US20060229471A1 - Oxidation catalyst - Google Patents
Oxidation catalyst Download PDFInfo
- Publication number
- US20060229471A1 US20060229471A1 US10/565,886 US56588604A US2006229471A1 US 20060229471 A1 US20060229471 A1 US 20060229471A1 US 56588604 A US56588604 A US 56588604A US 2006229471 A1 US2006229471 A1 US 2006229471A1
- Authority
- US
- United States
- Prior art keywords
- group
- oxidation
- compound
- diphenyl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 307
- 230000003647 oxidation Effects 0.000 title claims abstract description 216
- 239000003054 catalyst Substances 0.000 title claims abstract description 170
- -1 hydrazine compound Chemical class 0.000 claims abstract description 176
- 239000000758 substrate Substances 0.000 claims abstract description 98
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 93
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 40
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical class [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 129
- 238000000034 method Methods 0.000 claims description 128
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 86
- 125000001424 substituent group Chemical group 0.000 claims description 77
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical group NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 72
- 125000001931 aliphatic group Chemical group 0.000 claims description 55
- 125000003118 aryl group Chemical group 0.000 claims description 46
- 125000005843 halogen group Chemical group 0.000 claims description 42
- 125000003277 amino group Chemical group 0.000 claims description 38
- 125000002252 acyl group Chemical group 0.000 claims description 36
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 36
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 36
- 125000000623 heterocyclic group Chemical group 0.000 claims description 36
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 35
- 125000001188 haloalkyl group Chemical group 0.000 claims description 35
- 125000003545 alkoxy group Chemical group 0.000 claims description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 33
- 125000004104 aryloxy group Chemical group 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 30
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 30
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 30
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 30
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 30
- 125000004414 alkyl thio group Chemical group 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 29
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 125000005110 aryl thio group Chemical group 0.000 claims description 28
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 28
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 28
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 28
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 28
- 150000003141 primary amines Chemical class 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 125000004434 sulfur atom Chemical group 0.000 claims description 20
- 125000004429 atom Chemical group 0.000 claims description 19
- 239000007983 Tris buffer Substances 0.000 claims description 16
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 15
- 150000002828 nitro derivatives Chemical class 0.000 claims description 15
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000003464 sulfur compounds Chemical class 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000012429 reaction media Substances 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 8
- 150000003623 transition metal compounds Chemical group 0.000 claims description 8
- PXTLWLYMJZWFKH-UHFFFAOYSA-N 2-[4-(fluoromethyl)-2,6-dinitrophenyl]-1,1-diphenylhydrazine Chemical compound [O-][N+](=O)C1=CC(CF)=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 PXTLWLYMJZWFKH-UHFFFAOYSA-N 0.000 claims description 7
- NPWBPAMPKBJBMW-UHFFFAOYSA-N 4-(2,2-diphenylhydrazinyl)-3,5-dinitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC(C#N)=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 NPWBPAMPKBJBMW-UHFFFAOYSA-N 0.000 claims description 7
- KJEBAQNNTMWJJI-UHFFFAOYSA-N 6-hydroxy-2-phenylpyridazin-3-one Chemical compound N1=C(O)C=CC(=O)N1C1=CC=CC=C1 KJEBAQNNTMWJJI-UHFFFAOYSA-N 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- FRLJBDXFYGRMJG-UHFFFAOYSA-N n-(2,4,6-trinitrophenyl)carbazol-9-amine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN1C2=CC=CC=C2C2=CC=CC=C21 FRLJBDXFYGRMJG-UHFFFAOYSA-N 0.000 claims description 7
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- QONKHQYUKPRLPQ-UHFFFAOYSA-N 2-(2,2-diphenylhydrazinyl)benzene-1,3,5-tricarbonitrile Chemical compound N#CC1=CC(C#N)=CC(C#N)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 QONKHQYUKPRLPQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- HCTZYGGLKQYBKK-UHFFFAOYSA-N (2,4,6-trinitrophenyl)hydrazine Chemical compound NNC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O HCTZYGGLKQYBKK-UHFFFAOYSA-N 0.000 claims description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 5
- MRCMWXNLYCLFAO-UHFFFAOYSA-N 1,3,5-triphenyl-2h-tetrazin-6-one Chemical compound O=C1N(C=2C=CC=CC=2)NN(C=2C=CC=CC=2)N=C1C1=CC=CC=C1 MRCMWXNLYCLFAO-UHFFFAOYSA-N 0.000 claims description 5
- FEGGBPURWBKGQC-UHFFFAOYSA-N 1,3,5-triphenyl-2h-tetrazine-6-thione Chemical compound S=C1N(C=2C=CC=CC=2)NN(C=2C=CC=CC=2)N=C1C1=CC=CC=C1 FEGGBPURWBKGQC-UHFFFAOYSA-N 0.000 claims description 5
- ZZVGBDZWJAETJG-UHFFFAOYSA-N 1-phenyl-1-[4-(trifluoromethyl)phenyl]-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC(=CC=1)C(F)(F)F)C1=CC=CC=C1 ZZVGBDZWJAETJG-UHFFFAOYSA-N 0.000 claims description 5
- QNHHPOGLKUAZQA-UHFFFAOYSA-N 2,3,4,6-tetraphenyl-1,3-dihydro-1,2,4,5-tetrazine Chemical compound N1N(C=2C=CC=CC=2)C(C=2C=CC=CC=2)N(C=2C=CC=CC=2)N=C1C1=CC=CC=C1 QNHHPOGLKUAZQA-UHFFFAOYSA-N 0.000 claims description 5
- TZDGXIDRXRKXPR-UHFFFAOYSA-N 2,4,6-triphenyl-1,3-dihydrotetrazine Chemical compound C1=CC=CC=C1C1=CN(C=2C=CC=CC=2)NN(C=2C=CC=CC=2)N1 TZDGXIDRXRKXPR-UHFFFAOYSA-N 0.000 claims description 5
- DHORJGJIZSYQQV-UHFFFAOYSA-N 3-phenyl-2h-phthalazine-1,4-dione Chemical compound O=C1C2=CC=CC=C2C(O)=NN1C1=CC=CC=C1 DHORJGJIZSYQQV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- 150000003254 radicals Chemical class 0.000 description 57
- 229910052760 oxygen Inorganic materials 0.000 description 50
- 239000001301 oxygen Substances 0.000 description 50
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 41
- 239000000126 substance Substances 0.000 description 35
- 125000004432 carbon atom Chemical group C* 0.000 description 32
- 239000007800 oxidant agent Substances 0.000 description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 25
- 0 *NN([1*])[2*].[1*]N([2*])N[3*] Chemical compound *NN([1*])[2*].[1*]N([2*])N[3*] 0.000 description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
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- 239000002904 solvent Substances 0.000 description 18
- 150000003335 secondary amines Chemical class 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 229910052796 boron Inorganic materials 0.000 description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 description 16
- 125000004437 phosphorous atom Chemical group 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 16
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- 239000010936 titanium Substances 0.000 description 14
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
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- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
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- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
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- MFHKEJIIHDNPQE-UHFFFAOYSA-N n-nonylnonan-1-amine Chemical compound CCCCCCCCCNCCCCCCCCC MFHKEJIIHDNPQE-UHFFFAOYSA-N 0.000 description 1
- QXJGVICBAANVMZ-UHFFFAOYSA-N n-octyloctan-1-imine oxide Chemical compound CCCCCCCC[N+]([O-])=CCCCCCCC QXJGVICBAANVMZ-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- MWBQWQYVNFFKFE-UHFFFAOYSA-N n-propan-2-ylpropan-2-imine oxide Chemical compound CC(C)[N+]([O-])=C(C)C MWBQWQYVNFFKFE-UHFFFAOYSA-N 0.000 description 1
- IYSYLWYGCWTJSG-XFXZXTDPSA-N n-tert-butyl-1-phenylmethanimine oxide Chemical compound CC(C)(C)[N+](\[O-])=C\C1=CC=CC=C1 IYSYLWYGCWTJSG-XFXZXTDPSA-N 0.000 description 1
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- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- CXISHLWVCSLKOJ-UHFFFAOYSA-N phenylacetaldehyde oxime Chemical compound ON=CCC1=CC=CC=C1 CXISHLWVCSLKOJ-UHFFFAOYSA-N 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 238000011403 purification operation Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
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- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
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- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- 125000003039 tetrahydroisoquinolinyl group Chemical group C1(NCCC2=CC=CC=C12)* 0.000 description 1
- DBDCNCCRPKTRSD-UHFFFAOYSA-N thieno[3,2-b]pyridine Chemical compound C1=CC=C2SC=CC2=N1 DBDCNCCRPKTRSD-UHFFFAOYSA-N 0.000 description 1
- 229940125670 thienopyridine Drugs 0.000 description 1
- 239000002175 thienopyridine Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- TUBPWKHKOQUJNE-UHFFFAOYSA-L titanium(2+);sulfate Chemical compound [Ti+2].[O-]S([O-])(=O)=O TUBPWKHKOQUJNE-UHFFFAOYSA-L 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SPASJIOXZJNDQO-UHFFFAOYSA-N trimethyl 2-(2,2-diphenylhydrazinyl)benzene-1,3,5-tricarboxylate Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(C(=O)OC)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 SPASJIOXZJNDQO-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions
- the present invention relates to an oxidation catalyst useful for chemical synthesis. More particularly, the present invention is concerned with an oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen, comprising at least one member selected from the group consisting of a specific hydrazyl radical and a specific hydrazine compound.
- an oxidation catalyst of the present invention By the use of the oxidation catalyst of the present invention, oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen can be efficiently performed under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity.
- the present invention is also concerned with a method for producing a chemical compound by using the oxidation catalyst of the present invention.
- An oxidation reaction is one of the most basic methods for material conversion in the field of organic synthesis.
- a number of oxidation processes have been put into practical use.
- oxidation reactions for example, oxygen oxidation reactions
- it has been desired to develop a new oxidation process which can be efficiently performed with high selectivity and at a low cost.
- Useful chemical compounds can be efficiently produced under moderate conditions with high selectivity by performing a selective oxidation reaction, using an oxidizing agent (such as hydrogen peroxide or an organic or inorganic peroxide) which can produce an active oxygen species (an electrophilic oxygen species) having high chemical potential (see, for example, “Shin Jikken Kagaku Koza 15, Sanka to Kangen I-2 (New Lecture on Experimental Chemistry 15, Oxidation and Reduction, I-2)”, edited by the Japan Chemical Society, p. 605, 1976, Japan; and “Catalytic Oxidations with Hydrogen Peroxide as Oxidant”, G. Strukul, Kluwer Academic Publishers, 1992, the Netherlands).
- an oxidizing agent such as hydrogen peroxide or an organic or inorganic peroxide
- Examples of selective oxidation reactions include oxidation of an alkane, oxidation of an alcohol, epoxidation of an olefin, oxidation of a ketone, oxidation of an aldehyde, oxidation of an ether, hydroxylation of an aromatic compound, oxidation of an amine and oxidation of a sulfur compound.
- t-butylhydroperoxide is also known.
- t-butylhydroperoxide has been produced, for example, by a method in which t-butanol or isobutylene as a substrate, namely a raw material, is reacted with a strong acid, such as sulfuric acid, and hydrogen peroxide (see, for example, “Yuki-Kasankabutsu (Organic Peroxides)”, edited by the Organic Peroxide Research Group, p. 220, 1972, Japan).
- the conventional method is disadvantageous from the viewpoint of economy and safety; specifically, the conventional method has disadvantages in that hydrogen peroxide (which is expensive) is necessary, and the raw material is reacted with a liquid mixture of a high concentration aqueous sulfuric acid (60 to 70 wt %) and a high concentration aqueous hydrogen peroxide (30 to 50 wt %).
- this method poses problems not only in that the catalyst activity of an imido compound is unsatisfactory, thus rendering it necessary to use the imido compound catalyst in an amount as large as about 10 mole %, based on the molar amount of the substrate, but also in that the imido compound is decomposed and consumed during the reaction, thus increasing the cost of producing a chemical compound by this method.
- a nitroxyl radical such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)
- TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
- an alcohol is converted selectively into a carbonyl compound or the like by using a catalyst comprising a combination of TEMPO and a ruthenium compound.
- this method poses problems in that not only is the catalyst activity unsatisfactory, but also the nitroxyl radical undergoes degradation during the reaction.
- a metal metalloporphyrin complex or a metallosalen complex is used as a catalyst
- a metal metalloporphyrin complex or a metallosalen complex is used as a catalyst
- an oxidative acetoxylation reaction of a diene by using a ternary catalyst system of [Pd salt/Co-porphyrin complex/hydroquinone] see Angew. Chem. Int. Ed. Engl., 32, 263, 1993
- a method in which a ternary catalyst system of [Ru complex/Co-salen complex/hydroquinone] is used to perform an oxidation reaction of a primary alcohol to form aldehyde or an oxidation reaction of a secondary alcohol to form a ketone
- Oxime compounds and nitro compounds are important chemical compounds for use as, for example, ordinary and fine chemicals and intermediates for synthesis of pharmaceuticals.
- Examples of methods for producing an oxime compound by oxidation of a primary amine include a method which uses dimethyl dioxirane as an oxidizing agent (see J. Org. Chem., 57, 6759, 1992), a method which uses hydrogen peroxide as an oxidizing agent and uses a sodium tungsten catalyst (see Angew. Chem., 72, 135, 1960), a method which uses hydrogen peroxide as an oxidizing agent and uses a methyltrioxorhenium catalyst (see Bull. Chem. Soc.
- Examples of methods for producing a nitro compound by oxidation of a primary amine include a method which uses m-chloroperbenzoic acid or a pertrifluoroacetic acid as an oxidizing agent (see J. Org. Chem., 58, 1372, 1993), a method which uses potassium permanganate as an oxidizing agent (see Org. Synth., 52, 77, 1972), a method which uses ozone as an oxidizing agent (see Synthetic Commun., 20, 1073, 1990), a method which uses t-butylhydroperoxide as an oxidizing agent and uses a catalyst comprising chromium carried on a silica carrier (see J. Chem. Soc.
- Cyclohexanone oxime which is an oxime compound, is a chemical compound useful as an intermediate for producing ⁇ -caprolactam which is a raw material for producing nylon-6. Cyclohexanone oxime can be synthesized by reacting a cyclohexyl amine as a raw material with an oxidizing agent. Examples of methods for producing cyclohexanone oxime by using hydrogen peroxide as an oxidizing agent include (1) a method which uses a catalyst containing at least one metal selected from the group consisting of Mo, W and U (see U.S. Pat. No.
- Examples of methods for producing cyclohexanone oxime by using a molecular oxygen as an oxidizing agent include (4) a method in which a gaseous phase reaction is performed using a solid catalyst comprising an SiO 2 gel, ⁇ -Al 2 0 3 and optionally WO 3 (see U.S. Pat. Nos.
- the above-mentioned methods (1) to (3) have problems not only in that the oxidizing agent used (i.e., hydrogen peroxide or an organic hydroperoxide) is expensive, but also in that the selectivity for and yield of the cyclohexanone oxime produced are not always high, and also there is the known operational danger (explosiveness) of the oxidizing agent when the reaction is performed on a commercial scale.
- the oxidizing agent used i.e., hydrogen peroxide or an organic hydroperoxide
- an organic hydroperoxide there is also a problem in that a by-product generated by reduction of the organic hydroperoxide is contained in the reaction mixture, thus rendering cumbersome the separation and purification operations.
- the above-mentioned methods (4) to (7) which use a molecular oxygen (such as air or oxygen gas), have been proposed.
- the gaseous phase reaction is performed under relatively stringent reaction conditions using a reaction temperature of from 120 to 250° C.
- a reaction temperature of from 120 to 250° C.
- the above-mentioned methods (4) and (5) pose a problem in that, when the reaction temperature is 160° C. or more, a tar-like by-product and a high boiling point organic carbonaceous material accumulate on the surface of the catalyst, thus causing a rapid deactivation of the catalyst.
- the methods (4) and (5) are disadvantageous in that the selectivity for cyclohexanone oxime is as low as about 50 to 60% at a conversion of 20%, thus causing a lowering of the amount of reaction product per unit volume of the space of reaction, i.e., a lowering of the productivity.
- the gaseous phase reaction is performed under relatively moderate reaction conditions using a reaction temperature of from 50 to 150° C.
- the prior art document describing the method (6) discloses a reaction in which t-butanol is used as a reaction solvent and phosphotungstic acid is used as a catalyst; however, the method (6) has a problem in that the yield of cyclohexanone oxime is as low as only few percent.
- the prior art document describing the method (7) discloses a reaction in which a titanium compound is used as a catalyst, and diethylene glycol dimethyl ether (i.e., diglyme), t-butanol, dimethyl formamide, acetonitrile, triethylamine or water is used as a reaction solvent; however, the method (7) has problems in that the selectivity for cyclohexanone oxime is as low as about 30 to 50% and also the catalyst activity is low.
- Nitrone compounds which are induced by oxidation of amines, are important chemical compounds for use as intermediates for synthesis of pharmaceuticals, agrichemicals and fine chemicals, such as an ⁇ -substituted amine compound, an amino acid and an alkaloid.
- a method for producing a nitrone compound there is known a method in which a secondary amine is reacted with hydrogen peroxide. Examples of such methods for producing a nitrone compound include a method which uses a sodium tungsten catalyst (see Unexamined Japanese Patent Application Laid-Open Specification No. Sho 59-164762 (corresponding to U.S. Pat. No.
- an oxidation method which can be used to produce various desired chemical compounds (for example, to produce an oxime compound or a nitro compound from a primary amine or produce a nitrone compound from a secondary amine) by an oxidation reaction (such as an oxygen oxidation reaction) performed under moderate conditions with high selectivity and high efficiency. It has also been desired to develop a high performance oxidation catalyst used for the oxidation method.
- an oxidation catalyst which can be used to efficiently perform oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity.
- a substrate such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound
- an oxidation catalyst comprising a specific hydrazyl radical (such as 2,2-diphenyl-1-picrylhydrazyl) and/or a specific hydrazine compound (such as 2,2-diphenyl-1-picrylhydrazine) or by the use of an oxidation catalyst comprising a combination of the above-mentioned hydrazyl radical and/or hydrazine compound with an oxidation promoter (such as a transition metal compound), oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen can be performed under moderate conditions, thereby enabling production of a desired chemical compound with high selectivity and high efficiency.
- the present invention has been completed, based on this finding.
- an object of the present invention is to provide an oxidation catalyst which can be used to efficiently perform oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity.
- a substrate such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound
- Another object of the present invention is to provide a method for producing a chemical compound by using the above-mentioned oxidation catalyst.
- oxidation catalyst of the present invention By the use of the oxidation catalyst of the present invention, oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen can be efficiently performed under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity.
- a substrate such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound
- an oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen comprising at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) below and a hydrazine compound represented by the formula (2) below,
- a method for producing a chemical compound comprising contacting a substrate with a molecular oxygen in the presence of the above-mentioned oxidation catalyst, thereby performing an oxidation reaction to form a chemical compound.
- An oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen comprising at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) below and a hydrazine compound represented by the formula (2) below,
- each of R 1 , R 2 and R 3 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- each of R 4 , R 5 , R 6 , R 7 and R 8 independently represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
- each of R 1 and R 2 has the same definition as each of R 4 to R 8 except that any of R 1 and R 2 does not represent a hydrogen atom;
- R 1 and R 2 are optionally bonded to each other, to thereby form a ring
- substituents selected from the group consisting of a pair of substituents R 4 and R 5 , a pair of substituents R 5 and R 6 , a pair of substituents R 6 and R 7 and a pair of substituents R 7 and R 8 , the substituents of the or each pair are optionally bonded to each other, to thereby form a ring or two rings.
- hydrazyl radical is selected from the group consisting of 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, N,N-diphenyl-N′-(2,4,6 tricyanophenyl)hydrazyl, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazyl, carbazol-9-yl(2,4,6-trinitrophenyl)amidogen and N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazyl, and
- the hydrazine compound is selected from the group consisting of 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazine, carbazol-9-yl(2,4,6-trinitrophenyl)amine and N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazine.
- each of R 1 , R 2 and R 9 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- hydrazyl radical is selected from the group consisting of 1-phenylpyrazolidone-(3)-radical and 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl, and
- the hydrazine compound is selected from the group consisting of 1-phenylpyrazolidine-3-one, 1-phenyl-1,2-dihydropyridazine-3,6-dione and 2-phenyl-2,3-dihydrophthalazine-1,4-dione.
- each of R 10 , R 11 and R 12 independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkyl-thio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
- R 13 has the same definition as each of R 10 to R 12 except that R 13 does not represent a hydrogen atom
- hydrazyl radical is selected from the group consisting of 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5,6-tetraphenylverdazyl, 1,3,5-triphenyl-6-oxoverdazyl and 1,3,5-triphenyl-6-thioxoverdazyl, and
- the hydrazine compound is selected from the group consisting of 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 1,3,5-triphenyl-6-oxotetrazine and 1,3,5-triphenyl-6-thioxotetrazine.
- oxidation catalyst according to any one of items 1 to 8 above, which further comprises an oxidation promoter.
- transition metal is at least one member selected from the group consisting of the elements of the Groups 3 to 12 of the Periodic Table.
- transition metal is at least one member selected from the group consisting of lanthanoids, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn and Cd.
- a method for producing a chemical compound comprising contacting a substrate with a molecular oxygen in the presence of the oxidation catalyst of any one of items 1 to 12 above, thereby performing an oxidation reaction to form a chemical compound.
- the substrate is selected from the group consisting of a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound and a heterocyclic compound.
- each of R 1 and R 2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, provided that R 1 and R 2 are not simultaneously hydrogen atoms;
- R 1 and R 2 are optionally bonded to each other, to thereby form a ring.
- each of R 1 and R 2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, and R 3 has the same definition as each of R 1 and R 2 except that R3 does not represent a hydrogen atom;
- aprotic solvent is at least one member selected from the group consisting of a nitrile, a nitro compound, an ester, an ether and an amide.
- nitrile is at least one member selected from the group consisting of acetonitrile and benzonitrile.
- amide is at least one member selected from the group consisting of dimethylformamide and dimethylacetamide.
- oxidation catalyst further comprises an oxidation promoter, and the oxidation promoter is used in an amount of from 0.00005 to 0.8 mole per mole of the substrate.
- the oxidation catalyst of the present invention is an oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen, comprising at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) below and a hydrazine compound represented by the formula (2) below,
- each of R 1 , R 2 and R 3 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- the aliphatic group mentioned above may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the aromatic group mentioned above may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the hydroxyl group mentioned above may form a salt with a metal atom.
- a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- the aliphatic group has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; the aromatic group has 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms; the acyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; the alkoxycarbonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; the aryloxycarbonyl group has 5 to 10 carbon atoms; the alkoxyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; the aryloxy group has 5 to 10 carbon atoms; the haloalkyl group has 1 to 6 carbon atoms; and the alkylthio group has 1 to 6 carbon atoms.
- heterocyclic group means a substituent formed from a heteromonocyclic compound, such as furan, thiophene, pyrrole, ⁇ -pyran, thiopyran, pyridine, morpholine, thiazole, imidazole, pyrimidine and 1,3,5-triazine; or a condensed heterocyclic compound, such as indole, quinoline, purine, pteridine, chromane, carbazole, benzothiazole, benzotriazole, benzoisoquinoline and thienopyridine.
