metal complex as an active ingredient that can reduce the amount of benzoquinone produced than the amount of phenol produced. An object is to provide a catalyst.
親水性を有する新規単核系金属錯体を合成し、この新規単核系金属錯体を用いて、ベンゼンからフェノールが生成する酸化反応を試みたところ、ベンゾキノンの生成量をフェノールの生成量よりも少なくできることがわかり、本発明を創出するに至った。 A novel mononuclear metal complex with hydrophilicity was synthesized, and an oxidation reaction in which phenol was produced from benzene was attempted using this new mononuclear metal complex. The amount of benzoquinone produced was less than the amount of phenol produced. It turns out that it can be done, and came to create this invention.
すなわち、請求項１に記載の発明は、一般式（Ｉ）で表される新規単核金属錯体である。
[１]
なお、式中のＲ１，Ｒ２，Ｒ３は、それぞれ独立に、水素原子及び炭素数１〜３の炭化水素基から選択されるいずれかであり、Ｒ４は炭素数０〜３で末端にスルホ基を持つ置換基である。またＭは、平面四配位型の配位構造を形成する金属原子であり、３つのＸのうち１つのＸはハロゲン原子もしくはカウンターイオンであり、残り２つのＸが溶媒分子である。
That is, the invention described in claim 1 is a novel mononuclear metal complex represented by the general formula (I).
[1]
In the formula, R 1 , R 2 and R 3 are each independently selected from a hydrogen atom and a hydrocarbon group having 1 to 3 carbon atoms, and R 4 is a terminal having 0 to 3 carbon atoms. Is a substituent having a sulfo group. M is a metal atom that forms a planar four-coordinated coordination structure, one of the three Xs is a halogen atom or a counter ion, and the remaining two X are solvent molecules.
この新規単核金属錯体は、少なくともベンゼンからフェノールが生成する酸化反応における触媒機能を有し、ベンゼンからフェノールが生成する酸化反応における触媒として用いた場合に、ベンゾキノンの生成量をフェノールの生成量よりも少なくできる。 This new mononuclear metal complex has at least a catalytic function in the oxidation reaction in which phenol is produced from benzene, and when used as a catalyst in the oxidation reaction in which phenol is produced from benzene, the amount of benzoquinone produced from the amount of phenol produced Can also be reduced.
[２] 請求項２に記載の発明は、一般式（Ｉ）におけるＲ１，Ｒ２がエチル基、Ｒ３が水素原子、Ｒ４がプロピルスルホ基、Ｍが銅である請求項１に記載の新規単核系金属錯体である。 [2] The invention according to claim 2 is the invention according to claim 1 , wherein R 1 and R 2 in the general formula (I) are ethyl groups, R 3 is a hydrogen atom, R 4 is a propylsulfo group, and M is copper. It is a novel mononuclear metal complex.
[３] 請求項３に記載の発明は、請求項１または２に記載の単核系金属錯体を有効成分とする新規酸化触媒である。 [3] The invention according to claim 3 is a novel oxidation catalyst comprising the mononuclear metal complex according to claim 1 or 2 as an active ingredient.
[４] 請求項４に記載の発明は、請求項１または２に記載の単核系金属錯体を有効成分とする酸化触媒と、反応溶媒としてのプロトン性溶媒とを用い、ベンゼンの一段階酸化によりフェノールを合成するフェノールの合成方法である。プロトン性溶媒としては、例えば、メタノール、水等が挙げられる。
これによれば、後述する実施例からわかるように、ベンゾキノンの生成を抑制しつつ、フェノールを合成することができる。
[4] The invention according to claim 4 is a one-step oxidation of benzene using an oxidation catalyst comprising the mononuclear metal complex according to claim 1 or 2 as an active ingredient and a protic solvent as a reaction solvent. This is a method for synthesizing phenol by synthesizing phenol. Examples of the protic solvent include methanol, water and the like.
According to this, as can be seen from the examples described later, it is possible to synthesize phenol while suppressing the production of benzoquinone.
本発明の酸化触媒は、一般式（Ｉ）で表される新規単核金属錯体（単核のベンズイミダゾリル錯体）を有効成分として含むものである。なお、新規単核金属錯体のみによって酸化触媒が構成されていても良い。
この新規単核金属錯体は、一般式（ＩＩ）で表される配位子を用いて合成されるものである。
一般式（Ｉ）、（ＩＩ）におけるＲ１，Ｒ２，Ｒ３は、それぞれ独立に、水素原子及び炭素数１〜３の炭化水素基から選択されるいずれかである。 R 1 , R 2 and R 3 in the general formulas (I) and (II) are each independently selected from a hydrogen atom and a hydrocarbon group having 1 to 3 carbon atoms.