- a heteromonocyclic compound such as furan, thiophene, pyrrole, ⁇ -pyran, thiopyran, pyridine, morpholine, thiazole, imidazole, pyrimidine and 1,3,5-triazine
- a condensed heterocyclic compound such as indole, quinoline, purine, pteridine, chromane, carbazole
- R 1 and R 2 in the formulae (1) and (2) above include an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a haloalkyl group and a heterocyclic group.
- Preferred examples of R 3 include an aliphatic group, an aromatic group, a cyano group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloalkyl group and a heterocyclic group.
- These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- hydrazyl radicals represented by the formula (1) above and a hydrazine compound represented by the formula (2) above there can be mentioned a hydrazyl radical and a hydrazine compound respectively represented by the following formulae (3) and (4):
- each of R 4 , R 5 , R 6 , R 7 and R 8 independently represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups; each of R 1 and R 2 has the same definition as
- R 1 and R 2 are optionally bonded to each other, to thereby form a ring
- substituents selected from the group consisting of a pair of substituents R 4 and R 5 , a pair of substituents R 5 and R 6 , a pair of substituents R 6 and R 7 and a pair of substituents R 7 and R 8 , the substituents of the or each pair are optionally bonded to each other, to thereby form a ring or two rings.
- the aliphatic group mentioned above may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the aromatic group mentioned above may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the hydroxyl group mentioned above may form a salt with a metal atom.
- a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an
- R 1 and R 2 in the formulae (3) and (4) include an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a haloalkyl group and a heterocyclic group.
- R 4 , R 5 , R 6 , R 7 and R 8 include a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a nitro group, a cyano group, an amino group, an imino group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- hydrazyl radicals represented by the formula (3) above include triphenyl-hydrazyl, 2,2-diphenyl-1-(5′-phenyl-m-terphenyl-2′-yl)hydrazyl, 2,2-diphenyl-(2-nitrophenyl)hydrazyl, 2,2-diphenyl-(2,4-dinitrophenyl)hydrazyl, 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(3-chloro-2,4,6-trinitrophenyl)hydrazyl, 1-[3-(4-morpholinyl)-2,4,6-trinitrophenyl]-2,2-diphenylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, N′-(2,4-dinitro-6-trifluoromethylphenyl)-N,N-diphenylhydrazyl, 2,2-diphenyl-1-
- hydrazyl radicals represented by the formula (3) include 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-methoxycarbonyl-phenyl)hydrazyl, N,N-diphenyl-N′-(2,6-dinitro-4-sulfophenyl)hydrazyl, N,N-diphenyl-N-(2,4,6-tricyanophenyl)hydrazyl, 2,2-diphenyl-1-(2,4,6-tricyano-3,5-difluorophenyl)hydrazyl, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 1,3,5
- hydrazyl radicals more preferred are 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazyl, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazyl, carbazol-9-yl(2,4,6-trinitrophenyl)amidogen, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazyl and the like, and especially preferred is 2,2-diphenyl-1-picrylhydrazy
- hydrazine compounds represented by the formula (4) above include triphenylhydrazine, 2,2-diphenyl-1-(5′-phenyl-m-terphenyl-2′-yl)hydrazine, 2,2-diphenyl-(2-nitrophenyl)hydrazine, 2,2-diphenyl-(2,4-dinitrophenyl)hydrazine, 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(3-chloro-2,4,6-trinitrophenyl)hydrazine, 1-[3-(4-morpholinyl)-2,4,6-trinitrophenyl]-2,2-diphenylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, N′-(2,4-dinitro-6-trifluoromethylphenyl)-N,N-diphenylhydrazine, 2,2-diphenyl-1-(
- hydrazine compounds represented by the formula (4) include 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-methoxycarbonyl-phenyl)hydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-sulfophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyano-3,5-difluorophenyl)hydrazine, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 1,3,
- hydrazine compounds more preferred are 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazine, carbazol-9-yl(2,4,6-trinitrophenyl)amine, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazine and the like, and especially preferred is 2,2-diphenyl-1
- hydrazyl radicals represented by the formula (1) and a hydrazine compound represented by formula (2) there can be mentioned a hydrazyl radical and a hydrazine compound respectively represented by the following formulae (5) and (6):
- each of R 1 , R 2 and R 9 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- the aliphatic group mentioned above may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the aromatic group mentioned above may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the hydroxyl group mentioned above may form a salt with a metal atom.
- a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an
- R 1 and R 2 in the formulae (5) and (6) above include an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a haloalkyl group and a heterocyclic group.
- Preferred examples of R 9 include an aliphatic group, an aromatic group, an alkoxyl group, an aryloxy group, a haloalkyl group and a heterocyclic group.
- These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- hydrazyl radicals represented by the formula (5) above include N-benzoyl-N,N′-diphenylhydrazyl, 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazyl, N-(2-nitrobenzoyl)-N′,N′-diphenylhydrazyl, N-benzoyl-N′,N′-bis-(4-nitrophenyl)hydrazine, 1-(trifluoroacetyl)-2,2-bis(3,5-di-tert-butylphenyl)hydrazyl, tribenzoylhydrazoyl radical, 1-phenylpyrazolidone-(3)-radical, 5-methyl-1-phenyl-3-pyrazolidone radical, 2,5-dioxo-4-phenyl-[1,3,4]oxadiazolidine-3-yl, 4,4-dimethyl-3,5-dioxo-2-phenyl-1-pyrazolidinyl, 1-phenyl
- hydrazyl radicals represented by the formula (5) above include 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazyl, tribenzoyl-hydrazoyl radical, 1-phenylpyrazolidone-(3)-radical, 2,5-dioxo-4-phenyl-[1,3,4]oxadiazolidine-3-yl, 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl and 3,4-dihydro-3-(4-nitrophenyl)-1,4-dioxo-2-phthalazinyl.
- hydrazyl compounds more preferred are 1-phenylpyrazolidone-(3)-radical, 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl and the like.
- hydrazine compounds represented by the formula (6) above include benzoic acid-(N′,N′-diphenylhydrazide), 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazine, 2-nitro-benzoic acid-(N′,N′-diphenylhydrazide), benzoic acid-[N′,N′-bis-(4-nitrophenyl)hydrazide], 1-(trifluoroacetyl)-2,2-bis(3,5-di-tert-butylphenyl)hydrazide, tribenzoyl-hydrazine, 1-phenylpyrazolidine-3-one, 5-methyl-1-phenyl-3-pyrazolidine-3-one, 3-phenyl-[1,3,4]oxadiazolidine-2,5-dione, 4,4-dimethyl-1-phenylpyrazolidine-3,5-dione, 4,4-diethyl-1-phenylpyrazolidine-3,5-
- hydrazine compounds represented by the formula (6) above include 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazine, tribenzoyl-hydrazine, 1-phenylpyrazolidine-3-one, 3-phenyl-[1,3,4]oxadiazolidine-2,5-dione, 1-phenyl-1,2-dihydropyridazine-3,6-dione, 2-phenyl-2,3-dihydrophthalazine-1,4-dione and 2-(4-nitrophenyl)-2,3-dihydrophthalazine-1,4-dione.
- hydrazine compounds more preferred are 1-phenylpyrazolidine-3-one, 1-phenyl-1,2-dihydropyridazine-3,6-dione, 2-phenyl-2,3-dihydrophthalazine-1,4-dione and the like.
- hydrazyl radicals represented by the formula (1) and a hydrazine compound represented by the formula (2) there can be mentioned hydrazyl radical and hydrazine compound respectively represented by the following formulae (7) and (8):
- each of R 10 , R and R 12 independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
- R 13 has the same definition as each of R 10 to R 12 except that R 13 does not represent a hydrogen atom; and wherein two substituents selected from the group consisting of R 11 , R 12 and R 13 are optionally bonded to each other, to thereby form a ring.
- the aliphatic group may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the aromatic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- the hydroxyl group may form a salt with a metal atom.
- a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may also be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an
- R 10 , R 11 and R 12 in the formulae (7) and (8) above include a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a nitro group, an amino group, an imino group, a carbonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxyl group, an aryloxy group, and a heterocyclic group.
- preferred examples of R 13 are the same as those (except a hydrogen atom) exemplified in connection with R 10 , R 11 and R 12 .
- These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- hydrazyl radicals represented by the formula (7) include 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5-tris-(p-chlorophenyl)verdazyl, 2,6-diphenyl-4-pentafluorophenylverdazyl, 2,4-bisperfluorophenyl-6-phenylverdazyl, 2,4,6-trisperfluorophenylverdazyl, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]verdazyl, 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,4,5]verdazyl, 1-(4-nitrophenyl)-3,5-diphenylverdazyl, 6-anthracene-9yl-2,4-dip
- hydrazyl radicals represented by the formula (7) include 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,3,4]verdazyl, 1-(4-nitrophenyl)-3,5-diphenylverdazyl, 6-anthracene-9-yl-2,4-diphenyl1,2,3,4-tetrahydro-[1,2,4,5]verdazyl, 1,3,5,6-tetraphenylverdazyl, 6-methyl-3-nitro-1,5-diphenylverdazyl, 1,3,5-triphenyl-6-oxoverdazyl and 1,3,5-triphenyl-6-thioxoverdazyl.
- hydrazyl radicals more preferred are 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5,6-tetraphenylverdazyl, 1,3,5-triphenyl-6-oxoverdazyl, 1,3,5-triphenyl-6-thioxoverdazyl and the like.
- hydrazine compounds represented by the formula (8) include 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 1,3,5-tris-(p-chlorophenyl)tetrazine, 2,6-diphenyl-4-pentafluoro-1,2,3,4-tetrahydro-tetrazine, 2,4-bis(perfluorophenyl)-6-phenyl-1,2,3,4-tetrahydro-tetrazine, 2,4,6-tris(perfluorophenyl)-1,2,3,4-tetrahydro-tetrazine, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2-(2-(
- Preferred examples of hydrazine compounds represented by the formula (8) include 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2-(4-nitrophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 6-anthracene-9-yl-2,4-diphenyll,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 3-methyl-6-nitro-2,4-diphen
- hydrazine compounds more preferred are 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 1,3,5-triphenyl-6-oxotetrazine, 1,3,5-triphenyl-6-thioxotetrazine and the like.
- hydrazyl radical of formula (1) and/or hydrazine compound of formula (2) may be used individually or in combination (hereinafter, the above-mentioned at least one member is frequently referred to as “hydrazyl radical of formula (1) and/or hydrazine compound of formula (2)”).
- the amount of hydrazyl radical of formula (1) and/or hydrazine compound of formula (2) may vary depending on the type of the oxidation reaction, and there is no particular limitation as long as the desired catalytic effect can be achieved. However, the amount is generally from 0.0001 to 1 mole, preferably from 0.0005 to 0.5 mole, more preferably 0.001 to 0.3 mole, per mole of the substrate.
- the amount of each compound is generally from 0.001 to 0.999 mole, preferably from 0.01 to 0.99 mol, more preferably 0.1 to 0.9 mole per mole of the other compound.
- the at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2) may be carried on a carrier.
- carriers include an organic polymer or a porous inorganic carrier, such as silica, silica-alumina, zeolite and activated carbon.
- the hydrazyl radical of formula (1) and/or hydrazine compound of formula (2) may be used in the form a complex with an oxidation promoter (such as a transition metal compound which is explained below), wherein, in the complex, the oxidation promoter serves as a carrier for the hydrazyl radical of formula (1) and/or hydrazine compound of formula (2).
- a hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2) can be prepared by conventional reaction methods.
- a hydrazine compound represented by the formula (2) is prepared as follows: a hydrazine compound having substituents which are the same as R 1 and R 2 in the formula (2) and a halide having a substituent which is the same as R 3 in the formula (2) are subjected to condensation reaction, thereby obtaining a hydrazine compound represented by the formula (2).
- an oxidizing agent such as PbO 2 , KMnO 4 or CrO 3 , there is obtained a hydrazyl radical represented by the formula (1).
- 2,2-diphenyl-1-picrylhydrazine can be obtained by heating under reflux a mixture of diphenylhydrazine, picryl chloride and sodium hydrogencarbonate in an ethanol solvent and, then, crystallizing the resultant with benzene-ethanol.
- 2,2-Diphenyl-1-picrylhydrazyl can be obtained by oxidizing the obtained 2,2-diphenyl-1-picrylhydrazine with PbO 2 in a benzene solvent in the presence of sodium sulfate, wherein the PbO 2 is used in a molar amount which is 10 to 20 times the molar amount of the hydrazine.
- hydrazine compounds and hydrazyl radicals can be easily prepared by the above-mentioned method using respective corresponding materials.
- the oxidation promoter which is optionally used in the present invention, promotes an oxidation reaction when added to the reaction system together with the at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2).
- a hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2).
- an oxidation promoter there can be used various types of metals including the metal elements of Groups 1 to 16 of the Periodic Table.
- An oxidation promoter may be used in the form of a metal oxide, a metal salt, or an organometal compound. However, it is preferred that an oxidation promoter is a metal compound which contains at least one metal element selected from the group of transition metal elements.
- transition metal elements of the transition metal compounds at least one element selected from the elements of Groups 3 to 12 of the Periodic Table is preferred.
- the elements of Group 3 preferred are lanthanoids, such as La, Ce, Sm, Eu, Ac and Th.
- the elements of Group 4 preferred are Ti, Zr and Hf.
- the elements of Group 5 preferred are V, Nb and Ta.
- the elements of Group 6 preferred are Cr, Mo and W.
- the elements of Group 7 preferred are Mn and Re.
- preferred preferred are Fe, Ru and Os.
- the elements of Group 10 preferred are Ni, Pd and Pt.
- the elements of Group 11 preferred are Cu, Ag and Au.
- the elements of Group 12 preferred are Zn and Cd.
- transition metal compounds include inorganic metal compounds, such as simple substances of the above-mentioned transition metal elements, hydroxides, oxides (including compound oxides), halides (a fluoride, a chloride, a bromide and an iodide), oxo-acid salts (e.g., a nitrate, a sulfate, a phosphate, a borate, a perchlorate and a carbonate), oxo-acids and polyacids (isopoly acids and heteropoly acids); and organometal compounds, such as organic salts (e.g., an acetate, a propionate, a thiocyanate, a naphthenate and a stearate) and complexes.
- inorganic metal compounds such as simple substances of the above-mentioned transition metal elements, hydroxides, oxides (including compound oxides), halides (a fluoride, a chloride, a bromide and
- ligands which form the above-mentioned complexes there can be mentioned hydroxyl, alkoxyl, acyl, alkoxycarbonyl, acetylacetonato, cyclopentadienyl, a halogen atom, carbonyl, an oxygen atom; and compounds, such as H 2 0 (aquo), phosphine, CN, NO, NO 2 , NO 3 , NH 3 (ammine), ethylenediamine, pyridine and phenanthroline.
- the above-mentioned metal compounds can be used individually or in combination.
- metal elements or metal compounds may be used in the form of a salt or a complex with the oxidation catalyst of the present invention (comprising hydrazyl radical of formula (1) and/or hydrazine compound of formula (2)).
- transition metal compounds include tungsten compounds, such as metal tungsten, tungsten oxide, tungsten oxytetrachloride, tungstic acid, sodium tungstate, zinc tungstate, cobalt tungstate, cesium tungstate, tungsten hexacarbonyl, tungsten pentaethoxide, tungsten hexaphenoxide, silicotungstate, metatungstate, phosphotungstate, cobalt tungstate, molybdenum tungstate, manganese tungstate and manganese molybdenum tungstate.
- tungsten compounds such as metal tungsten, tungsten oxide, tungsten oxytetrachloride, tungstic acid, sodium tungstate, zinc tungstate, cobalt tungstate, cesium tungstate, tungsten hexacarbonyl, tungsten pentaethoxide, tungsten hexaphenoxide, silicotungstate, metatungstate, phosphotungstate, cobalt
- titanium compounds include metal titanium, titanium oxide, titanium tetrachloride, titanium(II) sulfate, (acetylacetonato)titanium oxide, titanium tetraethoxide, titanium tetra-iso-propoxide, titaniumu tetra-iso-butoxide, titanium naphthenate, titanium silicalite molecular sieves, titanium phosphate, zirconium titanate, sodium titanate and barium titanate.
- metal titanium titanium oxide, titanium tetrachloride, titanium(II) sulfate, (acetylacetonato)titanium oxide, titanium tetraethoxide, titanium tetra-iso-propoxide, titaniumu tetra-iso-butoxide, titanium naphthenate, titanium silicalite molecular sieves, titanium phosphate, zirconium titanate, sodium titanate and barium titanate.
- molybdenum compounds include metal molybdenum, molybdenum oxide, molybdenum chloride, molybdenum 2-ethylhexanate, molybdenum hexacarbonyl, bis(acetylacetonato) molybdenum oxide, molybdic acid, sodium molybdate, molybdophosphate, molybdosilicate, cobalt molybdate, manganese molybdate, vanadomolybdophosphate, manganese vanadium molybdate and manganese vanadium molybdophosphate.
- compounds of other metal elements there can be mentioned compounds corresponding to the above-mentioned tungsten compounds, titanium compounds and molybdenum compounds.
- Transition metal compounds may be homogenous or heterogeneous, and may be a heterogeneous solid wherein metal components are carried on an appropriate carrier.
- carriers there can be mentioned activated carbon, SiO 2 , Al 2 O 3 , SiO 2 /Al 2 O 3 , TiO 2 , ZrO 2 , ZnO, barium sulfate, potassium carbonate, silious earth and zeolite.
- methods used for preparing an oxidation promoter in which metal components are carried on a carrier there can be mentioned methods used for producing conventional carrier-supported catalysts, for example, an absorption method, an impregnation method, a coprecipitation method and a sol-gel method.
- the amount of metal components carried on a carrier is from 0.0001 to 0.8 part by weight, preferably from 0.001 to 0.5 part by weight, more preferably from 0.01 to 0.3 part by weight, relative to 1 part by weight of the carrier.
- the amount of an oxidation promoter is generally from 0.00005 to 0.8 mole, preferably from 0.0001 to 0.4 mole, still more preferably from 0.0005 to 0.2 mole, per mole of the substrate.
- the amount ratio (molar ratio) of hydrazyl radical of formula (1) and/or hydrazine compound of formula (2) (referred to as “oxidation catalyst” below) to an oxidation promoter (i.e., “oxidation catalyst/oxidation promoter” molar ratio) is generally from 99/1 to 1/99, preferably from 90/10 to 10/90, still more preferably from 80/20 to 20/80.
- substrates which can be used in the oxidation reaction method of the present invention include various substrates which can be used in the selective oxidation reactions explained above under “Prior Art”, such as hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and heterocyclic compounds.
- Oxidation products are as follows: from hydrocarbons, there can be obtained alcohols, aldehydes, ketones, epoxy compounds, carboxylic acids, peroxides and the like; from alcohols, there can be obtained aldehydes, ketones, carboxylic acids, peroxides and the like; from carbonyl compounds, there can be obtained carboxylic acids, peroxides and the like; from ethers, there can be obtained esters, acid anhydrides and the like; from amines, there can be obtained Schiff bases, nitriles, oximes, nitro compounds, hydroxylamines, nitrones, N-oxides and the like; from sulfur compounds, there can be obtained disulfides, sulfonic acids, sulfoxides and the like; and from heterocyclic compounds, there can be obtained N-oxides, sulfoxides and the like.
- the above-mentioned substrates may be substituted with various substituents, such as an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group.
- substituents such as an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro
- hydrocarbons include unsaturated or saturated, linear or branched aliphatic hydrocarbons, such as propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentan, 3-methylpentan, propylene, 2-butene, isobutene, butadiene, isoprene, 1-pentene, 1-hexene, 1-heptene, 3-methyl-1-butene, 2,3-dimethyl-1-butene and allyl chloride; unsaturated or saturated alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, chlorocyclohexane, methoxycyclohexane, cyclopentene, cyclohexene, cyclooc
- alcohols include unsaturated or saturated aliphatic alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, t-butanol, n-pentanol, n-hexanol, n-heptanol, allyl alcohol and crotyl alcohol; unsaturated or saturated alicyclic alcohols, such as cyclopentanol, cyclohexanol, cycloheptanol, methylcyclohexanol, cyclohexene-1-ol; aliphatic or alicyclic polyhydric alcohols, such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,2-cyclohexanediol and 1,4-cyclohedxanediol; and aromatic alcohols, such as benzyl alcohol, salicyl
- carbonyl compound means a compound which has at least one carbonyl group in a molecule thereof.
- specific examples of carbonyl compounds include aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 1-pentanal, 1-hexnal, 1-heptanal, 1-octanal, 1-nonanal, 1-decanal, acrolein, methacrolein, benzaldehyde, nitrobenzaldehyde, aminobenzaldehyde, glutaraldehyde, adipaldehyde; and ketones, such as acetone, methylethylketone, methylpropylketone, methylisopropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, cyclohexanone, cyclooctanone, cycl
- ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methylethyl ether, methylbutyl ether, ethylbutyl ether, diallyl ether, methyl vinyl ether, anisole, dibenzyl ether and phenyl benzyl ether.
- amines include aliphatic amines, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diusopropylamine, butylamine, dibutylamine, tributylamine, allylamine, diallylamine and triallylamine; alicyclic amines, such as cyclopentylamine, cyclohexylamine, cycloheptylamine and cyclooctylamine; and aromatic amines, such as aniline, N-methylaniline, N,N-dimethylaniline, toluidine, benzylamine and phenylenediamine.
- aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropy
- sulfur compounds include thiols, such as methanethiol, ethanethiol, 1-propanethiol, 1-butanethiol, 1-hexanethiol, 1-octanethiol, ethylene thioglycol, propylene thioglycol, cyclopentanthiol, cyclohexanethiol, methylcyclohexanethiol, phenylmethanethiol and 2-phenylethanethiol; and sulfides, such as diethyl sulfide, dipropyl sulfide, diusopropyl sulfide, dibutyl sulfide, methyl ethyl sulfide, methyl butyl sulfide, ethyl butyl sulfide, diallyl sulfide, methyl phenyl sulfide, ethyl phenyl
- heterocyclic compounds include furan, thiophene, pyrrole, thiopyran, pyridine, piperidine, morpholine, thiazole, imidazole, pyrimidine, 1,3,5-triazine, indole, quinoline, purine, chroman, carbazol, benzothiazole and benzoisoquinoline.
- substrates may be used individually or in combination. Further, it is not necessarily that a substrate be purified.
- a substrate may be used in the form of a mixture with other organic or inorganic compounds.
- amines are preferred.
- a primary amine and a secondary amine are preferred.
- the primary amines used in the present invention there is no particular limitation as long as the primary amine has a structure wherein an amino group has a substituent bonded thereto through a carbon atom thereof, wherein the carbon atom through which the substituent is bonded to the amino group has at least one hydrogen atom bonded thereto.
- the primary amine contains one or more of such an amino group in the molecule thereof.
- each of R 1 and R 2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, provided that R 1 and R 2 are not simultaneously hydrogen atoms;
- R 1 and R 2 are optionally bonded to each other, to thereby form a ring.
- the aliphatic group mentioned above represents an unsaturated or saturated, linear or branched aliphatic hydrocarbon group, or an unsaturated or saturated, alicyclic hydrocarbon group.