また、一般式（Ｉ）、（ＩＩ）におけるＲ４は炭素数０〜３で末端にスルホ基を持つ置換基であり得る。このように、本発明の新規単核金属錯体は、スルホ基を有するため、親水性を帯びている。 R 4 in general formulas (I) and (II) may be a substituent having 0 to 3 carbon atoms and having a sulfo group at the terminal. Thus, since the novel mononuclear metal complex of the present invention has a sulfo group, it is hydrophilic.
なお、置換基として、スルホ基を持つものを用いたのは、一般式（Ｉ）中のＭ（金属）との配位による構造への影響を考慮したためである。また、Ｒ４がスルホ基であるのは、スルホ基の位置が他の位置である場合よりも、単核金属錯体の合成が容易だからである。
また、一般式（Ｉ）におけるＭは、平面四配位型の配位構造を形成する金属原子（例えばＣｕ）である。今回はスルホ基の影響により、配位子が負の電荷を帯びており、分子サイズの大きなカウンターアニオンを１つだけ必要とし安定化する。金属イオン（例えば銅イオン）周りの平面性を高めるために五配位の平面四角錐型構造を取ったと考えられる。
また、一般式（Ｉ）における３つのＸのうち１つのＸは塩素 (Cl)や臭素 (Br)などのハロゲン原子もしくは過塩素酸 (ClO4 -) などのカウンターイオンであり、残り２つのＸが水、エタノール（EtOH）などの溶媒分子である。カウンターイオンとしては、さらに、ＳｂＦ６ −、ＣＦ３ＳＯ３ −、ＰＦ６ −等が挙げられる。
The reason why a substituent having a sulfo group was used was that the influence on the structure due to coordination with M (metal) in general formula (I) was taken into consideration. R 4 is a sulfo group because the synthesis of a mononuclear metal complex is easier than when the sulfo group is located at other positions.
Further, M in the general formula (I) is a metal atom (for example, Cu) that forms a planar four-coordinate coordination structure. This time, due to the influence of the sulfo group, the ligand is negatively charged, and only one counter anion with a large molecular size is needed for stabilization. In order to improve the planarity around metal ions (for example, copper ions), a five-coordinate planar square pyramid structure is considered.
One of the three Xs in the general formula (I) is a halogen atom such as chlorine (Cl) or bromine (Br) or a counter ion such as perchloric acid (ClO 4 − ), and the remaining two X Are solvent molecules such as water and ethanol (EtOH). Examples of the counter ion further include SbF 6 − , CF 3 SO 3 − , PF 6 − and the like.
新規単核金属錯体の例としては、Ｒ１，Ｒ２がエチル基、Ｒ３が水素原子、Ｒ４がプロピルスルホ基であり、金属原子Ｍが銅 (Cu)、Ｘが水、エタノール、過塩素酸である単核銅錯体[Cu(E2pbbim)(EtOH)(H2O)(ClO4)]が挙げられる。 Examples of new mononuclear metal complexes include R 1 and R 2 are ethyl groups, R 3 is a hydrogen atom, R 4 is a propylsulfo group, metal atom M is copper (Cu), X is water, ethanol, hydrogen A mononuclear copper complex [Cu (E 2 pbbim) (EtOH) (H 2 O) (ClO 4 )] which is chloric acid can be mentioned.
この新規単核金属錯体は、後述する実施例の記載からわかるように、少なくともベンゼンからフェノールが生成する酸化反応における触媒機能を有し、ベンゼンからフェノールが生成する酸化反応における酸化触媒として用いた場合に、ベンゾキノンの生成量をフェノールの生成量よりも少なくできる。 This novel mononuclear metal complex has a catalytic function in at least an oxidation reaction in which phenol is produced from benzene, and is used as an oxidation catalyst in an oxidation reaction in which phenol is produced from benzene, as can be seen from the description of Examples below. In addition, the amount of benzoquinone produced can be less than the amount of phenol produced.
本発明の酸化触媒は、種々の形態をとることができる。例えば、上述したいずれかの金属錯体またはその塩（錯体塩）を粉末状、塊状等の状態で含む形態とすることができる。 The oxidation catalyst of the present invention can take various forms. For example, any of the metal complexes described above or a salt thereof (complex salt) may be included in a powdery or massive state.
また、本発明の酸化触媒は、上記錯体が液状媒体中に存在している形態をとることができる。この液状媒体としては、水、アセトニトリル、低級アルコール（例えば、炭素数１〜４程度のアルコール）、アセトンその他の低級ケトン（例えば、炭素数３〜５程度のケトン）等から選択される一種または二種以上を用いることができる。かかる酸化触媒は、典型的には、上述したいずれかの錯体の塩を液状媒体に溶解させる工程を含む処理によって調製（製造）することができる。また、液状媒体中に上記錯体またはその塩が分散した形態の酸化触媒であってもよい。 Moreover, the oxidation catalyst of the present invention can take a form in which the complex is present in a liquid medium. As the liquid medium, one or two selected from water, acetonitrile, lower alcohol (for example, alcohol having about 1 to 4 carbon atoms), acetone and other lower ketones (for example, ketone having about 3 to 5 carbon atoms), and the like. More than seeds can be used. Such an oxidation catalyst can be typically prepared (manufactured) by a treatment including a step of dissolving a salt of any of the above-described complexes in a liquid medium. Moreover, the oxidation catalyst of the form which the said complex or its salt disperse | distributed in the liquid medium may be sufficient.
また、本発明の酸化触媒のとり得る他の形態として、上記錯体が固体状の担体に保持されている形態が挙げられる。錯体を担持する担体としては、微粒子状物質、多孔質体等を好ましく用いることができる。例えば、活性炭等の微粒子を好ましく用いることができる。また、ゼオライト、シリカ等の材質からなる多孔質体を好ましく用いることができる。そのような多孔質体が粒子状、繊維状、ハニカム状等に成形されたものであってもよい。質量当たりの表面積が広いものが好ましい。例えば、表面積が１０００ｍ２／ｇ以上（典型的には、１２００〜１５００ｍ２／ｇ）である担体を好ましく用いることができる。なお、微粒子状の担体に錯体を担持したもの（錯体担持微粒子）が液状媒体に分散している形態は、「錯体が液状媒体中に存在している形態」の一例である。 In addition, as another form that can be taken by the oxidation catalyst of the present invention, a form in which the complex is held on a solid support can be mentioned. As the carrier for supporting the complex, a particulate material, a porous body, and the like can be preferably used. For example, fine particles such as activated carbon can be preferably used. A porous body made of a material such as zeolite or silica can be preferably used. Such a porous body may be formed into particles, fibers, honeycombs or the like. Those having a large surface area per mass are preferred. For example, a carrier having a surface area of 1000 m 2 / g or more (typically 1200 to 1500 m 2 / g) can be preferably used. The form in which the complex is supported on the fine particle carrier (complex-supporting fine particles) is dispersed in the liquid medium is an example of “the form in which the complex is present in the liquid medium”.
本発明の酸化触媒は、ベンゼンからフェノールが生成する酸化反応の他に、以下の酸化反応に利用することもできる。
・芳香環を有する基質化合物を酸化してフェノール類を生成する反応。
・メチルフェニルチオエーテル等のチオエーテル（ＳＲ２，ここでＲは同一のまたは異なる一価の有機基である。）を酸化してＳ（＝Ｏ）Ｒ２を生成する反応。
シクロヘキセン等の不飽和炭化水素（典型的にはアルケン、シクロアルケン等）を酸化して、ケトン、アルコール（典型的にはエノール型化合物）、エポキシ化合物等の一種または二種以上を生成する反応。
・イソプロピルベンゼン等の、芳香環（典型的にはベンゼン環）に結合した一または二以上の第二級炭素上に水素原子を有する基質化合物を酸化して、該第二級炭素に結合した水素原子を水酸基に置換する反応。
・トルエン等の、芳香環に結合した一または二以上のＣＨ３基を有する（典型的には他の官能基を有しない）基質化合物を酸化して、上記ＣＨ３基がＣＨ２ＯＨに変換された化合物および該ＣＨ３基がＣＨＯに変換された化合物の一種または二種以上を生成する反応。
・シクロヘキサン、メタン等の飽和炭化水素（典型的にはアルカン、シクロアルカン等）を酸化して、アルコール、ケトン、アルデヒド等の一種または二種以上を生成する反応。
The oxidation catalyst of the present invention can be used for the following oxidation reaction in addition to the oxidation reaction in which phenol is produced from benzene.