- the above-mentioned aliphatic group, aromatic group and aralkyl group may be substituted with a substituent, such as an aliphatic group, an aromatic group, an aralkyl group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo
- rings formed by bonding R 1 and R 2 include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring and a cyclododecane ring.
- the aliphatic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms;
- the aromatic group has 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms;
- the aralkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms.
- Such primary amines include methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, isopropylamine, isobutylamine, sec-butylamine, 1-methylbutylamine, 2-methylbutylamine, cyclopentylamine, cyclohexylamine, cyclododecylamine, benzylamine, 4-methylbenzylamine, 1-methylbenzylamine, 1-phenylethylamine, 3-aminomethylpyridine, 1-(4-chlorophenyl)ethylamine, 1-(3-methoxyphenyl)ethylamine, 1-(4-trifluoromethyl-phenyl)ethylamine, 1-phenylpropylamine, 1-(4
- R 1 and R 2 are as defined above for formula (9).
- oxime compounds include formaldehyde oxime, acetoaldehyde oxime, propionaldehyde oxime, n-butylaldehyde oxime, n-pentylaldehyde oxime, n-hexylaldehyde oxime, n-heptylaldehyde oxime, n-octylaldehyde oxime, n-nonylaldehyde oxime, n-decylaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, sec-butylaldehyde oxime, isopentylaldehyde oxime, 1-methyl propyl ketone oxime, 2-methylbutylaldehyde oxime, cyclobutanone oxime, cyclopentanone oxime, cyclohexanone oxi
- nitro compounds include nitromethane, nitroethane, 1-nitropropane, 1-nitrobutane, 1-nitropentane, 1-nitrohexane, 1-nitroheptane, 1-nitropropane, 2-nitrobutane, 3-methyl-1-nitrobutane, 1-methyl-1-nitrobutane, 2-methyl-1-nitrobutane, nitrocyclobutane, nitrocyclopentane, nitrocyclohexane, nitrocyclododecane, phenylnitromethane, 1-phenyl-1-nitroethane, 2-phenyl-1-nitroethane, 1-(4-chloro-phenyl)-1-nitroethane, 1-(3-methoxyphenyl)-1-nitro-ethane, 1-(2,4-dichlorophenyl)-1-nitroethane, 1-(4-tri-fluoromethylphenyl)-1-nitroethane, 1-phenyl-1-nitro-propane, 1-phenyl-2-(
- a primary amine which is especially preferred in the present invention is cyclohexylamine which generates cyclohexanone oxime as an oxidation product thereof.
- the secondary amines used in the present invention there is no particular limitation as long as the secondary amine has a structure wherein an amino group has two substituents bonded thereto each through a carbon atom thereof, wherein at least one of the two carbon atoms through which the two substituents are, respectively, bonded to the amino group has at least one hydrogen atom bonded thereto.
- the secondary amine contains one or more of such an amino group in the molecule thereof.
- each of R 1 and R 2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, and R 3 has the same definition as each of R 1 and R 2 except that R 3 does not represent a hydrogen atom;
- the aliphatic group mentioned above represents an unsaturated or saturated, linear or branched aliphatic hydrocarbon group, or an unsaturated or saturated, alicyclic hydrocarbon group.
- the above-mentioned aliphatic group, aromatic group and aralkyl group may be substituted with a substituent, such as an aliphatic group, an aromatic group, an aralkyl group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxy group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group
- rings formed by bonding two substituents selected from the group consisting of R 1 , R 2 and R 3 include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclododecane ring, a pyrrolidine ring, a pyperidine ring and a tetrahydroisoquinoline ring.
- the aliphatic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms; the aromatic group has 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms; and the aralkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms.
- Such secondary amines include N,N-dimethylamine, N,N-diethylamine, N,N-di-(n-propyl)amine, N,N-di-(n-butyl)amine, N,N-di-(n-pentyl)-amine, N,N-di-(n-hexyl)amine, N,N-di-(n-heptyl)amine, N,N-di-(n-octyl)amine, N,N-di-(n-nonyl)amine, N,N-di-(n-decyl)amine, N,N-diisopropylamine, N,N-isobutyl-amine, N,N-di-(sec-butyl)amine, N-ethyl-tert-butylamine, N,N-dibenzylamine, N-benzyl-tert-butylamine, N-benzyl-aniline, 1,
- R 1 , R 2 and R 3 are as defined above for formula (10).
- nitrone compounds include N-methylidenemethylamine N-oxide, N-ethylidenemethyl-amine N-oxide, N-propylidenemethylamine N-oxide, N-butylidenebutylamine N-oxide, N-pentylideneamylamine N-oxide, N-octylideneoctylamine N-oxide, N-nonylidenenonylamine N-oxide, N-decylidenedecylamine N-oxide, N-dodecylidenedodecylamine N-oxide, N-isopropylideneisopropylamine N-oxide, N-isobutylideneisobutylamine N-oxide, N-sec-butylidene-sec-butylamine N-oxide, N-isoamilideneisoamylamine N-oxide, N-ethylidene-tert-butylamine
- the oxidation reaction of the secondary amine when the oxidation reaction of the secondary amine is performed in the presence of an acceptor for a nitrone compound (the oxidation product), especially an olefin, it becomes possible to directly synthesize an addition product of the nitrone compound.
- the nitrone compound obtained by the method of the present invention is an excellent 1,3-dipole which undergoes an addition reaction with various olefins, to thereby generate a 1,3-dipole adduct.
- a dipole adduct is a precursor for physiological substances, such as an alkaloid, and is a very useful compound. Therefore, in the present invention, it is commercially very advantageous to perform the oxidation reaction of a secondary amine in the presence of an olefin.
- the oxidation reaction may be performed in either the liquid phase or the gaseous phase, and a liquid phase is preferred. Specifically, when the oxidation reaction is performed in the liquid phase, the oxidation reaction is either performed in a reaction medium which is at least one member selected from the group consisting of water and an organic solvent, or performed using the substrate as a reaction medium.
- organic solvent means either a protic organic solvent or an aprotic organic solvent.
- protic solvents include organic carboxylic acids, such as a primary, secondary or tertiary C 1 -C 10 alcohol (e.g., methanol, ethanol, isopropyl alcohol or t-butyl alcohol), formic acid, acetic acid and propionic acid.
- aprotic solvents include aliphatic hydrocarbons, such as hexane and octane; aromatic hydrocarbons, such as benzene and toluene; halogenated hydrocarbons, such as chloroform, dichloromethane, carbon tetrachloride and chlorobenzene; nitriles, such as acetonitrile, propionitrile and benzonitrile; nitro compounds, such as nitrobenzene, nitromethane and nitroethane; ethers, such as dimethylether, diethylether, dilsopropylether and dioxane; esters, such as ethylacetate and butylacetate; and amides, such as formamide, acetoamide, dimethylformamide, dimethylacetoamide, diethylacetoamide and hexamethylphosphoric triamide.
- aliphatic hydrocarbons such as hexane and octane
- aromatic hydrocarbons such
- nitriles, nitro compounds, esters, ethers and amides are preferred, and more preferred are are nitriles, such as acetonitrile and benzonitrile, and amides, such as dimethylformamide and dimethylacetoamide.
- the concentration of a substrate is generally in the range of from 0.1 to 95% by weight, preferably from 1 to 30% by weight, based on the total weight of the water and/or the organic solvent and the substrate.
- the oxidation reaction is performed by contacting a substrate with a molecular oxygen in the presence of an oxidation catalyst.
- the reaction may be performed by a fixed-bed process or a suspension-bed process and in any conventional manner of reaction, such as a batchwise manner, a semi-batchwise manner or a continuous manner.
- the molecular oxygen is purified oxygen, air or a gaseous mixture of oxygen and an inert gas, such as nitrogen or helium.
- the oxygen concentration of the gaseous mixture is in the range of from 2 to 23% by volume, more advantageously from 3 to 11% by volume; however, it is preferred that the oxygen concentration is in a range such that the resultant gaseous phase does not have an explosive composition.
- the oxidation of a substrate is performed in the liquid phase. Therefore, it is required that the molecular oxygen (which has been introduced as a gas into the reaction system) be dissolved in a desired concentration in the liquid phase containing the catalyst, under the conditions for the oxidation.
- a molecular oxygen hereinafter, frequently referred to as a “molecular oxygen-containing gas”
- a molecular oxygen-containing gas when a molecular oxygen (hereinafter, frequently referred to as a “molecular oxygen-containing gas”) is introduced into the reaction system under reduced pressure or atmospheric pressure and at a temperature at which a liquid reaction mixture containing the substrate, the reaction product and/or the solvent is refluxed, only a very small amount of oxygen can be dissolved in the liquid phase. Therefore, for achieving a desired concentration of oxygen dissolved in the liquid phase, it is preferred to use a method in which the molecular oxygen-containing gas is contacted with the liquid phase under superatmospheric pressure (which is not more than 20 MPa).
- the oxidation may be performed by introducing a gaseous mixture having an appropriate oxygen concentration and an appropriate total pressure into the reaction system, wherein the oxygen concentration and the total pressure are determined, taking into consideration the amount of the substrate to be oxidized (i.e., the amount of oxygen needed to oxidize the substrate) which varies depending on the type of catalyst and the reaction conditions.
- the total pressure of the reaction system is in the range of from 0.1 to 20 MPa, preferably from 1 to 10 MPa.
- the molecular oxygen-containing gas may be introduced either directly into the liquid phase which is formed in the reaction vessel, or into the gaseous phase (which is in contact with the liquid phase) in the reaction vessel.
- the molecular oxygen consumed in the reaction can be compensated by introducing purified oxygen, air or diluted oxygen gas into the reaction system either continuously or intermittently, so as to maintain a desired partial pressure of oxygen in the gaseous phase.
- purified oxygen, air or diluted oxygen gas into the reaction system either continuously or intermittently, so as to maintain a desired partial pressure of oxygen in the gaseous phase.
- an oxygen-containing gas into the reaction system, which gas contains oxygen in an amount sufficient for oxidizing a desired amount of the substrate, it becomes possible to continue the reaction without compensating for the consumed molecular oxygen until a desired conversion is achieved.
- the reaction temperature is generally in the range of from 0 to 200° C., more advantageously from 40 to 180° C., most advantageously from 60 to 160° C.
- the reaction temperature depends on the chemical reaction performed, when the temperature exceeds 200° C., a gradual decomposition or gradual oxidation of the obtained product is promoted and a by-product having a high boiling point is formed in a higher ratio, thus lowering the selectivity for the desired product.
- the temperature is lower than 0° C., the reaction rate tends to become low.
- the reaction time is not particularly limited and can be appropriately selected in accordance with the desired values of the selectivity for and yield of the desired product. Usually, the reaction time is selected from the range of from several seconds to several hours.
- the reaction product can be easily separated and purified by conventional methods, for example, separation methods, such as a distillation, an extraction, a condensation, a filtration, a crystal deposition, a recrystallization, a column chromatography or a combination of two or more separation methods.
- separation methods such as a distillation, an extraction, a condensation, a filtration, a crystal deposition, a recrystallization, a column chromatography or a combination of two or more separation methods.
- separation methods such as a distillation, an extraction, a condensation, a filtration, a crystal deposition, a recrystallization, a column chromatography or a combination of two or more separation methods.
- separation methods such as a distillation, an extraction, a condensation, a filtration, a crystal deposition, a recrystallization, a column chromatography or a combination of two or more separation methods.
- the unreacted substrate is recycled to the reaction vessel.
- the catalyst is contained in the reaction medium after
- a hydrazyl radical represented by formula (1) is used as an oxidation catalyst of the present invention, and a specific example of a hydrazyl radical of formula (1) is a free radical, such as 2,2-diphenyl-1-picrylhydrazyl (DPPH), which removes a hydrogen atom from chemical linkages (such as C—H, N—H, PhO—H and S—H) of an organic substrate, to thereby selectively produce a corresponding radical species.
- DPPH 2,2-diphenyl-1-picrylhydrazyl
- DPPH 2,2-diphenyl-1-picrylhydrazyl
- DPPH 2 2,2-diphenyl-1-picrylhydrazine
- DPPH and DPPH 2 function as a hydrogen mediator while undergoing reversible mutual transformation. More specifically, it is presumed that the following catalyst cycle is established in the reaction system: DPPH 2 is generated in the reaction system by a reaction between a substrate and DPPH; the generated DPPH 2 directly activates an oxygen molecule to thereby generate an electrophilic oxygen active species and DPPH; and the generated DPPH pulls out a hydrogen atom from a reaction intermediate which is formed by addition of an oxygen molecule to the substrate, thereby regenerating DPPH 2 .
- the oxidation reaction can be controlled as desired by selecting an appropriate oxidation promoter in accordance with the type of the substrate used and the type of the desired oxidation product. For example, as demonstrated in Examples 14 and 15 below, in the oxidation reaction of cyclohexylamine, each of cyclohexanone oxime and nitrocyclohexane can be produced selectively by changing the type of the oxidation promoter used.
- each of the hydrazyl radical represented by formula (1) (such as DPPH) and the hydrazine compound represented by formula (2) (such as DPPH 2 ) functions as a catalyst in the oxidation reaction of an organic substrate in the presence of oxygen.
- DPPH and DPPH 2 can undergo reversible mutual transformation (see, for example, Electrochemistry Communications, 1, 406 (1999)); however, it has not been reported that, in the presence of oxygen, DPPH and DPPH 2 exhibit a catalytic function as a hydrogen mediator while undergoing reversible mutual transformation.
- the hydrazyl radical represented by formula (1) such as a DPPH radical, has the ability to pull out a hydrogen radical from various organic substrates. Therefore, the oxidation catalyst of the present invention can be applied to oxygen oxidation reaction of various organic substrates.
- the conversion of a substrate and the selectivity for an oxidation product which were used for evaluating the results of the oxidation reaction of a substrate in the Examples and Comparative Examples, are defined by the following formulae, respectively.
- Conversion of a substrate (%) (molar amount of a reacted substrate/molar amount of fed substrate) ⁇ 100
- Selectivity for an oxidation product (%) (molar amount of an oxidation product/molar amount of a reacted substrate) ⁇ 100
- the reaction product was analyzed by gas chromatography under the following conditions.
- Carrier gas helium
- the amounts of metals contained in the solid powdery product were determined by means of an X-ray fluorescence analyzer under the following conditions.
- Single crystal used for a monochromator polyethylene terephthalate for the determination of Al and Si, and lithium fluoride for the determination of other metals
- tablets (standard samples) containing the metal oxide were produced in substantially the same manner as mentioned above, except that, instead of the oxidation promoter, different amounts of the metal oxide were, respectively, used for producing the tablets.
- the obtained tablets were analyzed by X-ray fluorescence spectrometry, thereby obtaining a calibration curve for determination of the metal contents of the oxidation promoter.
- oxidation promoter a solid powdery product
- alumina having supported thereon tungsten oxide (WO 3 /Al 2 O 3 ).
- tungsten oxide WO 3 /Al 2 O 3
- the obtained oxidation promoter was examined by X-ray fluorescence spectrometry. As a result, it was found that the oxidation promoter had a tungsten content of 21.8% by weight.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that a mixture of 0.024 g (0.06 mmol) of 2,2-diphenyl-1-picrylhydrazyl and 0.026 g (0.065 mmol) of 2,2-diphenyl-1-picrylhydrazine was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1.
- a mixture of 0.024 g (0.06 mmol) of 2,2-diphenyl-1-picrylhydrazyl and 0.026 g (0.065 mmol) of 2,2-diphenyl-1-picrylhydrazine was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.077 g (0.125 mmol) of 2,2-di(4-t-octylphenyl)-1-picrylhydrazyl (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1.
- 0.077 g (0.125 mmol) of 2,2-di(4-t-octylphenyl)-1-picrylhydrazyl manufactured and sold by Sigma-Aldrich Japan K.K., Japan
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.041 g (0.25 mmol) of 1-phenylpyrazolidine-3-one (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1.
- 0.041 g (0.25 mmol) of 1-phenylpyrazolidine-3-one manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan
- the conversion of cyclohexylamine was 30.2% and the selectivity for cyclohexanone oxime was 86.2%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.047 g (0.25 mmol) of 1-phenyl-1,2-dihydropyridazine-3,6-dione (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1.
- 0.047 g (0.25 mmol) of 1-phenyl-1,2-dihydropyridazine-3,6-dione manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan
- WO 3 /Al 2 O 3 i.e., alumina having supported thereon tungsten oxide
- WO 3 /ZrO 2 i.e., zirconium having supported thereon tungsten oxide
- WO 3 /TiO 2 i.e., titanium oxide having supported thereon tungsten oxide
- TiO 2 P25; manufactured and sold by Degussa AG, Germany
- TiO 2 -mesopore manufactured and sold by Sigma-Aldrich Japan K.K., Japan
- H+-ETS-10 manufactured and sold by N
- TiOi-Pr 4 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), TiO(acac) 2 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), and Nb 2 O 5 -mesopore (manufactured and sold by Sigma-Aldrich Japan K.K., Japan)
- TiO(acac) 2 stands for titanium(II) oxide acetylacetonate which is represented by the formula: TiO(CH 3 COCHCOCH 3 ) 2
- Ti(Oi-Pr) 4 stands for titanium tetraisopropoxide which is represented by the formula: Ti[OCH(CH 3 ) 2 ] 4 ).
- the amount of the oxidation promoter was the same as in Example 1, namely 0.1 g, except that each of Ti(Oi-Pr) 4 and TiO(acac) 2 was used in an amount of 0.125 mmol.
- the obtained products were individually analyzed by gas chromatography. As shown in Table 1, cyclohexanone oxime was selectively obtained by using different oxidation promoters.
- a commercially available ZrO 2 (RC100; manufactured and sold by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD., Japan) was dried at 120° C. overnight, and the dried ZrO 2 was used as a carrier for an oxidation promoter.
- 1.4 g of ammonium paratungstate pentahydrate was dissolved in 60 g of water, followed by addition of 10 g of the dried ZrO 2 , to thereby obtain a suspension.
- the obtained suspension was charged into a glass flask, and the flask was set in a rotary evaporator.
- the flask attached to the rotary evaporator was immersed in an oil bath having a temperature of 90° C., and the contents of the flask were slowly stirred under atmospheric pressure for 1.5 hours, to thereby obtain a slurry.
- the temperature of the oil bath was elevated from 90° C. to 100° C., and the slurry in the flask was stirred at 100° C. under atmospheric pressure to evaporate water from the slurry in the flask, thereby obtain a dry powder.
- the obtained dry powder was further dried at 120° C.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.125 mmol of Na 2 MoO 4 .2H 2 O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation promoter instead of the oxidation promoter used in Example 1, and that the amount of 2,2-diphenyl-1-picrylhydrazyl was changed to 0.2 g (0.5 mmol).
- 0.125 mmol of Na 2 MoO 4 .2H 2 O manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan
- 2,2-diphenyl-1-picrylhydrazyl was changed to 0.2 g (0.5 mmol).
- Example 2 An oxidation reaction was performed in substantially the same manner as in Example 1 except that various solvents as indicated in Table 3 below were individually used instead of the solvent used in Example 1. The obtained products were individually analyzed by gas chromatography. As shown in Table 3, cyclohexanone oxime was selectively obtained by using different solvents.
- An oxidation reaction was performed using various reaction systems in which different primary amines as indicated in Table 4 below were individually used as a substrate and in which the substrate was used as a solvent (reaction medium).
- the reaction was performed in substantially the same manner as in Example 1 except that 0.03 g (0.075 mmol) of 2,2-diphenyl-1-picrylhydrazyl (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) as an oxidation catalyst, 0.1 g of WO 3 /Al 2 O 3 (oxidation promoter) and 30 mmol of each individual primary amine (as a substrate and solvent) as indicated in Table 4 below were charged into a high pressure autoclave. The obtained products were individually analyzed by gas chromatography.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that the amounts of oxidation catalyst (DPPH) and oxidation promoter (WO 3 /Al 2 O 3 ) were changed as indicated in Table 6 below, and that the reaction time was changed to 2 hours.
- the obtained products were individually analyzed by gas chromatography. As shown in Table 6, cyclohexanone oxime was selectively obtained by using various amounts of DPPH and WO 3 /Al 2 O 3 .
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.646 g (5 mmol) of dibutylamine (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of dibutylamine was 43.5% and the selectivity for N-butylidenebutylamine-N-oxide was 72.1%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.986 g (5 mmol) of dibenzylamine (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of dibenzylamine was 49.5% and the selectivity for N-benzylidenebutylamine-N-oxide was 73.4%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.426 g (5 mmol) of piperidine (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of piperidine was 48.3% and the selectivity for 2,3,4,5-tetrapyridine-N-oxide was 62.1%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.541 g (5 mmol) of benzyl alcohol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction temperature was changed to 100° C. As a result, it was found that the conversion of benzyl alcohol was 15.4% and the selectivity for benzaldehyde was 99.0%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that, instead of the substrate, solvent and oxidation promoter used in Example 1, 0.5 g (5 mmol) of cyclohexanol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate, 3 ml of dimethylformamide was used as a solvent, and 0.041 g (0.125 mmol) of MoO 2 (acac) 2 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation promoter, and that the reaction temperature was changed to 100° C. As a result, it was found that the conversion of cyclohexanol was 14.3% and the selectivity for cyclohexanone was 97.2%.
- Example 2 An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.451 g (5 mmol) of 1-butanethiol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1. As a result, it was found that the conversion of 1-butanethiol was 9.5% and the selectivity for butyldisulfide was 96.1%.
- 1-butanethiol manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that, instead of the substrate, solvent and oxidation promoter used in Example 1, 0.451 g (5 mmol) of 1-butanethiol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate, 3 ml of methanol was used as a solvent, and 0.066 g (0.2 mmol) of Na 2 WO 4 -2H 2 O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation promoter.
- solvent and oxidation promoter used in Example 1 0.451 g (5 mmol) of 1-butanethiol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate, 3 ml of methanol was used as a solvent, and 0.066 g (0.2 mmol) of Na 2 WO 4 -2H 2 O (manufactured and
- An operation for effecting an oxidation reaction was performed in substantially the same manner as in Example 1 except that none of a hydrazyl radical and a hydrazine compound was used as an oxidation catalyst. As a result, the reaction did not proceed at all and, hence, no cyclohexanone oxime was obtained. Further, an operation for effecting an oxidation reaction was performed in substantially the same manner as in Example 1 except that benzylamine, N,N-dibutylamine, piperidine, benzyl alcohol and 1-butanethiol were individually used as a substrate instead of the substrate used in Example 1, and that none of a hydrazyl radical and a hydrazine compound was used as an oxidation catalyst. As a result, it was found that no oxidation product was obtained by the reaction.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that, instead of the oxidation catalyst used in Example 1, there was used 0.044 g (0.25 mmol) of p-trifluoro-phenylhydrazine (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) having a structure different from that of the oxidation catalyst of the present invention.
- p-trifluoro-phenylhydrazine manufactured and sold by Sigma-Aldrich Japan K.K., Japan
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.039 g (0.25 mmol) of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1.
- TEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl
- An oxidation reaction of cyclohexylamine was performed using hydrogen peroxide as an oxidizing agent, in accordance with the conventional techniques (e.g., U.S. Pat. No. 2,706,204) described under “Prior Art” above. Specifically, a reaction was performed as follows. Into a flask having a volume of 30 ml were charged 0.066 g (0.2 mmol) of Na 2 WO 4 .2H 2 O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), 10 ml of methanol and 0.496 g (5 mmol) of cyclohexylamine, and the internal temperature of the flask was elevated to 30° C.
- oxidation catalyst of the present invention oxidation of various substrates with a molecular oxygen can be efficiently performed under moderate conditions, thereby enabling production of a useful chemical compound economically and safely with high selectivity.
- the oxidation catalyst of the present invention can solve the various problems of the conventional processes for oxidation of a substrate, i.e., the problems that it is necessary to use an oxidizing agent which is expensive and/or explosive, that the selectivity for and yield of a desired compound become low, that complicated operations are necessary for purifying an oxidation product to remove therefrom a large amount of by-products, and that a large amount of energy is consumed.
- the oxidation catalyst of the present invention can be advantageously used for performing selective oxidation reaction of various types of substrates, especially, e.g., a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound and a heterocyclic compound.
- substrates especially, e.g., a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound and a heterocyclic compound.
- selective oxidation reactions using a molecular oxygen to produce an oxime compound or a nitro compound from a primary amine or produce a nitrone compound from a secondary amine can be performed without using an expensive oxidizing agent, such as hydrogen peroxide or an organic hydroperoxide and under moderate conditions with high selectivity and high efficiency.
Abstract
An oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen, comprising at least one member selected from the group consisting of a specific hydrazyl radical (such as 2,2-diphenyl-1-picrylhydrazyl) and a specific hydrazine compound (such as 2,2-diphenyl-1-picrylhydrazine). A method for producing a chemical compound, comprising contacting a substrate with a molecular oxygen in the presence of the above-mentioned oxidation catalyst.
Description
- 2. Field of the Invention
- The present invention relates to an oxidation catalyst useful for chemical synthesis. More particularly, the present invention is concerned with an oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen, comprising at least one member selected from the group consisting of a specific hydrazyl radical and a specific hydrazine compound. By the use of the oxidation catalyst of the present invention, oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen can be efficiently performed under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity. The present invention is also concerned with a method for producing a chemical compound by using the oxidation catalyst of the present invention.
- 2. Prior Art
- An oxidation reaction is one of the most basic methods for material conversion in the field of organic synthesis. A number of oxidation processes have been put into practical use. However, in many cases of oxidation reactions, for example, oxygen oxidation reactions, there are disadvantages not only in that high temperature and high pressure conditions are necessary for activation of a molecular oxygen, thus leading to a lowering of the selectivity for a desired compound, but also in that, because of the generation of various by-products, it is necessary to perform various separation steps for removing the by-products. Therefore, the conventional oxidation processes are not at a satisfactory technical level from the viewpoint of economy, safety, and environmental protection. Thus, it has been desired to develop a new oxidation process which can be efficiently performed with high selectivity and at a low cost.
- Conventionally, oxidation reactions which are well known in the industry, especially a selective oxidation reaction, have been carried out by employing the techniques as described below.
- Useful chemical compounds can be efficiently produced under moderate conditions with high selectivity by performing a selective oxidation reaction, using an oxidizing agent (such as hydrogen peroxide or an organic or inorganic peroxide) which can produce an active oxygen species (an electrophilic oxygen species) having high chemical potential (see, for example, “Shin Jikken Kagaku Koza 15, Sanka to Kangen I-2 (New Lecture on Experimental Chemistry 15, Oxidation and Reduction, I-2)”, edited by the Japan Chemical Society, p. 605, 1976, Japan; and “Catalytic Oxidations with Hydrogen Peroxide as Oxidant”, G. Strukul, Kluwer Academic Publishers, 1992, the Netherlands). Examples of selective oxidation reactions include oxidation of an alkane, oxidation of an alcohol, epoxidation of an olefin, oxidation of a ketone, oxidation of an aldehyde, oxidation of an ether, hydroxylation of an aromatic compound, oxidation of an amine and oxidation of a sulfur compound.
- On the other hand, it is well known that, as a conventional method for producing hydrogen peroxide, which is a useful oxidizing agent as mentioned above, an autoxidation reaction using alkylanthraquinone is commercially used (see “Kagaku Binran, Oyo-kagaku-hen I (Chemical Handbook, Applied Chemistry I)”, edited by the Japan Chemical Society, p. 302, 1986, Japan). However, the conventional method for producing hydrogen peroxide is economically disadvantageous not only in that the method requires a large amount of an organic solvent, but also in that, due to the generation of various by-products and degradation of a catalyst, the method requires various additional steps for separation of by-products and for regeneration of the degraded catalyst. Therefore, it has been desired to develop a production method by which hydrogen peroxide can be produced at a low cost, as compared to the case of the conventional method.
- In addition, as a useful organic peroxide, t-butylhydroperoxide is also known. Conventionally, t-butylhydroperoxide has been produced, for example, by a method in which t-butanol or isobutylene as a substrate, namely a raw material, is reacted with a strong acid, such as sulfuric acid, and hydrogen peroxide (see, for example, “Yuki-Kasankabutsu (Organic Peroxides)”, edited by the Organic Peroxide Research Group, p. 220, 1972, Japan). However, the conventional method is disadvantageous from the viewpoint of economy and safety; specifically, the conventional method has disadvantages in that hydrogen peroxide (which is expensive) is necessary, and the raw material is reacted with a liquid mixture of a high concentration aqueous sulfuric acid (60 to 70 wt %) and a high concentration aqueous hydrogen peroxide (30 to 50 wt %).
- For these reasons, from the practical and commercial viewpoint, it has been desired to develop a method by which various types of selective oxidation reactions mentioned above can be performed by directly activating and oxidizing a substrate with oxygen in the presence of a catalyst without using an expensive oxidizing agent, such as hydrogen peroxide. For example, a method for producing phenol directly from benzene and oxygen in the presence of a catalyst has long been studied. However, the reaction method which has been studied has the following problems. First, a high temperature is necessary for the reaction. Further, although various types of catalysts can catalyze the reaction, many of such catalysts pose a problem in that the reaction system containing such catalysts causes phenol as a reaction product to have higher reactivity than benzene as a substrate, so that, although the reaction rate of benzene can be increased, the selectivity for phenol is decreased. Thus, the above-mentioned method is not commercially employable. With respect not only to such reaction system (which causes phenol as a reaction product to have higher reactivity than benzene) but also to other oxidation reactions using oxygen, great efforts have been made for increasing the selectivity for a desired reaction product. However, there is no method which is satisfactory from the view-point of economy and safety. It is considered that the reason why such an oxidation reaction using oxygen does not proceed with high selectivity for a desired product resides in that, when oxygen molecules are activated by a catalyst, an electron transfer from the catalyst to the oxygen molecules inevitably occurs, so that oxygen molecules are mainly converted to nucleophilic oxygen anion active species, thus rendering it difficult for an electrophilic addition reaction to proceed (see Catalysis Today, 45, 3-12, 1998, the U.S.A.).
- In recent years, in order to alleviate the above-mentioned problems, studies on a new method have been made for synthesizing a chemical compound, in which a catalyst system which is similar to a biological catalyst system is used. Monooxygenase, which is an enzyme present in the living body, activates an oxygen molecule by utilizing the reducing ability of NADPH. In imitation of this mechanism, in the synthetic chemistry, a method can be used in which oxygen and a reducing agent, such as hydrogen, carbon monoxide, aldehyde or hydrazine, are contacted with each other in the presence of a catalyst system, thereby generating an active oxygen species stoichiometrically under moderate conditions. In this case, since energy necessary to cleave an oxygen bond is supplied through the oxidation of the reducing agent, an electrophilic active oxygen species can be selectively generated without using a large amount of energy.
- There are also known methods similar to such method, such as a method for producing phenol, comprising contacting oxygen, benzene and hydrogen with each other in the presence of a Pt—V2O5/SiO2 catalyst (Appl. Catal., A, 131, 33, 1995, U.S.A.); a method for producing cyclohexene oxide, comprising contacting oxygen, cyclohexene and hydrogen with each other in the presence of an Mn complex/Pt colloidal catalyst (J. Am. Chem. Soc., 101, 6456, 1979, U.S.A.); a method for producing cyclohexanone and cyclohexanol, comprising contacting oxygen, cyclohexane and acetoaldehyde with each other in the presence of an Fe2O3 catalyst in an acetic acid solvent (J. Mol. Catal., A: Chemical, 117, 21, 1979); and a method for producing cyclohexanone and cyclohexanol, comprising contacting oxygen, cyclohexane and 1,2-diphenylhydrazine with each other in the presence of an Fe(pyridine)4Cl2 catalyst (Polyhedron, 7(6), 425, 1988). These methods exhibit an improved selectivity for a desired product. However, each of these methods has problems not only in that the presence of a reducing agent poses a high danger of explosion, but also in that the use efficiency of a reducing agent is low and an oxidation product of a reducing agent is by-produced. Therefore, these methods cannot be commercially practically employed.
- On the other hand, as described below, studies are now being performed for developing a new oxidation catalyst which can be used to perform oxidation of various substrates with a molecular oxygen under moderate conditions without using a reducing agent.
- There has been proposed a method in which a substrate, such as an alkane, an alcohol or a ketone, is subjected to oxidation with a molecular oxygen by using, as an oxidation catalyst, an imido compound, such as N-hydroxyphthalimide (see, for example, Unexamined Japanese Patent Application Laid-Open Specification No. Hei 10-286467 (corresponding to U.S. Pat. No. 5,981,420 and EP 858835 B1)). In this method, selective oxidation of a substrate can be performed under moderate conditions. However, this method poses problems not only in that the catalyst activity of an imido compound is unsatisfactory, thus rendering it necessary to use the imido compound catalyst in an amount as large as about 10 mole %, based on the molar amount of the substrate, but also in that the imido compound is decomposed and consumed during the reaction, thus increasing the cost of producing a chemical compound by this method.
- Also, it is known to use as a catalyst a nitroxyl radical (such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)) in a method for selective oxidation of an alcohol (see Chem. Comm., p.1591, 1999). In this method, an alcohol is converted selectively into a carbonyl compound or the like by using a catalyst comprising a combination of TEMPO and a ruthenium compound. However, this method poses problems in that not only is the catalyst activity unsatisfactory, but also the nitroxyl radical undergoes degradation during the reaction.
- As methods in which a metal metalloporphyrin complex or a metallosalen complex is used as a catalyst, there can mentioned, for example, an oxidative acetoxylation reaction of a diene by using a ternary catalyst system of [Pd salt/Co-porphyrin complex/hydroquinone] (see Angew. Chem. Int. Ed. Engl., 32, 263, 1993), a method in which a ternary catalyst system of [Ru complex/Co-salen complex/hydroquinone] is used to perform an oxidation reaction of a primary alcohol to form aldehyde or an oxidation reaction of a secondary alcohol to form a ketone (see J. Chem. Soc., Chem. Commun., p. 1037, 1994), an oxidation reaction of an amine by using an azaindole/copper complex (see “Nihon Kagakukai Dai-67 Shunki Nenkai Kouen Yokou-shu II (the preliminary text II for the lectures at the 67th Spring Annual Meeting of the Chemical Society of Japan), p. 1025, 1994, Japan), an oxidative dehydrogenation reaction of an amine by using a heteropolyacid (see “Nihon Kagakukai Dai-67 Shunki Nenkai Kouen Yokou-shu II (see the preliminary text II for the lectures at the 67th Spring Annual Meeting of the Chemical Society of Japan), p. 761, 1994, Japan), and an oxidation reaction of an alkane by using iron-disubstituted tungstosilicic acid (Chem. Lett., p. 1263, 1998). However, these methods pose problems not only in that the reaction rate and the selectivity for and yield of a desired chemical compound are not always high, but also in that the catalyst has the following disadvantages: the preparation of the catalyst requires a complicated operation and, hence, the catalyst is expensive, and also the catalyst is unstable and likely to be decomposed during the reaction.
- Next, an explanation is made below on the conventional methods for producing an oxime compound, a nitro compound and a nitrone compound which are induced by oxidation of an amine.
- Oxime compounds and nitro compounds are important chemical compounds for use as, for example, ordinary and fine chemicals and intermediates for synthesis of pharmaceuticals. Examples of methods for producing an oxime compound by oxidation of a primary amine include a method which uses dimethyl dioxirane as an oxidizing agent (see J. Org. Chem., 57, 6759, 1992), a method which uses hydrogen peroxide as an oxidizing agent and uses a sodium tungsten catalyst (see Angew. Chem., 72, 135, 1960), a method which uses hydrogen peroxide as an oxidizing agent and uses a methyltrioxorhenium catalyst (see Bull. Chem. Soc. Jpn., 70, 877, 1997), and a method which uses hydrogen peroxide as an oxidizing agent and uses a titanium silicalite molecular sieves (TS-1) as a catalyst (see J. Chem. Soc. Perkin Trance. I, 2665, 1993). However, these methods have a problem in that an explosive oxidizing agent (dimethyl dioxirane or hydrogen peroxide) is used or that an expensive oxidizing agent or an expensive catalyst is used. These methods are also disadvantageous in that the catalyst activity is unsatisfactory and the selectivity for and yield of an oxime compound are not always high. Therefore, these methods are commercially unsatisfactory.
- Examples of methods for producing a nitro compound by oxidation of a primary amine include a method which uses m-chloroperbenzoic acid or a pertrifluoroacetic acid as an oxidizing agent (see J. Org. Chem., 58, 1372, 1993), a method which uses potassium permanganate as an oxidizing agent (see Org. Synth., 52, 77, 1972), a method which uses ozone as an oxidizing agent (see Synthetic Commun., 20, 1073, 1990), a method which uses t-butylhydroperoxide as an oxidizing agent and uses a catalyst comprising chromium carried on a silica carrier (see J. Chem. Soc. Commun., 1523, 1995), and a method which uses dimethyl dioxirane as an oxidizing agent (see Tetrahedron Lett., 27, 2335, 1986). However, these methods have a problem in that an expensive peroxide, an excess amount of a heavy metal-containing oxidizing agent or an explosive oxidizing agent (such as ozone, an organic hydroperoxide or dimethyl dioxirane) is used. Therefore, these methods are commercially unsatisfactory.
- Cyclohexanone oxime, which is an oxime compound, is a chemical compound useful as an intermediate for producing ε-caprolactam which is a raw material for producing nylon-6. Cyclohexanone oxime can be synthesized by reacting a cyclohexyl amine as a raw material with an oxidizing agent. Examples of methods for producing cyclohexanone oxime by using hydrogen peroxide as an oxidizing agent include (1) a method which uses a catalyst containing at least one metal selected from the group consisting of Mo, W and U (see U.S. Pat. No. 2,706,204), (2) a method which uses titanium silicalite or vanadium silicalite as a catalyst (see Tetrahedron, 51(41), 11305, 1995, and Catal. Lett., 28(2 to 4), 263, 1994), and (3) a method which uses a catalyst containing at least one metal selected from the group consisting of Ti, V, Cr, Se, Zr, Nb, Mo, Te, Ta, W, Re and U (see U.S. Pat. No. 3,960,954).
- Examples of methods for producing cyclohexanone oxime by using a molecular oxygen as an oxidizing agent include (4) a method in which a gaseous phase reaction is performed using a solid catalyst comprising an SiO2 gel, γ-Al203 and optionally WO 3 (see U.S. Pat. Nos. 4,337,358 and 4,504,681), (5) a method in which a gaseous phase reaction is performed using a solid catalyst comprising a combination of tungsten oxide and one member selected from the group consisting of γ-Al2O3, SiO2 and hydrotalcite (see Journal of Molecular Catalysis A; Chemical, 160, 393, 2000), (6) a method in which a liquid phase reaction is performed using, as a catalyst, tungstic acid, phosphotungstic acid, molybdic acid, selenic acid, selenious acid or the like in the presence of a tertiary alcohol, preferably in the presence of a tertiary alcohol and ammonia gas (see Examined Japanese Patent Application Publication No. Sho 47-25324), and (7) a method in which a liquid phase reaction is performed using, as a catalyst, a compound containing at least one element selected from the Group 4 (Ti, Zr and Hf) of the Periodic Table (see EP 395046 B1).
- However, these prior art methods have problems. For example, the above-mentioned methods (1) to (3) have problems not only in that the oxidizing agent used (i.e., hydrogen peroxide or an organic hydroperoxide) is expensive, but also in that the selectivity for and yield of the cyclohexanone oxime produced are not always high, and also there is the known operational danger (explosiveness) of the oxidizing agent when the reaction is performed on a commercial scale. In addition, when an organic hydroperoxide is used, there is also a problem in that a by-product generated by reduction of the organic hydroperoxide is contained in the reaction mixture, thus rendering cumbersome the separation and purification operations. For solving these problems, the above-mentioned methods (4) to (7), which use a molecular oxygen (such as air or oxygen gas), have been proposed.
- In the above-mentioned methods (4) and (5), the gaseous phase reaction is performed under relatively stringent reaction conditions using a reaction temperature of from 120 to 250° C. In the studies by the present inventors, it has been found that the above-mentioned methods (4) and (5) pose a problem in that, when the reaction temperature is 160° C. or more, a tar-like by-product and a high boiling point organic carbonaceous material accumulate on the surface of the catalyst, thus causing a rapid deactivation of the catalyst. Also, the methods (4) and (5) are disadvantageous in that the selectivity for cyclohexanone oxime is as low as about 50 to 60% at a conversion of 20%, thus causing a lowering of the amount of reaction product per unit volume of the space of reaction, i.e., a lowering of the productivity. In the above-mentioned methods (6) and (7), the gaseous phase reaction is performed under relatively moderate reaction conditions using a reaction temperature of from 50 to 150° C. The prior art document describing the method (6) discloses a reaction in which t-butanol is used as a reaction solvent and phosphotungstic acid is used as a catalyst; however, the method (6) has a problem in that the yield of cyclohexanone oxime is as low as only few percent. The prior art document describing the method (7) discloses a reaction in which a titanium compound is used as a catalyst, and diethylene glycol dimethyl ether (i.e., diglyme), t-butanol, dimethyl formamide, acetonitrile, triethylamine or water is used as a reaction solvent; however, the method (7) has problems in that the selectivity for cyclohexanone oxime is as low as about 30 to 50% and also the catalyst activity is low.
- Nitrone compounds, which are induced by oxidation of amines, are important chemical compounds for use as intermediates for synthesis of pharmaceuticals, agrichemicals and fine chemicals, such as an α-substituted amine compound, an amino acid and an alkaloid. As a method for producing a nitrone compound, there is known a method in which a secondary amine is reacted with hydrogen peroxide. Examples of such methods for producing a nitrone compound include a method which uses a sodium tungsten catalyst (see Unexamined Japanese Patent Application Laid-Open Specification No. Sho 59-164762 (corresponding to U.S. Pat. No. 4,596,874)), a method which uses a selenium dioxide catalyst (see Unexamined Japanese Patent Application Laid-Open Specification No. Sho 63-63651), and a method which uses a methyltrioxorhenium catalyst (see Bull. Chem. Soc. Jpn., 70, 877, 1997). However, these methods have problems not only in that hydrogen peroxide (which is expensive) or an expensive catalyst is used, but also in that the catalyst activity is unsatisfactory and the selectivity for and yield of a nitrone compound are not always high. Thus, these methods are unsatisfactory from the commercial viewpoint. There is also known another method for producing a nitrone compound, which uses a molecular oxygen as an oxidizing agent and uses hydrazine (reducing agent) and a flavin catalyst (see J. Am. Chem. Soc., 125, 2868, 2003). This method exhibits a high selectivity for a desired chemical compound; however, this method has problems not only in that hydrazine as a reducing agent is expensive, but also in that the catalyst has disadvantages in that the preparation of the catalyst requires a complicated operation and, hence, the catalyst is expensive. Thus, this method is unsatisfactory from the commercial viewpoint.
- As apparent from the above, it has been desired to develop an oxidation method which can be used to produce various desired chemical compounds (for example, to produce an oxime compound or a nitro compound from a primary amine or produce a nitrone compound from a secondary amine) by an oxidation reaction (such as an oxygen oxidation reaction) performed under moderate conditions with high selectivity and high efficiency. It has also been desired to develop a high performance oxidation catalyst used for the oxidation method.
- Thus, in the prior art, there has not yet been obtained an oxidation catalyst which can be used to efficiently perform oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity.
- In this situation, the present inventor has made extensive and intensive studies with a view toward solving the above-mentioned problems. As a result, he has unexpectedly found that, by the use of an oxidation catalyst comprising a specific hydrazyl radical (such as 2,2-diphenyl-1-picrylhydrazyl) and/or a specific hydrazine compound (such as 2,2-diphenyl-1-picrylhydrazine) or by the use of an oxidation catalyst comprising a combination of the above-mentioned hydrazyl radical and/or hydrazine compound with an oxidation promoter (such as a transition metal compound), oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen can be performed under moderate conditions, thereby enabling production of a desired chemical compound with high selectivity and high efficiency. The present invention has been completed, based on this finding.
- Accordingly, an object of the present invention is to provide an oxidation catalyst which can be used to efficiently perform oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity.
- Another object of the present invention is to provide a method for producing a chemical compound by using the above-mentioned oxidation catalyst.
- The foregoing and other objects, features and advantages of the present invention will be apparent from the following detailed description and appended claims.
- By the use of the oxidation catalyst of the present invention, oxidation of a substrate (such as a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound or a heterocyclic compound) with a molecular oxygen can be efficiently performed under moderate conditions, thereby enabling economical production of a useful chemical compound with high selectivity.
- In one aspect of the present invention, there is provided an oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen, comprising at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) below and a hydrazine compound represented by the formula (2) below,
-
- wherein each of R1, R2 and R3 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- wherein two substituents selected from the group consisting of R1, R2 and R3 are optionally bonded to each other, to thereby form a ring.
- In another aspect of the present invention, there is provided a method for producing a chemical compound, comprising contacting a substrate with a molecular oxygen in the presence of the above-mentioned oxidation catalyst, thereby performing an oxidation reaction to form a chemical compound.
- For an easier understanding of the present invention, the essential features and various preferred embodiments of the present invention are enumerated below.
-
- wherein each of R1, R2 and R3 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- wherein two substituents selected from the group consisting of R1, R2 and R3 are optionally bonded to each other, to thereby form a ring.
-
- wherein each of R4, R5, R6, R7 and R8 independently represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
- each of R1 and R2 has the same definition as each of R4 to R8 except that any of R1 and R2 does not represent a hydrogen atom; and
- wherein R1 and R2 are optionally bonded to each other, to thereby form a ring, and wherein with respect to one or two pairs of substituents selected from the group consisting of a pair of substituents R4 and R5, a pair of substituents R5 and R6, a pair of substituents R6 and R7 and a pair of substituents R7 and R8, the substituents of the or each pair are optionally bonded to each other, to thereby form a ring or two rings.
- 3. The oxidation catalyst according to item 1 or 2 above, wherein the hydrazyl radical is selected from the group consisting of 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, N,N-diphenyl-N′-(2,4,6 tricyanophenyl)hydrazyl, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazyl, carbazol-9-yl(2,4,6-trinitrophenyl)amidogen and N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazyl, and
- the hydrazine compound is selected from the group consisting of 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazine, carbazol-9-yl(2,4,6-trinitrophenyl)amine and N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazine.
- 4. The oxidation catalyst according to any one of items 1 to 3 above, wherein the hydrazyl radical is 2,2-diphenyl-1-picrylhydrazyl, and the hydrazine compound is 2,2-diphenyl-1-picrylhydrazine.
-
- wherein each of R1, R2 and R9 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- wherein two substituents selected from the group consisting of R1, R2 and R9 are optionally bonded to each other, to thereby form a ring.
- 6. The oxidation catalyst according to item 1 or 5 above, wherein the hydrazyl radical is selected from the group consisting of 1-phenylpyrazolidone-(3)-radical and 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl, and
- the hydrazine compound is selected from the group consisting of 1-phenylpyrazolidine-3-one, 1-phenyl-1,2-dihydropyridazine-3,6-dione and 2-phenyl-2,3-dihydrophthalazine-1,4-dione.
-
- wherein each of R10, R11 and R12 independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkyl-thio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
- R13 has the same definition as each of R10 to R12 except that R13 does not represent a hydrogen atom; and
- wherein two substituents selected from the group consisting of R11, R12 and R13 are optionally bonded to each other, to thereby form a ring.
- 8. The oxidation catalyst according to item 1 or 7 above, wherein the hydrazyl radical is selected from the group consisting of 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5,6-tetraphenylverdazyl, 1,3,5-triphenyl-6-oxoverdazyl and 1,3,5-triphenyl-6-thioxoverdazyl, and
- the hydrazine compound is selected from the group consisting of 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 1,3,5-triphenyl-6-oxotetrazine and 1,3,5-triphenyl-6-thioxotetrazine.
- 9. The oxidation catalyst according to any one of items 1 to 8 above, which further comprises an oxidation promoter.
- 10. The oxidation catalyst according to item 9 above, wherein the oxidation promoter is a transition metal compound.
- 11. The oxidation catalyst according to item 10 above, wherein the transition metal is at least one member selected from the group consisting of the elements of the Groups 3 to 12 of the Periodic Table.
- 12.The oxidation catalyst according to item 11 above, wherein the transition metal is at least one member selected from the group consisting of lanthanoids, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn and Cd.
- 13.A method for producing a chemical compound, comprising contacting a substrate with a molecular oxygen in the presence of the oxidation catalyst of any one of items 1 to 12 above, thereby performing an oxidation reaction to form a chemical compound.
- 14.The method according to item 13 above, wherein the substrate is selected from the group consisting of a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound and a heterocyclic compound.
- 15.The method according to item 14 above, wherein the amine is a primary amine, and the chemical compound produced is an oxime compound or a nitro compound.
-
- wherein each of R1 and R2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, provided that R1 and R2 are not simultaneously hydrogen atoms; and
- wherein R1 and R2 are optionally bonded to each other, to thereby form a ring.
- 17. The method according to item 16 above, wherein the primary amine is cyclohexylamine, and the chemical compound produced is cyclohexanone oxime.
- 18. The method according to item 14 above, wherein the amine is a secondary amine, and the chemical compound produced is a nitrone compound.
-
- wherein each of R1 and R2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, and R3 has the same definition as each of R1 and R2 except that R3 does not represent a hydrogen atom; and
- wherein two substituents selected from the group consisting of R1, R2 and R3 are optionally bonded to each other, to thereby form a ring.
- 20. The method according to any one of items 13 to 19 above, wherein the oxidation reaction is either performed in a reaction medium which is at least one member selected from the group consisting of water and an organic solvent, or performed using the substrate as a reaction medium.
- 21. The method according to item 20 above, wherein the organic solvent is an aprotic solvent.
- 22. The method according to item 21 above, wherein the aprotic solvent is at least one member selected from the group consisting of a nitrile, a nitro compound, an ester, an ether and an amide.
- 23. The method according to item 22 above, wherein the nitrile is at least one member selected from the group consisting of acetonitrile and benzonitrile.
- 24. The method according to item 22 above, wherein the amide is at least one member selected from the group consisting of dimethylformamide and dimethylacetamide.
- 25. The method according to any one of items 13 to 24 above, wherein the at least one compound selected from the group consisting of the hydrazyl radical and the hydrazine compound is used in an amount of from 0.0001 to 1 mole per mole of the substrate.
- 26. The method according to any one of items 13 to 25 above, wherein the oxidation catalyst further comprises an oxidation promoter, and the oxidation promoter is used in an amount of from 0.00005 to 0.8 mole per mole of the substrate.
- 27. The method according to any one of items 13 to 26 above, wherein the oxidation reaction is performed under reaction conditions wherein the temperature is from 0 to 200° C. and the pressure is from atmospheric pressure to 20 MPa.
- Hereinbelow, the present invention is described in detail.
- The oxidation catalyst of the present invention is an oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen, comprising at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) below and a hydrazine compound represented by the formula (2) below,
- wherein each of R1, R2 and R3 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- wherein two substituents selected from the group consisting of R1, R2 and R3 are optionally bonded to each other, to thereby form a ring.
- The aliphatic group mentioned above may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The aromatic group mentioned above may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The hydroxyl group mentioned above may form a salt with a metal atom. A nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned groups are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group. In general, the aliphatic group has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms; the aromatic group has 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms; the acyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; the alkoxycarbonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; the aryloxycarbonyl group has 5 to 10 carbon atoms; the alkoxyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms; the aryloxy group has 5 to 10 carbon atoms; the haloalkyl group has 1 to 6 carbon atoms; and the alkylthio group has 1 to 6 carbon atoms. In the present invention, the term “heterocyclic group” means a substituent formed from a heteromonocyclic compound, such as furan, thiophene, pyrrole, γ-pyran, thiopyran, pyridine, morpholine, thiazole, imidazole, pyrimidine and 1,3,5-triazine; or a condensed heterocyclic compound, such as indole, quinoline, purine, pteridine, chromane, carbazole, benzothiazole, benzotriazole, benzoisoquinoline and thienopyridine.
- Preferred examples of R1 and R2 in the formulae (1) and (2) above include an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a haloalkyl group and a heterocyclic group. Preferred examples of R3 include an aliphatic group, an aromatic group, a cyano group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloalkyl group and a heterocyclic group. These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned groups are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
-
- wherein each of R4, R5, R6, R7 and R8 independently represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups; each of R1 and R2 has the same definition as each of R4 to R8 except that any of R1 and R2 does not represent a hydrogen atom; and
- wherein R1 and R2 are optionally bonded to each other, to thereby form a ring, and wherein with respect to one or two pairs of substituents selected from the group consisting of a pair of substituents R4 and R5, a pair of substituents R5 and R6, a pair of substituents R6 and R7 and a pair of substituents R7 and R8, the substituents of the or each pair are optionally bonded to each other, to thereby form a ring or two rings.
- The aliphatic group mentioned above may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The aromatic group mentioned above may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The hydroxyl group mentioned above may form a salt with a metal atom.
- A nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned groups are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group. With respect to the number of carbon atoms of each substituent above, the same explanation as made above in connection with the formulae (1) and (2) applies here.
- Preferred examples of R1 and R2 in the formulae (3) and (4) include an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a haloalkyl group and a heterocyclic group. Further, preferred examples of R4, R5, R6, R7 and R8 include a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a nitro group, a cyano group, an amino group, an imino group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned groups are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- Specific examples of hydrazyl radicals represented by the formula (3) above include triphenyl-hydrazyl, 2,2-diphenyl-1-(5′-phenyl-m-terphenyl-2′-yl)hydrazyl, 2,2-diphenyl-(2-nitrophenyl)hydrazyl, 2,2-diphenyl-(2,4-dinitrophenyl)hydrazyl, 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(3-chloro-2,4,6-trinitrophenyl)hydrazyl, 1-[3-(4-morpholinyl)-2,4,6-trinitrophenyl]-2,2-diphenylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, N′-(2,4-dinitro-6-trifluoromethylphenyl)-N,N-diphenylhydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, 4-(N′,N′-diphenylhydrazyl)3,5-dinitrobenzoyl chloride, N,N-diphenyl-N′-(2,6-dinitro-4-carboxyphenyl)hydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-methoxycarbonyl-phenyl)hydrazyl, N,N-diphenyl-N′-(2,6-dinitro-4-sulfophenyl)hydrazyl, N,N-diphenyl-N′-(2,4-dinitro-6-sulfophenyl)hydrazyl, N-cyclohexyl-4-(N′,N′-diphenylhydrazyl)-3,5-dinitrobenzamide, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazyl, N,N-diphenyl-N′-(3,5-dichloro-2,4,6-tricyanophenyl)hydrazyl, 2,2-diphenyl-1-(2,4,6-tricyano-3,5-difluorophenyl)hydrazyl, 2,2-diphenyl-1-[2,4,6-tris-(methoxycarbonyl)-phenyl]hydrazyl, 2,2-diphenyl-1-(2,4,6-tris(trifluoromethylsulfonyl)phenyl)hydrazyl, N,N-diphenyl-3,5-dichloro-2,4,6-tricyanophenolhydrazyl, 1,3-bis-(N,N-diphenylhydrazyl)-5-chloro-2,4,6-tricyanobenzol, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-trinitrobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazyl, 1-picryl-2,2-di-(biphenylyl-(4))hydrazyl, 2,2-di-2-naphthyl-1-picrylhydrazyl, 1-(1)naphthyl-1-phenyl-1-picrylhydrazyl, carbazol-9-yl(2,4,6-trinitrophenyl)amidogen, 2-(4-fluorophenyl)-2-phenyl-1-(2,4,6-trinitrophenyl)hydrazyl, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazyl, (3-chloro-carbazol-9-yl)-(2,4,6-trinitrophenyl) amidogen, 9-amino-N-picryl-3,6-dibromocarbazyl, 1-picryl-2,2-bis-(4-methoxycarbonyl-phenyl)hydrazyl, p,p′-disulfo-1,1-diphenyl-2-picrylhydrazyl, N′-phenyl-N′-thiazole-2-yl-N-(2,4,6-trinitrophenyl)hydrazyl, N′-benzothiazole-2-yl-N′-phenyl-N-(2,4,6-trinitrophenyl)hydrazyl, N′-benzoxazole-2-yl-N′-phenyl-N-(2,4,6-trinitrophenyl)hydrazyl, carbazol-9-yl(2,6-dinitrophenyl)amidogen, N-carbazoyl-N-2,4,6-trinitro-5-chlorophenylaminyl radical, 9-amino-N-(3-cyano-2,4,6-trinitrophenyl)carbazyl, N-carbazol-9-yl-2,4,6-trinitro-3-piperidino-anilino, carbazol-9-yl-(3-morpholine-4-yl-2,4,6-trinitrophenyl)-aminyl and N′-benzoxazole-2-yl-N′-phenyl-N-(2,4-trinitrophenyl)hydrazyl.
- Preferred examples of hydrazyl radicals represented by the formula (3) include 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-methoxycarbonyl-phenyl)hydrazyl, N,N-diphenyl-N′-(2,6-dinitro-4-sulfophenyl)hydrazyl, N,N-diphenyl-N-(2,4,6-tricyanophenyl)hydrazyl, 2,2-diphenyl-1-(2,4,6-tricyano-3,5-difluorophenyl)hydrazyl, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-trinitrobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazyl, carbazol-9-yl(2,4,6-trinitrophenyl) amidogen, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazyl, 1-picryl-2,2-bis-(4-methoxycarbonyl-phenyl)hydrazyl, p,p′-disulfo-1,1-diphenyl-2-picrylhydrazyl and 9-amino-N-(3-cyano-2,4,6-trinitrophenyl)carbazyl. Among the above-mentioned hydrazyl radicals, more preferred are 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazyl, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazyl, carbazol-9-yl(2,4,6-trinitrophenyl)amidogen, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazyl and the like, and especially preferred is 2,2-diphenyl-1-picrylhydrazyl.
- Specific examples of hydrazine compounds represented by the formula (4) above include triphenylhydrazine, 2,2-diphenyl-1-(5′-phenyl-m-terphenyl-2′-yl)hydrazine, 2,2-diphenyl-(2-nitrophenyl)hydrazine, 2,2-diphenyl-(2,4-dinitrophenyl)hydrazine, 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(3-chloro-2,4,6-trinitrophenyl)hydrazine, 1-[3-(4-morpholinyl)-2,4,6-trinitrophenyl]-2,2-diphenylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, N′-(2,4-dinitro-6-trifluoromethylphenyl)-N,N-diphenylhydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, 4-(N′,N′-diphenylhydrazino)3,5-dinitrobenzoyl chloride, N,N-diphenyl-N′-(2,6-dinitro-4-carboxyphenyl)hydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-methoxycarbonyl-phenyl)hydrazine, N,N-diphenyl-N′-(2,6-dinitro-4-sulfophenyl)hydrazine, 2,2-diphenyl-1-(2,4-dinitro-6-sulfophenyl)hydrazine, N-cyclohexyl-4-(N′,N′-diphenylhydrazino)-3,5-dinitrobenzamide, N,N-diphenyl-N-(2,4,6-tricyanophenyl)hydrazine, N,N-diphenyl-N′-(3,5-dichloro-2,4,6-tricyanophenyl)hydrazine, 2,2-diphenyl-1-(2,4,6-tricyano-3,5-difluorophenyl)hydrazine, 2,2-diphenyl-1-[2,4,6-tris-(methoxycarbonyl)-phenyl]hydrazine, 2,2-diphenyl-1-(2,4,6-tris(trifluoromethylsulfonyl)phenyl)hydrazine, 2,4-dichloro-6-(N,N′-diphenylhydrazino)-benzene-1,3,5-tricarbonitrile, tricyano-monochloro-bis-(diphenylhydrazino)benzol, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-trinitrobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazine, 1-picryl-2,2-di-(biphenylyl-(4))hydrazine, 2,2-di-2-naphthyl-1-picrylhydrazine, 1-(l)naphthyl-1-phenyl-1-picrylhydrazine, carbazol-9-yl(2,4,6-trinitrophenyl)amine, 2-(4-fluorophenyl)-2-phenyl-1-(2,4,6-trinitrophenyl)hydrazine, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazine, (3-chloro-carbazol-9-yl)-(2,4,6-trinitrophenyl)amine, (3,6-dibromocarbazol-9-yl)-(2,4,6-trinitrophenyl)amine, 1-picryl-2,2-bis-(4-methoxycarbonyl-phenyl)hydrazine, p,p′-disulfo-1,1-diphenyl-2-picrylhydrazine, N′-phenyl-N′-thiazole-2-yl-N-(2,4,6-trinitrophenyl)hydrazine, N′-benzothiazole-2-yl-N′-phenyl-N-(2,4,6-trinitrophenyl)hydrazine, N′-benzoxazole-2-yl-N′-phenyl-N-(2,4,6-trinitrophenyl)hydrazine, carbazol-9-yl(2,6-dinitrophenyl)amine, carbazol-9-yl(3-chloro-2,4,6-trinitrophenyl)amine, 3-(carbazol-9-yl-amino)-2,4,6-trinitro-benzonitrile, carbazol-9-yl-(2,4,6-trinitro-3-piperidine-1-yl-phenyl)amine, carbazol-9-yl-(3-morpholine-4-yl-2,4,6-trinitrophenyl)amine and 2-(2,4,6-trinitro-anilino)-isoindoline-1,3-dione.
- Preferred examples of hydrazine compounds represented by the formula (4) include 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-methoxycarbonyl-phenyl)hydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-sulfophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyano-3,5-difluorophenyl)hydrazine, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-trinitrobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazine, carbazol-9-yl(2,4,6-trinitrophenyl)amine, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazine, 1-picryl-2,2-bis-(4-methoxycarbonyl-phenyl)hydrazine, p,p′-disulfo-1,1-diphenyl-2-picrylhydrazine and 3-(carbazol-9-yl-amino)-2,4,6-trinitro-benzonitrile. Among the above-mentioned hydrazine compounds, more preferred are 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazine, carbazol-9-yl(2,4,6-trinitrophenyl)amine, N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazine and the like, and especially preferred is 2,2-diphenyl-1-picrylhydrazine.
-
- wherein each of R1, R2 and R9 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
- wherein two substituents selected from the group consisting of R1, R2 and R9 are optionally bonded to each other, to thereby form a ring.
- The aliphatic group mentioned above may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The aromatic group mentioned above may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The hydroxyl group mentioned above may form a salt with a metal atom. A nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned groups are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group. With respect to the number of carbon atoms of each substituent above, the same explanation as made above in connection with the formulae (1) and (2) applies here.
- Preferred examples of R1 and R2 in the formulae (5) and (6) above include an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a haloalkyl group and a heterocyclic group. Preferred examples of R9 include an aliphatic group, an aromatic group, an alkoxyl group, an aryloxy group, a haloalkyl group and a heterocyclic group. These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned groups are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- Specific examples of hydrazyl radicals represented by the formula (5) above include N-benzoyl-N,N′-diphenylhydrazyl, 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazyl, N-(2-nitrobenzoyl)-N′,N′-diphenylhydrazyl, N-benzoyl-N′,N′-bis-(4-nitrophenyl)hydrazine, 1-(trifluoroacetyl)-2,2-bis(3,5-di-tert-butylphenyl)hydrazyl, tribenzoylhydrazoyl radical, 1-phenylpyrazolidone-(3)-radical, 5-methyl-1-phenyl-3-pyrazolidone radical, 2,5-dioxo-4-phenyl-[1,3,4]oxadiazolidine-3-yl, 4,4-dimethyl-3,5-dioxo-2-phenyl-1-pyrazolidinyl, 1-phenyl-4,4-diethylpyrazolidine-3,5-dione-radical, 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl, 3,4-dihydro-3-(4-nitrophenyl)-1,4-dioxo-2-phthalazinyl, 1-tert-butyl-4-methylurazole-radical, 4-(1,1-dimethylethyl)3,5-dioxo-2-phenyl-1,2,4-triazolidine, 1-a-cumyl-4-tert-butylurazole-radical, 1-tert-butyl-4-phenylurazole-radical and 3,5-dioxo-2,4-diphenyl-1,2,4-triazolidine.
- Preferred examples of hydrazyl radicals represented by the formula (5) above include 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazyl, tribenzoyl-hydrazoyl radical, 1-phenylpyrazolidone-(3)-radical, 2,5-dioxo-4-phenyl-[1,3,4]oxadiazolidine-3-yl, 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl and 3,4-dihydro-3-(4-nitrophenyl)-1,4-dioxo-2-phthalazinyl. Among the above-mentioned hydrazyl compounds, more preferred are 1-phenylpyrazolidone-(3)-radical, 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl and the like.
- Specific examples of hydrazine compounds represented by the formula (6) above include benzoic acid-(N′,N′-diphenylhydrazide), 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazine, 2-nitro-benzoic acid-(N′,N′-diphenylhydrazide), benzoic acid-[N′,N′-bis-(4-nitrophenyl)hydrazide], 1-(trifluoroacetyl)-2,2-bis(3,5-di-tert-butylphenyl)hydrazide, tribenzoyl-hydrazine, 1-phenylpyrazolidine-3-one, 5-methyl-1-phenyl-3-pyrazolidine-3-one, 3-phenyl-[1,3,4]oxadiazolidine-2,5-dione, 4,4-dimethyl-1-phenylpyrazolidine-3,5-dione, 4,4-diethyl-1-phenylpyrazolidine-3,5-dione, 1-phenyl-1,2-dihydropyridazine-3,6-dione, 2-phenyl-2,3-dihydrophthalazine-1,4-dione, 2-(4-nitrophenyl)-2,3-dihydrophthalazine-1,4-dione, 1-tert-butyl-4-methyl-[1,2,4]triazolidine-3,5-dione, 4-methyl-1-phenyl-[1,2,4]triazolidine-3,5-dione, 4-tert-butyl-1-(1-methyl-1-phenyl-ethyl)-[1,2,4]triazolidine-3,5-dione, 1-tert-butyl-4-phenyl-[1,2,4]triazolidine-3,5-dione, and 1,4-diphenyl-[1,2,4]triazolidine-3,5-dione.
- Preferred examples of hydrazine compounds represented by the formula (6) above include 1-(3,5-dinitrobenzoyl)-2,2-diphenylhydrazine, tribenzoyl-hydrazine, 1-phenylpyrazolidine-3-one, 3-phenyl-[1,3,4]oxadiazolidine-2,5-dione, 1-phenyl-1,2-dihydropyridazine-3,6-dione, 2-phenyl-2,3-dihydrophthalazine-1,4-dione and 2-(4-nitrophenyl)-2,3-dihydrophthalazine-1,4-dione. Among the above-mentioned hydrazine compounds, more preferred are 1-phenylpyrazolidine-3-one, 1-phenyl-1,2-dihydropyridazine-3,6-dione, 2-phenyl-2,3-dihydrophthalazine-1,4-dione and the like.
-
- wherein each of R10, R and R12 independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
- R13 has the same definition as each of R10 to R12 except that R13 does not represent a hydrogen atom; and wherein two substituents selected from the group consisting of R11, R12 and R13 are optionally bonded to each other, to thereby form a ring.
- The aliphatic group may be unsaturated or saturated, may be unsubstituted or substituted with a substituent, and may be linear, cyclic or branched. Further, the aliphatic group may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The aromatic group may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. The hydroxyl group may form a salt with a metal atom. A nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group may also be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned group are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group. With respect to the number of carbon atoms of each substituent above, the same explanation as made above in connection with the formulae (1) and (2) applies here.
- Preferred examples of R10, R11 and R12 in the formulae (7) and (8) above include a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a nitro group, an amino group, an imino group, a carbonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxyl group, an aryloxy group, and a heterocyclic group. Further, preferred examples of R13 are the same as those (except a hydrogen atom) exemplified in connection with R10, R11 and R12. These groups may be unsubstituted or substituted with a substituent, and may contain one or more members selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom and a halogen atom. When the above-mentioned groups are substituted with a substituent, examples of substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group and a heterocyclic group.
- Specific examples of hydrazyl radicals represented by the formula (7) include 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5-tris-(p-chlorophenyl)verdazyl, 2,6-diphenyl-4-pentafluorophenylverdazyl, 2,4-bisperfluorophenyl-6-phenylverdazyl, 2,4,6-trisperfluorophenylverdazyl, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]verdazyl, 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,4,5]verdazyl, 1-(4-nitrophenyl)-3,5-diphenylverdazyl, 6-anthracene-9yl-2,4-diphenyl1,2,3,4-tetrahydro-[1,2,4,5]verdazyl, 3-nitro-1,5-diphenylverdazyl, 3-(3-pyridyl)-1,5-diphenylverdazyl, 2-benzothiazole-2-yl-4,6-diphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5,6-tetraphenylverdazyl, 3-(4-nitrophenyl)-1,5,6-triphenylverdazyl, 6-methyl-3-nitro-1,5-diphenylverdazyl, 1,5-dimethyl-3-phenyl-6-oxoverdazyl, 1,5-dimethyl-3-(2-pyridyl)-6-oxoverdazyl, 1,3,5-triphenyl-6-oxoverdazyl, 1,3,5-trimethyl-6-thioxoverdazyl, 1,3,5-triphenyl-6-thioxoverdazyl and 3-(4-nitrophenyl)-1,5-diphenyl-6-thioxoverdazyl.