A reaction that oxidizes a substrate compound having an aromatic ring to generate phenols.
A reaction in which thioether such as methylphenyl thioether (SR 2 , where R is the same or different monovalent organic group) is oxidized to produce S (═O) R 2 .
A reaction in which unsaturated hydrocarbons such as cyclohexene (typically alkenes, cycloalkenes, etc.) are oxidized to produce one or more of ketones, alcohols (typically enol-type compounds), epoxy compounds and the like.
Hydrogen bonded to the secondary carbon by oxidizing a substrate compound having a hydrogen atom on one or more secondary carbons bonded to an aromatic ring (typically a benzene ring), such as isopropylbenzene Reaction that replaces an atom with a hydroxyl group.
Oxidizing a substrate compound having one or more CH 3 groups bonded to an aromatic ring, such as toluene (typically having no other functional groups), and converting the CH 3 groups into CH 2 OH To produce one or two or more compounds obtained by converting the CH 3 group into CHO.
A reaction that oxidizes saturated hydrocarbons such as cyclohexane and methane (typically alkanes, cycloalkanes, etc.) to produce one or more of alcohols, ketones, aldehydes, etc.
〈新規配位子の合成〉
より親水性の高い構造を有した新規配位子４，４−ビス（Ｎ−エチルベンズイミダゾリル）−ブタンスルホン酸（以下E2pbbimと示す）を以下に示す合成法にて合成した。
嫌気下でテトラヒドロフラン（THF）50 mlに１，１−ビス（Ｎ−エチルベンズイミダゾリル）メタン（Et2bbim）1.0 g (3.28 mmol) を溶解させ、-78℃にて1.66 mol/lのｎ−ブチルリチウム2.2 ml (3.60 mmol) を５分かけて滴下した。ゆっくり室温まで昇温し、１時間撹拌後、再び-78℃に戻し、プロパンスルトン0.30 ml (3.28 mmol) を加えた。１時間撹拌後、再びゆっくり室温まで昇温し、さらに１２時間撹拌させた。１Ｎ塩酸10 mlを加えてｐＨ試験紙で弱酸性になったことを確認した後、炭酸ナトリウムを加えた。再びｐＨ試験紙で弱塩基性になったことを確認し、減圧濃縮を行った。クロロホルムと水を用いて抽出を行い、水相の減圧濃縮を行い、黄白色粉末を得た。これをアセトニトリルを加えて洗浄、吸引濾過を行い、濾液を減圧濃縮した。このようにしてE2pbbimを黄色粉末として得た。収量は0.41 g、収率は29.3 %であった。
<Synthesis of novel ligands>
A novel ligand 4,4-bis (N-ethylbenzimidazolyl) -butanesulfonic acid (hereinafter referred to as E 2 pbbim) having a more hydrophilic structure was synthesized by the following synthesis method.
Under anaerobic conditions, 1.0 g (3.28 mmol) of 1,1-bis (N-ethylbenzimidazolyl) methane (Et 2 bbim) was dissolved in 50 ml of tetrahydrofuran (THF) at 1.78 mol / l n- Butyl lithium (2.2 ml, 3.60 mmol) was added dropwise over 5 minutes. The mixture was slowly warmed to room temperature, stirred for 1 hour, returned to -78 ° C, and 0.30 ml (3.28 mmol) of propane sultone was added. After stirring for 1 hour, the temperature was slowly raised to room temperature again, and the mixture was further stirred for 12 hours. After adding 10 ml of 1N hydrochloric acid and confirming that it became weakly acidic with pH test paper, sodium carbonate was added. After confirming that it was weakly basic again with pH test paper, it was concentrated under reduced pressure. Extraction was performed using chloroform and water, and the aqueous phase was concentrated under reduced pressure to obtain a yellowish white powder. Acetonitrile was added thereto, followed by washing and suction filtration, and the filtrate was concentrated under reduced pressure. In this way, E 2 pbbim was obtained as a yellow powder. The yield was 0.41 g, and the yield was 29.3%.
得られたE2pbbimのスペクトルデータを以下のとおりである。
1H-NMR (D2O, 300 MHz, d / ppm from TSP); 7.7, 7.5 (t, 2H), 7.3 (m, 4H), 4.9 (t, 1H), 4.2 (d, 4H), 3.0 (t, 2H), 2.5 (m, 2H), 1.8 (m, 2H), 0.8 (t, 6H).