- Preferred examples of hydrazyl radicals represented by the formula (7) include 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,3,4]verdazyl, 1-(4-nitrophenyl)-3,5-diphenylverdazyl, 6-anthracene-9-yl-2,4-diphenyl1,2,3,4-tetrahydro-[1,2,4,5]verdazyl, 1,3,5,6-tetraphenylverdazyl, 6-methyl-3-nitro-1,5-diphenylverdazyl, 1,3,5-triphenyl-6-oxoverdazyl and 1,3,5-triphenyl-6-thioxoverdazyl. Among the above -mentioned hydrazyl radicals, more preferred are 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5,6-tetraphenylverdazyl, 1,3,5-triphenyl-6-oxoverdazyl, 1,3,5-triphenyl-6-thioxoverdazyl and the like.
- Specific examples of hydrazine compounds represented by the formula (8) include 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 1,3,5-tris-(p-chlorophenyl)tetrazine, 2,6-diphenyl-4-pentafluoro-1,2,3,4-tetrahydro-tetrazine, 2,4-bis(perfluorophenyl)-6-phenyl-1,2,3,4-tetrahydro-tetrazine, 2,4,6-tris(perfluorophenyl)-1,2,3,4-tetrahydro-tetrazine, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2-(4-nitrophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 6-anthracene-9-yl-2,4-diphenyl1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 6-nitro-2,4-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 3-(3-pyridyl)-1,5-diphenyltetrazine, 2-benzothiazole-2-yl-4,6-diphenyl-1(6),2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 3-(4-nitrophenyl)-1,5,6-triphenyltetrazine, 3-methyl-6-nitro-2,4-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 1,4-dihydro-2,4-dimethyl-6-phenyl-1,2,4,5-tetrazine-3(2H)-one, 2,4-dimethyl-6-pyridine-2-yl-1,4-dihydro-2H-[1,2,4,5]tetrazine-3-one, 1,3,5-triphenyl-6-oxotetrazine, 1,3,5-trimethyl-6-thioxotetrazine, 1,3,5-triphenyl-6-thioxotetrazine and 3-(4-nitrophenyl)-1,5-diphenyl-6-thioxotetrazine.
- Preferred examples of hydrazine compounds represented by the formula (8) include 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 2-(2,3,4,5,6-pentafluorophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2-(4-nitrophenyl)-4,6-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 6-anthracene-9-yl-2,4-diphenyll,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 3-methyl-6-nitro-2,4-diphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 1,3,5-triphenyl-6-oxotetrazine and 1,3,5-triphenyl-6-thioxotetrazine. Among the above-mentioned hydrazine compounds, more preferred are 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 1,3,5-triphenyl-6-oxotetrazine, 1,3,5-triphenyl-6-thioxotetrazine and the like.
- These compounds (at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2)) may be used individually or in combination (hereinafter, the above-mentioned at least one member is frequently referred to as “hydrazyl radical of formula (1) and/or hydrazine compound of formula (2)”). Further, the amount of hydrazyl radical of formula (1) and/or hydrazine compound of formula (2) may vary depending on the type of the oxidation reaction, and there is no particular limitation as long as the desired catalytic effect can be achieved. However, the amount is generally from 0.0001 to 1 mole, preferably from 0.0005 to 0.5 mole, more preferably 0.001 to 0.3 mole, per mole of the substrate.
- When the above-mentioned compounds (i.e., hydrazyl radical of formula (1) and hydrazine compound of formula (2)) are used in combination as a mixture, the amount of each compound is generally from 0.001 to 0.999 mole, preferably from 0.01 to 0.99 mol, more preferably 0.1 to 0.9 mole per mole of the other compound.
- The at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2) may be carried on a carrier. Examples of carriers include an organic polymer or a porous inorganic carrier, such as silica, silica-alumina, zeolite and activated carbon. Further, the hydrazyl radical of formula (1) and/or hydrazine compound of formula (2) may be used in the form a complex with an oxidation promoter (such as a transition metal compound which is explained below), wherein, in the complex, the oxidation promoter serves as a carrier for the hydrazyl radical of formula (1) and/or hydrazine compound of formula (2).
- A hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2) can be prepared by conventional reaction methods. For example, a hydrazine compound represented by the formula (2) is prepared as follows: a hydrazine compound having substituents which are the same as R1 and R2 in the formula (2) and a halide having a substituent which is the same as R3 in the formula (2) are subjected to condensation reaction, thereby obtaining a hydrazine compound represented by the formula (2). Further, when the obtained hydrazine compound is oxidized with an oxidizing agent, such as PbO2, KMnO4 or CrO3, there is obtained a hydrazyl radical represented by the formula (1). More specifically, for example, 2,2-diphenyl-1-picrylhydrazine can be obtained by heating under reflux a mixture of diphenylhydrazine, picryl chloride and sodium hydrogencarbonate in an ethanol solvent and, then, crystallizing the resultant with benzene-ethanol. 2,2-Diphenyl-1-picrylhydrazyl can be obtained by oxidizing the obtained 2,2-diphenyl-1-picrylhydrazine with PbO2 in a benzene solvent in the presence of sodium sulfate, wherein the PbO2 is used in a molar amount which is 10 to 20 times the molar amount of the hydrazine. Other hydrazine compounds and hydrazyl radicals can be easily prepared by the above-mentioned method using respective corresponding materials. (With respect to the details of production methods of hydrazine compounds and hydrazyl radicals, reference can be made to, for example, Tetrahedron, 13, 258, 1961, J. Phys. Chem. 65, 710, 1961, Can. J. Chem.58, 723, 1980, and Revue Roumaine de Chimie, 46(4), 363, 2001. )
- The oxidation promoter, which is optionally used in the present invention, promotes an oxidation reaction when added to the reaction system together with the at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) and a hydrazine compound represented by the formula (2). As an oxidation promoter, there can be used various types of metals including the metal elements of Groups 1 to 16 of the Periodic Table. An oxidation promoter may be used in the form of a metal oxide, a metal salt, or an organometal compound. However, it is preferred that an oxidation promoter is a metal compound which contains at least one metal element selected from the group of transition metal elements. As transition metal elements of the transition metal compounds, at least one element selected from the elements of Groups 3 to 12 of the Periodic Table is preferred. Among the elements of Group 3, preferred are lanthanoids, such as La, Ce, Sm, Eu, Ac and Th. Among the elements of Group 4, preferred are Ti, Zr and Hf. Among the elements of Group 5, preferred are V, Nb and Ta. Among the elements of Group 6, preferred are Cr, Mo and W. Among the elements of Group 7, preferred are Mn and Re. Among the elements of Group 8, preferred are Fe, Ru and Os. Among the elements of Group 9, preferred are Co, Rh and Ir. Among the elements of Group 10, preferred are Ni, Pd and Pt. Among the elements of Group 11, preferred are Cu, Ag and Au. Among the elements of Group 12, preferred are Zn and Cd.
- Examples of transition metal compounds include inorganic metal compounds, such as simple substances of the above-mentioned transition metal elements, hydroxides, oxides (including compound oxides), halides (a fluoride, a chloride, a bromide and an iodide), oxo-acid salts (e.g., a nitrate, a sulfate, a phosphate, a borate, a perchlorate and a carbonate), oxo-acids and polyacids (isopoly acids and heteropoly acids); and organometal compounds, such as organic salts (e.g., an acetate, a propionate, a thiocyanate, a naphthenate and a stearate) and complexes. As ligands which form the above-mentioned complexes, there can be mentioned hydroxyl, alkoxyl, acyl, alkoxycarbonyl, acetylacetonato, cyclopentadienyl, a halogen atom, carbonyl, an oxygen atom; and compounds, such as H20 (aquo), phosphine, CN, NO, NO2, NO3, NH3 (ammine), ethylenediamine, pyridine and phenanthroline. The above-mentioned metal compounds can be used individually or in combination. Further, the above-mentioned metal elements or metal compounds may be used in the form of a salt or a complex with the oxidation catalyst of the present invention (comprising hydrazyl radical of formula (1) and/or hydrazine compound of formula (2)).
- Specific examples of transition metal compounds include tungsten compounds, such as metal tungsten, tungsten oxide, tungsten oxytetrachloride, tungstic acid, sodium tungstate, zinc tungstate, cobalt tungstate, cesium tungstate, tungsten hexacarbonyl, tungsten pentaethoxide, tungsten hexaphenoxide, silicotungstate, metatungstate, phosphotungstate, cobalt tungstate, molybdenum tungstate, manganese tungstate and manganese molybdenum tungstate.
- Examples of titanium compounds include metal titanium, titanium oxide, titanium tetrachloride, titanium(II) sulfate, (acetylacetonato)titanium oxide, titanium tetraethoxide, titanium tetra-iso-propoxide, titaniumu tetra-iso-butoxide, titanium naphthenate, titanium silicalite molecular sieves, titanium phosphate, zirconium titanate, sodium titanate and barium titanate.
- Further, examples of molybdenum compounds include metal molybdenum, molybdenum oxide, molybdenum chloride, molybdenum 2-ethylhexanate, molybdenum hexacarbonyl, bis(acetylacetonato) molybdenum oxide, molybdic acid, sodium molybdate, molybdophosphate, molybdosilicate, cobalt molybdate, manganese molybdate, vanadomolybdophosphate, manganese vanadium molybdate and manganese vanadium molybdophosphate. As compounds of other metal elements, there can be mentioned compounds corresponding to the above-mentioned tungsten compounds, titanium compounds and molybdenum compounds.
- Transition metal compounds may be homogenous or heterogeneous, and may be a heterogeneous solid wherein metal components are carried on an appropriate carrier. As examples of carriers, there can be mentioned activated carbon, SiO2, Al2O3, SiO2/Al2O3, TiO2, ZrO2, ZnO, barium sulfate, potassium carbonate, silious earth and zeolite. As a method for preparing an oxidation promoter in which metal components are carried on a carrier, there can be mentioned methods used for producing conventional carrier-supported catalysts, for example, an absorption method, an impregnation method, a coprecipitation method and a sol-gel method. The amount of metal components carried on a carrier is from 0.0001 to 0.8 part by weight, preferably from 0.001 to 0.5 part by weight, more preferably from 0.01 to 0.3 part by weight, relative to 1 part by weight of the carrier.
- The amount of an oxidation promoter is generally from 0.00005 to 0.8 mole, preferably from 0.0001 to 0.4 mole, still more preferably from 0.0005 to 0.2 mole, per mole of the substrate.
- The amount ratio (molar ratio) of hydrazyl radical of formula (1) and/or hydrazine compound of formula (2) (referred to as “oxidation catalyst” below) to an oxidation promoter (i.e., “oxidation catalyst/oxidation promoter” molar ratio) is generally from 99/1 to 1/99, preferably from 90/10 to 10/90, still more preferably from 80/20 to 20/80.
- The “Periodic Table” used herein is that prescribed in the IUPAC (International Union of Pure and Applied Chemistry) nomenclature sytem of inorganic chemistry (1989).
- Examples of substrates which can be used in the oxidation reaction method of the present invention include various substrates which can be used in the selective oxidation reactions explained above under “Prior Art”, such as hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and heterocyclic compounds. Oxidation products are as follows: from hydrocarbons, there can be obtained alcohols, aldehydes, ketones, epoxy compounds, carboxylic acids, peroxides and the like; from alcohols, there can be obtained aldehydes, ketones, carboxylic acids, peroxides and the like; from carbonyl compounds, there can be obtained carboxylic acids, peroxides and the like; from ethers, there can be obtained esters, acid anhydrides and the like; from amines, there can be obtained Schiff bases, nitriles, oximes, nitro compounds, hydroxylamines, nitrones, N-oxides and the like; from sulfur compounds, there can be obtained disulfides, sulfonic acids, sulfoxides and the like; and from heterocyclic compounds, there can be obtained N-oxides, sulfoxides and the like.
- The above-mentioned substrates may be substituted with various substituents, such as an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group.
- Specific examples of hydrocarbons include unsaturated or saturated, linear or branched aliphatic hydrocarbons, such as propane, n-butane, isobutane, n-pentane, n-hexane, 2-methylpentan, 3-methylpentan, propylene, 2-butene, isobutene, butadiene, isoprene, 1-pentene, 1-hexene, 1-heptene, 3-methyl-1-butene, 2,3-dimethyl-1-butene and allyl chloride; unsaturated or saturated alicyclic hydrocarbons, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, chlorocyclohexane, methoxycyclohexane, cyclopentene, cyclohexene, cyclooctene, cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, adamantane, limonene and terpinene; and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, propylbenzene, cumene, styrene, diphenylmethane, triphenylmethane, bibenzyl, stilbene, indene, naphthalene, tetralin and anthracene.
- Specific examples of alcohols include unsaturated or saturated aliphatic alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, t-butanol, n-pentanol, n-hexanol, n-heptanol, allyl alcohol and crotyl alcohol; unsaturated or saturated alicyclic alcohols, such as cyclopentanol, cyclohexanol, cycloheptanol, methylcyclohexanol, cyclohexene-1-ol; aliphatic or alicyclic polyhydric alcohols, such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,2-cyclohexanediol and 1,4-cyclohedxanediol; and aromatic alcohols, such as benzyl alcohol, salicyl alcohol and benzhydrol.
- The term “carbonyl compound” means a compound which has at least one carbonyl group in a molecule thereof. Specific examples of carbonyl compounds include aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 1-pentanal, 1-hexnal, 1-heptanal, 1-octanal, 1-nonanal, 1-decanal, acrolein, methacrolein, benzaldehyde, nitrobenzaldehyde, aminobenzaldehyde, glutaraldehyde, adipaldehyde; and ketones, such as acetone, methylethylketone, methylpropylketone, methylisopropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, cyclohexanone, cyclooctanone, cyclododecanone, 2-methylcyclohexanone, 2-ethylcyclohexanone, 2,6-dimethylcyclohexanone, acetophenone, propiophenone, benzophenone, 4-chloroacetophenone and 1-acetonaphthone.
- Specific examples of ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methylethyl ether, methylbutyl ether, ethylbutyl ether, diallyl ether, methyl vinyl ether, anisole, dibenzyl ether and phenyl benzyl ether.
- Specific examples of amines include aliphatic amines, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diusopropylamine, butylamine, dibutylamine, tributylamine, allylamine, diallylamine and triallylamine; alicyclic amines, such as cyclopentylamine, cyclohexylamine, cycloheptylamine and cyclooctylamine; and aromatic amines, such as aniline, N-methylaniline, N,N-dimethylaniline, toluidine, benzylamine and phenylenediamine.
- Specific examples of sulfur compounds include thiols, such as methanethiol, ethanethiol, 1-propanethiol, 1-butanethiol, 1-hexanethiol, 1-octanethiol, ethylene thioglycol, propylene thioglycol, cyclopentanthiol, cyclohexanethiol, methylcyclohexanethiol, phenylmethanethiol and 2-phenylethanethiol; and sulfides, such as diethyl sulfide, dipropyl sulfide, diusopropyl sulfide, dibutyl sulfide, methyl ethyl sulfide, methyl butyl sulfide, ethyl butyl sulfide, diallyl sulfide, methyl phenyl sulfide, ethyl phenyl sulfide, diphenyl sulfide and dibenzyl sulfide.
- Specific examples of heterocyclic compounds include furan, thiophene, pyrrole, thiopyran, pyridine, piperidine, morpholine, thiazole, imidazole, pyrimidine, 1,3,5-triazine, indole, quinoline, purine, chroman, carbazol, benzothiazole and benzoisoquinoline.
- The above-mentioned substrates may be used individually or in combination. Further, it is not necessarily that a substrate be purified. A substrate may be used in the form of a mixture with other organic or inorganic compounds.
- In the present invention, as a substrate, amines are preferred.
- As amines used in the present invention, a primary amine and a secondary amine are preferred. With respect to the primary amines used in the present invention, there is no particular limitation as long as the primary amine has a structure wherein an amino group has a substituent bonded thereto through a carbon atom thereof, wherein the carbon atom through which the substituent is bonded to the amino group has at least one hydrogen atom bonded thereto. The primary amine contains one or more of such an amino group in the molecule thereof.
-
- wherein each of R1 and R2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, provided that R1 and R2 are not simultaneously hydrogen atoms; and
- wherein R1 and R2 are optionally bonded to each other, to thereby form a ring.
- The aliphatic group mentioned above represents an unsaturated or saturated, linear or branched aliphatic hydrocarbon group, or an unsaturated or saturated, alicyclic hydrocarbon group. Further, the above-mentioned aliphatic group, aromatic group and aralkyl group may be substituted with a substituent, such as an aliphatic group, an aromatic group, an aralkyl group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group. Examples of rings formed by bonding R1 and R2 include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring and a cyclododecane ring. In general, the aliphatic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms; the aromatic group has 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms; and the aralkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms.
- Specific examples of such primary amines include methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, isopropylamine, isobutylamine, sec-butylamine, 1-methylbutylamine, 2-methylbutylamine, cyclopentylamine, cyclohexylamine, cyclododecylamine, benzylamine, 4-methylbenzylamine, 1-methylbenzylamine, 1-phenylethylamine, 3-aminomethylpyridine, 1-(4-chlorophenyl)ethylamine, 1-(3-methoxyphenyl)ethylamine, 1-(4-trifluoromethyl-phenyl)ethylamine, 1-phenylpropylamine, 1-naphthyl-ethylamine and 1,6-hexanediamine. Further examples of primary amines include an optically active amine having an asymmetric carbon atom in the molecule thereof and a primary amine salt of an acid (such as hydrochloric acid, sulfuric acid or nitric acid).
- When a primary amine is contacted with a molecular oxygen in the presence of the oxidation catalyst of the present invention, there is obtained an oxime compound or a nitro compound, each of which is formed by the oxidation of an amino group of the primary amine.
-
- wherein R1 and R2 are as defined above for formula (9).
- Specific examples of oxime compounds include formaldehyde oxime, acetoaldehyde oxime, propionaldehyde oxime, n-butylaldehyde oxime, n-pentylaldehyde oxime, n-hexylaldehyde oxime, n-heptylaldehyde oxime, n-octylaldehyde oxime, n-nonylaldehyde oxime, n-decylaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, sec-butylaldehyde oxime, isopentylaldehyde oxime, 1-methyl propyl ketone oxime, 2-methylbutylaldehyde oxime, cyclobutanone oxime, cyclopentanone oxime, cyclohexanone oxime, cyclododecanone oxime, benzaldehyde oxime, acetophenone oxime, phenylacetoaldehyde oxime, 4-chloroacetophenone oxime, 3-methoxyphenylacetophenone oxime, 2,4-dichloroacetophenone oxime, 4-trifluoromethylacetophenone oxime, phenyl ethyl ketone oxime, phenyl isopropyl ketone oxime and phenyl (4-methylphenyl) methyl ketone oxime.
- Specific examples of nitro compounds include nitromethane, nitroethane, 1-nitropropane, 1-nitrobutane, 1-nitropentane, 1-nitrohexane, 1-nitroheptane, 1-nitropropane, 2-nitrobutane, 3-methyl-1-nitrobutane, 1-methyl-1-nitrobutane, 2-methyl-1-nitrobutane, nitrocyclobutane, nitrocyclopentane, nitrocyclohexane, nitrocyclododecane, phenylnitromethane, 1-phenyl-1-nitroethane, 2-phenyl-1-nitroethane, 1-(4-chloro-phenyl)-1-nitroethane, 1-(3-methoxyphenyl)-1-nitro-ethane, 1-(2,4-dichlorophenyl)-1-nitroethane, 1-(4-tri-fluoromethylphenyl)-1-nitroethane, 1-phenyl-1-nitro-propane, 1-phenyl-2-(4-methylphenyl)-1-nitroethane and 1-(1-naphthyl)-1-nitroethane.
- A primary amine which is especially preferred in the present invention is cyclohexylamine which generates cyclohexanone oxime as an oxidation product thereof.
- With respect to the secondary amines used in the present invention, there is no particular limitation as long as the secondary amine has a structure wherein an amino group has two substituents bonded thereto each through a carbon atom thereof, wherein at least one of the two carbon atoms through which the two substituents are, respectively, bonded to the amino group has at least one hydrogen atom bonded thereto. The secondary amine contains one or more of such an amino group in the molecule thereof.
-
- wherein each of R1 and R2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, and R3 has the same definition as each of R1 and R2 except that R3 does not represent a hydrogen atom; and
- wherein two substituents selected from the group consisting of R1, R2 and R3 are optionally bonded to each other, to thereby form a ring.
- The aliphatic group mentioned above represents an unsaturated or saturated, linear or branched aliphatic hydrocarbon group, or an unsaturated or saturated, alicyclic hydrocarbon group. Further, the above-mentioned aliphatic group, aromatic group and aralkyl group may be substituted with a substituent, such as an aliphatic group, an aromatic group, an aralkyl group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxy group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sufinyl group, a sulfonyl group or a heterocyclic group. Examples of rings formed by bonding two substituents selected from the group consisting of R1, R2 and R3 include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclododecane ring, a pyrrolidine ring, a pyperidine ring and a tetrahydroisoquinoline ring. In general, the aliphatic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms; the aromatic group has 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms; and the aralkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms.
- Specific examples of such secondary amines include N,N-dimethylamine, N,N-diethylamine, N,N-di-(n-propyl)amine, N,N-di-(n-butyl)amine, N,N-di-(n-pentyl)-amine, N,N-di-(n-hexyl)amine, N,N-di-(n-heptyl)amine, N,N-di-(n-octyl)amine, N,N-di-(n-nonyl)amine, N,N-di-(n-decyl)amine, N,N-diisopropylamine, N,N-isobutyl-amine, N,N-di-(sec-butyl)amine, N-ethyl-tert-butylamine, N,N-dibenzylamine, N-benzyl-tert-butylamine, N-benzyl-aniline, 1,2,3,4-tetrahydroquinoline, 6,7-methylenedioxy-1,2,3,4-tetrahydroisoquinoline, pyrrolidine, 2-methylpyrrolidine, 2-carbomethoxypyrrolidine, 3,4-dimethoxypyrrolidine, pyperidine, 2-methylpyperidine, 2-carbomethoxypyperidine and 2,6-dimethyl-pyperidine. Further examples of secondary amines include an optically active amine having an asymmetric carbon atom in the molecule thereof and a secondary amine salt with an acid (such as hydrochloric acid, sulfuric acid or nitric acid).
- When a secondary amine is contacted with a molecular oxygen in the presence of the oxidation catalyst of the present invention, there is obtained a nitrone compound which is formed by the oxidation of an amino group of the secondary amine.
-
- wherein R1, R2 and R3 are as defined above for formula (10).