ESI-TOF-Mass (in MeOH, ion mode negative) m/z425.2 [M - H]-.
FT-IR (KBr, cm-1): n 3057 (aromatic C-H), 2979, 2935 (aliphatic C-H), 1186 (SO3 -).
The spectrum data of the obtained E 2 pbbim are as follows.
1 H-NMR (D 2 O, 300 MHz, d / ppm from TSP); 7.7, 7.5 (t, 2H), 7.3 (m, 4H), 4.9 (t, 1H), 4.2 (d, 4H), 3.0 (t, 2H), 2.5 (m, 2H), 1.8 (m, 2H), 0.8 (t, 6H).
ESI-TOF-Mass (in MeOH, ion mode negative) m / z425.2 [M-H] - .
FT-IR (KBr, cm -1 ): n 3057 (aromatic CH), 2979, 2935 (aliphatic CH), 1186 (SO 3 -).
〈新規単核銅錯体[Cu(E2pbbim)(EtOH)(H2O)(ClO4)] の合成〉
新規錯体[Cu(E2pbbim)(EtOH)(H2O)(ClO4)] の合成法とキャラクタリゼーションの結果を以下に示す。
<Synthesis of a novel mononuclear copper complex [Cu (E 2 pbbim) (EtOH) (H 2 O) (ClO 4 )]>
The synthesis method and characterization results of the new complex [Cu (E 2 pbbim) (EtOH) (H 2 O) (ClO 4 )] are shown below.
Cu(ClO4)2 ・6H2O 43.5 mg (0.117 mmol) をエタノール 1 ml に溶解させた緑色の溶液に、エタノール 1 ml に溶かした4,4- bis(N-ethylbenzimidazolyl)-butane sulfone acid (E2pbbim) 50.0 mg (0.117 mmol) をゆっくり滴下し、沸騰直前まで温め2日間静置したところ、青色の結晶が生じた。吸引濾過を行い、真空ラインを用いて減圧乾燥し、青色結晶を得た。収量は64.4 mg、収率は63.4 %であった。 4,4-bis (N-ethylbenzimidazolyl) -butane sulfone acid dissolved in 1 ml of ethanol in a green solution of Cu (ClO 4 ) 2 · 6H 2 O 43.5 mg (0.117 mmol) in 1 ml of ethanol E 2 pbbim) 50.0 mg (0.117 mmol) was slowly added dropwise, and the mixture was warmed to just before boiling and allowed to stand for 2 days. As a result, blue crystals were formed. Suction filtration was performed, and vacuum drying was performed using a vacuum line to obtain blue crystals. The yield was 64.4 mg, and the yield was 63.4%.
得られた結晶を、元素分析、UV-visスペクトル、ESI-TOF-Massスペクトル、ESRスペクトル、IRスペクトルを測定した。測定結果は以下の通りである。
FT-IR (KBr, cm-1):n 3068 (aromatic C-H), 2982, 2938 (aliphatic C-H), 1498 (aromatic C=C), 1200 (SO3 -).
Anal. Calcd for C25H37ClCuN4O10S : C, 43.86; H, 5.45; N, 8.18. Found: C, 43.80; H, 5.71; N, 7.86.
UV-vis.[MeOH, lmax / nm (e / M-1cm-1)]:340 (240), 680 (70). [MeOH/H2O (1:1, v/v),
lmax /nm(e / M-1cm-1)]: 341 (242), 691 (63).
ESR:MeOH, g// = 2.30, g⊥ = 2.07, |A//| = 161 G; MeOH/H2O (1:1, v/v), g// = 2.30, g⊥ = 2.07, |A//| = 161 G.
Elemental analysis, UV-vis spectrum, ESI-TOF-Mass spectrum, ESR spectrum, and IR spectrum of the obtained crystal were measured. The measurement results are as follows.
FT-IR (KBr, cm -1 ): n 3068 (aromatic CH), 2982, 2938 (aliphatic CH), 1498 (aromatic C = C), 1200 (SO 3 -).
Anal. Calcd for C 25 H 37 ClCuN 4 O 10 S: C, 43.86; H, 5.45; N, 8.18. Found: C, 43.80; H, 5.71; N, 7.86.
UV-vis. [MeOH, l max / nm (e / M -1 cm -1 )]: 340 (240), 680 (70). [MeOH / H 2 O (1: 1, v / v),
l max / nm (e / M -1 cm -1 )]: 341 (242), 691 (63).