- Specific examples of nitrone compounds include N-methylidenemethylamine N-oxide, N-ethylidenemethyl-amine N-oxide, N-propylidenemethylamine N-oxide, N-butylidenebutylamine N-oxide, N-pentylideneamylamine N-oxide, N-octylideneoctylamine N-oxide, N-nonylidenenonylamine N-oxide, N-decylidenedecylamine N-oxide, N-dodecylidenedodecylamine N-oxide, N-isopropylideneisopropylamine N-oxide, N-isobutylideneisobutylamine N-oxide, N-sec-butylidene-sec-butylamine N-oxide, N-isoamilideneisoamylamine N-oxide, N-ethylidene-tert-butylamine N-oxide, N-benzylidenebenzylamine N-oxide, N-benzylidene-tert-butylamine N-oxide, N-benzylideneaniline N-oxide, 3,4-dihydroisoquinoline N-oxide, 6,7-methylenedioxy-3,4-dihydroisoquinoline N-oxide, 3,4-dihydroisoquinoline N-oxide, 6,7-methylenedioxy-3,4-dihydroisoquinoline N-oxide, 1-pyrroline N-oxide, 2-methyl-1-pyrroline N-oxide, 2-carbomethoxy-1-pyrroline N-oxide, 3,4-dimethoxy-1-pyrroline N-oxide, 2,3,4,5-tetrahydropyridine N-oxide, 2-methyl-2,3,4,5-tetra-hydropyridine N-oxide, 2-carbomethoxy-2,3,4,5-tetra-hydropyridine N-oxide and 2,6-dimethyl-2,3,4,5-tetra-hydropyridine N-oxide.
- In the method of the present invention, when the oxidation reaction of the secondary amine is performed in the presence of an acceptor for a nitrone compound (the oxidation product), especially an olefin, it becomes possible to directly synthesize an addition product of the nitrone compound. The nitrone compound obtained by the method of the present invention is an excellent 1,3-dipole which undergoes an addition reaction with various olefins, to thereby generate a 1,3-dipole adduct. Such a dipole adduct is a precursor for physiological substances, such as an alkaloid, and is a very useful compound. Therefore, in the present invention, it is commercially very advantageous to perform the oxidation reaction of a secondary amine in the presence of an olefin.
- In the present invention, the oxidation reaction may be performed in either the liquid phase or the gaseous phase, and a liquid phase is preferred. Specifically, when the oxidation reaction is performed in the liquid phase, the oxidation reaction is either performed in a reaction medium which is at least one member selected from the group consisting of water and an organic solvent, or performed using the substrate as a reaction medium.
- The term “organic solvent” means either a protic organic solvent or an aprotic organic solvent. Examples of protic solvents include organic carboxylic acids, such as a primary, secondary or tertiary C1-C10 alcohol (e.g., methanol, ethanol, isopropyl alcohol or t-butyl alcohol), formic acid, acetic acid and propionic acid. Examples of aprotic solvents include aliphatic hydrocarbons, such as hexane and octane; aromatic hydrocarbons, such as benzene and toluene; halogenated hydrocarbons, such as chloroform, dichloromethane, carbon tetrachloride and chlorobenzene; nitriles, such as acetonitrile, propionitrile and benzonitrile; nitro compounds, such as nitrobenzene, nitromethane and nitroethane; ethers, such as dimethylether, diethylether, dilsopropylether and dioxane; esters, such as ethylacetate and butylacetate; and amides, such as formamide, acetoamide, dimethylformamide, dimethylacetoamide, diethylacetoamide and hexamethylphosphoric triamide. In the oxidation reaction performed by the method of the present invention, use of an aprotic solvent is preferred. Especially, nitriles, nitro compounds, esters, ethers and amides are preferred, and more preferred are are nitriles, such as acetonitrile and benzonitrile, and amides, such as dimethylformamide and dimethylacetoamide.
- The above-mentioned solvents can be used individually or in combination. When the oxidation reaction is performed in the presence of water and/or an organic solvent, the concentration of a substrate is generally in the range of from 0.1 to 95% by weight, preferably from 1 to 30% by weight, based on the total weight of the water and/or the organic solvent and the substrate.
- In the method of the present invention for performing an oxidation reaction, the oxidation reaction is performed by contacting a substrate with a molecular oxygen in the presence of an oxidation catalyst. The reaction may be performed by a fixed-bed process or a suspension-bed process and in any conventional manner of reaction, such as a batchwise manner, a semi-batchwise manner or a continuous manner. In general, the molecular oxygen is purified oxygen, air or a gaseous mixture of oxygen and an inert gas, such as nitrogen or helium. When a gaseous mixture of oxygen and an inert gas is used as the molecular oxygen, it is preferred that the oxygen concentration of the gaseous mixture is in the range of from 2 to 23% by volume, more advantageously from 3 to 11% by volume; however, it is preferred that the oxygen concentration is in a range such that the resultant gaseous phase does not have an explosive composition.
- In the method of the present invention, it is preferred that the oxidation of a substrate is performed in the liquid phase. Therefore, it is required that the molecular oxygen (which has been introduced as a gas into the reaction system) be dissolved in a desired concentration in the liquid phase containing the catalyst, under the conditions for the oxidation. However, for example, when a molecular oxygen (hereinafter, frequently referred to as a “molecular oxygen-containing gas”) is introduced into the reaction system under reduced pressure or atmospheric pressure and at a temperature at which a liquid reaction mixture containing the substrate, the reaction product and/or the solvent is refluxed, only a very small amount of oxygen can be dissolved in the liquid phase. Therefore, for achieving a desired concentration of oxygen dissolved in the liquid phase, it is preferred to use a method in which the molecular oxygen-containing gas is contacted with the liquid phase under superatmospheric pressure (which is not more than 20 MPa).
- With respect to the total pressure of the reaction system, for example, when it is intended to perform the oxidation in a batchwise manner by using a gaseous mixture of oxygen and an inert gas, the oxidation may be performed by introducing a gaseous mixture having an appropriate oxygen concentration and an appropriate total pressure into the reaction system, wherein the oxygen concentration and the total pressure are determined, taking into consideration the amount of the substrate to be oxidized (i.e., the amount of oxygen needed to oxidize the substrate) which varies depending on the type of catalyst and the reaction conditions. In general, the total pressure of the reaction system is in the range of from 0.1 to 20 MPa, preferably from 1 to 10 MPa.
- With respect to the method for introducing the molecular oxygen-containing gas into the reaction system, there is no particular limitation. For example, the molecular oxygen-containing gas may be introduced either directly into the liquid phase which is formed in the reaction vessel, or into the gaseous phase (which is in contact with the liquid phase) in the reaction vessel.
- The molecular oxygen consumed in the reaction can be compensated by introducing purified oxygen, air or diluted oxygen gas into the reaction system either continuously or intermittently, so as to maintain a desired partial pressure of oxygen in the gaseous phase. Alternatively, when the oxidation is performed in a batchwise manner, by introducing an oxygen-containing gas into the reaction system, which gas contains oxygen in an amount sufficient for oxidizing a desired amount of the substrate, it becomes possible to continue the reaction without compensating for the consumed molecular oxygen until a desired conversion is achieved.
- In the method of the present invention, it is preferred that the reaction temperature is generally in the range of from 0 to 200° C., more advantageously from 40 to 180° C., most advantageously from 60 to 160° C. Although the reaction temperature depends on the chemical reaction performed, when the temperature exceeds 200° C., a gradual decomposition or gradual oxidation of the obtained product is promoted and a by-product having a high boiling point is formed in a higher ratio, thus lowering the selectivity for the desired product. On the other hand, when the temperature is lower than 0° C., the reaction rate tends to become low.
- The reaction time is not particularly limited and can be appropriately selected in accordance with the desired values of the selectivity for and yield of the desired product. Usually, the reaction time is selected from the range of from several seconds to several hours.
- From the reaction mixture obtained by the reaction, the reaction product can be easily separated and purified by conventional methods, for example, separation methods, such as a distillation, an extraction, a condensation, a filtration, a crystal deposition, a recrystallization, a column chromatography or a combination of two or more separation methods. Generally, it is preferred that the unreacted substrate is recycled to the reaction vessel. When the catalyst is contained in the reaction medium after separating the reaction product, such reaction medium may be recycled to the reaction vessel and reused for the oxidation reaction.
- Next, the reaction mechanism of the oxidation reaction using the oxidation catalyst of the present invention is explained below, taking as an example a reaction for producing cyclohexanone oxime from cyclohexylamine and oxygen.
- A hydrazyl radical represented by formula (1) is used as an oxidation catalyst of the present invention, and a specific example of a hydrazyl radical of formula (1) is a free radical, such as 2,2-diphenyl-1-picrylhydrazyl (DPPH), which removes a hydrogen atom from chemical linkages (such as C—H, N—H, PhO—H and S—H) of an organic substrate, to thereby selectively produce a corresponding radical species. In the reaction between DPPH and an organic substrate, DPPH itself is transformed into 2,2-diphenyl-1-picrylhydrazine (DPPH2); that is, in the reaction between DPPH and an organic substrate, DPPH functions as a receptor for a hydrogen radical. This reaction has been known for a long time and it is applied to a stoichiometric coupling reaction and the like (see, for example, Can. J. Chem. 39, 1588, 1961). The present inventor has found that, when the hydrazyl radical represented by formula (1), which has the above-mentioned reaction characteristics, is contacted with a substrate in the presence of a molecular oxygen, the hydrazyl radical functions as a catalyst, thereby enabling production of a desired oxidation product under moderate conditions with high selectivity and in high yield. The same effects can also be obtained by using, as an oxidation catalyst, a hydrazine compound represented by formula (2) or a mixture of a hydrazyl radical represented by formula (1) and a hydrazine compound represented by formula (2).
- The functional mechanism of the catalyst system of the present invention has not yet been fully elucidated. However, it is presumed that DPPH and DPPH2 function as a hydrogen mediator while undergoing reversible mutual transformation. More specifically, it is presumed that the following catalyst cycle is established in the reaction system: DPPH2 is generated in the reaction system by a reaction between a substrate and DPPH; the generated DPPH2 directly activates an oxygen molecule to thereby generate an electrophilic oxygen active species and DPPH; and the generated DPPH pulls out a hydrogen atom from a reaction intermediate which is formed by addition of an oxygen molecule to the substrate, thereby regenerating DPPH2.
- During the course of the studies by the present inventor, the present inventor analyzed the functional mechanism of the catalyst system by using as a model the reaction of DPPH with N-cyclohexylhydroxylamine which is presumed to be a reaction intermediate of an oximation reaction of cyclohexylamine. As a result, it became apparent that the reaction represented by formula (i) below proceeds stoichiometrically in the reaction system. Further, it was found that, when the reaction represented by formula (i) below is performed in the presence of WO3/Al2O3 (alumina having supported thereon tungsten oxide) (oxidation promoter) under high oxygen pressure conditions, DPPH functions like a catalyst in the reaction system. It was also found that, even when DPPH2 is used instead of DPPH, the reaction proceeds in a catalytic manner. These results obtained from the analyses performed by the present inventor suggest that DPPH and DPPH2 function as a hydrogen mediator while undergoing reversible mutual transformation, and that the activation of oxygen molecules (such as the reaction represented by formula (ii) below) is efficiently performed by using the substrate as a hydrogen source. That is, it is presumed that DPPH2 causes a reduction of an oxygen molecule; then, the resultant oxygen molecule in a reduced form generates an oxygen active species on the metal atom of the oxidation promoter; and, then, the oxygen active species participates in the oxidation reaction of the substrate. It is known that the oxidative activity of the oxygen active species, which is generated on the metal atom of the oxidation promoter, varies depending on the metal compound used as the oxidation promoter. Therefore, in the reaction system of the present invention, the oxidation reaction can be controlled as desired by selecting an appropriate oxidation promoter in accordance with the type of the substrate used and the type of the desired oxidation product. For example, as demonstrated in Examples 14 and 15 below, in the oxidation reaction of cyclohexylamine, each of cyclohexanone oxime and nitrocyclohexane can be produced selectively by changing the type of the oxidation promoter used.
C6H11NHOH+2DPPH→C6H10═NOH+2DPPH2 (i)
2DPPH2+O2→2DPPH+O* (oxygen active species)+H2O (ii) - As explained above, each of the hydrazyl radical represented by formula (1) (such as DPPH) and the hydrazine compound represented by formula (2) (such as DPPH2) functions as a catalyst in the oxidation reaction of an organic substrate in the presence of oxygen. From electrochemical experiments, it has conventionally been known that DPPH and DPPH2 can undergo reversible mutual transformation (see, for example, Electrochemistry Communications, 1, 406 (1999)); however, it has not been reported that, in the presence of oxygen, DPPH and DPPH2 exhibit a catalytic function as a hydrogen mediator while undergoing reversible mutual transformation. As mentioned above, the hydrazyl radical represented by formula (1), such as a DPPH radical, has the ability to pull out a hydrogen radical from various organic substrates. Therefore, the oxidation catalyst of the present invention can be applied to oxygen oxidation reaction of various organic substrates.
- Hereinbelow, the present invention will be described in more detail with reference to the following Examples and Comparative Examples, which should not be construed as limiting the scope of the present invention.
- In the Examples and Comparative Examples, various properties were measured and evaluated as follows.
- 1) Conversion of a Substrate and Selectivity for an Oxidation Product
- The conversion of a substrate and the selectivity for an oxidation product, which were used for evaluating the results of the oxidation reaction of a substrate in the Examples and Comparative Examples, are defined by the following formulae, respectively.
Conversion of a substrate (%)=(molar amount of a reacted substrate/molar amount of fed substrate)×100
Selectivity for an oxidation product (%)=(molar amount of an oxidation product/molar amount of a reacted substrate)×100 - The reaction product was analyzed by gas chromatography under the following conditions.
- Apparatus: gas chromatograph Model GC-14A, manufactured and sold by Shimadzu Corporation, Japan (including a flame ionization detector (FID))
- Column: capillary column DB-1701, manufactured and sold by J&W Scientific, U.S.A. (0.25 mm×30 m)
- Carrier gas: helium
- Flow rate: 20 ml/min
- Analysis mode: maintained at 50° C. for 10 min; then, temperature-elevated to 280° C. at a rate of 10° C./min; and, then, maintained at 280° C. for 5 min.
- 2) Determination of the amounts of metals contained in the oxidation promoter (solid powdery product)
- The amounts of metals contained in the solid powdery product were determined by means of an X-ray fluorescence analyzer under the following conditions.
- Apparatus : RIX-3000, manufactured and sold by Rigaku Corporation, Japan
- (X-ray Excitation Conditions)
- Target element: Rh
- Tube voltage: 50 kV
- Tube current: 50 mA
- Single crystal used for a monochromator: polyethylene terephthalate for the determination of Al and Si, and lithium fluoride for the determination of other metals
- Detector: scintillation counter
- (Preparation of Samples)
- A predetermined amount of the solid powdery product was mixed and diluted with a crystalline cellulose (as a binder) to obtain a powder mixture (solid powdery product/crystalline cellulose (weight ratio)=½ to ⅓), and the obtained powder mixture was formed into tablets under a pressure of 20 tons by using a tableting machine in which the powder mixture was held by an aluminum ring (as a mold).
- (Preparation of the Calibration Curve)
- With respect to each of the metal oxides used in the oxidation promoter, tablets (standard samples) containing the metal oxide were produced in substantially the same manner as mentioned above, except that, instead of the oxidation promoter, different amounts of the metal oxide were, respectively, used for producing the tablets. The obtained tablets were analyzed by X-ray fluorescence spectrometry, thereby obtaining a calibration curve for determination of the metal contents of the oxidation promoter.
-
- The nomenclatures of the compounds above are listed below. Compounds (d) to (h) were synthesized in accordance with a conventional method (for example, a method described in Tetrahedron, 24, 1063, 1968; or Revue Roumaine de Chimie, 46(4), 363, 2001). With respect to other compounds, commercially available products were used.
- [Nomenclatures of Hydrazyl Radicals and Hydrazine Compounds]
- (a) 2,2-diphenyl-1-picrylhydrazyl
- (b) 2,2-diphenyl-1-picrylhydrazine
- (c) 2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl
- (d) 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine
- (e) N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine
- (f) 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)-hydrazine
- (g) carbazol-9-yl-(2,4,6-trinitrophenyl)amine
- (h) 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol
- (i) 1-phenyl-pyrazolidin-3-one
- (j) 1-phenyl-1,2-dihydro-pyridazine-3,6-dione
- (k) 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazin-1-yl
- (Preparation of an Oxidation Promoter)
- 100 g of a commercially available aluminum s-butoxide was placed in a glass beaker. Then, into the beaker was dropwise charged an aqueous solution of ammonium metatungstate (which had been prepared by dissolving 7.0 g of commercially available ammonium metatungstate in 100 g of water) while vigorously stirring by means of a glass rod. The resultant gel-like product was air-dried at room temperature for 1 hour, followed by vacuum-drying at 120° C. overnight. The resultant dried product was subjected to calcination treatment in a furnace at 400° C. for 4 hours under atmospheric pressure while feeding air into the furnace, thereby obtaining a solid powdery product (oxidation promoter) comprised of alumina having supported thereon tungsten oxide (WO3/Al2O3). The obtained oxidation promoter was examined by X-ray fluorescence spectrometry. As a result, it was found that the oxidation promoter had a tungsten content of 21.8% by weight.
- (Oxidation Reaction of Cyclohexylamine)
- Next, 0.049 g (0.125 mmol) of 2,2-diphenyl-1-picrylhydrazyl (i.e., DPPH) (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) as an oxidation catalyst, 0.1 g of the above-prepared WO3/Al2O3 (oxidation promoter), 3 ml of acetonitrile as a solvent and 0.496 g (5 mmol) of cyclohexylamine as a substrate were charged into a high pressure autoclave having an internal volume of 120 ml, which was made of stainless steel SUS 316 and was equipped with a magnetic stirrer. After closing the autoclave, the inside of the autoclave was purged with nitrogen gas, and a gaseous mixture of nitrogen and oxygen (oxygen content=7% by volume) was introduced into the gaseous phase in the autoclave, so as to elevate the pressure in the autoclave to 5 MPa. Then, the autoclave was secured to an oil bath, and the mixture in the autoclave was heated to 80° C., followed by an oxidation reaction at a reaction temperature of 80° C. for 4 hours while stirring, to thereby produce cyclohexanone oxime.
- After cooling the autoclave, the residual pressure was removed therefrom, and the autoclave was opened. The resultant reaction mixture having dispersed therein the catalyst was recovered from the autoclave and diluted with ethanol. The diluted reaction mixture was subjected to a filtration to thereby remove the catalyst and obtain a filtrate. The obtained filtrate was analyzed by gas chromatography.
- As a result, it was found that the cyclohexylamine conversion was 58.9%, and the selectivity for cyclohexanone oxime was 94.9%. Further, decomposition of 2,2-diphenyl-1-picrylhydrazyl was not observed even after the reaction and, therefore, it was confirmed that this oxidation catalyst is stable during the oxidation reaction.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that the reaction time was changed to 8 hours. As a result, it was found that the conversion of cyclohexylamine was 80.3% and the selectivity for cyclohexanone oxime was 93.0%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.049 g (0.125 mmol) of 2,2-diphenyl-1-picrylhydrazine (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 40.7% and the selectivity for cyclohexanone oxime was 95.7%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that a mixture of 0.024 g (0.06 mmol) of 2,2-diphenyl-1-picrylhydrazyl and 0.026 g (0.065 mmol) of 2,2-diphenyl-1-picrylhydrazine was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 53.1% and the selectivity for cyclohexanone oxime was 95.2%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.077 g (0.125 mmol) of 2,2-di(4-t-octylphenyl)-1-picrylhydrazyl (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 62.4% and the selectivity for cyclohexanone oxime was 95.6%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.047 g (0.125 mmol) of 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 45.1% and the selectivity for cyclohexanone oxime was 91.4%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.042 g (0.125 mmol) of N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 41.2% and the selectivity for cyclohexanone oxime was 93.0%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.052 g (0.125 mmol) of 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 50.1% and the selectivity for cyclohexanone oxime was 89.0%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.049 g (0.125 mmol) of carbazol-9-yl(2,4,6-trinitrophenyl)amine was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 43.2% and the selectivity for cyclohexanone oxime was 94.5%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.087 g (0.125 mmol) of 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 60.1% and the selectivity for cyclohexanone oxime was 92.7%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.041 g (0.25 mmol) of 1-phenylpyrazolidine-3-one (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 30.2% and the selectivity for cyclohexanone oxime was 86.2%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.047 g (0.25 mmol) of 1-phenyl-1,2-dihydropyridazine-3,6-dione (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 25.0% and the selectivity for cyclohexanone oxime was 84.1%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.079 g (0.25 mmol) of 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 20.5% and the selectivity for cyclohexanone oxime was 83.7%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that the oxidation promoters indicated in Table 1 below were individually used in the concentrations mentioned below. With respect to the oxidation promoters indicated in Table 1, the following should be noted. WO3/Al2O3 (i.e., alumina having supported thereon tungsten oxide) was prepared in the same manner as in Example 1; WO3/ZrO2 (i.e., zirconium having supported thereon tungsten oxide) and WO3/TiO2 (i.e., titanium oxide having supported thereon tungsten oxide) were individually prepared by the methods explained below; and the below-mentioned commercially available products were individually used as the other oxidation promoters: TiO2 (P25; manufactured and sold by Degussa AG, Germany), TiO2-mesopore (manufactured and sold by Sigma-Aldrich Japan K.K., Japan), H+-ETS-10 (manufactured and sold by N.E. Chemcat Corporation, Japan), Ti(Oi-Pr)4 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), TiO(acac)2 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), and Nb2O5-mesopore (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) (wherein “TiO(acac)2” stands for titanium(II) oxide acetylacetonate which is represented by the formula: TiO(CH3COCHCOCH3)2; and “Ti(Oi-Pr)4” stands for titanium tetraisopropoxide which is represented by the formula: Ti[OCH(CH3)2]4). The amount of the oxidation promoter was the same as in Example 1, namely 0.1 g, except that each of Ti(Oi-Pr)4 and TiO(acac)2 was used in an amount of 0.125 mmol. The obtained products were individually analyzed by gas chromatography. As shown in Table 1, cyclohexanone oxime was selectively obtained by using different oxidation promoters.
- (Preparation of WO3/ZrO2)
- A commercially available ZrO2 (RC100; manufactured and sold by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD., Japan) was dried at 120° C. overnight, and the dried ZrO2 was used as a carrier for an oxidation promoter. 1.4 g of ammonium paratungstate pentahydrate was dissolved in 60 g of water, followed by addition of 10 g of the dried ZrO2, to thereby obtain a suspension.
- The obtained suspension was charged into a glass flask, and the flask was set in a rotary evaporator. The flask attached to the rotary evaporator was immersed in an oil bath having a temperature of 90° C., and the contents of the flask were slowly stirred under atmospheric pressure for 1.5 hours, to thereby obtain a slurry. The temperature of the oil bath was elevated from 90° C. to 100° C., and the slurry in the flask was stirred at 100° C. under atmospheric pressure to evaporate water from the slurry in the flask, thereby obtain a dry powder. The obtained dry powder was further dried at 120° C. overnight and, then, a predetermined amount of the powder was charged into a glass tubular furnace and calcined at 500° C. for 4 hours under atmospheric pressure while feeding air into the furnace, thereby obtaining a solid powdery product comprised of ZrO2 having supported thereon tungsten oxide (WO3/ZrO2). The obtained solid powdery product was examined by X-ray fluorescence spectrometry. As a result, it was found that the solid powdery product had a tungsten content of 9.2% by weight.
- (Preparation of WO3/TiO2)
- Substantially the same procedure as in the above-mentioned method for preparing WO3/ZrO2 was repeated except that TiO2 (P25; manufactured and sold by Degussa AG, Germany) was used as a carrier instead of ZrO2, thereby obtaining a solid powdery product (WO3/TiO2). The obtained solid powdery product was examined by X-ray fluorescence spectrometry. As a result, it was found that the solid powdery product had a tungsten content of 9.5% by weight.