ESR: MeOH, g // = 2.30, g ⊥ = 2.07, | A // | = 161 G; MeOH / H 2 O (1: 1, v / v), g // = 2.30, g ⊥ = 2.07, | A // | = 161 G.
また、X線結晶構造解析により得られた結晶構造を図１に示す。図１に示すように、得られた化合物は、一般式（Ｉ）の単核銅錯体において、Ｒ１，Ｒ２がエチル基、Ｒ３が水素原子、Ｒ４がプロピルスルホ基であり、金属原子Ｍが銅 (Cu)、３つのＸがそれぞれ水、エタノール、過塩素酸である単核銅錯体[Cu(E2pbbim)(EtOH)(H2O)(ClO4)]である。なお、一般式（Ｉ）中の３つのＸを左から順にＸ１、Ｘ２、Ｘ３とすると、Ｘ２が過塩素酸(ClO4)である。 The crystal structure obtained by X-ray crystal structure analysis is shown in FIG. As shown in FIG. 1, the obtained compound is a mononuclear copper complex of the general formula (I), wherein R 1 and R 2 are ethyl groups, R 3 is a hydrogen atom, R 4 is a propylsulfo group, A mononuclear copper complex [Cu (E 2 pbbim) (EtOH) (H 2 O) (ClO 4 )] in which the atom M is copper (Cu) and the three Xs are water, ethanol and perchloric acid, respectively. Incidentally, when the general formula 3 X in (I) from left X 1, X 2, X 3 in this order, X 2 is perchlorate (ClO 4).
〈新規単核銅錯体を用いてのベンゼンの酸化反応〉
上記合成法によって得られた新規単核銅錯体[Cu(E2pbbim)(EtOH)(H2O)(ClO4)]を用いて、次の酸化反応スキームに示されるベンゼンの酸化反応を試みた。
Using the new mononuclear copper complex [Cu (E 2 pbbim) (EtOH) (H 2 O) (ClO 4 )] obtained by the above synthesis method, the oxidation reaction of benzene shown in the following oxidation reaction scheme was attempted. It was.
銅(II)錯体2.0 mmol、基質2.0 mmol (1000 eq)をメタノール溶媒（MeOH）またはメタノール：水＝1 : 1の混合溶媒（MeOH/H2O）2 mlに溶解させ反応溶液に封入し、Ar置換を行った。これを恒温水槽25 oCにおいて、過酸化水素 4 mmol (2000 eq)をシリンジにて添加して攪拌することにより２４時間反応を行った。反応終了後、反応溶液を約20 ml取り出し、2 mlのジエチルエーテルを添加し脱金属を行った後、内部標準物質として15 mMのｏ-ジクロロベンゼン/ジエチルエーテル溶媒20 ml 1を加えた溶液を用いてGC-Massクロマトグラフ測定を行った。 Copper (II) complex 2.0 mmol, substrate 2.0 mmol (1000 eq) was dissolved in 2 ml of methanol solvent (MeOH) or methanol: water = 1: 1 mixed solvent (MeOH / H 2 O), and sealed in the reaction solution. Ar substitution was performed. This was reacted for 24 hours by adding 4 mmol (2000 eq) of hydrogen peroxide with a syringe and stirring in a constant temperature water bath at 25 ° C. After completion of the reaction, about 20 ml of the reaction solution is taken out, 2 ml of diethyl ether is added and demetalized, and then a solution containing 15 mM o-dichlorobenzene / diethyl ether solvent 20 ml 1 is added as an internal standard substance. GC-Mass chromatograph measurement was performed.
その結果、反応生成物としてフェノールのみが存在することを確認した。すなわち、所定量のフェノールを含む溶液（検量線用試料）のＧＣ測定においてフェノールのピークが１２．２分に検出されたのに対し、測定試料のＧＣ測定においても上記検量線とほぼ一致する時間（１２．２分）にピークが検出された。同様に、所定量の１，４−ベンゾキノンを含む溶液（検量線用試料）のＧＣ測定において１，４−ベンゾキノンのピークが８．７分に検出されたのに対し、測定試料のＧＣ測定においては検出されなかった。さらにマススペクトルにおいて分子量９４に有機物のピークが観測され、フェノールのスペクトルパターンと良い一致を示した。これらの測定結果から、ベンゼンの一段階酸化（直接酸化）にフェノールのみが生成したことを確認した。 As a result, it was confirmed that only phenol was present as a reaction product. That is, while the peak of phenol was detected at 12.2 minutes in the GC measurement of a solution containing a predetermined amount of phenol (sample for calibration curve), the time almost coincided with the calibration curve in the GC measurement of the measurement sample. A peak was detected at (12.2 minutes). Similarly, the peak of 1,4-benzoquinone was detected at 8.7 minutes in the GC measurement of a solution (calibration curve sample) containing a predetermined amount of 1,4-benzoquinone, whereas in the GC measurement of the measurement sample Was not detected. Furthermore, in the mass spectrum, an organic peak was observed at a molecular weight of 94, which was in good agreement with the phenol spectrum pattern. From these measurement results, it was confirmed that only phenol was produced in the one-step oxidation (direct oxidation) of benzene.
同様の操作を、メタノールの代わりにアセトニトリル（MeCN）やアセトニトリル：水＝1：1の混合溶媒（MeCN/H2O）を用いて行った。このとき反応生成物としてフェノール、ベンゾキノンが共に生成したことをGC-MSにより確認した。 The same operation was performed using acetonitrile (MeCN) or a mixed solvent of acetonitrile: water = 1: 1 (MeCN / H 2 O) instead of methanol. At this time, it was confirmed by GC-MS that both phenol and benzoquinone were formed as reaction products.
生成したフェノール、ベンゾキノンの生成量をGC測定により求め、この反応における錯体のＴＯＮ（Turn Over Number）を算出した結果を表１に示す。なお、本例におけるＴＯＮは、単核銅錯体一分子当たりの値として算出した。
酸化反応の結果、今回合成した親水性（極性）の単核銅錯体はベンゼンの触媒的酸化能を有することが分かった。 As a result of the oxidation reaction, it was found that the hydrophilic (polar) mononuclear copper complex synthesized this time has catalytic oxidation ability of benzene.
さらに、表１に示されるように、反応溶媒に極性非プロトン性溶媒であるアセトニトリル（MeCN）およびそれと水との混合溶媒（MeCN/H2O）を用いた場合では、フェノールの方がベンゾキノンよりもＴＯＮが大きくなった。 Furthermore, as shown in Table 1, when the reaction solvent is acetonitrile (MeCN), which is a polar aprotic solvent, and a mixed solvent thereof (MeCN / H 2 O), phenol is more preferable than benzoquinone. TON became bigger.
また、反応溶媒に極性プロトン性溶媒であるメタノール（MeOH）やそれと水との混合溶媒（MeOH/H2O）を用いた場合では、フェノールのみの生成を確認し、高選択的な水酸化反応が生じた。この理由の一つとして、親水性（極性）の単核銅錯体と極性プロトン性溶媒を用いたことでフェノールの過酸化が進まなかったのではないかと考えられる。 In addition, when methanol (MeOH), which is a polar protic solvent, or a mixed solvent of water and water (MeOH / H 2 O) is used as the reaction solvent, it is confirmed that only phenol is produced and a highly selective hydroxylation reaction is performed. Occurred. One reason for this is thought to be that the peroxidation of phenol did not proceed by using a hydrophilic (polar) mononuclear copper complex and a polar protic solvent.
Claims (4)
（式中のＲ１，Ｒ２，Ｒ３は、それぞれ独立に、水素原子及び炭素数１〜３の炭化水素基から選択されるいずれかであり、Ｒ４は炭素数０〜３で末端にスルホ基を持つ置換基であり得る。また、Ｍは、平面四配位型の配位構造を形成する金属原子であり、３つのＸのうち１つのＸはハロゲン原子もしくはカウンターイオンであり、残り２つのＸが溶媒分子である。）
で表される単核系金属錯体。 The following general formula (I):
(In the formula, R 1 , R 2 and R 3 are each independently selected from a hydrogen atom and a hydrocarbon group having 1 to 3 carbon atoms, and R 4 has 0 to 3 carbon atoms at the end. M may be a substituent having a sulfo group, M is a metal atom that forms a planar four-coordinated coordination structure, one of the three Xs is a halogen atom or a counter ion, and the rest Two X are solvent molecules.)
A mononuclear metal complex represented by
A method for synthesizing phenol, comprising synthesizing phenol by one-step oxidation of benzene, using an oxidation catalyst comprising the mononuclear metal complex according to claim 1 or 2 as an active ingredient and a protic solvent as a reaction solvent.
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