TABLE 1 Conversion Selectivity Oxidation of amine for oxime promoter (%) (%) WO3/Al2O3 58.9 94.9 WO3/ZrO2 62.8 86.0 WO3/TiO2 22.3 63.6 TiO2 35.7 89.9 TiO2-mesopore 32.4 87.8 H+-ETS-10 13.9 92.7 Ti(Oi-Pr)4 67.2 87.8 TiO(acac)2 60.5 89.3 Nb2O5-mesopore 50.1 79.6 - An oxidation reaction was performed in substantially the same manner as in Example 1 except that the oxidation promoters indicated in Table 2 below were individually used in the concentrations mentioned below. The below-mentioned commercially available products were individually used as the oxidation promoters: WO3 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), Na2WO4.2H2O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), H2WO4 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), Na2MoO4.2H2O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), MoO2(acac)2 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), and Mo(CO)6 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) (wherein “MoO2(acac)2” stands for molybdenum oxide bis(acetylacetonate) which is represented by the formula: MoO2(CH3COCHCOCH3)2). Each of these oxidation promoters was used in an amount of 0.125 mmol, except that WO3 was used in an amount of 0.1 g. The obtained products were individually analyzed by gas chromatography. As shown in Table 2, nitrocyclohexane was selectively obtained by using different oxidation promoters.
TABLE 2 Conversion Selectivity for Oxidation of amine nitrocyclohexane promoter (%) (%) WO3 9.1 62.3 Na2WO42H2O 13.3 55.6 H2WO4 28.3 50.8 Na2MoO42H2O 7.0 72.7 MoO2(acca)2 9.5 68.6 Mo(CO)6 11.8 57.4 - An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.125 mmol of Na2MoO4.2H2O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation promoter instead of the oxidation promoter used in Example 1, and that the amount of 2,2-diphenyl-1-picrylhydrazyl was changed to 0.2 g (0.5 mmol). As a result, it was found that the conversion of cyclohexylamine was 29.3% and the selectivity for nitrocyclohexane was 79.1%.
- An oxidation reaction was performed in substantially the same manner as in Example 16 except that the reaction temperature was changed to 90° C. As a result, it was found that the conversion of cyclohexylamine was 62.5% and the selectivity for nitrocyclohexane was 76.3%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that various solvents as indicated in Table 3 below were individually used instead of the solvent used in Example 1. The obtained products were individually analyzed by gas chromatography. As shown in Table 3, cyclohexanone oxime was selectively obtained by using different solvents.
TABLE 3 Conversion Selectivity of amine for oxime Solvent (%) (%) 1,4-dioxane 11.6 88.8 benzene 6.3 84.3 chlorobenzene 4.1 95.8 pyridine 6.5 82.7 ethylacetate 41.2 93.8 nitrobenzene 46.8 96.5 benzonitrile 42.1 94.2 acetonitrile 58.9 94.9 dimethylformamide 76.5 96.6 dimethylacetoamide 46.4 95.2 water 5.1 83.4 methanol 14.4 90.9 t-butanol 8.6 92.5 - An oxidation reaction was performed in substantially the same manner as in Example 1 except that 3 ml of dimethylformamide was used as a solvent instead of the solvent used in Example 1, and that the reaction time was changed to 9 hours. As a result, it was found that the conversion of cyclohexylamine was 95.1% and the selectivity for cyclohexanone oxime was 96.3%.
- An oxidation reaction was performed using various reaction systems in which different primary amines as indicated in Table 4 below were individually used as a substrate and in which the substrate was used as a solvent (reaction medium). The reaction was performed in substantially the same manner as in Example 1 except that 0.03 g (0.075 mmol) of 2,2-diphenyl-1-picrylhydrazyl (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) as an oxidation catalyst, 0.1 g of WO3/Al2O3 (oxidation promoter) and 30 mmol of each individual primary amine (as a substrate and solvent) as indicated in Table 4 below were charged into a high pressure autoclave. The obtained products were individually analyzed by gas chromatography. As shown in Table 4, an oxime corresponding to each primary amine used was selectively obtained.
TABLE 4 Conversion Selectivity of amine for oxime Primary amine (%) (%) n-butylamine 9.3 61.8 sec-butylamine 4.5 92.3 n-hexylamine 9.3 70.8 n-octylamine 7.5 73.1 cyclopentylamine 24.0 78.5 cyclohexylamine 22.1 89.0 cyclooctylamine 10.3 87.9 benzylamine 30.4 51.3 4-methylbenzylamine 27.3 51.5 3-aminomethylpyridine 16.7 47.5 1-phenylethylamine 12.6 63.4 - An oxidation reaction was performed in substantially the same manner as in Example 1 except that the reaction conditions, such as reaction temperature, oxygen pressure and reaction time were changed as indicated in Table 5 below. The obtained products were individually analyzed by gas chromatography. As shown in Table 5, cyclohexanone oxime was selectively obtained under different reaction conditions.
TABLE 5 Reaction conditions Oxygen Conversion Selectivity Temperature pressure Time of amine for oxime (° C.) (MPa) (hr) (%) (%) 60 5 2 5.4 97.5 80 5 2 20.8 97.9 90 5 2 40.0 94.8 100 5 2 59.3 92.7 110 5 2 85.2 89.8 80 3 4 47.5 94.9 80 5 4 58.9 94.9 80 10 4 83.2 93.0 - An oxidation reaction was performed in substantially the same manner as in Example 1 except that the amounts of oxidation catalyst (DPPH) and oxidation promoter (WO3/Al2O3) were changed as indicated in Table 6 below, and that the reaction time was changed to 2 hours. The obtained products were individually analyzed by gas chromatography. As shown in Table 6, cyclohexanone oxime was selectively obtained by using various amounts of DPPH and WO3/Al2O3.
TABLE 6 Reaction conditions Conversion Selectivity DPPH WO3/Al2O3 of amine for oxime (mmol) (g) (%) (%) 0 0.1 0 0 0.125 0.1 20.8 97.9 0.25 0.1 46.0 95.0 0.375 0.1 66.9 94.7 0.125 0 3.2 40.6 0.125 0.02 11.9 93.4 0.125 0.05 19.0 95.6 0.125 0.1 20.8 97.9 0.125 0.2 18.6 95.1 - An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.646 g (5 mmol) of dibutylamine (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of dibutylamine was 43.5% and the selectivity for N-butylidenebutylamine-N-oxide was 72.1%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.986 g (5 mmol) of dibenzylamine (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of dibenzylamine was 49.5% and the selectivity for N-benzylidenebutylamine-N-oxide was 73.4%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.666 g (5 mmol) of 1,2,3,4-tetrahydroisoquinoline (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of 1,2,3,4-tetrahydroisoquinoline was 39.0% and the selectivity for 3,4-dihydroisoquinoline-N-oxide was 78.4%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.356 g (5 mmol) of pyrrolidine (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of pyrrolidine was 55.4% and the selectivity for 1-pyrroline-N-oxide was 65.3%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.426 g (5 mmol) of piperidine (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction time was changed to 8 hours. As a result, it was found that the conversion of piperidine was 48.3% and the selectivity for 2,3,4,5-tetrapyridine-N-oxide was 62.1%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.541 g (5 mmol) of benzyl alcohol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction temperature was changed to 100° C. As a result, it was found that the conversion of benzyl alcohol was 15.4% and the selectivity for benzaldehyde was 99.0%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.5 g (5 mmol) of cyclohexanol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1, and that the reaction temperature was changed to 100° C. As a result, it was found that the conversion of cyclohexanol was 9.1% and the selectivity for cyclohexanone was 98.4%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that, instead of the substrate, solvent and oxidation promoter used in Example 1, 0.5 g (5 mmol) of cyclohexanol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate, 3 ml of dimethylformamide was used as a solvent, and 0.041 g (0.125 mmol) of MoO2(acac)2 (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation promoter, and that the reaction temperature was changed to 100° C. As a result, it was found that the conversion of cyclohexanol was 14.3% and the selectivity for cyclohexanone was 97.2%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.451 g (5 mmol) of 1-butanethiol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate instead of the substrate used in Example 1. As a result, it was found that the conversion of 1-butanethiol was 9.5% and the selectivity for butyldisulfide was 96.1%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that, instead of the substrate, solvent and oxidation promoter used in Example 1, 0.451 g (5 mmol) of 1-butanethiol (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as a substrate, 3 ml of methanol was used as a solvent, and 0.066 g (0.2 mmol) of Na2WO4-2H2O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation promoter. As a result, it was found that the conversion of 1-butanethiol was 13.2% and the selectivity for butyldisulfide was 95.4%.
- An operation for effecting an oxidation reaction was performed in substantially the same manner as in Example 1 except that none of a hydrazyl radical and a hydrazine compound was used as an oxidation catalyst. As a result, the reaction did not proceed at all and, hence, no cyclohexanone oxime was obtained. Further, an operation for effecting an oxidation reaction was performed in substantially the same manner as in Example 1 except that benzylamine, N,N-dibutylamine, piperidine, benzyl alcohol and 1-butanethiol were individually used as a substrate instead of the substrate used in Example 1, and that none of a hydrazyl radical and a hydrazine compound was used as an oxidation catalyst. As a result, it was found that no oxidation product was obtained by the reaction.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that, instead of the oxidation catalyst used in Example 1, there was used 0.044 g (0.25 mmol) of p-trifluoro-phenylhydrazine (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) having a structure different from that of the oxidation catalyst of the present invention. As a result, it was found that the conversion of cyclohexylamine was 4.2% and the selectivity for cyclohexanone oxime was 62.1%. It was also found that the amount of cyclohexanone oxime obtained was not more than the stoichiometric amount corresponding to the amount of hydrazine compound used, indicating that the hydrazine compound used in this Comparative Example 2 did not catalyze the oxidation unlike the oxidation catalyst of the present invention. Further, an oxidation reaction was performed in substantially the same manner as in Example 1 except that, instead of the oxidation catalyst used in Example 1, hydrazine monohydrate, 1,2-diphenylhydrazine, 2,4-dinitrophenylhydrazine, phthalic hydrazine and benzenesulfonylhydrazine were used individually as an oxidation catalyst. As a result, it was found that the amount of cyclohexanone oxime obtained was not more than the stoichiometric amount corresponding to the amount of hydrazine compound used, and that the selectivity for cyclohexanone oxime was as low as 50% or less. It was also found that the hydrazine compounds used in this Comparative Example 2 had been decomposed during the reaction.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.039 g (0.25 mmol) of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) (manufactured and sold by Sigma-Aldrich Japan K.K., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 2.9% and the selectivity for cyclohexanone oxime was 44.7%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.028 g (0.25 mmol) of hydroquinone (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 3.1% and the selectivity for cyclohexanone oxime was 54.3%.
- An oxidation reaction was performed in substantially the same manner as in Example 1 except that 0.082 g (0.5 mmol) of N-hydroxyphthalimide (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan) was used as an oxidation catalyst instead of the oxidation catalyst used in Example 1. As a result, it was found that the conversion of cyclohexylamine was 2.8% and the selectivity for cyclohexanone oxime was 79.6%.
- An oxidation reaction of cyclohexylamine was performed using hydrogen peroxide as an oxidizing agent, in accordance with the conventional techniques (e.g., U.S. Pat. No. 2,706,204) described under “Prior Art” above. Specifically, a reaction was performed as follows. Into a flask having a volume of 30 ml were charged 0.066 g (0.2 mmol) of Na2WO4.2H2O (manufactured and sold by Wako Pure Chemical Industries, Ltd., Japan), 10 ml of methanol and 0.496 g (5 mmol) of cyclohexylamine, and the internal temperature of the flask was elevated to 30° C. Subsequently, 1.7 g (15 mmol) of a 30% aqueous solution of hydrogen peroxide was dropwise added to the contents of the flask. The resultant mixture in the flask was then subjected to reaction for 3 hours while stirring and maintaining the temperature of the flask at 30° C., to thereby obtain cyclohexanone oxime. As a result, it was found that the conversion of cyclohexylamine was 76.4% and the selectivity for cyclohexanone oxime was 79.2%.
- The above-described results of the oximation of cyclohexylamine performed in each of Examples 1 to 14 and 18 to 22 and Comparative Example 6 show that, when an oxidation reaction of a substrate is performed by using the oxidation catalyst of the present invention and using a molecular oxygen as an oxidizing agent, advantages are obtained in that oxidation products can be produced with high selectivity and high efficiency, as compared to the case where hydrogen peroxide is used as an oxidizing agent.
- As described hereinabove, by the use of the oxidation catalyst of the present invention, oxidation of various substrates with a molecular oxygen can be efficiently performed under moderate conditions, thereby enabling production of a useful chemical compound economically and safely with high selectivity.
- The oxidation catalyst of the present invention can solve the various problems of the conventional processes for oxidation of a substrate, i.e., the problems that it is necessary to use an oxidizing agent which is expensive and/or explosive, that the selectivity for and yield of a desired compound become low, that complicated operations are necessary for purifying an oxidation product to remove therefrom a large amount of by-products, and that a large amount of energy is consumed.
- The oxidation catalyst of the present invention can be advantageously used for performing selective oxidation reaction of various types of substrates, especially, e.g., a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound and a heterocyclic compound. For example, by the use of the oxidation catalyst of the present invention, selective oxidation reactions using a molecular oxygen to produce an oxime compound or a nitro compound from a primary amine or produce a nitrone compound from a secondary amine, can be performed without using an expensive oxidizing agent, such as hydrogen peroxide or an organic hydroperoxide and under moderate conditions with high selectivity and high efficiency.
Claims (27)
1. An oxidation catalyst for use in the oxidation of a substrate with a molecular oxygen, comprising at least one member selected from the group consisting of a hydrazyl radical represented by the formula (1) below and a hydrazine compound represented by the formula (2) below,
wherein each of R1, R2 and R3 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
wherein two substituents selected from the group consisting of R1, R2 and R3 are optionally bonded to each other, to thereby form a ring.
2. The oxidation catalyst according to claim 1 , wherein said hydrazyl radical and said hydrazine compound are, respectively, represented by the following formulae (3) and (4):
wherein each of R4, R5, R6, R7 and R8 independently represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
each of R1 and R2 has the same definition as each of R4 to R8 except that any of R1 and R2 does not represent a hydrogen atom; and
wherein R1 and R2 are optionally bonded to each other, to thereby form a ring, and wherein with respect to one or two pairs of substituents selected from the group consisting of a pair of substituents R4 and R5, a pair of substituents R5 and R6, a pair of substituents R6 and R7 and a pair of substituents R7 and R8, the substituents of the or each pair are optionally bonded to each other, to thereby form a ring or two rings.
3. The oxidation catalyst according to claim 1 , wherein said hydrazyl radical is selected from the group consisting of 2,2-diphenyl-1-picrylhydrazyl, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazyl, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazyl, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazyl, 1,3,5-tris(N,N-diphenylhydrazyl)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazyl, carbazol-9-yl(2,4,6-trinitrophenyl)amidogen and N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazyl, and
said hydrazine compound is selected from the group consisting of 2,2-diphenyl-1-picrylhydrazine, 2,2-diphenyl-1-(2,6-dinitro-4-fluoromethylphenyl)hydrazine, 2,2-diphenyl-1-(4-cyano-2,6-dinitrophenyl)hydrazine, N,N-diphenyl-N′-(2,4,6-tricyanophenyl)hydrazine, 1,3,5-tris(N,N-diphenylhydrazino)-2,4,6-tricyanobenzol, 2,2-di-(4-tert-octylphenyl)picrylhydrazine, carbazol-9-yl(2,4,6-trinitrophenyl)amine and N-phenyl-N-(4-trifluoromethylphenyl)-N′-(2,4,6-trinitrophenyl)hydrazine.
4. The oxidation catalyst according to claim 1 , wherein said hydrazyl radical is 2,2-diphenyl-1-picrylhydrazyl, and said hydrazine compound is 2,2-diphenyl-1-picrylhydrazine.
5. The oxidation catalyst according to claim 1 , wherein said hydrazyl radical and said hydrazine compound are, respectively, represented by the following formulae (5) and (6):
wherein each of R1, R2 and R9 independently represents an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atom and groups; and
wherein two substituents selected from the group consisting of R1, R2 and R9 are optionally bonded to each other, to thereby form a ring.
6. The oxidation catalyst according to claim 1 , wherein said hydrazyl radical is selected from the group consisting of 1-phenylpyrazolidone-(3)-radical and 3,4-dihydro-1,4-dioxo-3-phenyl-2-phthalazinyl, and
said hydrazine compound is selected from the group consisting of 1-phenylpyrazolidine-3-one, 1-phenyl-1,2-dihydropyridazine-3,6-dione and 2-phenyl-2,3-dihydrophthalazine-1,4-dione.
7. The oxidation catalyst according to claim 1 , wherein said hydrazyl radical and said hydrazine compound are, respectively, represented by the following formulae (7) and (8):
wherein each of R10, R11 and R12 independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxyl group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfinyl group, a sulfonyl group or a heterocyclic group, or alternatively a group having two or more of these atoms and groups;
R13 has the same definition as each of R10 to R12 except that R13 does not represent a hydrogen atom; and
wherein two substituents selected from the group consisting of R11, R12 and R13 are optionally bonded to each other, to thereby form a ring.
8. The oxidation catalyst according to claim 1 , wherein said hydrazyl radical is selected from the group consisting of 2,4,6-triphenyl-3,4-dihydro-2H-[1,2,4,5]tetrazine-1-yl, 1,3,5,6-tetraphenylverdazyl, 1,3,5-triphenyl-6-oxoverdazyl and 1,3,5-triphenyl-6-thioxoverdazyl, and
said hydrazine compound is selected from the group consisting of 2,4,6-triphenyl-1,2,3,4-tetrahydro-[1,2,3,4]tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-[1,2,4,5]tetrazine, 1,3,5-triphenyl-6-oxotetrazine and 1,3,5-triphenyl-6-thioxotetrazine.
9. The oxidation catalyst according to claim 1 , which further comprises an oxidation promoter.
10. The oxidation catalyst according to claim 9 , wherein said oxidation promoter is a transition metal compound.
11. The oxidation catalyst according to claim 10 , wherein said transition metal is at least one member selected from the group consisting of the elements of the Groups 3 to 12 of the Periodic Table.
12. The oxidation catalyst according to claim 11 , wherein said transition metal is at least one member selected from the group consisting of lanthanoids, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn and Cd.
13. A method for producing a chemical compound, comprising contacting a substrate with a molecular oxygen in the presence of the oxidation catalyst of any one of claims 1 to 12 , thereby performing an oxidation reaction to form a chemical compound.
14. The method according to claim 13 , wherein said substrate is selected from the group consisting of a hydrocarbon, an alcohol, a carbonyl compound, an ether, an amine, a sulfur compound and a heterocyclic compound.
15. The method according to claim 14 , wherein said amine is a primary amine, and said chemical compound produced is an oxime compound or a nitro compound.
16. The method according to claim 15 , wherein said primary amine is represented by the following formula (9):
17. The method according to claim 16 , wherein said primary amine is cyclohexylamine, and said chemical compound produced is cyclohexanone oxime.
18. The method according to claim 14 , wherein said amine is a secondary amine, and said chemical compound produced is a nitrone compound.
19. The method according to claim 18 , wherein said secondary amine is represented by the following formula (10):
wherein each of R1 and R2 independently represents a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, and R3 has the same definition as each of R1 and R2 except that R3 does not represent a hydrogen atom; and
wherein two substituents selected from the group consisting of R1, R2 and R3 are optionally bonded to each other, to thereby form a ring.
20. The method according to claim 13 , wherein said oxidation reaction is either performed in a reaction medium which is at least one member selected from the group consisting of water and an organic solvent, or performed using said substrate as a reaction medium.
21. The method according to claim 20 , wherein said organic solvent is an aprotic solvent.
22. The method according to claim 21 , wherein said aprotic solvent is at least one member selected from the group consisting of a nitrile, a nitro compound, an ester, an ether and an amide.
23. The method according to claim 22 , wherein said nitrile is at least one member selected from the group consisting of acetonitrile and benzonitrile.
24. The method according to claim 22 , wherein said amide is at least one member selected from the group consisting of dimethylformamide and dimethylacetamide.
25. The method according to claim 13 , wherein said at least one compound selected from the group consisting of the hydrazyl radical and the hydrazine compound is used in an amount of from 0.0001 to 1 mole per mole of said substrate.
26. The method according to claim 13 , wherein said oxidation catalyst further comprises an oxidation promoter, and said oxidation promoter is used in an amount of from 0.00005 to 0.8 mole per mole of said substrate.
27. The method according to claim 13 , wherein said oxidation reaction is performed under reaction conditions wherein the temperature is from 0 to 200° C. and the pressure is from atmospheric pressure to 20 MPa.
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2004
- 2004-07-22 CN CN2004800230296A patent/CN1835800B/en active Active
- 2004-07-22 US US10/565,886 patent/US20060229471A1/en not_active Abandoned
- 2004-07-22 JP JP2005512017A patent/JP4895610B2/en not_active Expired - Fee Related
- 2004-07-22 KR KR1020067001401A patent/KR100676115B1/en active IP Right Grant
- 2004-07-22 EP EP04747810.2A patent/EP1655070B1/en active Active
- 2004-07-22 WO PCT/JP2004/010399 patent/WO2005009613A1/en active IP Right Grant
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2009
- 2009-11-13 US US12/591,266 patent/US8133834B2/en active Active
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US2966455A (en) * | 1957-08-14 | 1960-12-27 | Sun Oil Co | Refining hydrocarbons with hydrazines and hydrogenation catalysts |
US3095394A (en) * | 1960-05-03 | 1963-06-25 | Union Carbide Corp | Polyolefin oxides stabilized with 1, 1-diphenyl-2-picrylhydrazine and 1, 1-diphenyl-2-picrylhydrazyl |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070244274A1 (en) * | 2006-04-18 | 2007-10-18 | University of Victoria Innovation | Verdazyl agents for the production of free standing polymers |
US7638587B2 (en) * | 2006-04-18 | 2009-12-29 | University of Victoria Innovation and Development Corporatin | Verdazyl agents for the production of free standing polymers |
US20100050583A1 (en) * | 2008-09-02 | 2010-03-04 | 3M Innovative Properties Company | Ammonia-free gaseous air filter |
US8293333B2 (en) * | 2008-09-02 | 2012-10-23 | Jeffrey R. Dahn | Ammonia-free gaseous air filter |
US9656950B2 (en) | 2013-03-27 | 2017-05-23 | Sumitomo Chemical Company, Limited | Method for producing oxime |
Also Published As
Publication number | Publication date |
---|---|
US8133834B2 (en) | 2012-03-13 |
WO2005009613A1 (en) | 2005-02-03 |
JP4895610B2 (en) | 2012-03-14 |
CN1835800B (en) | 2010-04-28 |
EP1655070B1 (en) | 2015-07-15 |
CN1835800A (en) | 2006-09-20 |
EP1655070A1 (en) | 2006-05-10 |
EP1655070A4 (en) | 2009-11-11 |
KR100676115B1 (en) | 2007-02-02 |
US20100069670A1 (en) | 2010-03-18 |
JPWO2005009613A1 (en) | 2007-09-20 |
KR20060027407A (en) | 2006-03-27 |
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